CN1057792C - Bleaching compositions comprising peroxyacid activators having amide moieties - Google Patents

Bleaching compositions comprising peroxyacid activators having amide moieties Download PDF

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CN1057792C
CN1057792C CN94192173A CN94192173A CN1057792C CN 1057792 C CN1057792 C CN 1057792C CN 94192173 A CN94192173 A CN 94192173A CN 94192173 A CN94192173 A CN 94192173A CN 1057792 C CN1057792 C CN 1057792C
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bleach
alkyl
composition
activating agent
formula
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CN1124038A (en
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A·D·韦利
M·E·宾恩斯
R·T·哈斯霍恩
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Procter and Gamble Co
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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
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • 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
    • C11D3/3917—Nitrogen-containing compounds

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Abstract

The present invention relates to a method of cleaning fabrics in washing machines which have parts made of natural rubber using laundry detergents comprising amido-derived bleaching activators and a source of hydrogen peroxide, such that said natural rubber parts of said machines are substantially undamaged by products of the perhydrolysis reaction between the activator and hydrogen peroxide.

Description

Contain bleaching composition with amide moieties peroxyacid activators
Field of the present invention
The present invention relates to contain the detergent for washing clothes of activated bleaching system.
Background of the present invention
People know already peroxygen bleach for get on from fabric except that spot and/or dirt be effectively, but this SYNTHETIC OPTICAL WHITNER is a temperature dependent.In 60 ℃ the laundry aqueous solution, peroxygen bleach only part is effective.In temperature was lower than 60 ℃ the aqueous solution, peroxygen bleach became relative nullity.Therefore, people carried out a large amount of industry research with exploitation contain activator bleach systems so that peroxygen bleach in being lower than 60 ℃ the laundry aqueous solution effectively.
Open in the prior art as many materials of effective bleach-activating agent.Can widely used a kind of activator be tetraacetyl ethylene diamine (TAED).TAED especially provides effective hydrophilic cleaning to the beverage spot, but for dark yellow spot, as those spots that the grease by human secretory produces, the effect of TAED is limited.Another kind of type activator such as nonanoly acyloxy benzene sulfonate (NOBS) and to contain chain alkyl other activator partly usually be hydrophobic in essence and provide fabulous cleaning performance for dark spot.Yet many hydrophobic activation agent of being developed so far can cause damage for natural rubber parts used in some washing machine.Because to this negative interaction of part of washing machine, therefore the selection for the washing composition that adds bleach systems is restricted.Especially all the more so for the used washing composition/SYNTHETIC OPTICAL WHITNER in Europe, because many washing machines that make in Europe have been equipped with key part, as drainage tray flexible pipe and electronic packing ring, they are that natural rubber makes.Therefore need a kind of bleach system, it can be removed dark dirt and not damage the natural rubber parts that exist in the washing machine fully.
Now determined generally to contain hydrophobic bleach activator and hydroperoxide source in the conventional bleaching system, activator passed through hydrolysis reaction and formed peroxyacid bleach.The by product of crossing hydrolysis reaction between this bleach-activating agent and the hydrogen peroxide is diacyl peroxide (DAP) material.People also further find, the oily mater insoluble often by the DAP material that hydrophobic bleach activator produces, that difference is dispersed, and it has constituted the residue that can be deposited on the natural rubber machine part that contacts with the aqueous solution of doing washing.This oily DAP residue can form film on the natural rubber machine part, and rubber is produced free radical and superoxide damage, finally causes component failure.Especially for the rubber components that contacts with wash water solution for a long time, all the more so as the drainage tray flexible pipe.
According to the present invention, have now found that a class has formed hydrophobic amido peracid derived from the hydrophobic bleach activator of amic acid through hydrolysis reaction, and do not produce deleterious oily DAP class material.The present invention without limits here, it is believed that by derived from the bleach-activating agent of amic acid to cross the DAP class material that hydrolysis reaction produces be insoluble crystalline solid.This solid DAP material does not form mulch film; Therefore the natural rubber part of washing machine does not contact with DAP class material for a long time, and keeps not damaged by bleach system of the present invention substantially.
Therefore the invention solves for effective hydrophobic bleach agent system need problem for a long time, this hydrophobic bleach system does not produce free radical for the natural rubber parts in the washing machine and superoxide damages.The invention provides in washing machine method, and natural rubber is not damaged by bleach system substantially with the bleach system laundering of textile fabrics with parts that natural rubber makes.
Background technology
The people's such as Burn that on January 6th, 1987 issued U.S.4,634,551 disclose amido peroxy acid bleach compound used among the present invention and their such precursors.Also referring to the people's such as Burn that issued on August 1st, 1989 U.S.4,852,989 and the people's such as Hodge that issue October 30 nineteen ninety U.S.4,966,723.
General introduction of the present invention
The present invention relates to the method for laundering of textile fabrics in automatic washing machine with parts (it is responsive for oxidative degradation) that natural rubber makes.This method comprises fabric contained in said washing machine in the aqueous solution of bleach system and stirs; this bleach system contains bleach-activating agent; the generation peroxy acid is reacted in peroxide source in this bleach-activating agent and the said aqueous solution; and not generating oily diacyl peroxide (DAP), said like this natural rubber parts are not damaged by the by product of said reaction substantially.
The amido deutero-peroxy acid that is produced by reaction has general formula:
Figure C9419217300081
R in the formula 1For containing about 1 alkyl, aryl, alkaryl, R to about 14 carbon atoms 2For containing about 1 alkylidene group, arylidene or alkyl arylene, R to about 14 carbon atoms 3For H or contain have an appointment 1 alkyl, aryl, alkaryl to about 10 carbon atoms.
The bleach system of said method comprises: a) at least about 0.1%, preferred about 1% can produce the peroxy bleaching compound of hydrogen peroxide to about 75% (weight) in the aqueous solution; And b) at least about 0.1%, preferred about 0.1% to about 50% (weight) bleach-activating agent, and it is selected from: i) Or its mixture, R in the formula 1For containing alkyl, aryl or the alkaryl of 1 to 14 carbon atom of having an appointment: R 2For containing have an appointment 1 alkylidene group, arylidene or alkyl arylene, R to about 14 carbon atoms 5For H or contain have an appointment 1 alkyl to about 10 carbon atoms, aryl or alkaryl, L is a leavings group; Ii)
Figure C9419217300091
R in the formula 1Be H, alkyl, alkaryl, aryl, aralkyl, R 2, R 3, R 4And R 5Can be identical or different substituting group, be selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino, COOR 6(R wherein 6Be H or alkyl) and carbonyl functional group: and ii) i) and mixture ii).
Preferably by the hydrogen peroxide and the bleach-activating agent b that a) produce) mol ratio greater than about 1.0.Most preferably by the hydrogen peroxide and the bleach-activating agent b that a) produce) mol ratio at least about 1.5.That the present invention also comprises is granular, the laundry composition of pulpous state, liquid or stick form, and it contains aforesaid bleach system and decontamination component, and the content of decontamination component in said composition hereinafter has been described.
Preferred b) i) bleach-activating agent of type is R in the formula 1For containing about 6 alkyl, R to about 12 carbon atoms 2Contain about 1 to about 8 carbon atoms and R 5Those bleach-activating agents for H or methyl.Particularly preferred b) i) the type bleach-activating agent is R in the above general formula 1For containing about 7 to about 10 carbon atoms, R 2Those bleach-activating agents that contain about 4 to 5 carbon atoms.
Preferred b) ii) the type bleach-activating agent is R in the formula 2, R 3, R 4And R 5Be H, R 1Those bleach-activating agents for phenyl.
Peroxy bleaching compound can be arbitrarily peroxide source, be preferably selected from Sodium peroxoborate monohydrate, peroxyboric acid tetrahydrate, SPC-D, trisodium phosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide and its mixture.Most preferred peroxy bleaching compound is selected from Sodium peroxoborate monohydrate, sodium perborate tetrahydrate, SPC-D and its mixture.Most preferred peroxy bleaching compound is a SPC-D.
Also can be used in combination as TAED with bleach-activating agent of the present invention and to the hydrophilic completely activator of rubber, the weight ratio of general amido deutero-activator and TAED is 1: 5 to 5: 1, preferred about 1: 1.Another kind ofly important the hydrophilic completely activator of rubber is comprised the N-acyl caprolactam activators, wherein acyl moiety has formula R 1-CO-, R in the formula 1Contain 6 or be lower than 6 carbon atoms.Most preferred hydrophilic Caprolactam activator comprises formyl radical hexanolactam, ethanoyl hexanolactam and benzoyl caprolactam.
Method of cleaning fabrics comprises fabric contained in the aqueous solution of detergent composition and stirs that this detergent composition contains at least about the conventional detergent component of 200ppm, at least about the 25ppm bleaching compounds with at least about the 25ppm bleach-activating agent in said washing machine.Preferably, the aqueous solution contains the 900ppm that has an appointment to about 20, the conventional detergent component of 000ppm, and about 100ppm is to about 25000ppm bleaching compounds and about 100ppm about 2500ppm bleach-activating agent extremely.This method can be lower than under about 60 ℃ in temperature successfully carries out, certainly in wash temperature up under the boiling point, this method is in full force and effect and rubber components is still completely.
It is about 1% to 99.8% that the conventional detergent component that uses in the detergent composition of comprehensive preparation provided by the invention can comprise, preferably the detersive surfactant of about 5%-80%.The detergent composition alternative contains the 5%-80% decontamination lotion promoter of having an appointment.Other selectivity detergent component also can be included in the washing composition/bleaching composition of comprehensive preparation provided by the invention.
Except as otherwise noted, all percentage ratios, ratio and ratio herein is by weight.All documents of quoting are as this paper reference.
Detailed description of the present invention
The present invention relates to the method for laundering of textile fabrics in the automatic washing machine of the parts that the rubber that has the oxidative degradation sensitivity makes.The bleach system that uses among the present invention comprises that to the natural rubber article that natural rubber part of washing machine and other contact with bleach system the fabric that contains natural rubber and natural rubber elastic material is safe.The bleach system that uses among the present invention can be effectively and the fabric face bleaching is provided fully, gets on except that spot and/or dirt from fabric thus, comprises " dead color " dirt.Dark-coloured dirt be repeatedly use with cycles of washing after still amass dirt on fabric, therefore, it causes that white fabrics becomes ash or yellow hue at last.These dirts may be the mixtures of particle and greasy material.Remove this type dirt and be sometimes referred to as " cleaning dark-coloured fabric ".
Other advantages that bleach system of the present invention and activator provide are, they are safe to fabric unexpectedly and cause fading still less than other activator when using by method provided by the invention.
Its bleaching mechanism, especially superficial bleaching mechanism is not fully by known to the people.Yet, it is generally acknowledged that bleach-activating agent has formed peroxycarboxylic acid through carrying out nucleophilic attack by superoxide anion (it is to be produced by the hydrogen peroxide that peroxygen bleach is emitted).This reaction was commonly referred to hydrolysis reaction.
It is also believed that the bleach-activating agent among the present invention can even more effectively emit peroxygen bleach under laundry aqueous temperature (wherein bleach-activating agent does not need the temperature of activated bleaching agent, promptly more than 60 ℃).Therefore, use bleach system of the present invention, only need a small amount of peroxygen bleach just to obtain obtaining the superficial bleaching performance of par with independent use peroxygen bleach.
Bleach-activating agent
The hydrophobic bleach activator that the present invention uses is compound or its mixture with acid amides replacement of following general formula:
Figure C9419217300121
R in the formula 1, R 2And R 5As above definition, in fact L can be the leavings group of any suitable.Leavings group can be any group that is replaced from bleach-activating agent owing to peroxide oxide compound negatively charged ion nucleophilic attack bleach-activating agent.Like this, cross the hydrolysis reaction result and formed peroxycarboxylic acid.Usually, for the leavings group that is fit to, it must have the electrophilic effect.It also should form stable entity so that its reversed reaction speed can be ignored.This helped oxyhydroxide negatively charged ion nucleophilic attack.
The L group must have enough reactivities for the reaction that takes place in Best Times scope (for example cycles of washing).Yet if the L reactivity is too strong, this activator is used for bleaching composition and will be difficult to stabilized.These character are parallel with the PKa of the conjugate acid of leavings group generally.The leavings group that shows this shape and be normally their conjugate acid has PKa about 4 to about 13 scopes, and preferred about 6 to about 11, most preferably from about those groups of 8 to about 11.
Preferred bleach-activating agent is R in the above general formula 1, R 2And R 5Be selected from those bleach-activating agents of following group and its mixture with definition, the L of peroxy acid:
Figure C9419217300122
Figure C9419217300131
R wherein 1For containing have an appointment 1 alkyl, aryl or alkaryl, R to about 14 carbon atoms 3For containing 1 alkyl chain, R to about 8 carbon atoms 4Be H or R 3, Y is H or solubilizing group.
Preferred solubilizing group is-SO 3 -M +,-CO 2 -M +,-SO 4 -M +,-N +(R 3) 4X -And O＜N (R 3) 3, most preferably-SO 3 -M +With-CO 2 -M +, R wherein 3For containing about 1 to about 4 carbon atom alkyl chains, M is for offering the deliquescent positively charged ion of bleach-activating agent, and X is for offering the deliquescent negatively charged ion of bleach-activating agent.Preferred M is the ammonium cation of basic metal, ammonium or replacement, and sodium and potassium are most preferred, and X is halogenide, oxyhydroxide, Methylsulfate or acetate negatively charged ion.Should be noted that the bleach-activating agent that has leavings group (not containing solubilizing group) should be scattered in the liquid lime chloride well for the dissolving that helps them.
Preferred bleach-activating agent is those bleach-activating agents that L is selected from following group in the above general formula:
Figure C9419217300132
R in the formula 3As above definition, Y is-SO 3 -M +Or-CO 2 -M +, wherein M as above defines.
The another kind of important bleach-activating agent of organic peracid of the present invention is provided and since this activator ring of superoxide anion nucleophilic attack on the carbonylic carbon atom result generation ring-opening reaction.This ring-opening reaction comprises by hydrogen peroxide or its negatively charged ion encircling the attack of carbonyl.The example of open loop bleach-activating agent can be authorized people's such as Hodge U.S.4,966,723 referring to October 30 nineteen ninety.
Comprise benzoxazine type activator by the disclosed this activator compound of Hodge, have formula:
Figure C9419217300141
The activator that comprises the benzoxazine type of replacement: R in the formula 1Be H, alkyl, alkaryl, aryl, aralkyl, R 2, R 3, R 4And R 3It can be identical or different substituting groups.It is selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino, COCR 6(R wherein 6Be H or alkyl) and the carbonyl functional group.
Preferred benzoxazine type activator is:
Figure C9419217300151
The used bleach-activating agent of the present invention be bleach system or detergent composition weight at least about 0.1%, preferably about 0.1-50%, more preferably about 1%-30%, 3%-25% most preferably from about.
When using activator to advance, between about 8.5 and 10.5, preferably between 9.5 to 10.5, obtained best superficial bleaching performance to help the washing soln of crossing hydrolysis reaction for pH.With known for the material of buffer reagent can obtain this pH scope usually, this material is the optional ingredient of this paper bleach system.
Peroxy bleaching compound
Wherein use the bleach system of bleach-activating agent also to contain the peroxygen bleach that can in the aqueous solution, discharge hydrogen peroxide of promising main ingredient.
The peroxygen bleach system that the present invention uses is to produce those of hydrogen peroxide in the aqueous solution.These compounds are well known in the prior art, comprise hydrogen peroxide and alkali metal peroxide, organic peroxy bleaching compounds such as globefish superoxide and inorganic persalts bleaching compounds such as alkali-metal perborate, percarbonate, superphosphate etc.If desired, also can use the mixture of two or more this bleaching compounds.
Preferred peroxy bleaching compound comprises Sodium peroxoborate, commercial available one, three and Sodium peroxoborate, SPC-D, trisodium phosphate peroxyhydrate, the urea peroxyhydrate of tetrahydrate form.And sodium peroxide.Particularly preferably be sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D.SPC-D is particularly preferred, because it is very stable and can also be dissolved in the aqueous bleaching solution very soon when storing.It is believed that this quick dissolving result has formed the percarboxylic acids of high level, therefore strengthened the superficial bleaching performance.
Most preferred percarbonate is not coat or coat form.The mean particle size of the percarbonate of Bao Fuing not is about 400 to about 1200 microns, and most preferred about 400 to about 600 micrometer ranges.If use the percarbonate that coats, preferably coat the mixture that material comprises carbonate and vitriol, silicate, borosilicate or aliphatic carboxylic acid.
Peroxy bleaching compound be bleach system or detergent composition weight at least about 0.1%, preferred about 1% to about 75%, more preferably about 3% to about 40%, most preferably from about 3% to about 25%.
In bleach system, generally in about 2: 1 to about 1: 5 scopes, in preferred embodiments, proportional range is about 1: 1 to about 1: 3 to the weight ratio of bleach-activating agent and peroxy bleaching compound.
Bleach-activating agent/bleaching compounds system itself can be used as the albic material use herein.But this bleach system is particularly useful in can containing various detergent additive tensio-active agents, washing assistant, enzyme, composition like disclosed component hereinafter.
Detersive surfactant
The amount of included detersive surfactant in the detergent composition of comprehensive preparation provided by the invention, its according to employed concrete tensio-active agent and desired effect can be detergent composition weight about 1% to about 99.8% scope.The preferred stain release tensio-active agent is about 5% to about 80% of a composition weight.
Detersive surfactant can be nonionic, negatively charged ion, both sexes, zwitter-ion or cats product.Also can use these surfactant mixtures.Preferred detergent composition comprises the mixture of anionic detersive surfactant or anion surfactant and other tensio-active agent, especially nonionogenic tenside.
The non-limiting example of the tensio-active agent that uses among the present invention comprises conventional C 11-C 18Alkylbenzene sulfonate and primary, secondary and random alkyl-sulphate, C 10-C 18Alkyl alkoxy sulfate, C 10-C 18The poly-glycosides of alkylpolyglycosides and their corresponding sulfations, C 12-C 18α-sulfonated fatty acid ester, C 12-C 18Alkyl alkoxylates and C 12-C 18Alkyl phenolic alkoxy thing (especially ethoxylate and blended oxyethyl group/propoxylated glycerine), C 12-C 18Trimethyl-glycine and sultaine (" sultaines "), C 10-C 18Amine oxide etc.Other conventional useful tensio-active agent is listed in the general document.
Especially in the present invention the additional ionic surfactant pack of a useful special class is drawn together the polyhydroxy fatty acid amide of following formula:
Figure C9419217300171
R wherein 1Be H, C 1-C 8Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, preferred C 1-C 4Alkyl, C more preferably 1Or C 2Alkyl, C most preferably 1Alkyl (being methyl); R 2Be C 3-C 32Hydrocarbyl portion, preferred straight chain C 7-C 19Alkyl or alkenyl, straight chain C more preferably 9-C 17Alkyl or alkenyl, most preferably straight chain C 11-C 19Alkyl or alkenyl or its mixture: Z are connected in polyhydroxy alkyl part on the linear hydrocarbyl chain or the derivative of its alkoxyl group (preferred oxyethyl group or propoxy-) for having at least 2 hydroxyls (in the situation of Glycerose) or at least 3 hydroxyls (in the situation of other reducing sugar) straight chain.Z is preferably derived from the reducing sugar in the reductive amination reaction; More preferably Z is a glycosyl part, and suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar and Glycerose.Can use as raw material be high glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle and above listed monose.Can obtain being used as the sugar component mixture of Z by these maize treacle.It should be understood that we want to get rid of other suitable raw material anything but.Z is preferably selected from-CH 2-(CHOH) n-CH 2OH ,-CH (CH 2OH)-(CHOH) N-1-CH 2CH ,-CH 2-(CHOH) 2(CHOR ') (CHOH)-CH 2OH wherein n is 1 to 5 integer, comprise 1 and 5 itself, R ' be the single or many saccharidess of H or cyclic and its alkoxy derivative.Glycosyl most preferably, wherein n is 4, particularly-CH 2-(CHOH) 4-CH 2OH.
In formula (I), R 1Can be for example N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-isobutyl-, N-2-hydroxyethyl or N-2-hydroxypropyl.In order to obtain best whipability, R 1Be preferably methyl or hydroxyalkyl.Low if desired whipability, R 1Be preferably C 2-C 8Alkyl, especially n-propyl, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl and 2-ethylhexyl.
Figure C9419217300181
Can be for example coconut monoethanolamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc.
Decontamination lotion promoter
The selectivity detergent component of Shi Yonging comprises that inorganic and/or organic decontamination lotion promoter is to help control mineral hardness in the present invention.If use these washing assistants, it is about 5% to about 80% of a detergent composition weight.
Inorganic detergent builders comprises, but be not restricted to this, polyphosphate (exemplify and be tri-polyphosphate, pyrophosphate salt and glassy polymeric metaphosphate), phosphoric acid salt, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate) yet, basic metal, ammonium, the alkylammonium salt of vitriol and silico-aluminate need not have the washing assistant of phosphoric acid salt in some occasion.
The example of silicate-like builder is an alkalimetal silicate, particularly has SiO 2: Na 2O is than those silicate in 1.6: 1 to 3.2: 1 scopes, and layered silicate, as is described in the lamina sodium silicate in the United States Patent (USP) 4,664,839 of the H.P.Rieck that authorized on March 12nd, 1987, can buy from Hoechs, and trade mark is " SKS ".SKS-6 is particularly preferred layered silicate washing assistant.
Carbonate builders, especially surface-area is greater than 10m 2The lime carbonate of the porphyrize of/g is the washing assistant that preferably can be used in the granular composition.This alkaline carbonate helps the density of the washing composition of washing can be in the 450-850g/l scope.Water content preferably is lower than 4%.
The example of carbonate builders is alkaline-earth metal and the alkaline carbonate that is disclosed in the German patent application of delivering on November 15th, 1,973 2,321,001.
The silico-aluminate washing assistant is useful especially among the present invention.Preferred silico-aluminate is a zeolite builders, and it has following formula:
Naz[(AlO 2) z (SiO 2) y] xH 2O wherein z and y is at least 6 integer, and the mol ratio of z and y is 1.0 to about 0.5 scope, and x is about 15 to about 264 integer.
Useful silico-aluminate ion exchange material is commercial commercially available.These silico-aluminates can be crystallization or amorphous structure, and can be naturally occurring silico-aluminate or the synthetic silico-aluminate that obtains.The method for preparing the silico-aluminate ion exchange material is disclosed in the people's such as Krummel that invested on October 12nd, 1976 United States Patent (USP) 3,985, the people's such as Corkill that on August 12nd, 669 and 1986 issued U.S.4,605, in 509, be used for the preferred synthetic crystallization silico-aluminate of this paper ion exchange material and be by be registered as, Zeolite A, ZeoliteP (B) (comprise be disclosed among the EPO 384,070 those) and Zeolite X.Preferably aluminosilicate salt has the granularity of diameter for about 0.1-10 micron.
The suitable organic decontamination lotion promoter of the object of the invention comprises, but is not restricted to this, widely various many carbonyls phosphate compounds, as the ether multi-carboxylate, comprise the oxo disuccinate, as be disclosed in the U.S.3 that issued on April 7th, 1964,128, the people's such as Lamberti that on January 8th, 287 and 1972 issued U.S.3, in 635,830, also referring to the people's such as Bush that issued on May 5th, 1987 U.S.4, " TMS/TDS " in 663,071.
Other useful decontamination lotion promoter comprises the multipolymer, 1 of ether hydroxypolycarboxylic acid salt, maleic anhydride and ethene or vinyl methyl ether, 3,5-trihydroxybenzene-2,4, basic metal, ammonium and the substituted ammonium salt of 6-trisulfonic acid and carboxymethyl oxosuccinic acid, various polyacetic acid such as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), and multi-carboxylate such as mellitic acid, glass acid, oxidation disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and its water-soluble salt.
The Citrate trianion washing assistant, for example citric acid and its water-soluble salt (special is sodium salt) are preferred multi-carboxy acid salt washing agents, also can be used for granular composition, especially are used in combination with zeolite and/or layered silicate washing assistant.
Also having suitable in detergent composition of the present invention is the people's such as Bush that authorize on January 28th, 1986 U.S.4, the compound in 566,984.
In using phosphorated washing assistant situation, especially in the manual manipulation in the used stick prescription, can use various alkali metal phosphates, tripoly phosphate sodium STPP, trisodium phosphate and the sodium orthophosphate known as the crowd.Phosphate builders such as ethane-1-hydroxyl-1,1-diphosphate and other known phosphate (referring to, U.S.3 for example, 159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) also can be used.
The selectivity detergent additive
As embodiment preferred, the conventional detergent component that uses among the present invention can be selected from general detergent composition component, as detersive surfactant and decontamination lotion promoter.Detergent component optionally include help or strengthen cleaning performance, to the nursing of the basic thing that is washed or improve one or more other detergent additives of the aesthetic feeling of detergent composition.The detergent additive of common detergent composition is included in people's such as Baskerville U.S.3, the component of mentioning in 936,537.These additives that can be included in the detergent composition used in the present invention (are to use with the content that their routine techniquess are determined, be generally detergent component 0% to about 20%, preferred about 0.5% to about 10%), comprise enzyme, especially proteolytic enzyme, lipase and cellulase, pigment, suds booster, suds suppressor, anti-tarnishing agent and/or sanitas, soil-suspending agent, dirt release agent, dyestuff, add the material white dyes, sterilant, basifier, hydrotropic agent, antioxidant, spices, solvent, solubilizing agent, clay soil removal/anti is deposition agent again, polymeric dispersant, processing aid, fabric sofetening component control electrostatic reagent etc.
Bleach systems selectivity, but preferably also comprise sequestrant, it has not only strengthened bleach stability, and has assisted in removing the spot of polyphenol by the heavy metal ion that removing can make SYNTHETIC OPTICAL WHITNER decompose, as the tealeaves spot etc.Various sequestrants comprise the DEOUEST amino phosphonates do of being buied by Monsanto, nitrilotriacetic acid(NTA) salt, hydroxyethylethylene diamine tri-acetic acid salt etc., and their this purposes is known.Preferred biodegradable non-phosphorus integrated agent comprises ethylenediamine disuccinate (" EDDS ", referring to the U.S.4 of Hartman and Perkins, 704,233), quadrol-N, N '-glutaminate (EDDG) and 2-carbonyl propylene diamine-N, N '-disuccinate (HPDDS) compound.This sequestrant can their basic metal or the form of alkaline earth salt use, general content is about 0.1% to about 10% of the present composition.
Detergent composition used among the present invention optionally includes, and except bleach system of the present invention, also has one or more to plant other conventional whiteners, activator or stablizer, and it does not react with natural rubber or be harmless to natural rubber.Generally, the prescription teacher can guarantee that used bleaching compounds and detergent compositions are compatible, routine test, and as in the presence of component independent or preparation fully, the bleaching activity of test when storing can be used for above purpose test.
The object lesson that mixes the selectable bleach-activating agent in the present composition comprises tetraacetyl ethylene diamine (TAED) and N-acyl caprolactam.Most preferred N-acyl caprolactam comprise benzoyl caprolactam and wherein acyl group be formula R 1-CO-, R in the formula 1For containing 1 to 12 carbon atom, those of the alkyl of preferred 1 to 6 carbon atom, aryl, alkaryl, alkoxy aryl.
This class bleaching compounds and reagent can prior art be determined, and their conventional amount used optionally is included in the detergent composition, and generally their consumption is 0% to about 15% of a detergent composition weight.
Bleach-activating agent of the present invention is useful especially in the conventional laundry detergent composition, as at granulated detergent or laundry used those in the stick.The U.S.3 of the Okenfuss that issue April 13 nineteen sixty-five, 178,370 have described laundry detergent bar and their method of preparation.The Philippine patents 13,778 of the Anderson that on September 23rd, 1980 issued has been described synthetic detergent laundry stick.The method for preparing detergent for washing clothes by various pressing methods is commonly known in the art.
Following institute is in order to further specify the present invention to example, rather than is used for limiting the present invention.
Example I
Synthesizing of (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate (NACA-OBS)
6-nonanoyl hexosamine (NACA): be reflected in the 12L3 neck flask that thermometer, dropping funnel and mechanical stirrer are housed and carry out.In the solution (being cooled to room temperature) that 212g (5.3mol) sodium hydroxide and 6L water make, add 694.3g (5.3mol) 6-aminocaprolc acid.Mixture is cooled to 10 ℃, is that 10-15 ℃ slow logistics is to the 1L diethyl ether solution that wherein adds 694.3g (5.3mol) pelargonyl chloride (about 2.5 hours) to keep temperature.In reinforced process and thereafter in the acidifying process, make reaction remain on pH11-12 by regularly adding 50%NaOH.Add after the material, be reflected at 10 ℃ of following restir 2 hours, and make it to rise to room temperature, be acidified to pH1 with dense HCl afterwards.With the precipitated product vacuum filtration, filter cake 8L water washing twice, product spends the night at air drying.Then it is suspended in the 3L hexane, filters and with other 3L hexane wash.Then product vacuum-drying is spent the night (50 ℃ 1mm) obtain 1354g (94%) NACA.
Chloride of acid (NACA-Cl): be reflected in the 5L3 neck flask that dropping funnel, mechanical stirrer and argon purge are housed and carry out.In the 2L toluene suspension of 542g (2.0mol) NACA, add (through 30 minutes with slow logistics) 476g (4.0mol) thionyl chloride.In the solid dissolution process, this mixture was at room temperature stirred 4 hours.Solution is partly evaporated (30 ℃, 10mm) remove excessive thionyl chloride, obtain 905g NACA-Cl/ toluene solution (containing about 2mol NACA-Cl).IR spectrum confirms that COOH is converted into COCl.
(the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate (NACA-OBS): reactor is the 12L3 neck flask that condenser, mechanical stirrer and static argon gas feed are housed.(p-phenolsulfonic acid's disodium is previously prepared and in the vacuum still dry (110 ℃ before use to add 647g above-mentioned NACA-Cl/ toluene solution (1.43mol), 6L toluene and 310.8g (1.43mol) p-phenolsulfonic acid disodium salt in reactor, 0.1mmhg, 18 hours).This mixture was refluxed 18 hours.Be cooled to after the room temperature, product is collected on the Buchner funnel and drying obtains the thick solid of 725g.This crude product extracts with 87: 13 (v/v) methanol of 7L, and heat filtering also makes it recrystallization at room temperature.The throw out that obtains is filtered and vacuum-drying (50 ℃ 0.1mm) obtained the light brown product of 410g (being calculated as 64% by NACA) in 18 hours. 1The H spectrometry 6.75 and the 7.55ppm place have little bimodally, the unreacted phenolsulfonate of trace has been described.In addition, this spectrum is consistent with expected structure figure, does not observe other impurity.
Example II
Preparation comprises the granular detergent composition of following component:
Composition weight %
C 12Linear alkylbenzene sulfonate 22
Phosphoric acid salt (being tripoly phosphate sodium STPP) 30
Yellow soda ash 14
Water glass 3
SPC-D 5
Ethylenediamine disuccinate sequestrant (EDDS) 0.4
Sodium sulfate 5.5
(the amino caproyl of 5-nonanoyl) oxygen base benzene sulfonate 5
The micro substance additive *With water balance to 100%
*Can be selected from conventional substances, as CaCO 3, talcum powder, clay, silicate etc.
Use the bleachability of following measurement of test method said composition and to the influence of natural rubber part of washing machine.
Prepare aqueous mixture in the said detergent composition, spraying drying with mixing machine to heat and the stable component of alkalescence.Sneak into other component, make this mixture contain the component of listed content in the table.
This detergent particles and the 5lb (2.3kg) that will contain bleach-activating agent comprise the natural rubber article, as elastic in advance the washing fabric add together in the automatic washing machine that natural rubber drainage tray flexible pipe is housed.Use the washing composition and the bleach-activating agent of effective weight, make in the washing machine that 17 gallons of (65L) water are housed, the former concentration is 950ppm, and latter's concentration is 50ppm.Before adding washing composition and bleach system, used glassware for drinking water has 7g/ gallon hardness, and pH is 7 to 7.5 (after adding the detergent bleaching system, pH about 9 to about 10.5).
Fabric is done full cycle washing (12 minutes) under 35 ℃ (95 °F), and 21 ℃ of (70) rinsings.This washing methods is repeated cycles of washing 2000 times, the natural rubber parts is produced breaking property or palpability damage, also the natural rubber article is produced and damages.
EXAMPLE III
Preparation comprises the granular detergent composition of following component:
Composition weight %
Negatively charged ion alkyl-sulphate 7
Nonionogenic tenside 5
Zeolite (0.1-10 micron) 10
Trisodium citrate 2
SKS-6 silicate-like builder 10
Vinylformic acid toxilic acid polymkeric substance 4
(6-nonanoyl caproyl) oxygen base benzene sulfonate 5
SPC-D 15
Yellow soda ash 5
Ethylenediamine disuccinate sequestrant (EDDS) 0.4
Suds suppressor 2
Enzyme *1.5
Dirt release agent 0.2
Micro substance, additive *With water balance to 100%
*The mixture of 1: 1: 1 proteolytic enzyme, lipase and cellulase
*Can be selected from conventional substances, as CaCO 3, talcum powder, clay, silicate etc.
Use the bleachability of following this detergent composition of measurement of test method and to the influence of natural rubber part of washing machine.
Prepare aqueous mixture in the said detergent composition, spraying drying with mixing machine to heat and the stable component of alkalescence.Sneak into other component, make said composition contain the component of listed content in the table.
The detergent particles adding that will contain bleach-activating agent by dispersion slot is equipped with in the automatic washing machine of natural rubber drainage tray flexible pipe, adds the fabric that 5lb (2.3kg) washs in advance simultaneously together.Use the washing composition and the bleach-activating agent of effective weight, make in the washing machine that 17L water is housed, the former concentration is 8000ppm, and latter's concentration is 400ppm.Before adding washing composition and bleach system, used glassware for drinking water has 10g/ gallon hardness, and pH is 7 to 7.5 (after adding washing composition and bleach system, pH about 9 to about 10.5).
Fabric is done full cycle washing (40 minutes) under 40 ℃ (104 °F), and in 21 ℃ (70) rinsing down.This washing methods is repeated cycles of washing 2000 times, the natural rubber parts is produced breaking property or palpability damage.
EXAMPLE IV
With the step preparing washing agent composition that is same as EXAMPLE III: unique different be that nonanoyl oxygen base benzene sulfonate (NOBS) with equivalent replaces (the amino caproyl of 6-nonanoyl) the oxygen base benzene sulfonate bleach-activating agent in the EXAMPLE III.Repeat 1200 circulations of washing methods of EXAMPLE III, natural rubber drainage tray flexible pipe fracture approximately at this moment.
EXAMPLE V
With the step preparing washing agent composition that is same as EXAMPLE III, unique different be to replace (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate bleach-activating agent in the EXAMPLE III with equivalent benzoyl oxygen base benzene sulfonate (BOBS).Repeat the washing methods of EXAMPLE III, 1200 circulations, approximately at this moment, the fracture of natural rubber drainage tray flexible pipe.
Example VI
With the step preparing washing agent composition that is same as EXAMPLE III; different is replaces bleach-activating agent in the EXAMPLE III with 1: 1 mixture of 15% four acyl group quadrols and (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate bleach-activating agent, and the amount of SPC-D is 30%.Repeat 2000 circulations of washing methods of EXAMPLE III, the natural rubber parts are produced breaking property or palpability damage.
Example VII A
With step preparing washing agent composition with sub-EXAMPLE III; uniquely different be with 1 of 15% benzoyl caprolactam and (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate: the I mixture replaces the bleach-activating agent in the EXAMPLE III, and the amount of SPC-D is 30%.Repeat 2000 circulations of washing methods of EXAMPLE III, the natural rubber parts are produced breaking property or palpability damage.
Example VII A I
With the step preparing washing agent composition that is same as EXAMPLE III, with the U.S.4 people such as Hodge of equivalent, disclosed benzothiazine type bleach-activating agent replaces the bleach-activating agent in the EXAMPLE III in 966,723.Repeat 2000 circulations of washing methods of EXAMPLE III, the natural rubber parts are produced breaking property or palpability damage.
Example I X
With the step preparing washing agent composition that is same as EXAMPLE III; unique different be U.S.4 with people such as 6% (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate and Hodge; 1: 1 mixture of disclosed benzoxazine type bleach-activating agent replaces the bleach-activating agent in the EXAMPLE III in 966,723.Repeat 2000 circulations of washing methods of EXAMPLE III, the natural rubber parts are produced breaking property or palpability damage.
Embodiment X
With the step preparing washing agent composition that is same as EXAMPLE III; unique different be U.S.4 with people such as 6% four acyl group quadrols and Hodge; 1: 1 mixture of disclosed benzothiazine type bleach-activating agent replaces the bleach-activating agent in the EXAMPLE III in 966,723.Repeat 2000 circulations of washing methods of EXAMPLE III, the natural rubber parts are produced breaking property or palpability damage.
The method of processing bleach-activating agent
Available organic and inorganic substance processing bleach-activating agent is to make it to obtain to disperse fast in aqueous bleaching solution and guarantee to have good stability in detergent composition.Bleach-activating agent preferably uses particle form.
Preferred caprolactam bleach activators particulate example is the agglomerate of following component: about 65% (weight) benzoyl caprolactam; About 7% washing assistant, as silico-aluminate: about 15% yellow soda ash: about 9% dispersion agent, as the polyacrylate polymkeric substance; About 4% solubilizing agent is as straight chained alkyl carbonate.Preferred another example of caprolactam bleach activators particulate is the agglomerate of following component: about 80% to about 85% (weight) benzoyl caprolactam and about 15% to about 20% tackiness agent, as the tallow alcohol ethoxylate, preferred TAF25.
The preferred example of amido deutero-bleach activator particles comprises 1: 1: 1 mixture of (the amino caproyl of 6-decoyl) oxygen base benzene sulfonate, (the amino caproyl of 6-caprinoyl) oxygen base benzene sulfonate and citric acid powder.With mixture in food blending apparatus thorough mixing 5-10 minute.In the mixture that obtains, adding tallow alcohol ethoxylate (TAE25) nonionogenic tenside under 50 ℃, until forming particle.Generally the ratio with bleach-activating agent/citric acid solid mixture and nonionic tackiness agent is the granulation that can succeed at 3.5: 1.The product that obtains is granulous, oval-shaped and spheric, is the free-pouring of white.
The exemplary particles composition contains has an appointment 40% to about 60%, the mixture of preferred about 55% (weight) bleach-activating agent or bleach-activating agent, about 20%-40%, preferably about 25% (weight) citric acid; With about 15%-30%, preferred about 20% (weight) TAF 25 tackiness agents.In addition, can use 2: 1 mixtures of (the amino caproyl of 6-caprinoyl) oxygen base benzene sulfonate and citric acid powder.Be made as under the particulate situation at composition, said composition contains 55% bleach-activating agent, 25% citric acid and 20%TAE25 tackiness agent.Other preferred organic binder bond comprises anion surfactant (C 12Linear alkylbenzene sulfonate), polyoxyethylene glycol and TAE50.
Can change the particulate granularity of gained according to required performance/stability.The solvability that fine particle (＜250 μ m) surface goes out to improve is although thick particle (＞1180 μ m) is more stable under high temperature/wet environment.Generally, preferred granularity scope is 250-180 μ m, and the particle performance that meets this specification goes out fabulous stability and solvability.
Embodiment XI
Be suitable for hand-washing the laundry stick that the dirt fabric is used with the preparation of standard extrusion process, it comprises following component:
Composition weight %
C 12Linear alkylbenzene sulfonate 30
Phosphoric acid salt (as tripoly phosphate sodium STPP) 7
Yellow soda ash 25
Trisodium phosphate 7
Coconut single ethanol amide 2
Zeolite A (0.1-10 micron) 5
Carboxymethyl cellulose 0.2
Ethylenediamine disuccinate sequestrant (EDDS) 0.4
Polyacrylate (m.w.1400) 0.2
(the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate 5
SPC-D *5
Whitening agent, spices 0.2
Proteinase-10 .3
CaSO 4 1
MgSO 4 1
Water 4
Additive *Balance to 100%
*Mean particle size is the 400-1200 micron
*Can be selected from conventional substances such as CaCO 3, talcum powder, clay, silicate etc.
With the equipment of conventional soap of preparation or detergent bar, process this cloth-washing detergent stick as normally used equipment in the prior art.Test by the test method in the example II.Repeat 2000 cycles of washing of this washing methods, the natural rubber parts are produced fracture or palpability damage, also the natural rubber article are produced and damage.

Claims (19)

1. bleach system, it comprises:
A) bleach-activating agent of 0.1-50% weight is selected from formula (i) compound, formula (ii) compound and their mixture, wherein:
Compound is selected from likes i): With its mixture, R in the formula 1For containing alkyl, aryl or the alkaryl of 1 to 14 carbon atom; R 2For containing alkylidene group, arylidene or the alkyl arylene of 1 to 14 carbon atom, R 5Be H or methyl, L is the leavings group that is selected from following formula:
Figure C9419217300022
R wherein 3Be the alkyl that contains 1 to 8 carbon atom, Y is-SO 3 -M +Or-CO 2 -M +, wherein M is sodium or potassium; With
Formula ii) compound is:
Figure C9419217300023
R in the formula 1Be H, alkyl, alkaryl, aryl, aralkyl, R 2, R 3, R 4And R 5Can be identical or different substituting group, be selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino ,-COOR 6(R wherein 6Be H or alkyl) and the carbonyl functional group;
B) hydrophilic bleach-activating agent is selected from tetraacetyl ethylene diamine (TAED), N-acyl caprolactam activators, and wherein acyl moiety has formula R 1-CO-, wherein R 1Be to contain 6 or be less than the alkyl of 6 carbon atoms; With
C) peroxy bleaching compound of 0.1-75% weight,
Wherein (a): (b) be 5: 1 to 1: 5.
2. according to the composition of claim 1, the R in its Chinese style (i) 1For containing the alkyl of 7 to 10 carbon atoms, the R in the formula (i) 2Contain 4 to 5 carbon atoms.
3. according to the composition of claim 1, wherein hydrophilic caprolactam bleach activators is a benzoyl caprolactam.
4. according to the composition of claim 1, wherein bleach-activating agent is:
Figure C9419217300031
5. according to the composition of claim 1, wherein peroxy bleaching compound is selected from perborate and percarbonate.
6. according to the composition of claim 1, it also comprises sequestrant.
7. according to the composition of claim 6, wherein sequestrant is ethylenediamine disuccinate sequestrant or amino phosphonates do sequestrant.
8. according to the composition of the detergent for washing clothes form of claim 1, it also comprises detersive surfactant, washing assistant and decontamination annexing ingredient.
9. the method for a laundering of textile fabrics in automatic washing machine with the parts that make by natural rubber to the oxidative degradation sensitivity, this method comprises said fabric is stirred that the natural rubber parts of said washing machine are not damaged by bleach system basically in the aqueous solution of the bleach system that contains claim 1 in washing machine.
10. the method for claim claim 9, wherein bleach system comprises can react the bleach-activating agent that produces the following formula peroxy acid in the described aqueous solution:
Figure C9419217300041
R in the formula 1For containing alkyl, aryl, the alkaryl of 1 to 14 carbon atom, R 2For containing alkylidene group, arylidene, the alkyl arylene of 1 to 14 carbon atom, R 5Be H or methyl.
11. according to the method for claim 10, the wherein said aqueous solution also comprises:
(1) detersive surfactant of 5-80% weight;
(2) detergent builder compound of 5-80% weight;
(3) the conventional decontamination annexing ingredient of 0-20% weight.
12. according to the method for claim 11, wherein R 1For containing the alkyl of 6 to 12 carbon atoms, R 2Contain 1 to 8 carbon atom, R 5Be H or methyl.
13. according to the method for claim 12, wherein R 1For containing the alkyl of 7 to 10 carbon atoms, R 2Contain 4 to 5 carbon atoms.
14. according to the method for claim 11, wherein bleach-activating agent is:
Figure C9419217300042
15. according to the method for claim 11, wherein peroxy bleaching compound is selected from Sodium peroxoborate monohydrate, SPC-D, sodium perborate tetrahydrate, trisodium phosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide and its mixture.
16. according to the composition of claim 1, wherein said bleach-activating agent is granular.
17. according to the composition of claim 16, wherein said bleach activator particles comprises 1: 1 mixture of 40%-60% (weight) (the amino caproyl of 6-decoyl) oxygen base benzene sulfonate and (the amino caproyl of 6-caprinoyl) oxygen base benzene sulfonate; 20%-40% (weight) citric acid; And 15%-30% (weight) tallow alcohol ethoxylate nonionic surfactant.
18. according to the composition of claim 16, wherein said bleach activator particles contains 65% benzoyl caprolactam, 7% pure aluminium silicate, 15% yellow soda ash, 9% polyacrylate polymkeric substance and 4% linear alkyl benzene sulphonic acid.
19. according to the composition of claim 16, wherein said particle contains 80% benzoyl caprolactam and 20% tallow alcohol ethoxylate nonionic surfactant.
CN94192173A 1993-05-20 1994-05-12 Bleaching compositions comprising peroxyacid activators having amide moieties Expired - Fee Related CN1057792C (en)

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