CN1130456C - Detergent compsn contg optimally sized bleach activator particles - Google Patents
Detergent compsn contg optimally sized bleach activator particles Download PDFInfo
- Publication number
- CN1130456C CN1130456C CN 98813218 CN98813218A CN1130456C CN 1130456 C CN1130456 C CN 1130456C CN 98813218 CN98813218 CN 98813218 CN 98813218 A CN98813218 A CN 98813218A CN 1130456 C CN1130456 C CN 1130456C
- Authority
- CN
- China
- Prior art keywords
- bleach
- detergent composition
- activating agent
- alkyl
- extrudate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- 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
- C11D3/391—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—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
- C11D3/3915—Sulfur-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A bleach-containing detergent composition which contains a peroxygen bleaching compound and a bleach activator is disclosed. The bleach activator is in the form of particles having a mean particle diameter of 200 microns to 2000 microns. Also disclosed are bleach activator particles in the form of substantially cylindrically-shaped extrudates having a mean extrudate length of from about 500 microns to about 3500 microns and a mean extrudate diameter of from about 450 microns to about 850 microns.
Description
The cross reference of related application
This case is the part continuation application of US application serial No. 08/974784 of the existing approval of on November 20th, 1997 application.
Invention field
The present invention relates to contain the detergent composition of peroxy bleaching compound and bleach activator particles, the selected granularity of described bleach activator particles improves its stability and performance.
Background of invention
As known, the superficial bleaching of fabric is that bleaching mechanism occurs in the bleaching on the fabric face, removes spot and/or dirt thus.General bleaching composition contains peroxygen bleach that can produce hydrogen peroxide in the aqueous solution and the bleach-activating agent that strengthens bleachability.Known for a long time, peroxygen bleach can get on except that spot and/or dirt from fabric effectively, but they also have dependency to temperature.This SYNTHETIC OPTICAL WHITNER is higher than about 60 ℃ liquid lime chloride at solution temperature, promptly only can implement basically in the mixture of SYNTHETIC OPTICAL WHITNER and water and/or effectively.In the liquid lime chloride temperature is under about 60 ℃, and peroxygen bleach only part is effective, therefore in order to obtain the bleachability of required degree, and must be with in the extremely high-load peroxygen bleach adding system.This can not implement for the current Betengent product of large-scale commercial applications production economically.Be lower than 60 ℃ along with the liquid lime chloride temperature is reduced to, it is invalid that peroxygen bleach becomes, and how many amounts of the peroxygen bleach in the no matter adding system is.Peroxygen bleach is significantly to dependence on temperature, because this SYNTHETIC OPTICAL WHITNER is lower than in 60 ℃ the fabric washing process usually as the washing composition auxiliary components in the temperature of washing water of using automatic domestic washing machine.Because such wash temperature is used in the consideration of nursing fabric and energy.Because such washing process, carried out the material that a large amount of industrial research exploitations is commonly referred to bleach-activating agent, its make peroxygen bleach in being lower than 60 ℃ liquid lime chloride effectively.
Disclose in the prior art and be the multiple material of effective bleach-activating agent.For example, the bleach-activating agent with following general formula is disclosed in the prior art:
Wherein R is an alkyl, and L is a leavings group.This bleach-activating agent generally mixes in the Betengent product as the particle of composite grain, agglomerate or other types.Yet a problem relevant with this bleach-activating agent is before the human consumer uses, and keeps the stability of this activator.Bleach activator particles or agglomerate are along with there is the trend of degraded the time, owing to be subjected to the influence of environment for example hot and moist, this trend can increase the weight of.As a result, the bleach-activating agent of particle, agglomerate or other particle form is compared with other detergent components in the general granulated detergent product, must be big relatively.This causes another problem relevant with the Betengent product segregation again, and promptly bigger bleach activator particles tendency accumulates in the top or the close top of washing composition packing box, and the detergent components of relative low particle size accumulates in the bottom or the close bottom of box.In addition, size separation occurs in the manufacturing processed of washing composition, causes box to the box variability of washing composition active constituent to increase.The isolating net result of this undesirable product has reduced performance, because the user goes out product from the top to lower curtate with bale-out, every spoonful of bleach-activating agent or other detergent components with inhomogeneous amount, similarly, the influence that the product performance in the different boxes are changed by detergent composition.Therefore, wish that detergent composition contains stable before use improved bleach-activating agent, it emanates when storing before the packing or in the Betengent product box not obviously.In addition, wish to have such detergent composition, it also has acceptable physical properties, for example for a large amount of transportations as the required acceptable flowability matter of the composition of the part of scale operation washing composition.
Another problem relevant with above-mentioned bleach-activating agent relate to can not the above-mentioned bleach/bleach activator system of advertising to the sterilisation effect of fabric.Usually, if most government authorities requires because of use contains the Betengent product of SYNTHETIC OPTICAL WHITNER, and the result removes the microorganism of relative a large amount from the fabric of washing consistently, then only can nurse the sterilization advertising of fabric in this case.Yet the bleach-activating agent of relative macrobead of past, agglomerate or other particle form has hindered this sterilization advertising, and this is to have suppressed to remove a large amount of microorganisms consistently from the fabric of washing because have the product segregation effect of this larger particles.The bleach/bleach activator of carrying in washing process changes too greatly, can not satisfy the requirement of most of government organs to sterilization advertising.The detergent composition that contains SYNTHETIC OPTICAL WHITNER that therefore need have a kind of fabric that can be used for sterilizing.
Therefore, this area still needs to contain the detergent composition of stable improved bleach-activating agent before use.In addition, this area also needs a kind of detergent composition, and it contains in the Betengent product packing box not obvious isolating and bleach-activating agent with acceptable physical properties when storing.This area also needs a kind of like this detergent composition in addition, and it can provide bleach/bleach activator more consistently.
Background technology
Relate to the detergent composition that contains bleach-activating agent and/or sterilant below with reference to document: United States Patent (USP) 4412934 (the Procter ﹠amp that authorizes Chung etc.; Gamble); Authorize the United States Patent (USP) 5021182 (Roman A.Epp) of Jentsch; Authorize the United States Patent (USP) 5489434 (Ecolab) of Oakes etc. and authorize the United States Patent (USP) 4422950 (LeverBrothers Company) of Kemper etc.
Summary of the invention
The invention provides a kind of detergent composition, it contains peroxy bleaching compound and particle form, preferably is essentially the bleach-activating agent of the relative small grain size with selection of cylindrical extrudate form.The bleach activator particles of this reduced size unexpectedly keeps stable and has reduced the segregation of product in containing their detergent box, because the granularity of their more approaching other conventional detergent components of reflection through standing storage.In addition, bleach activator particles has acceptable flowability matter and makes detergent composition sterilisation effect is provided for more consistently washed fabric.
As described herein, term " particle " is meant agglomerate, sheet, extrudate or other forms of particle.Phrase " cylindrical extrudate " meaning is that the surface shape that has is by moving with the fixed straight line parallel and the straight line of the curve of crosscut fixed planar surface encloses produces extrudes particle." significant quantity " that contain the detergent composition of bleach-activating agent be meant when being washed by the human consumer, can be measured to from the fabric any amount that dirt and this two aspect of sterilization improve that gets on.Generally, but this amount wide range ground change.Term " sterilisation " as described herein, " antibiotic ", " sterilization " and " health " meaning are to kill the microorganism of the common discovery on the fabric that needs wash neutralizes it.The example of various microorganisms comprises germ, bacterium, virus, parasite and fungi/spore.As described herein, " free-water " content meaning is unconjugated in detergent composition or at other detergent components weight percentage of the water in the zeolite for example, some excessive water-contents of bonded that it is carried secretly, absorbs in other detergent components or other.
According to an aspect of the present invention, provide a kind of detergent composition that contains SYNTHETIC OPTICAL WHITNER.This detergent composition comprises: the peroxy bleaching compound that (a) can produce hydrogen peroxide in the aqueous solution; (b) have the bleach-activating agent of following general formula:
Wherein R is the alkyl that contains 5-18 the carbon atom of having an appointment, and the long linear alkyl that wherein extends from carbonyl carbon and comprise carbonyl carbon contains 6-12 the carbon atom of having an appointment, and L is a leavings group, the pK of its conjugate acid
aBe about 6-13, wherein the mol ratio of hydrogen peroxide that is produced by (a) and bleach-activating agent (b) is greater than about 1.0, and described bleach-activating agent is that median size is the particle form of about 200-2000 micron.
According to a further aspect in the invention, provide the method for using this detergent composition sterilization fabric.This method comprise with described fabric contact with the detergent composition described herein of significant quantity in the aqueous solution with the sterilization fabric step.Unless otherwise indicated, all percentage ratios described herein and ratio are percentage ratio (moisture-free basis) expressions by weight.All documents of quoting are quoted for referencial use at this paper.
Therefore, the purpose of this invention is to provide a kind of detergent composition, it contains the bleach activator particles that has satisfactory stability and acceptable physical properties before use.A present invention also purpose provides a kind of detergent composition, and it contains not obvious isolating bleach-activating agent when storing in the Betengent product box.Another object of the present invention provides a kind of like this Betengent product, and it can be used for the fabric of sterilizing.By reading the detailed description of following preferred embodiment and claims, these and other purposes of the present invention, feature and advantage thereupon are conspicuous for those skilled in the art.
Detailed description of the preferred embodiments
Detergent composition of the present invention mainly comprises two kinds of components, i.e. the bleach-activating agent of the median size with regulation of peroxy bleaching compound and particle form.In preferred mode, this particle is cylindrical extrudate form basically.Preferably, peroxy bleaching compound can produce hydrogen peroxide in the aqueous solution.Detergent composition of the present invention is unexpectedly stable through standing storage with regard to the maintenance or the aspect of not degrading about bleach-activating agent before use.Preferably, in bleach activator particles or extrudate, comprise one or more adhesive materials, include, but are not limited to: palmitinic acid, detersive surfactant, polyoxyethylene glycol and other lipid acid and polyacrylate.
Without being limited by theory; believe by selecting granularity described herein; adhesive material in concrete particle or extrudate descends by gravity or migrates to each particulate surface, therefore suppressed bleach-activating agent and for example too has been exposed under the envrionment conditions before use heat and wet condition.Therefore, comprise it being that those bleach activator particles of cylindrical extrudate is not degraded and kept stable basically, also have granularity simultaneously near other detergent components granularities in the reflection detergent composition.As described, the consistence of the granularity of interpolation makes detergent composition not too responsive to the segregation of the product in detergent box before use.As known, in the segregation of product generation loading and unloading, transportation and the store detergent composition process before use; Vibration, shake and other mobile Betengent product box, owing to the reason of granularity causes the composition segregation.Detergent composition of the present invention has reduced this problem by selecting granularity and shape.
About this respect, the particulate median size is about 200-2000 micron, more preferably from about 300-1000 micron, most preferably from about 350-750 micron.More preferably, particle is cylindrical extrudate basically, and the mean length of its extrudate is about 500 microns-3500 microns, more preferably from about 700-3000 micron, most preferably from about 900-2500 micron.Preferably, the extrudate mean diameter is about 450-850 micron, more preferably from about 500-800 micron, most preferably from about 550-750 micron.Average grain and the extrudate diameter mensuration that can in all sorts of ways, a kind of method wherein are to use the representative sample of measurement microscope extrudate and determine mean value by calculating.Available similar method or extrapolate to determine mean diameter by the diameter of mould extrusion.
For obtaining the required acceptable flowability of a large amount of transport particles, can add the flow promotor of thin inorganic powder as particle surface.This flow promotor includes, but are not limited to: thin silico-aluminate, silicon-dioxide, crystalline layered silicate, MAP zeolite, Citrate trianion, amorphous silicate, yellow soda ash and its mixture.By the weight of detergent composition, the preferred content of flow promotor is about 0.1%-10%, more preferably from about 1%-7%, most preferably from about 1.5%-5%.Most preferred flow promotor is a silico-aluminate.
Peroxy bleaching compound is preferably selected from Sodium peroxoborate monohydrate, sodium perborate tetrahydrate, yellow soda ash peroxyhydrate, trisodium phosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide and its mixture.Preferred detergent composition of the present invention contains and is less than approximately 3%, more preferably less than about 2.5%, most preferably is less than about 2% weight percent free water.Without being limited by theory, believe that bleach-activating agent is lowered by the tendency of hydrolytic deterioration before use by keep the free-water of this relative low levels in composition.Therefore, because the result who presses the above-mentioned selection free water content of this paper, the stability of bleach-activating agent is enhanced and even also prolongs.
Select relative bleach activator particles than small grain size, particularly cylindrical extrudate causes giving in the wash water solution more consistently activator is provided.In other words, owing to use the above-mentioned columniform extrudate that is essentially, the variation range of the target content of the bleach-activating agent that provides to washing soln unexpectedly has been provided the result.By accident, this makes detergent composition provide bleach-activating agent with more consistent content, to reach the sterilisation effect to laundering of textile fabrics.In order to meet the requirement of the jural sterilization advertisement of doing to the public, most government organs require the target content of bleach-activating agent or other sterilizing agents that very little variation range is arranged.Therefore, the present invention also provides the sterilization fabric to be fit to and method easily, and it is fit to carry out publicity.Preferably, it is about at least 50% that the number of the microorganism that exists on described fabric is lowered, and more preferably is lowered approximately at least 90%, most preferably is lowered about at least 99.9%.This sanitation method and sterilization of the present invention, antibiotic, kill germ, the method that causes the germ of smell extremely is used interchangeably.
In addition, specific bleach-activating agent in the detergent composition and peroxide bleaching compositions preferably exist with the specific molar ratio of hydrogen peroxide and bleach-activating agent.This composition provides extremely effectively fabric face bleaching, has removed spot and/or dirt from fabric thus.This composition is effective especially to removing dark dirt from fabric.Dark dirt is repeatedly to use and after wash(ing)cycle, accumulating in the dirt on the fabric, causes white fabrics to have the mottling of ash thus.These dirt tendencies are mixtures of particle and oily matter.Removal to this class dirt is sometimes referred to as " cleaning gloomy fabric ".The detergent composition that the present invention contains SYNTHETIC OPTICAL WHITNER provides this bleaching action under the liquid lime chloride temperature of wide region.Can reach this bleaching at solution temperature at least about 5 ℃ liquid lime chloride.Under no bleach-activating agent, this peroxygen bleach be lower than under about 60 ℃ of temperature invalid and/or can not implement.
In the present invention, by mole, need to obtain the low bleach-activating agent of measuring with the bleaching surface property of the same degree that obtains with similar bleach-activating agent, described similar bleach-activating agent is only containing 2-5 the carbon atom of having an appointment from the long linear alkyl carbonyl carbon extension and that comprise carbonyl carbon.Without being limited by theory, the acquisition of believing this effectiveness is because bleach-activating agent of the present invention shows surfactivity.This is soluble as follows: bleaching mechanism, particularly superficial bleaching mechanism generally imperfectly understands.But, it is generally acknowledged that bleach-activating agent has stood to cross the anionic nucleophilic attack of oxyhydroxide and formed percarboxylic acids, the described oxyhydroxide negatively charged ion of crossing is to be produced by the hydrogen peroxide that peroxygen bleach discharges.This reaction was commonly referred to hydrolysis.Percarboxylic acids forms active dimer with its negatively charged ion then, and it discharges singlet oxygen again, believes that singlet oxygen is active bleaching component.In theory, singlet oxygen must discharge at fabric face or near the fabric face place, so that superficial bleaching is provided.In addition, singlet oxygen also provides the bleaching that is not at fabric face.This bleaching is called as the solution bleaching, is about to the dirt bleaching in the liquid lime chloride.
In order to guarantee that singlet oxygen more effectively discharges on fabric face, necessary is has about 6-12 carbon atom from the long linear alkyl of carbonyl carbon percarboxylic acids that extend and that comprise carbonyl carbon.This percarboxylic acids is surface-active, and therefore tendency concentrates at fabric face.The percarboxylic acids that contains less carbon atom in this alkyl chain has similar redox potential energy, but does not have in the spissated ability of fabric face.Therefore, the bleach-activating agent of the scope of the invention is extremely effective, because by mole, need this bleach-activating agent of relatively low-levels just can reach superficial bleaching performance to the same degree that obtains with similar bleach-activating agent, described similar bleach-activating agent contains less carbon atom in this alkyl chain, it is not within the scope of the present invention.
With pH is about 8.5-10.5, and the liquid lime chloride of preferred 9-10 can obtain best superficial bleaching performance.Preferred this pH not only provides best superficial bleaching performance greater than 9, has undesirable smell but also suppressed liquid lime chloride.Observe, be lower than 9 in case the pH of liquid lime chloride is reduced to, liquid lime chloride just has undesirable smell.This pH can obtain with the material that is commonly referred to buffer reagent, and buffer reagent is a component optional in the bleaching composition of the present invention.
In highly preferred embodiment of the present invention, basically columniform extrudate comprises, weight by extrudate, about 60%-95% bleach-activating agent, about 0.1%-10% palmitinic acid, about 0.1%-1 0% detersive surfactant, about 0.1%-10% polyoxyethylene glycol and about 0.1%-10% lipid acid.
Bleach-activating agent
The bleach-activating agent that is used for bleach system of the present invention preferably has following structure:
Wherein R is the alkyl that contains 5-18 the carbon atom of having an appointment, and the long linear alkyl that wherein extends from carbonyl carbon and comprise carbonyl carbon contains 6-12 the carbon atom of having an appointment, and L is a leavings group, and the pKa of its conjugate acid is about 4-13, preferably about 6-11, most preferably from about 8-11.
L can be any suitable leavings group basically.Leavings group is owing to cross oxyhydroxide negatively charged ion nucleophilic attack bleach-activating agent, any group that the result sloughs from bleach-activating agent.This is crossed hydrolysis reaction and causes forming percarboxylic acids.Generally, must there be the electrophilic effect in the group for suitable leavings group.This helped the anionic nucleophilic attack of oxyhydroxide.
The L group must have enough reactivities to the reaction that takes place in the time period (for example wash(ing)cycle) of the best., if the L reactivity is too strong, this activator will be difficult to stablize so.The pK of the conjugate acid of the general and leavings group of these features
aCorresponding, but this conventional exception also is known.
Preferred bleach-activating agent is to have those of following general formula:
Or
R wherein
1Be the alkyl that contains about 12 carbon atoms of the 6-that has an appointment, R
2Be the alkylidene group that contains about 6 carbon atoms of 1-, R
5Be that hydrogen or alkyl, aryl or alkaryl and the L that contains about 10 carbon atoms of the 1-that has an appointment are selected from:
With
R wherein
6Be alkylidene group, arylidene or the alkyl arylene that contains about 14 carbon atoms of the 1-that has an appointment, R
3Be the alkyl chain that contains about 8 carbon atoms of the 1-that has an appointment, R
4Be H or R
3, Y is H or solubilizing group, Y is preferably selected from-SO
3 -M
+,-COO
-M
+,-CO
2H ,-CO
2 -M
+,-SO
4 -M
+, (N
+R '
3) X
-And O ← N (R '
3), wherein R ' is the alkyl chain that contains about 4 carbon atoms of the 1-that has an appointment, and M is for providing deliquescent positively charged ion to bleach-activating agent, and X is for providing deliquescent negatively charged ion to bleach-activating agent.Preferred M is the ammonium cation of basic metal, ammonium or replacement, most preferably sodium and potassium, and X is the negatively charged ion that is selected from halogen, hydroxide radical, methylsulfate and acetate moiety.More preferably Y is-SO
3 -M
+,-CO
2H and-COO
-M
+It should be noted that the bleach-activating agent with the leavings group that does not contain solubilizing group should be dispersed in the liquid lime chloride well, so that help their dissolving.Preferably:
R wherein
3With above definition, Y is-SO
3 -M
+,-COO
-M
+, wherein M is with above definition.
R in the particularly preferred bleach-activating agent
1Be the straight chained alkyl that contains about 12 carbon atoms of the 6-that has an appointment, R
2Be the straight-chain alkyl-sub-that contains about 6 carbon atoms of the 2-that has an appointment, R
5Be H, L is selected from:
With
R wherein
3With above definition, Y is-SO
3 -M
+Or-COO
-M
+, M is with above definition.
Preferred bleach-activating agent is:
R wherein
1Be H, alkyl, aryl or alkaryl.It is described in the United States Patent (USP) 4966723 of Hodge etc., and it quotes for referencial use at this paper.
Preferred bleach-activating agent is:
Or
R wherein
1Be H or the alkyl that contains about 6 carbon atoms of the 1-that has an appointment, R
2Be the alkyl that contains about 6 carbon atoms of the 1-that has an appointment, L is with above definition.
Preferred bleach-activating agent also is those activators of above general formula, and wherein L is with defining R in the general formula
1Be H or the alkyl that contains about 4 carbon atoms of the 1-that has an appointment.Even those bleach-activating agents of above general formula more preferably, wherein L in the general formula definition, R
1Be H.
Those bleach-activating agents that preferred bleach-activating agent is above general formula, wherein R is that to contain the 5-that has an appointment about 9, the straight chained alkyl of about 8 carbon atoms of preferably about 6-, L is selected from:
Wherein R, R
2, R
3With Y with above definition.
Those bleach-activating agents that particularly preferred bleach-activating agent is above general formula, wherein R is the alkyl that contains about 12 carbon atoms of the 5-that has an appointment, and wherein the long linear from carbonyl carbon alkyl chain that extend and that comprise carbonyl carbon partly contains 6-12 the carbon atom of having an appointment, and L is selected from:
With
R wherein
2Be that alkyl chain and the Y that contains about 8 carbon atoms of the 1-that has an appointment is-SO
3 -M
+Or-COO
-M
+, wherein M is the ammonium cation of basic metal, ammonium or replacement.
Those bleach-activating agents that particularly preferred bleach-activating agent is above general formula, wherein R is that to contain the 5-that has an appointment about 9, the straight chained alkyl of about 8 carbon atoms of preferably about 6-, L is selected from:
With
R wherein
2With above definition and Y be-SO
3 -M
+,-COO
-M
+, or-CO
2H, wherein M is with above definition.
Most preferred bleach-activating agent has formula:
Wherein R is that to contain the 5-that has an appointment about 9, the straight chained alkyl of about 8 carbon atoms of preferably about 6-, and M is sodium or potassium.Preferably, bleach-activating agent of the present invention is acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS) or benzoyloxy benzene sulfonic acid sodium salt (BOBS), bay acyloxy benzene sulfonic acid sodium salt (LOBS) or to caprinoyl aminobenzoic acid (DOBA).
Be used for bleaching composition of the present invention and also particularly preferably be following bleach-activating agent, it is to safe especially with the use of the machine with natural rubber parts.Believe that this is because the hydrolysis reaction of crossing of these amic acid deutero-bleach-activating agents does not produce butyrous diacyl peroxide (DAP), but generated the result of insoluble crystalline solid DAP ' s.Believe that these solids do not form and film that the natural rubber parts do not contact with DAP ' s for a long time thus.These preferred bleach-activating agents are selected from:
A) bleach-activating agent of following general formula or its mixture:
Wherein, R
1For containing alkyl, aryl or the alkaryl of 1-14 the carbon atom of having an appointment, R
2For containing alkylidene group, arylidene or the alkyl arylene of 1-14 the carbon atom of having an appointment, R
5For H or alkyl, aryl or the alkaryl and the L that contain 1-10 the carbon atom of having an appointment be leavings group;
B) the benzoxazine type bleach-activating agent of following general formula:
R wherein
1Be H, alkyl, alkaryl, aryl, aralkyl and R wherein
2, R
3, R
4And R
5Can be identical or different substituting group, it 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;
C) the N-acyl caprolactam bleach-activating agent of following general formula:
R wherein
6Be H or alkyl, aryl, alkoxy aryl or the alkaryl that contains 1-12 carbon atom; With
, b) and mixture c) d) a).
Preferred a) type bleach-activating agent is R wherein
1Be the alkyl that contains about 12 carbon atoms of the 6-that has an appointment, R
2Contain about 8 carbon atoms of the 1-that has an appointment and R
5Be those bleach-activating agents of H or methyl.Those bleach-activating agents that particularly preferred bleach-activating agent is above general formula, wherein R
1Be alkyl and the R that contains about 10 carbon atoms of the 7-that has an appointment
2Contain 4-5 the carbon atom of having an appointment.
Preferred b) the type bleach-activating agent is R wherein
2, R
3, R
4And R
5Be H and R
1Be those bleach-activating agents of phenyl.
Preferred described c) acyl moiety of the N-acyl caprolactam bleach-activating agent of type has formula R
6-CO
-, R wherein
6Be H or contain 2 carbon atoms of 1-1, alkyl, aryl, alkoxy aryl or the alkaryl of preferred 6-12 carbon atom.In highly preferred example, R
6Be selected from phenyl, heptyl, octyl group, nonyl, 2,4,4-tri-methyl-amyl, decene base and its mixture.
Amido deutero-bleach-activating agentA) the type bleach-activating agent that-the present invention uses is compound or its mixture that the acid amides of following general formula replaces:
R wherein
1, R
2And R
5With above definition, L can be any suitable leavings group basically.Preferred bleach-activating agent is to have those of above general formula, wherein R
1, R
2And R
5Be selected from defining in the peroxy acid with L:
With
With
With its mixture, wherein R
1For containing alkyl, aryl or the alkaryl of 1-14 the carbon atom of having an appointment, R
3For containing the alkyl chain of about 8 carbon atoms of 1-, R
4Be H or R
3, Y is H or solubilization radical.
Preferred solubilization radical 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
+, wherein, R
3For the alkyl chain M that contains 1-4 the carbon atom of having an appointment for deliquescent positively charged ion is provided to bleach-activating agent, X is for providing deliquescent negatively charged ion to bleach-activating agent.Preferred M is the ammonium cation of basic metal, ammonium or replacement, most preferably sodium and potassium, and X is halogen, hydroxide radical, methylsulfate or acetic acid anion.It should be noted that the bleach-activating agent with the leavings group that does not contain solubilizing group should be dispersed in the liquid lime chloride well, so that help their dissolving.
Preferred bleach-activating agent is those of above general formula, and wherein L is selected from:
With
R wherein
3As above definition, Y is-SO
3 -M
+,-CO
2 -M
+, or-CO
2H, wherein M is with above definition.
The bleach-activating agent of another kind of important kind comprises type b) and type c) those because the carbonyl carbon open loop as a result on the mistake oxyhydroxide negatively charged ion nucleophilic attack ring has obtained organic peracid described herein.For example, at type c) ring-opening reaction in the activator comprises the carbonyl of hydrogen peroxide or its negatively charged ion attack hexanolactam ring.Because hydrogen peroxide or its negatively charged ion attack acyl caprolactam preferably occur in the outer carbonyl of ring place, therefore obtaining tangible open loop part may need catalyzer.Another example of open loop bleach-activating agent can be found in type b) in the activator, those disclosed in the United States Patent (USP) 4966723 of the Hodge that authorizes in October 30 nineteen ninety etc. for example.
Benzoxazine type bleach-activating agent-comprising benzoxazine type activator by the disclosed this activator compound of Hodge, it has formula:
The benzoxazine that comprises the replacement of following type:
R wherein
1Be H, alkyl, alkaryl, aryl, aralkyl and R wherein
2, R
3, R
4And R
5Can be identical or different substituting group, it 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.
The preferred active agent of benzoxazine type is:
When using activator, for promoting hydrolysis reaction, the pH of washing soln is at about 8.5-10.5, and preferred 9.5-10.5, this washing soln have obtained the optimum performance on bleaching surface.This pH can be with known for the material of buffer reagent obtains usually, and it is the optional components of bleach system of the present invention.
N-acyl caprolactam bleach-activating agentThe type c that-the present invention uses) N-acyl caprolactam bleach-activating agent has formula:
R wherein
6Be H or alkyl, aryl, alkoxy aryl or the alkaryl that contains 1-12 carbon atom.R wherein
6Part contains at least about 6 carbon atoms, and the caprolactam activators of preferred about 12 carbon atoms of 6-provides hydrophobic bleach, and as mentioned above, it can clean nucleophilic and human body dirt.R wherein
6The caprolactam activators that contains about 6 carbon atoms of 1-provides hydrophilic bleaching thing, and it is effective especially to bleaching beverage spot.The present invention can use hydrophobic and hydrophilic hexanolactam generally with weight ratio 1: 5-5: 1, and preferred 1: 1 mixture is to obtain to remove the effect of mixing spot.
Highly preferred N-acyl caprolactam is selected from benzoyl caprolactam, capryloyl hexanolactam, nonanoyl hexanolactam, 3,5,5-trimethyl acetyl base hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam and its mixture.The method for preparing the N-acyl caprolactam is known in the art.
Opposite with the instruction in the United States Patent (USP) 4545784, bleach-activating agent preferably is not adsorbed onto in the peroxy bleaching compound.Otherwise do like this,, can cause safety issue existing under other organic decontamination components.
Type a), b) and bleach-activating agent c) account for bleach system or detergent composition weight at least about 0.1%, preferably about 0.1%-50%,, more preferably from about 1%-30%, most preferably from about 3%-25%.
Preferred amido deutero-of the present invention and caprolactam bleach activators also can with the hydrophilic activator of rubber safety, enzyme safety for example TAED be used in combination, generally the weight ratio with amido deutero-or caprolactam activators: TAED is 1: 5-5: 1, and preferred about 1: 1.
Peroxy bleaching compound
The useful peroxide bleaching system of the present invention is to produce those of hydrogen peroxide in the aqueous solution.These compounds are well known in the art and comprise hydrogen peroxide and alkali metal peroxide, organic peroxy bleaching compounds for example urea peroxide and inorganic persalt bleaching compounds, for example alkali metal perborate, percarbonate, superphosphate etc.If need, also can use the mixture of two or more such bleaching compounds.
Preferred peroxy bleaching compound comprises Sodium peroxoborate, commercial available be one, three and the tetrahydrate form, trisodium phosphate peroxyhydrate, urea peroxyhydrate, SPC-D and sodium peroxide.Particularly preferably be sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D.SPC-D is particularly preferred, because it is highly stable and be dissolved in the aqueous bleaching solution very fast in storage process.Believe that this dissolving fast causes forming high-load percarboxylic acids, has strengthened the performance on bleaching surface thus.
Highly preferred percarbonate can be uncoated or coated form.The mean particle size of uncoated percarbonate is about 400-1200 micron, most preferably from about the 400-600 micron.If use the percarbonate that applies, preferred coating material comprises mixture, silicate, borosilicate or the aliphatic carboxylic acid of carbonate and vitriol.
Peroxy bleaching compound account for bleach system or detergent composition weight at least about 0.1%, preferably about 1%-75%, more preferably from about 3%-40%, most preferably from about 3%-25%.In the bleach system, the weight ratio of bleach-activating agent and peroxy bleaching compound is generally about 2: 1-1: 5.Preferred proportional range is about 1: 1-1: 3.The hydrogen peroxide that is produced by peroxy bleaching compound and the mol ratio of bleach-activating agent be greater than about 1.0, more preferably greater than about 1.5, most preferably is 2.0-10.Preferably, bleaching composition of the present invention comprises about 0.5%-20%, most preferably from about 1%-10% weight peroxy bleaching compound.
Bleach-activating agent of the present invention/bleaching compounds system itself can be used as SYNTHETIC OPTICAL WHITNER.Yet this bleach system is specially adapted to comprise various decontamination subsidiaries for example in the composition of tensio-active agent, washing assistant etc.
The aucillary detergent component
Preferably, comprise the aucillary detergent component in the present composition, it is selected from enzyme, dirt release agent, dispersion agent, white dyes, suds suppressor, fabric softener, enzyme stabilizers, spices, dyestuff, filler, dye transfer inhibitor and its mixture.It below is the representative example that is applicable to the detergent surfactant in the detergent composition of the present invention.The water-soluble salt of higher fatty acid, promptly " soap class " is anion surfactant useful in the present composition.It comprises containing has an appointment 8 to about 24 carbon atoms, preferred about 12 alkali metal soaps to the higher fatty acid of about 18 carbon atoms, for example sodium, potassium, ammonium and alkanol ammonium salt.Soap can prepare by the direct saponification reaction of fat and oil or the neutralization reaction by free fatty acids.Useful especially is sodium and the sylvite that derives from the mixed fatty acid of Oleum Cocois and butter, i.e. butter and cocounut oil sodium or potash soap.
Be applicable to that in addition anion surfactant of the present invention comprises the water-soluble salt of organic sulfating reaction product, preferred as alkali, ammonium and alkanol ammonium salt have about 10 straight chained alkyl and sulfonic acid or sulfate groups to about 20 carbon atoms in their molecular structure.(moieties that comprises acyl group in the term " alkyl ").The example of this class synthetic surfactant is sodium alkyl sulfate and potassium, especially by sulfation higher alcohols (C
8-C
18Carbon atom) those that obtain, for example those higher alcoholss that produce from the glyceryl ester of reduction butter or Oleum Cocois; With sodium alkyl benzene sulfonate and potassium, wherein alkyl contains and has an appointment 9 to about 15 carbon atoms, is linear configuration, for example at United States Patent (USP) 2,220, and those types of describing in 099 and 2,477,383.Valuable especially is linear alkylbenzene sulfonate, and wherein the average carbon atom number of alkyl is about 11 to about 13, and it is abbreviated as C
11-C
13LAS.
Be applicable to that other anion surfactant of the present invention is the alkyl glycerylether sodium sulfonate, particularly those ether sulfonates of the higher alcohols that obtains by butter and Oleum Cocois; Coco-nut oil fatty acid monoglyceride sodium sulfonate and sodium sulfate; The sodium of oxyethane or sylvite, alkyl wherein contain has an appointment 8 to about 12 carbon atoms; With alkyl oxygen Vinyl Ether sodium sulfate or potassium, its per molecule contains 1 to the about 10 unitary oxyethane of having an appointment, and alkyl wherein contains has an appointment 10 to about 20 carbon atoms.
In addition, the anion surfactant that is fit to comprises the water-soluble salt of a-sulfonated fatty acid ester, contains in it is fatty acid-based and has an appointment 6 to about 20 carbon atoms, contains at ester group and has an appointment 1 to about 10 carbon atoms; The water-soluble salt of 2-acyloxy-alkane-1-sulfonic acid contains in its acyl group and has an appointment 2 to about 9 carbon atoms, contains at paraffin section and has an appointment 9 to about 23 carbon atoms; Sulfated alkyl ether, its contain have an appointment 10 to the alkyl and about 1 of about 20 carbon atoms to about 30 mole oxygen ethene; Contain and have an appointment 12 to the alkene of about 20 carbon atoms and the water-soluble salt of paraffin sulfonic acid; And β-alkoxy alkane sulfonate, in its alkyl, contain and have an appointment 1 to about 3 carbon atoms, contain at paraffin section and have an appointment 8 to about 20 carbon atoms.
The preferred necessary anion surfactant that is used for detergent composition is C
10-8Linear alkylbenzene sulfonate and C
10-18Alkyl-sulphate.If desired, (being lower than about 25% water) alkyl-sulphate lotion of low water content can be used as component unique in the surfactant paste.Most preferably straight or branched and any primary, second month in a season or uncle C
10-18Alkyl-sulphate.The preferred embodiment of the invention is that wherein surfactant paste comprises the about 40%C of about 20%-
10-13Linear alkylbenzene sulphonic acid and C
12-16Sodium alkyl sulfate is about 2 by weight: 1-1: 2 mixture.
Water miscible nonionogenic tenside also is suitable among the present invention.This nonionisable substance comprises those compounds that produced by alkylene oxide group (hydrophobic) and organic hydrophobic compound condensation that can be aliphatic series or alkyl aromatic character.And the chain length of the polyalkylene oxide groups of any specific hydrophobic base condensation can easily be conditioned to obtain having the water-soluble cpds of required balance degree between hydrophilic and hydrophobic fragment.
The ionic surfactant pack that is fit to is drawn together the alkylphenol-polyethenoxy condenses, for example has for the alkylphenol of containing of straight or branched configuration about 6 to the alkyl of about 15 carbon atoms, by every mole of alkylphenol, with the condensation product of about 3-12 moles of ethylene oxide.Comprise contain 8-22 carbon atom be the fatty alcohol of straight or branched configuration, by every mol of alcohol, with the dispersible condensation product of water-soluble and water of 3-12 moles of ethylene oxide.
Be applicable to that other one group of nonionogenic tenside of the present invention is a semi-polar nonionic surfactants, it comprises water-soluble amine oxides, it contains a moieties of 10-18 the carbon atom of having an appointment and is selected from and contains 12 parts to the alkyl and the hydroxyalkyl of about 3 carbon atoms; The water soluble oxidized phosphine, it contains a moieties of 10-18 the carbon atom of having an appointment and is selected from and contains 12 parts to the alkyl and the hydroxyalkyl of about 3 carbon atoms of having an appointment; With water-soluble sulfoxide, it contains a moieties of 10-18 the carbon atom of having an appointment and is selected from and contains 1 part to the alkyl and the hydroxyalkyl of about 3 carbon atoms of having an appointment.
Preferred nonionic has formula R
1(OC
2H
4)
nOH, wherein R
1Be C
10-C
16Alkyl or C
8-C
12Alkyl phenyl, n are 3-about 80.Particularly preferably be every mole of C
12-C
15The condensation product of alcohol and about 20 moles of ethylene oxide of about 5-, for example, every mole of C
12-C
13Pure and about 6.5 moles of ethylene oxide condensations.
The ionic surfactant pack of Shi Heing is drawn together polyhydroxy fatty acid amide in addition.Example is N-methyl N-1-deoxy-glucose base coconut monoethanolamide and N-methyl N-1-deoxy-glucose base oil acid amides.The method for preparing polyhydroxy fatty acid amide is known, can be referring to the US2965576 of Wilson and the US2703798 of Schwartz, and its disclosure is quoted for referencial use at this paper.
Amphoterics comprises heterocycle secondary and the aliphatic series of tertiary amine or the derivative of aliphatic derivatives, wherein the aliphatic series part can be a straight or branched, and one of them aliphatic substituting group contains 8-18 the carbon atom of having an appointment, and at least one aliphatic substituting group contains the water soluble group of anionic property.
Zwitterionics comprises the derivative of aliphatic quaternary ammonium, phosphorus and sulfonium compound, and one of them aliphatic substituting group contains 8-18 the carbon atom of having an appointment.
Cats product also can comprise in the present invention.Cats product comprises multiple compound, is characterised in that one or more organic hydrophobic grouping and the quaternary nitrogen atoms that links to each other with acid groups usually on the positively charged ion.The azo-cycle compound of pentavalent also is considered to the quaternary nitrogen compound.The negatively charged ion that is fit to is halogenide, Methylsulfate and oxyhydroxide.Tertiary amine is lower than about 8.5 times at washing soln pH and has the characteristic that is similar to cats product.The more detailed of these and other cats product that the present invention is suitable for openly can be referring to the US4228044 that authorizes the 14 days October in 1980 of Cambre, and it quotes for referencial use at this paper.
Cats product is normally used in the detergent composition, so that fabric sofetening and/or antistatic property to be provided.Some soft effects can be provided and be that the preferred static inhibitor of the present invention is at Baskerville, the quaternary ammonium salt of describing among the US3936537 that authorize the 3 days February in 1976 of Jr. etc., its disclosure is quoted for referencial use at this paper.
Except detersive surfactant, in detergent composition, preferably include for example washing assistant of at least a suitable aucillary detergent component.For example, washing assistant can be selected from silico-aluminate, crystalline layered silicate, MAP zeolite, Citrate trianion, amorphous silicate, multi-carboxylate, yellow soda ash and their mixture.Other auxiliary washing assistant that is fit to is described hereinafter.
Preferred washing assistant comprises aluminosilicate ion exchange material and yellow soda ash.The aluminosilicate ion exchange material as detergent builders that the present invention uses preferably has high-calcium ionic exchange capacity and high rate of exchange.Do not plan to be limited by theory, believe that this high-calcium ionic rate of exchange and ability are the functions by several mutual pass factor of the method generation for preparing aluminosilicate ion exchange material.About this point, aluminosilicate ion exchange material used herein is preferably pressed U.S. Pat 4605509 (the Procter ﹠amp of Corkill etc.; Gamble) preparation, its disclosed content is quoted for referencial use at this paper.
Aluminosilicate ion exchange material is " sodium " form preferably, because high rate of exchange and the ability that provides as na form is not provided for the potassium of this silico-aluminate and hydrogen form.In addition, aluminosilicate ion exchange material is the form of super-dry preferably, so that produce crisp detergent agglomerate as described herein.The aluminosilicate ion exchange material that the present invention uses preferably has makes it as the most effective particle diameter of detergent builders.The median size of the aluminosilicate ion exchange material of giving of analytical technology mensuration routinely represented in term used herein " particle diameter ", for example uses measurement microscope technology and scanning electron microscope (SEM).The preferred particle diameter of silico-aluminate is about 0.1-10 micron, more preferably from about the 0.5-9 micron.Most preferably, this particle diameter is about 1-8 micron.
Aluminosilicate ion exchange material preferably has following formula:
Na
z[(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 about 1-5, and x is about 10-264.More preferably silico-aluminate has following formula:
Na
12[(AlO
2)
12(SiO
2)
12] xH
2O wherein x is about 20 to about 30, especially about 27.These preferred silico-aluminates are commercially available, and for example zeolite A, zeolite B and X zeolite are purchased by name.In addition, be applicable to natural generation of the present invention or the synthetic aluminosilicate ion exchange material that obtains can be by method preparation described in the U.S. Pat 3985669 of Krummel etc., its disclosure is quoted for referencial use at this paper.
Silico-aluminate feature used herein also is their ion-exchange capacity, and it is at least about 200 milligramequivalent CaCO
3Hardness per gram is pressed moisture-free basis and is calculated, and is preferably about 300-352 milligramequivalent CaCO
3Hardness per gram.In addition, this aluminosilicate ion exchange material feature also is their calcium ion exchange rate, and it is at least about 2 grain Ca
++/ gallon per minute/-Ke/gallon, more preferably at about 2 grain Ca
++/ gallon per minute/-Ke/gallon is to about 6 grain Ca
++/ gallon per minute/-Ke/gallon scope.
For the present invention is more readily understood, with reference to following examples, it just is used for explanation and scope is not limited.
Example I-IV
Following component is added in the Littleford FM batch mixer: 83% acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (" NOBS "); 6% palmitinic acid, 3% linear alkylbenzene sulphonic acid tensio-active agent; 6% polyoxyethylene glycol (MW=4000); With 2% C
9Lipid acid.With this mixture mix and add the extrusion machine used in the laboratory (Fuji Paudel Co, Ltd, DomeGranulator, DG-L1) in and extrude by the mould that has 350 microns of diameters, 500 microns, 700 microns and 890 microns respectively.The columniform every kind of extrudate of being essentially of four kinds of different diameters made is of a size of 2000 microns of mean lengths and is mixed in the detergent composition that contains SYNTHETIC OPTICAL WHITNER with following prescription:
Component I II III IVC
12-16Linear alkylbenzene sulfonate 11.0 11.0 11.0 11.0C
14-15Alkyl-sulphate/C
14-1510.4 10.4 10.4 10.4 alkyl ethoxy sulfate Neodol 23-6.5
12.2 2.2 2.2 2.2 polyacrylates (MW=4500), 3.0 3.0 3.0 3.0 polyethylene glycol (MW=4000), 1.2 1.2 1.2 1.2 sodium sulphate, 10.5 10.5 10.5 10.5 alumino-silicates, 26.6 26.6 26.6 26.6 sodium carbonate, 21.0 21.0 21.0 21.0 proteinase-10 .4,0.4 0.4 0.4 sodium perborate monohydrates, 2.6 2.6 2.6 2.6 lipase 0.2 0.2 0.2 0.2 cellulases, 0.1 0.1 0.1 0.1NOBS extrudates (500 micron diameter) 6.0---NOBS extrudates (700 micron diameter)-6.0--NOBS extrudate (350 micron diameter)---6.0NOBS extrudate (890 micron diameter)--6.0-free water 2.0 2.0 2.0 2.0 auxiliary components (in conjunction with water, spices etc.)2.8 2.8 2.8 2.8
100.0 100.0 100.0 100.0
1The C that is purchased by Shell Oil company
12-13Alkylethoxylate (EO=6.5).
Stability in storage and product segregation trend according to the bleach-activating agent of each example I of measurement of test method, II, III and the IV composition that hereinafter describe in detail.
About storage stability test, the 20 gram composition sample that exemplify explanation above 8 are respectively put into independently vial and sealing.Rotate this bottle by planetary motion, mix each group in four groups of vials.Open vial then and be put in the controlled environment that remains on 80 (26.7 ℃) and 60% relative humidity.Weekly,, analyze the content of bleach-activating agent (for example NOBS) in the vial, use regression analysis, with one group of complete bleach activating agent content that data conversion one-tenth keeps in stored prod since finishing in 0 week to the 8th week.This test in, when the bleach activating agent content that in stored prod, keeps be initial content at least 90% the time, having shown has satisfactory stability.
In order to measure the segregation trend of product, carry out following steps.
The test of segregation trend
1. two funnels are placed on the ring support, a pipe is arranged at the top, make that the distance between the bottom of the neck of upper funnel and lower hopper is 37cm, below lower hopper, have enough spaces to place a bottle;
2. in this bottle, add 100 gram detergent composition, seal this bottle and rotate this bottle, with its inner material of thorough mixing by planetary motion;
3. clog upper funnel and the material in the bottle is poured in the upper funnel;
4. clog lower hopper, remove the stopper of upper funnel, inner material is flowed in the lower hopper;
5. by weight, weighing up the weight of an empty bottle, the material in the funnel is flowed in this bottle, is 25 grams until weight;
6. repeat 5 step,, remaining material is flowed in the 4th bottle more than twice;
7. analyze the bleach activating agent content in each bottle;
8. tapering index (CI)=100 * (overactivity agent content-minimum activator content)/average activator content, wherein CI is high more, and isolating trend is big more.
In this isolation test, think that tapering index (CI) is unacceptable greater than 80 and the expression product has too isolating possibility.The result of stability and segregation trend shows the example I with the average extrudate diameter in the scope of the invention and II unexpectedly has good activator stability and product has less segregation trend.Comparative Example III with the average extrudate diameter outside the scope of the invention has unacceptable segregation possibility, and the Comparative Example IV that also has the outer average extrudate diameter of the scope of the invention has unacceptable bleach-activating agent stability in storage.
EXAMPLE V-VII
As above-mentioned example I-IV, prepare the NOBS extrudate by same procedure, just extrudate has 850 microns of mean diameters.Afterwards, in Quadro CO-Mill, grind three batches of NOBS extrudates, form the extrudate that has 4000 microns (EXAMPLE V) of mean length, 2000 microns (example VI) and 1000 microns (example VII A) respectively.Every batch mixing is gone into as in the above detergent composition that contains SYNTHETIC OPTICAL WHITNER that illustrates in example I-IV.Carry out activator stability and the test of segregation trend by example I-IV.The result shows that example VI and the VII in the scope of the invention unexpectedly has excellent stability and product segregation character, and the Comparative Example V with the average extrudate length outside the scope of the invention has unacceptable segregation possibility.
Example VII A I-X
As above-mentioned example I-IV, prepare bay acyloxy benzene sulfonic acid sodium salt (" LOBS ") extrudate by the method identical with example I, it is included in the prescription identical with example I, just replaces NOBS with LOBS.Afterwards, in Quadro CO-Mill, grind three batches of LOBS extrudates, form the extrudate that has 4000 microns (example VII A I) of mean length, 2000 microns (example I X) and 1000 microns (embodiment X) respectively.Every batch mixing is gone into as in the above detergent composition that contains SYNTHETIC OPTICAL WHITNER that illustrates in example I-IV.Carry out activator stability and the test of segregation trend by example I-IV.The result shows that example I X and the X in the scope of the invention unexpectedly has excellent stability and product segregation character, and the Comparative Example V III with the average extrudate length outside the scope of the invention has unacceptable segregation possibility.
Embodiment XI-XIII
As above-mentioned example I-IV, to caprinoyl aminobenzoic acid (" DOBA ") extrudate, it is included in the prescription identical with example I, just replaces NOBS with DOBA by the method preparation identical with example I.Afterwards, in Quadro CO-Mill, grind three batches of DOBA extrudates, form the extrudate that has 4000 microns of mean lengths (embodiment XI), 2000 microns (embodiment XII) and 1000 microns (embodiment XIII) respectively.Every batch mixing is gone into as in the above detergent composition that contains SYNTHETIC OPTICAL WHITNER that illustrates in example I-IV.Carry out activator stability and the test of segregation trend by example I-IV.The result shows that embodiment XIII and the XII in the scope of the invention unexpectedly has excellent stability and product segregation character, and the comparative example XI with the average extrudate length outside the scope of the invention has unacceptable segregation possibility.
Embodiment XIV
Synthetic (LOBS) of bay acyloxy benzene sulfonic acid sodium salt
2L three neck round-bottomed flasks are loaded onto mechanical stirrer, reflux exchanger and gas inlet pipe.With the lauroyl chloride of packing in this flask (
2, Aldrich, 96g, 0.44mol), toluene (500ml) and dry-out benzene sulfocarbolate (
3,78g, 0.40mol).Stir under hydrogen, the reacting by heating mixture kept 16 hours to refluxing.After being cooled to room temperature, with diethyl ether (500ml) diluted mixture thing, the solid of collecting precipitation washs and dry air with other diethyl ether after filtration.With this drying solid of methyl alcohol (750ml) titration that refluxes.After being cooled to room temperature, filter, drying, obtain 125g (83% theory) bay acyloxy benzene sulfonic acid sodium salt (LOBS,
1).
Embodiment XV
To synthesizing of caprinoyl aminobenzoic acid (DOBA)
The 2L beaker is loaded onto mechanical stirrer, pH electrode and temperature probe.With the P-hydroxybenzoic acid of packing in the beaker (
5, Aldrich, 138g, 1.0mol) and 1N sodium hydroxide (1.0L, 1.0mol), the pH of the solution that obtains is that 11.2. is cooled to 10 ℃ with this solution, dripped through 15 minutes under 0-15 ℃ the decanoyl chloride be dissolved in the 250ml diethyl ether (
6, Aldrich, 95g, 0.5mol), adding 50% sodium hydroxide solution maintenance pH simultaneously synchronously is 10.After adding decanoyl chloride, the pH of solution is 10.1, and the temperature of solution is 10 ℃.After adding, stirred 10 minutes at pH 10 and 10 ℃ of following continuation.Use the pH to 3 of dense HCl conditioned reaction mixture then, the solid of collecting precipitation after filtration, dry air obtains the thick product of 180g.With the ethyl alcohol recrystallization of 900ml 95% obtain 58g (40% theory) to the caprinoyl aminobenzoic acid (DOBA,
4), mp125-129 ℃.Analyze this product by NMR, show that purity is 93%, remaining is the 4-hydroxy-benzoic acid.
Described the present invention thus in detail, can do various variations not breaking away under the scope of the invention, this is obvious to those skilled in the art, and does not think and limit the invention in content described in the specification sheets.
Claims (15)
1. detergent composition that contains SYNTHETIC OPTICAL WHITNER, it comprises:
(a) in the aqueous solution, can produce the peroxy bleaching compound of hydrogen peroxide by detergent composition weight 0.1%-75%;
(b) have the bleach-activating agent of following general formula by detergent composition weight 0.1%-50%:
Wherein R is the alkyl that contains 5-18 carbon atom, M is sodium or potassium, the hydrogen peroxide that is produced by (a) and the mol ratio of bleach-activating agent (b) are greater than 1.0, with described bleach-activating agent be cylindrical basically extrudate form, its average extrudate length is that 500-3500 micron and average extrudate diameter are the 450-850 micron; With
(c) the aucillary detergent component of surplus.
2. the detergent composition of claim 1, wherein said average extrudate length is the 700-3000 micron.
3. the detergent composition of claim 1, wherein said average extrudate diameter is the 500-800 micron.
4. the detergent composition of claim 1, wherein said average extrudate length is the 900-2500 micron.
5. the detergent composition of claim 1, wherein said average extrudate diameter is the 550-750 micron.
6. the detergent composition of claim 1, wherein said peroxy bleaching compound is selected from Sodium peroxoborate monohydrate, sodium perborate tetrahydrate, yellow soda ash peroxyhydrate, trisodium phosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide and its mixture.
7. the detergent composition of claim 1, wherein said bleach-activating agent is an acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems.
8. the detergent composition of claim 1, the wherein said extrudate flow promotor dressing of 0.1-10% weight, described flow promotor is selected from thin silico-aluminate, silicon-dioxide, crystalline layered silicate, MAP zeolite, Citrate trianion, amorphous silicate, yellow soda ash and its mixture.
9. the detergent composition of claim 8, it also comprises the aucillary detergent component, and it is selected from enzyme, dirt release agent, dispersion agent, white dyes, suds suppressor, fabric softener, enzyme stabilizers, spices, dyestuff, filler, dye transfer inhibitor and its mixture.
10. the detergent composition of claim 1, wherein the content of free-water is lower than 3% weight.
11. the detergent composition of claim 1, wherein the content of free-water is lower than 2.5% weight.
12. the method for the fabric of sterilizing, it comprises the step that described fabric is contacted with the detergent composition according to the significant quantity of claim 1 in the aqueous solution.
13. the method for claim 12, wherein the number of the microorganism that exists on described fabric is lowered at least 50%.
14. the method for claim 12, wherein the number of the microorganism that exists on described fabric is lowered at least 90%.
15. the method for claim 12, wherein the number of the microorganism that exists on described fabric is lowered at least 99.9%.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/974,784 | 1997-11-20 | ||
| US08/974784 | 1997-11-20 | ||
| US08/974,784 US5795854A (en) | 1997-11-20 | 1997-11-20 | Detergent composition containing cylindrically-shaped bleach activator extrudates |
| US09/093,834 US5891838A (en) | 1997-11-20 | 1998-06-08 | Detergent composition containing optimally sized bleach activator particles |
| US09/093,834 | 1998-06-08 | ||
| US09/093834 | 1998-06-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1284124A CN1284124A (en) | 2001-02-14 |
| CN1130456C true CN1130456C (en) | 2003-12-10 |
Family
ID=26787948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98813218 Expired - Fee Related CN1130456C (en) | 1997-11-20 | 1998-09-23 | Detergent compsn contg optimally sized bleach activator particles |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1032639A1 (en) |
| CN (1) | CN1130456C (en) |
| AU (1) | AU2652099A (en) |
| CA (1) | CA2311378C (en) |
| MA (1) | MA24695A1 (en) |
| WO (1) | WO1999027061A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10134364A1 (en) | 2001-07-14 | 2003-01-23 | Clariant Gmbh | Process for the production of bleach activator granules |
| DE10136805A1 (en) | 2001-07-25 | 2003-02-13 | Clariant Gmbh | Process for the production of bleach activator granules |
| HUE029942T2 (en) | 2009-08-13 | 2017-04-28 | Procter & Gamble | Method of laundering fabrics at low temperature |
| DE102010034244A1 (en) * | 2010-08-13 | 2012-02-16 | Clariant International Limited | Process for the preparation of acyloxybenzoic acids |
| DE102010034243A1 (en) * | 2010-08-13 | 2012-02-16 | Clariant International Limited | Process for the preparation of acyloxybenzoic acids |
| MX2020013602A (en) * | 2018-06-15 | 2021-03-09 | Procter & Gamble | Particulate laundry detergent compositions comprising perfume particles, and method of using same. |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT339246B (en) * | 1974-08-14 | 1977-10-10 | Henkel & Cie Gmbh | BLEACHING AID SUITABLE AS A COMPONENT OF POWDERED DETERGENTS AND BLEACHING AGENTS |
| US4486327A (en) * | 1983-12-22 | 1984-12-04 | The Procter & Gamble Company | Bodies containing stabilized bleach activators |
| US5458801A (en) * | 1991-09-27 | 1995-10-17 | Kao Corporation | Process for producing granular bleach activator composition and granular bleach activator composition |
| DE69412092T2 (en) * | 1993-05-20 | 1999-04-01 | Procter & Gamble | FIBER WHICH CONTAINS A SUBSTITUTED BENZOYL CAPROLACTAM BLEACH ACTIVATOR |
| US5405413A (en) * | 1993-06-24 | 1995-04-11 | The Procter & Gamble Co. | Bleaching compounds comprising acyl valerolactam bleach activators |
| US5762647A (en) * | 1995-11-21 | 1998-06-09 | The Procter & Gamble Company | Method of laundering with a low sudsing granular detergent composition containing optimally selected levels of a foam control agent bleach activator/peroxygen bleaching agent system and enzyme |
| EP0880581A4 (en) * | 1996-01-29 | 2001-10-10 | Procter & Gamble | Process for making particulate bleach activator component |
| ATE263230T1 (en) * | 1996-06-28 | 2004-04-15 | Procter & Gamble | BLEACH PRECURSOR COMPOSITIONS |
-
1998
- 1998-09-23 CN CN 98813218 patent/CN1130456C/en not_active Expired - Fee Related
- 1998-09-23 WO PCT/US1998/019999 patent/WO1999027061A1/en not_active Application Discontinuation
- 1998-09-23 CA CA002311378A patent/CA2311378C/en not_active Expired - Fee Related
- 1998-09-23 EP EP98966939A patent/EP1032639A1/en not_active Withdrawn
- 1998-09-23 AU AU26520/99A patent/AU2652099A/en not_active Abandoned
- 1998-11-10 MA MA25339A patent/MA24695A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA2311378C (en) | 2004-04-20 |
| AU2652099A (en) | 1999-06-15 |
| EP1032639A1 (en) | 2000-09-06 |
| CA2311378A1 (en) | 1999-06-03 |
| WO1999027061A1 (en) | 1999-06-03 |
| MA24695A1 (en) | 1999-07-01 |
| CN1284124A (en) | 2001-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5795854A (en) | Detergent composition containing cylindrically-shaped bleach activator extrudates | |
| US20080070821A1 (en) | Post-added alpha-sulfofatty acid ester compositions and methods of making and using the same | |
| JPH08507098A (en) | Highly active enzyme granules | |
| CN1259163A (en) | Additive granules for moulded bodies having a detergent and cleaning action | |
| CN1130456C (en) | Detergent compsn contg optimally sized bleach activator particles | |
| JP4053124B2 (en) | Detergent particle composition and method for producing the same | |
| CN1268171A (en) | Particulate detergent composition | |
| US6596684B2 (en) | Granular detergent component and process for its preparation | |
| CN1578828A (en) | Perfumed coloured speckle composition and particulate laundry detergent compositions containing it | |
| CN1083859A (en) | Detergent composition | |
| CA2248994C (en) | Free-flowing agglomerated nonionic surfactant detergent composition and process for making same | |
| EP0482627A1 (en) | Tablet detergent composition | |
| AU2001263823A1 (en) | Granular detergent component and process for its preparation | |
| US6534464B1 (en) | Compositions containing α-sulfofatty acid ester and polyalkoxylated alkanolamide and methods of making and using the same | |
| CN1307629A (en) | Non-particulate detergent product containing bleach activator | |
| CN1301295A (en) | Detergent composition containing cylindrically-shaped bleach activator extrudates having enhanced flowability | |
| US6177397B1 (en) | Free-flowing agglomerated nonionic surfactant detergent composition and process for making same | |
| EP1550712B1 (en) | Process for producing a granular anionic surfactant | |
| CA2000310A1 (en) | Detergent composition | |
| KR100334733B1 (en) | method for producing high-density powder detergent | |
| JP2001181691A (en) | Vessel rotary type mixing machine and method for producing granular detergent composition | |
| JP4889870B2 (en) | Powder detergent composition for clothing | |
| PL174609B1 (en) | Detergent compositions | |
| KR100361131B1 (en) | Laundry powder detergent with high deusity and method of prepairing the same | |
| JP2001246238A (en) | Granulator, method for producing granule, and method for producing granular detergent composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |