CN1224457A - Process for mfg. bleaching compositions comprising chlorine and bromine sources and product thereof - Google Patents
Process for mfg. bleaching compositions comprising chlorine and bromine sources and product thereof Download PDFInfo
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- CN1224457A CN1224457A CN 96180375 CN96180375A CN1224457A CN 1224457 A CN1224457 A CN 1224457A CN 96180375 CN96180375 CN 96180375 CN 96180375 A CN96180375 A CN 96180375A CN 1224457 A CN1224457 A CN 1224457A
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Abstract
An improved process for the manufacture of alkaline bleaching compositions, especially liquid and/or gel compositions of high solubility and low abrasiveness, useful to the consumer, especially as products for hard surface cleaning, bleaching or disinfectancy. The products are made by a three-stage process and comprise particular chlorine and bromine bleach sources and particular aminofunctional materials such as low-impurity sulfamate. The process has mixing sequences and starting ingredient selections which provide unexpectedly improved product.
Description
Invention field
The present invention relates to prepare the method to the useful alkaline bleaching composition of human consumer, described composition especially as the cleaning of crust, is bleached or sterilized product.This product contains chlorine and bromine bleaching source.This method relates to the selection of blended order and initial substance, and they provide the product of the improvement that does not reckon with.
Background of invention
Hard surface cleaner, SYNTHETIC OPTICAL WHITNER and sterilizing agent are to know the consumer products for preparing.They are for handling various dirty kitchens, the bathroom, and tank, bathtub, shower bath, water closet and cupboard top surface are useful.
Known that such consumer products comprises hypochlorite bleaching.Because the high efficiency of hypochlorite is suitable as SYNTHETIC OPTICAL WHITNER and sterilizing agent.Yet it has many shortcomings, and this comprises that it is too fierce sometimes, tends to staying niff on hand, stores always unstable simultaneously in the consumer products prescription.
Bromine-containing compound has been used for bleaching or sterilization in Special Circumstances.Yet often price is expensive and than chlorine analogue higher requirement is arranged usually aspect package stability for they.
Thionamic acid is used for sanitising agent, especially in the acidic cleaning agent of the acid that discharges high density.
The chemistry that contains the thionamic acid salt system that has halogen is very complicated, and is still continuing up to the research in this field at present.
Although part is known the characteristic of this area, but have being suitable for the hard surface cleaner that the human consumer uses, the continuous needs of SYNTHETIC OPTICAL WHITNER and sterilizing agent, they should be effectively to improve on one or more its characteristics, this comprises the superior effectiveness that has as SYNTHETIC OPTICAL WHITNER and sterilizing agent, have still less pungency, be tending towards on hand staying few smell or or even stay happy smell, and in storing very high stability is arranged.
Therefore, the invention provides a kind of alkaline bleaching composition of improving one's methods and therefore obtaining of producing such composition.
The method here has some advantages, comprises that it is easily operation and is safely and effectively to the purposes of its needs.Surprisingly, it has provided a kind of product, and it is better than using the product that many other orders by merging just can obtain really.
Technical background
The common U.S.3 that transfers the possession of, 583,922 (Mc Clain and Meyer, on June 8th, 1971) and Canadian Patent CA 860279A (on January 5th, 1971 open) described a kind of solids composition, be used for removing fast the tannin acid stain, its pH is not less than 10.5, contain the 0-95% abradant, up to 10% tensio-active agent, 0-60% alkaline auxiliary lotion, a kind of stable compound, preferably the chlorating trisodium orthophosphate provides 0.5%-5% obtainable chlorine, and containing thionamic acid is 500 to 1: 1 with the preferred proportion that produces Cl and thionamic acid, preferably 3: 1 to 6: 1, randomly contain additive.Such additive can comprise bromide, spices or borax.Said composition be can regulate and the cleaning of tank or the dishwashing detergent of machinery are used for.
JP 63108099A (Lion Corp, on May 12nd, 1988 is open) has described a kind of SYNTHETIC OPTICAL WHITNER of controlling the smell of chlorine, and it contains hypochlorite and thionamic acid and/or the sulfamate and the pH regulator agent of specified proportion.This ratio is 2-8 (weight) % hypochlorite (sic) based on " amount of available chlorine ", and the molar ratio of thionamic acid and/or thionamic acid salt pair hypochlorite is 0.25 to 1.5.
JP 63161088A (Lion Corp, it is open to be published on July 4th, 1 988) the clothing bleaching composition described, it mainly comprises hydrogen peroxide and thionamic acid and/or water miscible sulfamate and hypohalous acid and/or water miscible hypohalite such as NaClO, Ca (OCl)
2, chlorinated lime or NaBrO, sulfamate exists with the amount of every mole of hypochlorite 0.5-5 mole.
The U.S.4 of Smyk etc., a kind of sterilization that comprises the corrosion inhibitor that contains nitrite has been described in 992,209 (1991, February 12), and system is for example cooled off by the fungicidal system, and it passes through NaBr and NaOCl or Cl
2With the reaction of thionamic acid sodium or thionamic acid and prepare, and claim that this product " reacts " in 5 hours preparation.
U.S.5, describe thionamic acid cleaning/(stripping) composition of stripping 431,839 (Guillou, July 11 nineteen ninety-five), contains the mixed polysaccharide thickening material.U.S.5,047,164 (on September 10th, 1991, Corby) describe and to contain between halogen and the composition of acid, be particularly suitable for handling the cleaning and the sterilization of milk and food device.U.S.4, describe the SYNTHETIC OPTICAL WHITNER of microencapsulation 279,764 (Brubaker, on July 21st, 1981), and it contains the chlorating isocyanurate of shelf-stable.U.S.4,233,173 (Mayer etc., on November 11st, 1980) and U.S.4,201,687 (Crutchfield etc.) describe the detergent composition that contains chloro imidodisulfate SYNTHETIC OPTICAL WHITNER.U.S.5 describes the moisture scrubbing agent with the thickening that improves rinsability 470,499 (Choy etc., November 28 nineteen ninety-five).The common U.S.4 that transfers the possession of, 051,056 (on September 27th, 1977 Hartman) was described the abrasive material abrasive cleaning composition that contains perlite and hypochlorite bleaching.The common U.S.3 that transfers the possession of describes scrub clean agent composition 715,314 (Morgenstern, on February 6th, 1973).The common U.S.5 that transfers the possession of describes the stable thickened aqueous bleaching composition that contains chlorine bleach and phytinic acid 384,061 (Wise, January 24 nineteen ninety-five).The thionamic acid that industry is used is included in one piece of literature review, sees " inorganic sulfur chemistry ", G, Nickless, Ed, Elsevier, 1968, the 18 chapters, " amino and imino--sulfonic acid " 607-667 and at this reference of quoting; Also referring to Kirk, Othmer " encyclopedia of chemical technology ", the third edition, Wiley-Interscience, the 21st volume, " thionamic acid and sulfamate ", pp 949-960.Chloramines, bromo-amine and N-halogen amine are more generally summarized in Kirk Othmer " encyclopedia of chemical technology ", Wiley-Interscience, the 4th edition, the 5th chapter, pp911-932; Also see corresponding article in this encyclopaedical third edition.Chlorine mixes with the solution that contains thionamic acid in advance; See Korshak etc., Zh, Obsch.Khim, the 18th volume (1948), the 753-756 page or leaf, but this mixture decomposes.
Summary of the invention
The present invention includes a kind of alkaline bleaching composition of a kind of production, a kind of method of aqueous liquid bleaching composition packed preferably, this method comprises three phases at least.These stages comprise in order (I) preceding-the bromine stage.(II) bromine compounds adds stage and (III) product stabilization stage, and each above-mentioned stage has a step mixing step at least.
In the method, said before-the bromine stage (I) comprises a step (a), with the random order blending ingredients, component comprises the hypochlorite source and has the amino functional of stablize the N-halo derivatives to roll into a ball compound; So formation stage (I) mixture; Precondition be before this-during the end in bromine stage, it is about 11 that the pH of this stage (I) mixture is no more than, preferably lower; The addition stage (II) of said bromine compounds begins under above-mentioned pH and comprises step (b), mixes the mixture of above-mentioned steps (I), bromine compounds with random order; Thereby formation stage (II) mixture; Comprise that with the said product stabilization stage (III) step (c) is mixed the mixture of above-mentioned steps (II) with random order at least, the alkali of appropriate amount is at least about 13 so that the product final pH of this method reaches.
The product that present method provides has unique advantage, and promptly extraordinary bleaching effect makes simultaneously minimum " bleaching smell " on skin.Preferred product is that yellow transparent is liquid, aqueous, its thickening at random and/or perfuming.
All percentage ratios herein, ratio and ratio are based on weight, unless otherwise noted.The document of all references all is included in this as a reference.
Accompanying drawing is briefly described
Fig. 1 represents the signal of the inventive method, and expression is transformed into product by a series of stages with initial substance (component), and this comprises being stage (I), stage (II) and stage (IV) in order.In each stage, as described, comprise one or more steps.Step (I) comprises basic step, i.e. step (a).Stage (II) comprises basic step, i.e. step (b), and stage (III) comprises basic step, i.e. step (c).Drawing the method for the present invention of the form of simplifying most from Fig. 1, comprise sequenced three steps (a), is (b) afterwards, is (c) at last.Stage that each is basic and step and the component that suits and the characteristic of product are described in detail in this paper back.
Detailed Description Of The Invention
According to the present invention, find, reach the satisfactory alkaline bleaching composition of human consumer in order to obtain to have superior technical feature, two kinds of dissimilar halogenic ingredients need be provided, this halogenic ingredient comprises at least a, has the component of the form of hypohalite at the first bruss in the component of the form that has bromine compounds at the first bruss and at least one class.Also found to select especially and comprised that certain amino functional group compound is important; And an especially specific method with regard to order by merging is provided, guarantee the advantage of product.The alkalescence bleaching composition
Therefore, the present invention relates to make method and its product of alkaline bleaching composition." the alkaline bleaching composition " of the present invention's definition is alkaline." alkaline bleaching composition " of the present invention has pH and is at least about 13, and is to be prepared by the composition that contains hypochlorite source and bromine compounds and at least one special amino functional group compound of selecting.As hard-surface cleaning, bleaching or disinfectant product are useful to alkaline bleaching composition of the present invention to the human consumer.Usually they can have any nonlimiting examples of suitable physical, particle for example, and sheet, paste, gel or liquid form, and can be aqueous or non-water.Yet method herein especially is well suited to prepare aqueous, alkalescence, liquid form or gel form bleaching composition.Unless otherwise noted, the embodiment of description present method after this and product of the present invention refers to aqueous liquid form.The method stage
The inventive method generally includes three phases at least:
(I) preceding-the bromine stage
(II) bromine compounds add the stage and
(III) product stabilization stage.
Each stage be (I) (II) (III) more then in order.Each stage is represented in Fig. 1.Each stage comprises one or more steps.With the simplest form, present method comprises, in stage (I), and step (a); In stage (II), step (b) and in stage (III), step (c).Additional step for example adds and/or mixes other composition such as spices, and tensio-active agent etc. can insert before or after basic step.Its condition be they do not influence the indicated order of basic step and also in addition their operation to be complementary with the strict demand of pH described herein.
In more detail, the stage (I), preceding-the bromine stage, be the stage that is used for hypochlorite is originated and special amino functional based compound is mixed together; In the stage (II), bromine compounds adds the stage, is the stage that is used to introduce bromine compounds, and the stage (II), and the stabilization stage is by improving the stage of pH with stable prod.
Therefore the present invention includes the method for producing alkaline bleaching composition, this method comprised at least three stages, comprised in order, (I) preceding-the bromine stage, (II) bromine compounds adds stage and (III) product stabilization stage, and there is at least one step mixing step in each above-mentioned stage; In the method, before this-the bromine stage comprises a step (a), and with the random order blending ingredients, they comprise the hypochlorite source and have the amino functional of stablize the N-halo derivatives to roll into a ball compound; Therefore formation stage (I) mixture, as long as before this-during the end in bromine stage, this stage, the pH of (I) mixture was no more than about 11; Preferably lower; In the adding stage (II) of above-mentioned bromine compounds, beginning and comprise a step (b) under above-mentioned pH mixes the mixture of above-mentioned steps (I), bromine compounds with random order; So formation stage (II) mixture; With the said product stabilization stage (III), it comprises at least one step (c), mixes the mixture of above-mentioned steps (II) with random order, and the alkali of appropriate amount is at least about 13 so that the product final pH of this method reaches.
Is conditional in this particularly preferred method with regard to when adding bromine compounds.In a preferred method, have only the stage (II) and only in steps (b) include the adding of bromine compounds.Surprisingly, found product performance are had bad influence at other local bromine compounds that adds of this order.The optional approach step
Present method can comprise many optional step.A useful optional step of the present invention illustrates that with dilution step this step comprises in the method finishes the stage (III) afterwards.Such step in fact can be by manufacturers as dilution step, or by stage (I), (II), the user of (III) product carries out.Dilution step can be included in the stage (I) of present method usually, in stage (2) or stage (3), though preferably, is diluted in these stages and avoids.Typically, in factory, do not carry out dilution step, but undertaken by the human consumer who uses said composition for best package stability.Dilution can cause pH to change, and causes pH to descend usually.
Other useful optional step of the present invention comprises that tensio-active agent adds step, or adds or mix any suitable optional member, and for example those think the step of " optional member " after this.Square law device
Can use any suitable device to finish present method.Reactor should be an inert chemically to halogen bleaching agent and strong alkaline condition, the pollution minimum that the device of plastics and/or borosilicate glass liner helps weather resistance and makes the metal pair product.Do not need reactor design to operate under pressure, its condition is if provide suitable ventilation.Can be with any suitable mixing tank, for example the oar of motor-promotion is finished the mixing of component.Perhaps, can use impeller pump that the cyclic spray of product solution is provided, to promote the stirring of mixture.Other useful method means of the present invention comprise the method for removing steam from Working environment.Such means comprise conventional scrubber etc.Method condition temperature
In general present method can be carried out in wide temperature range.Preferably, each this step (b) and (c) can be carrying out to about 80 ℃ temperature range from about 5 ℃, preferably from about 10 ℃ to about 45 ℃, most preferably be or be bordering on room temperature, for example about 20 ℃.Here, method very preferably is with in stage (I), and steps all in (II) and (III) are finished under such temperature.When higher temperatures, the decomposition that may occur increasing tendency and when lesser temps, solidifying may be problem.The pH value
Present method requires to have special restriction in the pH variation.General requirement is when preceding-bromine stage finishes and during the beginning in bromine stage, and the stage, (I) mixture pH was no more than about 11.In preferred embodiments, it is about 8 that this pH is no more than, more preferably, it from about 1 to about 6.9 scope.
In preferred embodiments, when the stage I finished, entire method was to carry out in the pH that raises gradually.This pH that raises gradually be suitably be at least the single bit per minute of pact+0.1pH, be preferably about+0.5pH list bit per minute, or higher dpH/dt is corresponding.
In such embodiments, obviously the inventive method includes the pH minimum value.When the position of this minimum value in all orders of present method is found to be in the end in stage (I).Pressure
Can in officely how to carry out present method in the pressure easily.For example, can be with chlorine and alkali reaction under pressure, for example, in the stage (I) before adding amino functional group compound up to about 5 normal atmosphere; Stage subsequently can carry out in normal atmosphere, perhaps even under reduced pressure carries out, if provide scrubber or condenser to collect the halogen that loses.Preferable methods is under atmospheric pressure to carry out.Time
Can be intermittently or continuous fashion carry out present method.Unless otherwise noted, this paper back is an intermittent mode to the description of present method.Finishing a collection of time generally can extensively change.Typically, to each stage (I), (II) and (III) extremely about 1.5 hours time was common in about 5 minutes.In preferred embodiments, make the stage (II) have at least the enough time with allow carry out the stage (III) before bromine compounds dissolve substantially.Also preferably, the continuation stage (II) is yellow up to producing in stage (II) mixture.In general, the long method time is relevant with large-scale process.The present invention preferably makes total reaction time minimum, and particularly, when there is enough time in the permission stage (II), otherwise the stage that proceeds to (III) of delay finish.In addition, when step (a) is finished and between during step (b) beginning, and step (b) is when finishing and the arbitrary time minimum between during step (c) beginning.Concentration and concentration ratio
Present method can be carried out in the broad range of constituent concentration in water.In preferred embodiments, the feature of present method is that dilution factor in stage (I) stage summation afterwards is no more than about two times.Usually, the concentration of adjusting composition makes the stage product of (III) contain from about 0.01% to about 10% available chlorine.Equally, for the relative proportion between composition, present method preferably depends on [Br] between halogen: [OCl
-] ratio is from about 10: 1 to about 1: 10, is preferably 1: 2 to 1: 5, wherein [Br] representative is added to the Br and the [OCl of the total mole number of this method from described bromine compounds
-] representative is added to total mole hypochlorite of this method from described hypochlorite source.In addition, amino-halogen ratio [A] that preferable methods of the present invention is used: [X] be from about 10: 1 to 1: 10, wherein [A] representative be used to form total mole number of amino part in the described amino functional group compound of the present composition and wherein [X] represent the total mole number that is added in the said composition as the bleaching halogen of detectable available chlorine.
Most preferably be that above-mentioned amino-halogen ratio is from about 1.0: 1.0 to about 1.5: 1.0.
Be explanation and above-mentioned relevant amount, the thionamic acid that contains one mole amino part in every mole compound can be easy to calculate with above-mentioned relation; [A] only is the mole number of thionamic acid; But when using melamine, then provide another kind of explanation, [A] be employed melamine taken advantage of in any one mole amino part mole number (it is 3) that melamine contained.Composition hypochlorite source
Usually, can use any hypochlorite easily source in the methods of the invention.Preferred hypochlorite source is a chlorine, hypochlorous acid, and the alkaline metal hypochlorite, the alkaline-earth metal hypochlorite mixes the compound of hypochlorite-release and the product of alkaline solution, and their mixture.The compound that above-mentioned suitable hypochlorite discharges illustrates that with dichlorocyanuric acid and its sodium salt and hydrate their hydrolysis easily discharge hypochlorite.Compound and alkaline solution product of mixing that the present invention hypochlorite source very preferably is selected from the alkaline metal hypochlorite and above-mentioned hypochlorite is discharged.Amino functional group's compound
From thousands of available amino functionals group compound, the present invention selected limited be found to be exercisable several.In the method for the invention, suitable amino functional group compound is that those have the halogenated derivative of the N-of stablizing.Here term " has and stablizes the halogenated derivative of N-" and be defined as " can form the N-halo derivatives and it is stable " and must not be " having stable N-halo part when present method begins ".Satisfying suitable amino functional of the present invention group compound is to be selected from (ⅰ) primary amino functional group compound, and it is selected from thionamic acid, basic metal sulfamate, alkaline-earth metal sulfamate, thionamic acid tetraalkylammonium salt and its mixture; (ⅱ) secondary amino group functional group compound, it is selected from has formula RR ' NH or (R ")
2The secondary amine derivative of NH, R wherein, R ' and R " be organic moiety and wherein the carbon atom of this organic moiety be covalently bound with NH; (ⅲ) the sulphonamide amine is selected from sulphonamide, para toluene sulfonamide, imidodisulfuramide, benzsulfamide, alkyl sulfonamide and its mixture; (ⅳ) melamine, cyanamide; (ⅴ) its mixture.
Suitable secondary amino group functional group compound (ⅱ) comprises that those are not at (ⅰ), (ⅲ), special indicated compound (ⅳ) and (ⅴ), R wherein, R ' and R " be independently selected from the C1-C12 straight chain saturated with the saturated part of C3-C12 side chain; they can be alkyl, and aryl or heterocyclic radical are replaced by carboxylic acid or carboxylicesters arbitrarily; The example of latter's carboxylic acid-substituted derivative is the butyrine ester.Preferred secondary amino group functional group compound is known to sterilizing agent, and especially those have water miscible and to be those to the vibrations relative insensitivity have a halogenated derivative of N-.
In other words, the hydrolytic constant that has when amino functional group compound as giving a definition, that is, K is from about 10
-6To about 10
-9In the time of in the scope, method of the present invention is considered to applicable:
K=[HOCl][RNH
2]/[RNHCl]
Or K=[HOCl] [RR ' NH]/[RR ' NCl]
Or K=[HOCl] [(R ")
2NH]/[(R ")
2NCl]
Its condition is that tricarbimide or chlorating tricarbimide are not included in the basic amino functional group compound.
Be well known in the art and be conventional definition as above-mentioned hydrolytic constant.See, for example, " encyclopedia of chemical technology " of Kirk Othmer, the third edition, classification, article title " chloramines and bromo-amine " is especially seen 567 pages and Kirk Othmer " encyclopedia of chemical technology ", the third edition, volume 3 is especially seen the 940-941 page or leaf, and these articles are listed in this and comprise as a reference.
Retrained by the requirement of above-mentioned definition, preferred secondary amino group functional group compound can be selected from those and be defined in Kirk Othmer, " encyclopedia of chemical technology ", the 4th edition, 1993, in the 918-925 page or leaf and comprise and be defined in " organic chloramines and bromo-amine " under the title, " aliphatic compound ", " aromatic compound ", and the compound in " heterocyclic compound ".
Thionamic acid or thionamic acid sodium are the present invention's amino functional group compounds very preferably.Alkali
Suitable alkali is to be selected from basic metal in present method, the oxide compound of alkaline-earth metal and tetra-allkylammonium, oxyhydroxide, carbonate, supercarbonate, silicate, phosphoric acid salt, borate and its mixture.Bromine compounds
Bromine compounds suitable in present method is selected from, bromine, water miscible bromide salt, water miscible hypobromite, hypobromous acid and its mixture.The combination of all preferred composition
In the whole preferable methods of the present invention, described hypochlorite source is selected from the alkaline metal hypochlorite and the product of the aqueous solution of compound that hypochlorite is discharged and alkali; Described amino functional is rolled into a ball compound and is selected from thionamic acid, basic metal sulfamate, alkaline-earth metal sulfamate, thionamic acid tetraalkylammonium salt and their mixture; And described bromine compounds is to be selected from water miscible bromide salt.The present invention's method very preferably is that wherein above-mentioned hypochlorite source is a clorox, and it is that thionamic acid and above-mentioned bromine compounds are to be selected from Sodium Bromide that above-mentioned amino functional is rolled into a ball compound, the method for Potassium Bromide and their mixture.The composition or the impurity that need eliminating
Present method and products thereof has preferably limited some and has found that product stability and effectiveness are had dysgenic compound.Especially undesirable compound is that those can not form the amino functional group compound of stablizing the N-halo derivatives.Such compound comprises simple ammonium ion (NH
4 +) salt, as ammonium sulfate, urea; Amino acid such as aspartic acid and their mixture, wherein any one can, for example, produce the niff of undesirable chloramines.From start to finish and at least roll into a ball in the compound at basic amino functional in preferable methods of the present invention, do not comprise the composition of rolling into a ball impurity compound above about 1% the amino functional that has unstable N-halo derivatives.Term with practicality illustrates this requirement, and thionamic acid can be buied on each grade, and wherein some may comprise urea impurity.
The thionamic acid of finding the crystallization grade is preferred, and it at utmost reduces urea impurity.In other method embodiment, the present invention promptly, has got rid of insoluble material such as abrasive material with all being that water miscible initial substance carries out, and has therefore avoided any tendency that the surface catalysis SYNTHETIC OPTICAL WHITNER is decomposed.The acid or the alkali that are used for pH regulator
This alkali that can use any routine as pH regulator agent increase pH and this acid that can use any routine as pH regulator agent lower pH; Its condition always, such alkali or acid are not react with hypohalite.The alkali that is preferred for pH regulator comprises water miscible alkali such as sodium hydroxide, and potassium hydroxide or their mixture and preferred acid comprise common mineral acid such as sulfuric acid, and hypochlorous acid or nitric acid are though sulfuric acid is preferred in this group.Weak relatively in addition acid also can be used, and comprises acetic acid.
Acquainted operator will avoid the example of the alkali that uses in the method to comprise ammonia fully, because here chemical reaction can take place in it and other basal component, and purpose not to be pH change, but form, for example one type chloramines obtaining is not wished in formation when react with hypochlorite.
Usually, adding any simple mineral acid or alkali in the method can carry out in the mode that keeps this amino functional group compound chemistry integrity.For example, when using thionamic acid as amino functional group compound, the adding of mineral acid be under enough diluting, carry out to avoid the decomposition of thionamic acid.For example, known concentrated nitric acid is at HNO
3Concentration is 73% o'clock decomposition thionamic acid, especially when elevated temperature, has formed nitrous oxide, therefore should avoid so dense mineral acid and pyritous combination in the methods of the invention.Water
The water that is used to prepare liquid composition according to present method is the tap water that suits.Usually, can use firmly, soft, remollescent or deionized water.Distilled water or reverse osmosis treating water are ideal especially.When using the water of uncertain quality, for example from the iron-bearing water or the high manganese water of drilling well, with the method for conventional water treatment, for example oxidation, it is ideal that filtration and sedimentation reduce the dissolved metal content.Can use sequestrant or sequestering agent to come processing reaction water in addition.Monitoring or cycle detection are astute, and if desired, make in the water concentration of transition metal ion minimum with ordinary method, because transition metal ion is the well-known stability that can influence bleach product.The analytical procedure that is fit to is with atomic absorption spectrum or inductive couple plasma spectrum (ICP).PH measures
The present invention measures pH and adopts glass electrode or compound electrode such as Corning GeneralPurpose compound electrode Cat.No.476530 and the pH meter that can buy such as φ 40pH meter, and it can be buied by Beckman.PH trend
Downward pH trend (" trend " is arranged in present method, here being pH increases or reduces with respect to the linearity of time), pH trend is upwards arranged thereupon, as indicated in the method definition minimum value that pH is strong arranged, this is an ideal, and the characteristics of present method of also being known most at present really.In the back part of this method, as the uptrending of above-mentioned pointed pH, to measure by dpH/dt, it is in the scope of definition particularly, and is considered to interrelate with stable and product performance.The mensuration of bleach additive composition: available chlorine
" AvCl write a Chinese character in simplified form sometimes in the term " available chlorine " that the present invention uses
2", at " encyclopedia of chemical technology " of KirK Othmer, roll up and describe in 4, the four editions (1992) 274-275 pages or leaves (Wiley-Interscience publication).
The reaction that produces oxygenant from chlorine comprises following:
Any total concentration or amount based on the oxygenant of chlorine that provides expressed with the basis that equates usually, this just look like all oxygenants be chlorine.Therefore available chlorine is to need to produce the equivalent concentration of oxygenant or the chlorine of amount, for example according to above-mentioned reaction, and can be measured by ordinary method, for example the iodimetry,iodometry of reference in Kirk-Othmer (in the book that is drawn).
Available chlorine can be calculated by following relational expression:
Available chlorine (%)=70.9 * oxygenant mole number/(active Cl atom number/molecule) * 100
In the above-mentioned relation formula, term " active Cl atom " needs definition: because Cl
2Only accept two electronics, and HOCl and monochloramine, it has only " activity " Cl atom by this definition.
When the available chlorine of the product expection of measuring the inventive method, " mole number of oxygenant " in the above-mentioned relation formula replaced by " forming total mole number of the bleaching halogen that composition adds ".
Note also can being determined at " available chlorine " in the SYNTHETIC OPTICAL WHITNER that does not in fact form hypochlorite in the solution, as brominated SYNTHETIC OPTICAL WHITNER and other nonchlorine bleach agent.This is replaced by using the number of accepting electronics to remove with two the number of active chlorine atom in above-mentioned relation.Its also available iodimetric titration is measured.
Be also noted that available chlorine unit is the percentage ratio that relative unit is represented, rather than weight percent.From then on should find out significantly in the definition just generally speaking that the value that in fact might obtain surpassing 100% available chlorine compares Cl at chlorine bleach
2Under effectively many situations, above-mentioned phenomenon just can take place, because at Cl
2In only have a chlorine atom be the bleaching the chlorine atom; Yet, do not run into such concentration in the method.The amount of composition and ratio
Usually, concentration can be in very wide range in the amount of composition and the aqueous solution herein; But as in the definition of other place of this paper, the preferred value of one the best is arranged, and provides most economical concentration to use for example clorox of composition by their producer for ratio between special halogen, this commercial be attracting.Advantage
As propose, the present invention has significant advantage, for example improved bleaching is renderd a service." improved bleaching effectiveness " is meant, when with use other method, for example comprise and numerous pass through to add or the method for order by merging composition when making the same bleachability that composition provided and comparing, but can provide better bleachability to the bleaching soilng that steeps stain as tea with the composition that method of the present invention obtains.Importantly, when improving bleaching and rendeing a service, the prescription that is provided by present method stays a spot of remaining smell and than those SYNTHETIC OPTICAL WHITNER gentlenesses with other heterogeneity selection and/or addition sequence production on skin.In brief, all properties that is provided by present method and the combination of ideal cutaneous safety/aesthetic beauty are believed to be superior to the product that those are obtained by the method for any technical approval with recording out.Product performance
The product of present method is not limited to usually in form, though composition most preferably is to produce liquid aqueous solution or aqueous gel form.Another potential preferred product form of the present invention is " high water soluble solids enriched material or " high water soluble tablet " form.Such product form does not conform to abrasive material.Present method product be preferably transparent and as described at other place of this paper, pigmentable and perfuming.The processing of optional member
Present method and its product allow except minimum basically step (a), (b), also exist at least one step to add mixing step outside (c), wherein add a kind of composition, it is selected from tensio-active agent, buffer reagent, washing assistant, sequestrant, spices, tinting material, pigment, bleaching stibilizer, pigment, suds suppressor, anti-tarnishing agent and/or sanitas, soil-suspending agent, sterilant, alkali source, hydrotropic agent, oxidation inhibitor, clay soil removal/anti is deposition agent again, thickening material, solvent and their mixture.For other optional member, see U.S.3,583,922 or other reference of in background technology, quoting, recognize that this patent relates to the solids composition that is different from liquid composition of the present invention.Other details
Present method can add joins spices and tinting material, the most special known bleach stable tinting material such as various yellow; With the spices that lemon or pineapple flavor is provided.The spices that the present invention uses it is desirable to hydrophobic, and high relatively octanol/water partition ratio is arranged, and for example 6 or higher.With regard to present method condition, found that it is suitable (a) adding spices in the step afterwards in the stage (III).Be not limited to theory, it is believed that this is because when when the method later stage adds them, can reduce the gesture of inclining of the reaction of sulfamic acid derivatives and spices aldehyde.It is desirable to those that bleach stable thickening material such as those are mentioned and/or Laponite equally in background technology
, a kind of from the obtainable special clay of Laporte, and/or the fatty amine oxide compound, can be made up the product that has the broad range useful property to provide with present method.The detailed description of optional components
Now optional components is carried out introducing more in detail without limitation.These components comprise tensio-active agent, bleaching stibilizer, tinting material, whipping agent, suds suppressor, anti-tarnishing agent and/or sanitas, soil-suspending agent, sterilant, alkali source, hydrotropic agent, antioxidant, clay anti-tartar/anti redeposition agent, polymeric dispersant or the like, and composition thereof.
According to the composition of product, method herein can be used its tensio-active agent of measuring about 0.1-95% or its mixture, and it is selected from negatively charged ion, nonionic, both sexes and zwitterionic tensio-active agent.To liquid system, tensio-active agent preferably exists content from about 0.1-20%, though at for example viscous gel, in moisture lotion or the semisolid, higher concentration 30% is possible for example.
Anion surfactant can comprise the water-soluble salt of following substances, particularly an alkali metal salt, and these materials are C
8-C
22Organosulfur acidification reaction product and be selected from sulfonic acid and the group of sulfate group.Sodium alkyl sulfate or sylvite are particularly through sulfation C
8-C
18Those materials of alcohol gained, straight or branched alkylbenzene sulfonate, especially C
9-C
15Sodium salt or potassium salt form that alkyl replaces are useful.Equally also usefulness is alkyl glycerol base ether sulfonic acid sodium, and especially those are from those ethers of tallow and Oleum Cocois deutero-higher alcohols.Coco-nut oil fatty acid direactive glyceride sulfuric acid and sodium sulfonate, the sodium or the sylvite of the sulfuric ester of the product of 1 mole high fatty alcohol (for example tallow or coconut oleyl alcohol) and the reaction of about 1～10 moles of ethylene oxide, with the alkylphenol oxyethane ether sodium sulfate or the sylvite of the oxyethane of about 1～10 unit of per molecule, wherein alkyl contains 8～twelve carbon atom.From the sodium of the Oleum Cocois of methylamino esilate (lipid acid wherein for example is from the Oleum Cocois deutero-) fatty acid amide or sylvite and the derived fatty acid reaction product; And β-acetoxyl group or β-acetamido alkyl sodium sulfonate or potassium, wherein alkyl contains 8 to 22 carbon atoms.
In addition, conventional primary alkyl sulphates for example has general formula R OSO
3 -M
+(wherein R is typical straight chain C
8～C
22Alkyl and M are water-soluble cationics) be useful in the present invention, and contain the secondary alkyl sulfate of 8-20 carbon atom and/or the chain primary alkyl sulphates tensio-active agent (being side chain " PAS ") that props up, see EP 439,316 A Smith etc.Secondary alkyl sulfate surfactant comprises these materials, and the sulphate moiety of their institute's tools is along alkyl " skeleton " stochastic distribution of molecule.These materials can be represented with the following formula structure
CH
3(CH
2)
n(CHOSO
3 -M
+) (CH
2)
mCH
3Wherein m and n are 2 or bigger integer, and the m+n sum generally be about 9 to 17 and M be water-soluble cationic.
In addition, (2, the 3) alkyl sulfate surfactant second month in a season of the selection of the present invention's use can comprise corresponding to the formula I of 2-vitriol and 3-vitriol and the structure of formula II:
CH
3(CH
2)
x(CHOSO
3 -M
+)CH
3 Ⅰ
CH
3(CH
2)
y(CHOSO
3 -M
+) CH
2CH
3II the present invention also can use the mixture of 2-and 3-vitriol.In formula I and II, x and (y+1) each correspondingly is at least about 6 integer, and can be from being about 7～20, preferred about 10～16.M is a positively charged ion, basic metal for example, and ammonium, alkanol ammonium, three ethanol-ammonium, potassium, ammonium etc. also can use.
The secondary alkyl sulfate that preamble is mentioned makes by sulfuric acid is added to alkene.Use alhpa olefin and vitriolic typical case synthesis method to be disclosed in USP 3,234,258 (Morris was issued on February 8th, 1996) or USP 5,075,041 are in (Lutz was issued on December 24th, 1991).Should synthetic carry out in solvent, it obtains (2,3) the alkyl-sulphate second month in a season when cooling, and the product that it generates is worked as pure system to remove unreacted raw material, Sulfated material at random, the by product such as the C of non-sulfuric acidization
10Behind the alcohol of longer key, the secondary alkene sulfonate etc., be the mixture (some sodium sulfate may exist) of the 2-of typical 90+% purity and 3-sulfation material and be white, inviscid, obviously be the crystalline solid.Some 2, the 3-dithionate also may exist, but its content generally comprises 5% of the mixture that is not higher than (2,3) alkyl list-vitriol second month in a season.Such material can be from the Shell Oil Co. by trade(brand)name " DAN ", and for example " DAN 200 " are buied.
The particularly preferred tensio-active agent that is used for present method is those materials with best bleach stability, comprises C
8～C
22Fatty amine oxide such as hexadecyldimethyl benzyl ammonium amine n-oxide or saturated fatty alkyl alkoxy thing.Particularly preferred tensio-active agent has high degree of unsaturation for those and contains any tensio-active agent of hypohalite-active nitrogen part.The less problem that causes, but still be the potential challenges root be to use any alcohols.Therefore, when using alkyl ethoxy thing etc., so-called " end-blocking " form, i.e. end group-OH quilt-OCH wherein
3Or the similar form that nonactive reactive group replaced is particularly preferred.
Bleaching-stable and hydrolysis-stabilized surfactant can add in the various stages of present method, but, generally be in the time causing minimum foam, just to add them, because of the washing process that can slow down that bubbles for convenient meter.It is ideal that silicone defoamer bubbles to restriction; This defoamer can be buied from Dow Corning company.
When the tensio-active agent that uses the acidic hydrolysis sensitivity, during for example a kind of alkyl-sulphate, then be with its any stage in the method, promptly when this moment constituents mixt pH surpass approximately 7 the time, preferably, this pH surpasses at about 8 o'clock, just joins in the product.
Though preferable methods and composition do not have water-insoluble substance and abrasive material here, but the product of present method can be mixed with solid or thickness half-solid form and further comprise a kind of and tensio-active agent bonded abrasive material, such as expansible perlite abrasive material, filler, or it is combined to list in other optional scouring material compositions of this paper.When needs, abrasive material can be USP 4,051,056, included those in (Hartman, on September 27th, 1977 promulgation).
Other optional components used herein comprise damping fluid, and its purpose is to regulate is washed clean surface p H value, with the effect of largest optimization hard surface cleaner composition with respect to the dirt or the stain of special type.Can comprise that also buffer reagent is to keep mutual consistence between various aesthstic compositions with the stable auxilliary component that adds to prolong storage period or purpose.The optional buffer reagent that contains of hard surface cleaner of the present invention is to help regulating and keep pH about 13 or above in about 13 scopes.The non-limitative example of this suitable reducing is a salt of wormwood, yellow soda ash, and tertiary sodium phosphate.Certainly, the preparation teacher is not limited to these examples or its composition.
Also can be by the obtainable cleaning compositions of the inventive method: promptly add the heavy metal ion hierarchy of control by being prepared as follows, particularly a kind ofly comprise that one or more reagent are used to control because water-soluble, the bleaching instability that water-insoluble or CI and/or magnesium and/or copper cause.One simple but effective agents is a tripoly phosphate sodium STPP, its optional being carried on the partially polymerized at least hydrated sodium silicate.Example other chelatings or the heavy metal control agent is phytinic acid and ethyl-1-hydroxyl-1, and 1-di 2 ethylhexyl phosphonic acid (EH-HDP) is though also can use other material, some commodity phosphonates for example.Here preferred sequestrant is the position with alcohol, the nitrogen donor position of halogen-reactive behavior and hydrolysis sensitive part.With regard to method, the preferred time that adds at least some sequestrants or weight-metal ion control agent be or when beginning near process, for example be before step I (a) beginning immediately, or add simultaneously.Yet if its purpose to small part is when adding silicate in order to help to control heavy metal ion, it is to add on the position of and the peaked process steps of pH minimum away from the pH in the method.
General its concentration is from 0-5% when using spices.See USP 4,246,129 (Kacher, promulgations on January 20th, 1981).
Usually has yellow by the available composition of the inventive method.Yet, also can provide some other color to preferred solution, for example, by adding a kind of bleaching-stable dyestuff, more sometimes, preferred solution can be diluted at once, and it is difficult will detecting yellow in this case.During operation, preferably dyestuff is just added when operating process finishes, can monitor more easily in this case on the product of unassured toner and carry out " manufacturing of product ".
Can be mixed with various viscosity by the available liquid composition of the inventive method.The composition that obtains with this paper method in one embodiment of the invention has from the viscosity of about 1 to 150 cps.Said composition conveniently is used for spray bottle and uses.Similarly, this liquid composition that obtains by the present invention can be by further multiviscosisty, for example, and by adding the thickening material of additional bleach stable, as the DOWFAX that can buy from market.Suitable gel formula has the viscosity of about 2000cps extremely from about 100cps, is preferably from 300cps～1000cps, and with for example at " physico-chemical process " (Reilly, J and Rae, W.N; Vol1 (5th ed), 667-692 page or leaf, D.Van Nostran press) in method and the technology described measure.When inventive method adds thickening material, preferably when end of processing, just use, for example, after the stage (III), immediately, or add them simultaneously.
Embodiment I (I) is preceding-the bromine I stage
All operations are carried out at room temperature about 20 ℃.30g distilled water is presented to a kind of unreactiveness, in the plastic-lined reaction vessel.This container is used for atmospheric operation, simultaneously for careful, connect a scrubbing bottle to remove issuable small amounts of chlorine steam, device has the paddle agitator that an inert plastic applies on this container, when being stirred to 300rpm, add javelwater's liquid of 13.05g, contain 10.73% available chlorine after measured.After this add thionamic acid (2.2g, Aldrich, 99.3%, crystal) immediately and continue to stir and dissolve until added solid.At this moment, the pH value of stage (I) mixture is approximately 1.0.(II) bromine compounds adds the stage
In stage (I) mixture that stirs, add Sodium Bromide (0.5g, EM Science).Stir mixture until adding solid dissolving (about 5 minutes) and present yellow.The reaction mixture of this moment is called stage (II) mixture.(III) product stabilization stage
Add the pH value about 13.2 of sodium hydroxide (about 3.0g is in 50% water) to stage (II) mixture that stirs to mixture.
Add entry and be about 100g until the gross weight of stage (III) mixture.
The embodiment II
Repeat the method for embodiment I under following difference: working scale increases by 1000 times, at pretreatment stage, chlorine passes through sodium hydroxide solution, form the chlorine bleach liquor, the chlorine bleach liquor is passed through above-mentioned reactor in batches, handle with thionamic acid therein, formation stage (I) mixture carries out in step after the stage (I) such as the embodiment I.
The embodiment III
Repeat the method for embodiment II but following difference is arranged: replace thionamic acid with thionamic acid sodium.
In the following embodiments, thick line shows the stage (I) of division methods, the boundary of (II) and (III).
The embodiment IV
Repeat the method for embodiment III, following difference is arranged: finish the stage (I) and add hypochloric acid water solution before so that pH is reduced to about 7.0.
(7) 7.60 second parts of NaOH of embodiment V composition interpolation order (weight percent amount %) hydrated sodium silicate (2) 0.20 (Britesil H2O, PQ Corp) sodium phosphate trimer (3) 0.20 first parts of clorox (4) 0.90 sulfamic acid (5) 1.30 KBrs (6) 1.10 sodium phosphate trimers (8) 0.80 cocounut oil alkyl-dimethyl amine n-oxides (9) 0.25 dyestuff (10) 0.15 spices (11) 0.60 water (1) and (12) aequums (" aequum " refers to " balance to 100% ")
Embodiment VI composition addition sequence (weight percent amount %) clorox (2) 1.4 thionamic acids (3) 1.9 water glass (4) 0.04 Sodium Bromides (5) 1.8 sodium hydroxide (6) 1.6 tensio-active agents (7) 3.5 dyestuffs/spices (8) 0.28 water (1) and (9) equal amount are annotated: " tensio-active agent " refers to C
8Alkyl-sulphate, C
12～C
14Diformazan amine n-oxide or its mixture.
Embodiment VII composition addition sequence (weight percent amount %) clorox (1) 1.4 thionamic acid sodium/sulfuric acid (2) 2.2
*Sodium Bromide (3) 1.5 Potassium Bromides (4) 1.1 water glass (5) 0.05 spices (6) 0.1 sodium hydroxide (7) 1.8 sodium octyl sulfates (8) 5.5 yellow dyess (9) 0.28 water (10) equal amounts (" equal amount " refers to " balance to 100% ")
*Weight is equivalent to thionamic acid content, butt
Embodiment VIII composition addition sequence (weight percent amount %) cocounut oil alkyl-dimethyl amine n-oxide (1) 3.0 thionamic acid sodium/sulfuric acid (2) 0.5
*Calcium hypochlorite (3) 0.5 dichlorocyanuric acid sodium (4) 0.50 KBrs (5) 1.5 NaOH (6) 0.8 sodium phosphate trimers (7) 1.6 sodium acetates (8) 0.3 potassium hydroxide (9) 0.85 sodium octyl sulfates (10) 3.00 dyestuffs/spices (11) 0.28 water (12) aequums*Weight is equivalent to dry thionamic acid content, butt
Embodiment IX composition addition sequence, (weight percent amount %) surfactant, (2) 6.1 dichlorocyanuric acid sodium, (3) 1.2 melamines, (4) 0.23 KBrs, (5) 1.0 tetrapotassium pyrophosphates, (6) 13.0 tripotassium phosphates, (7) 12.0 sodium metasilicate, (8) 0.5 calcium carbonate, (9) 39.0 calcium oxide, (10) 2.8 pearl abrasive materials, (11) 22.5 NaOH, (12) 1.1 water, (1) and, (13); Separate equal amount
Weight ratio annotated 1 in 1: 1: " tensio-active agent " refers to C
8Alkylsulfonate, C
12～C
14Diformazan amine n-oxide or their mixture.
Claims (21)
1. method that is used to produce alkaline bleaching composition, this method comprised at least three stages, comprises in order,
(I) preceding-the bromine stage,
(II) bromine compounds add the stage and
In (III) product stabilization stage, there is at least one step mixing step in each above-mentioned stage; Wherein in this method, before above-mentioned-the bromine stage (I) comprises step (a), mix each composition with any order, this composition comprises hypochlorite source and the amino functional group compound of stablizing the N-halo derivatives is arranged, thereby formation stage (I) mixture, its condition is, before above-mentioned-and the bromine stage, the pH that this stage (I) mixture has was no more than about 11 when finishing; It is to begin under this pH that above-mentioned bromine compounds adds the stage (II), and comprises step (b), should mix mutually with bromine compounds by stage (I) mixture with any order, thus formation stage (II) mixture; With the said products stabilization stage (III), comprise at least one step (c), mix a kind of alkali of (III) mixture of above-mentioned stage and sufficient quantity with any order, so that reaching final pH, the product of present method is at least about 13.
According to the process of claim 1 wherein have only the stage (II) and only in steps (b) comprise the adding of bromine compounds.
3. according to the method for claim 2, each this step (b) and (c) be to about 80 ℃ temperature range, to carry out wherein from about 5 ℃.
4. according to the method for claim 3, wherein when the stage (I) finishes and the said pH when the stage (II) begins be from about 1 to about 6.9 scope.
5. according to the method for claim 3, wherein when the stage I finished, entire method was to carry out under the pH that raises gradually.
6. according to the method for claim 5, wherein the value with the said corresponding dpH/dt of pH that raises gradually is at least about+the single bit per minute of 0.1 pH.
7. according to the method for claim 6, it is characterized in that the dilution factor of the stage summation of stage (I) back is no more than about two times.
8. according to the method for claim 7, wherein said hypochlorite source is to be selected from chlorine, hypochlorous acid, alkaline metal hypochlorite, alkaline-earth metal hypochlorite and hypochlorite is discharged the product of aqueous mixture of compound and alkali and their mixture.
9. method according to Claim 8, wherein said amino functional group compound is selected from (ⅰ) primary amino functional group compound, and it is selected from thionamic acid, the basic metal sulfamate, the alkaline-earth metal sulfamate, thionamic acid tetraalkylammonium salt and their mixture; (ⅱ) secondary amino group functional group compound, it is selected from has formula RR ' NH or (R ")
2The secondary amine derivative of NH, R wherein, R ' and R " be organically part and wherein carbon atom and the NH of this organic moiety with covalent bonds; (ⅲ) sulfonamides is selected from sulphonamide, para toluene sulfonamide, imidodisulfuramide, benzsulfamide, alkyl sulfonamide and their mixture; (ⅳ) melamine, cyanamide; (ⅴ) their mixture.
10. according to the method for claim 9, wherein said bromine compounds is selected from: bromine, water-soluble bromide salt, water-soluble hypobromite, hypobromous acid and their mixture.
11. method according to claim 10, wherein said hypochlorous acid source is to be selected from the alkaline metal hypochlorite and hypochlorous acid is discharged compound and alkali aqueous solution product of mixing, said amino functional is rolled into a ball compound and is selected from thionamic acid, the basic metal sulfamate, the alkaline-earth metal sulfamate, thionamic acid tetraalkylammonium salt and their mixture; Said bromine compounds is selected from water-soluble bromide salt.
12. according to the method for claim 11, wherein said hypochlorite source is a clorox, it is thionamic acid that said amino functional is rolled into a ball compound; With said bromine compounds is to be selected from Sodium Bromide, Potassium Bromide and their mixture.
13. according to the method for claim 12, wherein any said amino functional group compound comprises and is no more than about 1% the amino functional group impurity compound that unstable N-halo derivatives is arranged.
14. according to the method for claim 13, wherein said alkali is selected from basic metal, the oxide compound of alkaline-earth metal and tetra-allkylammonium, oxyhydroxide, carbonate, supercarbonate, silicate, phosphoric acid salt, borate and their mixture.
15. according to the method for claim 14, it comprises at least one additional mixing step in addition, wherein adds a kind of component, it is selected from tensio-active agent, buffer reagent, washing assistant, sequestrant, abrasive material, spices, tinting material, pigment, bleaching stibilizer, pigment, the color spot agent, suds suppressor, anti-tarnishing agent and/or sanitas, soil-suspending agent, sterilant, alkali source, hydrotropic agent, oxidation inhibitor, clay soil removal/anti is deposition agent again, thickening material, solvent and their mixture.
16. the alkaline bleaching composition that obtains according to the method for claim 1.
17., include from about 0.01% to about 10% available chlorine according to the alkaline bleaching composition of claim 16.
18. according to the alkaline bleaching composition of claim 17, the ratio between halogen [Br] wherein: [OCl
-] be from about 10: 1 to about 1: 10, its Shen [Br] representative is added to Br total mole number and [OCl present method from said bromine compounds
-] representative is added to the total mole number of the hypochlorite present method from said hypochlorite source.
19. alkaline bleaching composition according to claim 18, amino-halogen ratio [A] wherein: [X] is from about 10: 1 to 1: 10, wherein [A] representative is used to form total mole number of the amino part of this amino functional group compound of said composition, wherein [X] represents the total mole number of the bleaching halogen that exists in this composition, records with available chlorine.
20. according to the alkaline bleaching composition of claim 19, wherein said amino-halogen ratio is from about 1.0: 1.0 to about 1.5: 1.0.
21., do not carry out in the presence of the water-insoluble solid matter having according to the method for claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96180375 CN1224457A (en) | 1996-05-15 | 1996-05-15 | Process for mfg. bleaching compositions comprising chlorine and bromine sources and product thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96180375 CN1224457A (en) | 1996-05-15 | 1996-05-15 | Process for mfg. bleaching compositions comprising chlorine and bromine sources and product thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1224457A true CN1224457A (en) | 1999-07-28 |
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ID=5127839
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115624033A (en) * | 2022-11-07 | 2023-01-20 | 传化集团有限公司日用品分公司 | Stable high-available-chlorine-content disinfection gel and preparation method thereof |
-
1996
- 1996-05-15 CN CN 96180375 patent/CN1224457A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115624033A (en) * | 2022-11-07 | 2023-01-20 | 传化集团有限公司日用品分公司 | Stable high-available-chlorine-content disinfection gel and preparation method thereof |
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