CN1078997A - The structured liquids that contains amido and imido peroxyacids - Google Patents

Abstract

The invention discloses a kind of aqueous cleaning composition, comprising a kind of water solubility less than 1 * 10 ^-4The amido of M or imino-organic peroxide acid, a kind of body structure surface active agent and a kind of keeping in storage period make the pH pH regulator system of 0.5pH unit at least that raises after pH is 3.5-8.5, dilute with water.

Description

The structured liquids that contains amido and imido peroxyacids

The present invention relates to a kind of detergent composition, it is a kind of structured liquids that comprises amido and imido peroxyacids SYNTHETIC OPTICAL WHITNER.

Organic peroxide acid can form steady suspension in liquid, aqueous, this has been well-known.

Relevant report the earliest is No. 3996152, United States Patent (USP) people such as () Edwards, it disclose a kind of by as the suspension of the diperoxy acid that the non-starch thickener of Carbopol 904 under low pH condition and so on forms in water medium.Suitable actives matter is that two nonane diacids, two of crossing are crossed brassylic acid, two and crossed sebacic acid and two and cross m-phthalic acid.United States Patent (USP) 4017412(Bradley) reported similar system, except using the starch base thickening material.From the research of a patent in back, people have known the following fact: the thickener types of mentioning in the former patent has formed the gel matrix, and it demonstrates the storage unstable under comparatively high temps.When high density, they can cause the too high and uncontrollable difficulty of viscosity.

United States Patent (USP) No. 4642198 (people such as Humphreys) has been described a series of plans and has been suspended in the insoluble organic peroxide acid of water in the moisture low pH liquid.This patent disclosure the tensio-active agent of using as suspension agent for the peroxy acid particle, the use of anionic and non-ionic tensio-active agent.Preferred oxygen species 1, the 12-diperoxy dodecanedioic acid (DPDA) crossed.

EP176124(de Jong) discloses a kind of pourable whitener composition that in aqeous suspension, contains peroxycarboxylic acid, wherein contained 0.5-15% alkyl benzene sulphonate (ABS) and a small amount of vitriol.

Above-mentioned patent has all been emphasized in order to improve physical stability, must make the suspension of liquid bleach or thickening chemical composition reach optimum.Yet, do not have one piece of a kind of system that allows stand-by composition in a large amount of washings, to use of above-mentioned patent suggestion as effective heavy duty liquid washing agent.

The possible way that addresses this problem is recently people such as United States Patent (USP) 4992194(Liberati) in disclosed.Wherein reported at the insoluble organic peroxide acid of water of N-O-phthalic amido peroxide caproic acid of industrial being referred to as " PAP " and so on, can be suspended in a kind of tensio-active agent, as long as also have a kind of pH regulator transition system and a kind of deflocculate polymkeric substance.Polyol and borate combine and are used to pH regulator transition system.The deflocculate polymkeric substance is hydrophilic and the monomeric multipolymer of hydrophobic.Although people's such as Liberti system has been represented an important step that reaches directed a kind of commercial acceptable heavy duty detergent for washing clothes of making by filling a prescription fully, still stay sizable room for development.

The present invention seeks provides a kind of water base heavy duty liquid laundry detergent compositions of making by prescription fully, and it contains and can be the viscosity that the user accepts and the stable suspersion peroxygen bleach of bleach clean-up performance.

Have been found that some amido or imido peroxyacids can successfully suspend, promptly they do not decompose in the aqueous surfactant structured liquids or without being separated in the time bar that desire is used.These peroxy acids be with have specific water-soluble be feature.

Therefore, the invention provides a kind of cleaning composition, comprise

What ⅰ) be used to bleach is water-soluble less than 1 * 10 ^-4M, a kind of amido or the imino-organic peroxide acid that exist with significant quantity;

ⅱ) a kind of tensio-active agent that exists with significant quantity of this peroxy acid that is used to suspend; With

ⅲ) a kind of being used for kept the pH regulator system that with significant quantity exist of pH between 3.5-8.5 at lay up period, and this system can make pH improve 0.5pH unit at least with the washing water dilution.

It is believed that this pH regulator system works in peroxy acid stable.

This amido or imino-organic peroxide acid preferably have less than 5 * 10 ^-5M's is water-soluble.

Composition of the present invention particularly can be done to use as heavy duty detergent for washing clothes liquid.

That peroxy acid of the present invention preferably is selected from is single-or the amido or the imino-acid of two-percarboxylic acids.The general formula of list-percarboxylic acids is:

Wherein:

R is selected from 1-16 carbon alkyl, 1-16 carbocyclic ring alkyl and 6-12 carbon aryl;

R ¹Be selected from hydrogen, 1-16 carbon alkyl, 1-16 carbocyclic ring alkyl and 6-12 carbon aryl;

R ²Be selected from hydrogen, 1-16 carbon alkyl, 1-16 carbocyclic ring alkyl and 6-12 carbon aryl and work as R ³Can form the carbonyl of ring when being arylidene with R;

R ³Be selected from 1-16 carbon alkylidene group, 5-12 carbocyclic ring alkylidene group and 6-12 carbon arylidene;

N and m are that summation is 1 integer; And

M is selected from hydrogen, basic metal, alkaline-earth metal, ammonium and alkanol ammonium cation and group.

Two percarboxylic acids of the present invention can be following general formulas

Wherein:

R ⁴Be selected from the combination of 1-12 carbon alkylidene group, 5-12 carbocyclic ring alkylidene group, 6-12 carbon arylidene and these groups;

R ⁵Be selected from H, 1-16 carbon alkyl, 6-12 carbon aryl and energy and R ³Form the carbonyl of ring together;

R ⁶Be selected from H, 1-16 carbon alkyl, 6-12 carbon aryl and and R ³Can form group of 3-12 isocyclic together;

R ³Be selected from 1-12 carbon alkylidene group, 5-12 ring alkylidene group and 6-12 carbon arylidene;

N ' and n " integer of respectively doing for oneself, selection mode be make the two add up to 1;

M ' and m " integer of respectively doing for oneself, selection mode be make the two add up to 1;

M is selected from H, basic metal, alkaline-earth metal, ammonium and alkanol ammonium cation and group.

Particularly preferred material is:

N, N '-two (4-crosses carboxylbenzoyl)-1,4-butanediamine;

N, N '-two (4-crosses carboxylbenzoyl)-1,2-phenylenediamine;

N, N '-succinyl-two (4-crosses carboxyl) aniline;

4-crosses carboxylbenzoyl aniline;

N, the amino peroxybenzoic acid of N-phthalyl-4-;

N, N '-two (4-crosses carboxylbenzoyl) ethylene diamine;

N, N '-two (4-crosses carboxyl aniline) terephthalate;

N, N, N ', N '-1,2,4,5-tetracarboxylic benzoyl-two (the amino carboxyl caproic acid of crossing of 6-);

N, N '-two (4-crosses carboxylbenzoyl) piperazine;

N, N '-two (4-crosses carboxylbenzoyl)-1,4-diamines-hexanaphthene;

N, N '-two (crossing the carboxyl adipyl) phenylenediamine; With

N, N '-two (crossing the carboxyl adipyl) ethylene diamine;

N, N '-terephthaloyl-two (the amino carboxyl caproic acid of crossing of 6-).

Particularly preferably be N, N '-terephthaloyl-two (the amino carboxyl caproic acid of crossing of 6-).

Also another material that can use in composition of the present invention is single nonyl acid amides of peroxide hexanodioic acid, and its preparation is existing the description in United States Patent (USP) 4686063.

The scope of amido of the present invention and imido peroxyacids is about 40% for about 0.1%-, the about 10%(weight of preferably about 1%-).

Another component of the present invention is a kind of tensio-active agent.This surfactant can be to be made by natural, and as soap, or a kind of synthetic, it is selected from anionic, non-ionic, amphoteric, zwitterionic, cationic promoting agent or its mixture.Many suitable promoting agents can derive from commodity, and fully describe in the literature, as at " tensio-active agent and washing composition " by Schwartz, Perry and Berch work, in I and the II volume.

The total content scope of surfactant can be up to 70% of composition weight, and preferred about 1% to about 50%, more preferably 4-45%.

The synthetic anion surfactant normally contains the organic sulfate of about 8-22 carbon alkyl or the water-soluble alkali metal salts of sulfonate, and term " alkyl " comprises the moieties of more senior aryl.

The example of suitable synthetic anionic detergent compound is sodium alkyl sulfate and alkylsurfuric acid ammonium, particularly those that are obtained by more senior (8-18 carbon) pure sulfation of for example producing from butter or Oleum Cocois; Alkyl (9-20 carbon) benzene sulfonic acid sodium salt and ammonium, particularly linear secondary alkyl (10-15 carbon) benzene sulfonic acid sodium salt; Alkyl glycerol base ether sodium sulfate, the particularly ether of those synthols of producing by butter or Oleum Cocois that go out than the ether of higher alcohols with from oil production; Coco-nut oil fatty acid direactive glyceride sodium sulfate and sodium sulfonate; The sodium salt of the sulfuric ester of more senior (9-18 carbon) Fatty Alcohol(C12-C14 and C12-C18) and the reaction product of ammonium salt and alkylene oxide are particularly with the reaction product of oxyethane; The reaction product of lipid acid is as with different thionic acid esterification and with the reaction product of the lipid acid of sodium hydroxide neutral coconut fatty acid and so on; The sodium salt of the fatty acid amide of N-methyltaurine or ammonium salt; The alkyl monosulfonate, as produce by the reaction of alpha-olefin (8-20 carbon) and sodium sulfite those and by paraffinic hydrocarbon and SO ₂And Cl ₂Those that reaction produces and a kind of free sulfonic salt that produces with a kind of basic hydrolysis then; 7-12 carbon dialkyl sulfosuccinate succsinic acid and ammonium; And alkenyl sulphonate, this term is used for expressing by alkene, and the alhpa olefin of 10-20 carbon particularly is with SO ₃Reaction, neutralization and the material that obtains of this reaction product of hydrolysis then.The preferred anionic surfactants detergent compound is a 11-15 carbon sodium alkyl benzene sulfonate; 16-18 carbon alkyl sodium sulfonate and 16-18 carbon sodium alkylether sulphate.

The example of the suitable non-ionic surfactant compound that also can be preferably uses with anionic surfactant compound, particularly comprise alkylene oxide, especially oxyethane, reaction product with 6-22 carbon alkylphenol, generally be 2-25EO, promptly contain 2-25 ethylene oxide unit in each molecule; The condensation product of aliphatics 8-18 carbon uncle or the second month in a season, linearity or branch's alcohols and oxyethane is generally 20-30EO, and propylene oxide and the reaction product of ethylene diamine and the condensation product of oxyethane.Other so-called ionic surfactant pack is drawn together ester, long chain tertiary amine oxide compound, long chain tertiary phosphine oxide and the dialkyl sulphoxide of alkyl polyglucoside, lipid acid and glucoside.

Both sexes or zwitterionics compound also can be used for composition of the present invention, but do not need owing to their high relatively costs.If you are using, in normally used synthetic anionic and tween based composition and use thereof in packaging, only account on a small quantity.

Detergent composition of the present invention also contains a kind of washing assistant usually.Builder material can be selected from 1) calcium (multivalence) sequestrant material, 2) sedimentable matter, 3) calcium ion-exchanged material and 4) their mixture.

The example of calcium ion-exchanged auxiliary agent comprises various types of water-insoluble crystallization shapes or amorphous aluminosilicate, its mesolite is the most representative, is also referred to as zeolite P as zeolite A, zeolite B(), zeolite C, X zeolite, zeolite Y and the zeolite P described in EP-A-0384070.

Specifically, composition of the present invention can contain any organic or inorganic washing assistant, as sodium salt, Trisodium Citrate, carboxymethyl malonate, carboxy methoxy-succinic acid salt, Tartaric acid salt, list and two succinate, oxygen base disuccinate, crystallization shape or the amorphous aluminosilicate and their mixture of tripoly phosphate sodium STPP or potassium, trisodium phosphate or potassium, sodium orthophosphate or potassium, yellow soda ash, nitrilotriacetic acid(NTA).

Homopolymerization of many carboxyls and multipolymer also can be used as washing assistant, and make pulverized structure agent or processing aid.Particularly preferably be polyacrylic acid (can buy the commodity that trade mark is called Acrysol) and vinylformic acid-maleic acid (can buy the commodity of trade mark Sokalan by name) and their an alkali metal salt or other metallic salt from BASF Corroration from Rohm and Haas company.

The amount of these washing assistants is for example 1-80%, preferred 3-30%(weight).

When using in washing water, the scope of the initial amount of peroxy acid is to make every liter washing water produce the about 250ppm active oxygen of about 0.05-, preferably about 1-50ppm active oxygen everywhere.The amount of the tensio-active agent that should exist in the washing water is every liter of about 0.05-3.0 gram, preferred every liter of 0.15-2.4 gram.Washing assistant is if exist, and the scope of its amount is about 0.1-3.0 grams per liter.

As everyone knows, the organic peroxide acid SYNTHETIC OPTICAL WHITNER is at low pH(3-6) following stabilizer pole, and at weak base pH(7-9) extremely effective as SYNTHETIC OPTICAL WHITNER in the solution.In order to keep the stability of peracid in storing, in order to reach required pH, use a pH transition system, between 3 and 8.5, and become weakly alkaline (pH7-9) when making after this in washing water tool bleaching and washing functions with the pH that keeps product.Epochmaking is to obtain pH transition at least 0.5 unit, preferred 1.0 units, preferably about 1.5 units.A kind of pH transition system is borax 10H ₂The O/ polyvalent alcohol.Borate ion and some are suitable-1, and 2-polyvalent alcohol title complex can cause the pH reduction when concentrated.After the dilution, this title complex disassociation disengages free borate its pH is raise.Show that pure have this examples of polyhydric alcohols of mechanism that cooperates with borate comprises pyrocatechol, melampyrum, fructose, sorbyl alcohol and quite where.From considering that economically sorbyl alcohol is a preferred polyhydric alcohols.In order to reach the required pH that is lower than 7 enriched material, the ratio of polyvalent alcohol and borax is greater than normally needing in about 1: 1.Therefore, the ratio of preferred polyhydric alcohols and borax should make and reach 1: 1 to about 10: 1 everywhere, and general range is 1: 10 to 10: 1.Boronic acid containing radical compound such as boric acid, boron oxide, the borax that contains ortho-boric acid sodium or sodium pyroborate also can be used as suitable borate component.

Preferred pH transition system is to about 40%(weight with about 1) the amount existence.

A kind of useful selective use component is a kind of deflocculate polymkeric substance in composition of the present invention.Hydrophilic and the monomeric multipolymer of hydrophobic is commonly used to form deflocculation agent.The acquisition methods of suitable polymers is, with maleic anhydride, acrylic or methacrylic acid or other hydrophilic monomer, as vinyl sulfonic acid ester or styrene sulfonate etc. with the hydrophobic group functionalization similar monomer carry out copolymerization.These comprise the ethers of acid amides, ester class, Fatty Alcohol(C12-C14 and C12-C18) or fatty alcohol ethoxylate.Remove fatty pure and mild ethoxylation beyond the region of objective existence, other hydrophobic group also can use as thiazolinyl or alkaryl.Primary is stratiform drop and the interactional hydrophobic group of hydrophilic radical that the acceptable oxidative stability of multipolymer tool and this multipolymer have this structured liquids, in case the flocculation of these drops, thereby can prevent physical instability and product separation.In practice, vinylformic acid and lauryl methacrylate(LMA) (molecular weight 3800) are effective when being found in content for 0.5-1.5%.These materials are people such as United States Patent (USP) 4992194(Liberati) in described fully, be hereby incorporated by reference.

Except that the component of having stated, detergent composition of the present invention can comprise those materials of usual amounts in the cleaning composition as conventional additives.The example of these additives comprises suds booster, as alkanolamide, the single ethanol amide that makes from palm kernel fatty acid and coconut fatty acid particularly, suds suppressor, as alkyl-sulphate and siloxanes, anti-redeposition agent, alkyl cellulose ether as Xylo-Mucine and alkyl or replacement, other stablizer, as ethylene diaminetetraacetic acid, fabric softener, inorganic salt such as sodium sulfate, with the white dyes, flavouring agent, the enzyme that exist with minute quantity usually, as proteolytic enzyme, cellulase, lipase and amylase, sterilant and tinting material.

Composition of the present invention can be used for cleaning multiple base-material, comprises the surface, particularly cleaning fabric.

Following limiting examples will more prove absolutely embodiment of the present invention.All umbers, percentage ratio and ratio in specification sheets and the claim all represent with weight, except as otherwise noted.

Example 1

Terephthalic acid monomethyl one potassium

At room temperature will be dissolved in 87.5% KOH(143g of 870ml methyl alcohol, 2.24mol) in 45 minutes, add the terephthalic acid dimethyl ester be dissolved in 2420ml toluene (434g, 2.24mol) in.Reaction mixture was heated 3 hours under 65 ℃ of stirrings, make it to be cooled to room temperature then.Filter the gained solid with 3500ml temperature toluene wash, the dry 464.08g(95% productive rate that produces) white solid.IR（nujol）1735，1600，1550，1410，1290，730cm ^-1。

N, N '-two (4-carboxymethoxyl benzoyl) piperazine

(175.8g 0.8056mol) is suspended in the interior toluene (2000ml) of 5 liters of three-necked bottles, and three-necked bottle is equipped with a top agitator, condenser and feed hopper with terephthalic acid monomethyl one potassium.Dropwise (58.76ml 0.8056mol) adds in the suspension stirring fast, and with mixture heating up to 67 ℃, keeps 3 hours with thionyl chloride.At room temperature stir and spend the night, reaction product is filtered through the B of bed of diatomaceous earth, keeps the filtrate that contains 4-carboxymethoxyl Benzoyl chloride.At this moment, this acyl chlorides can separate by adding an equal-volume ether, filters out the Repone K byproduct, removes in a vacuum and desolvates.Directly use toluene solution in most of steps.

With salt of wormwood (266.2g, 1.61mol) and piperazine (34.69g 0.4027mol) is dissolved in the water that is contained in the 1000ml in 5 liters of Morton flasks.Remain under 25 ℃ at the bottle interior reaction temperature, dropwise add the toluene solution of 4-carboxymethoxyl Benzoyl chloride.The mixture stirring is spent the night, filters,, obtain 127g(77% with toluene, water, 1N HCl and water elder generation after scouring) N, N '-two (4-carboxymethoxyl benzoyl) piperazine white solid.

mp.234-237℃;IR（nujol）1730，1630，1610，1510，1290，1260，1010，730cm ^-1.

¹H NMR(200MHz, CDCl ₃/ CD ₃COCD ₃) δ 7.48-8.11(8H, m), 3.93(6H, s), and 3.81(4H, br s), 3.56(4H, br s); ¹³C NMR(CDCl ₃/ CD ₃COCD ₃) δ 169.51,166.05,139.19,131.50,129.89,126.98,52.31,43.80,41.10; IR(nujol) 2920,2840,1720,1620,1605,1455,1430,1370,1360,1275,1260,1100,1000cm ^-1; Low res.MS(CI, Trimethylmethane) 411(MH ⁺).

N, N '-two (4-crosses carboxylbenzoyl) piperazine (PCBPIP)

N, (4.07g 0.0099mol) is dissolved in the methylsulfonic acid (14ml) N '-two (4-crosses carboxylbenzoyl) piperazine, and (3.37ml, 70% solution 0.0891mol) are handled it with 0 ℃ hydrogen peroxide.At room temperature stirred the mixture 5 hours, and be poured on ice-waterborne then.With solid collection on B, wash with water to pH be 5, air-dry overnight.Produce 3.91g(95%) white powder; Decompose before the fusing point 268(fusion).The titration of iodine method is designated as 65% peracid.IR(nujol) cm 1760((peracid carbonyl 3100(hydroxyl)) ^-1

Embodiment 2

N.N '-two (4-carbo methoxy group benzoyl) ethylene diamine

Use system N, N '-two (4-carbo methoxy group benzoyl) the described step of piperazine, (26.9ml 0.4028mol) replaces piperazine, is prepared without 1000ml water with 400ml water with ethylene diamine.Produce 88.6g(57%) product.

mp.297-299℃; ¹H NMR（200MHz，DMSO-d ₆）δ8.82（2H，br s），8.06-7.94（8H，m），3.88（6H，s），3.47（4H，s）;IR（nujol）3300，1730，1640，1550cm ^-1.

N, N '-two (4-crosses carboxylbenzoyl) ethylene diamine (PCBED)

N, (0.5g 0.0129mol) is dissolved in the 30ml methylsulfonic acid N '-two (4-carboxymethoxyl benzoyl) ethylene diamine, handles with 0 ℃ hydrogen peroxide (solution of 4.4ml 70%).Allow mixture rise to room temperature, and stirred 5 hours.Solution is poured on ice and the saturated ammonium sulfate, and the mistake filter solid is washed with water to pH5.Recording activeconstituents with iodometry is 78%.

Example 3

N, N '-two (4-carbo methoxy group benzoyl)-1,4-phenylenediamine

To be dissolved in chloroform (95ml) 4-carbo methoxy group Benzoyl chloride (9.32g, 0.046mol) add 4 ℃ be dissolved in triethylamine (4.81ml, 0.035mol) and chloroform (250ml) 1, the 4-phenylenediamine (2.59g, 0.023mol) in.Make reactant be warmed to room temperature, spend the night.Remove chloroform in a vacuum.Solid is poured on the cold 5%HCl, filter, with rare HCl washing.Use the DMF recrystallize, produce 6.16g(62%) buff powder, fusing point＞345 ℃

¹H NMR(DMSO-d ₆) δ 8.06(8H, s), 7.74(4H, s), 3.88(6H, s); ¹³C NMR(H ₂SO ₄/ CD ₃COCD ₃) (dec.to acid) δ 205,196,169.77,167.10,132.56,130.95,128.16,127.79,127.03,122.85,119.82,52.02; IR(nujol) 3330,2900,2840,1720,1640,1550,1455,1410,1375,1280,1190,1110cm ^-1; Low res.MS(CI, Trimethylmethane) 433(MH+), 271,257,223.

N, and N '-two (4-crosses carboxylbenzoyl) phenylenediamine (1,4-PCBPD)

N, (3.07g 0.0071mol) is dissolved in methylsulfonic acid (40ml) and also uses the hydrogen peroxide of room temperature (solution of 2.42ml 70%, 0.0639mol) processing N '-two (4-carboxymethoxyl benzoyl) phenylenediamine.Stirred 6 hours under the room temperature, reaction is remained on 3 ℃ reach 12 hours.Mixture is poured on ice-saturated ammonium sulphate solution, then as preceding method separate it, obtain 1.85g(59%) the orange powder, m.p.＞315 ℃.Iodimetric titration is designated as 60% peracid.IR(nujol) cm 1755(peracid carbonyl 3230(hydroxyl)) ^-1

Example 4

N, N '-two (4-carbo methoxy group benzoyl)-1,4-diamino-cyclohexane

(9.057g 0.0456mol) is dissolved in 500ml and is equipped with in the chloroform (180ml) in the three-necked flask of mechanical stirrer and feed hopper 4-carbo methoxy group Benzoyl chloride.In this solution, in 30 minutes, add 0 ℃ anti--1, the 4-diamino-cyclohexane (2.60g, 0.0228mol), triethylamine (7.5ml, 0.0535mol) and chloroform (80ml).Stir reaction down 2.5 hours, filtration product is removed chloroform.With 10%HCl and the wet solid of saturated NaCl solution washing.Product is dissolved in 0 ℃ of vitriol oil, and broken frozen water obtains white powder, 80% of productive rate, m.p.＞350 ℃. ¹H NMR（200MHz，D ₂SO ₄）δ8.30-7.94（8H，m），4.27-4.37（8H，m），2.34-1.80（8H，br m）， ¹³C NMR（200MHz，H ₂SO ₄/CD ₃COCD ₃）δ170.92，132.32，129.92，129.25，127.61，55.04，51.83，24.07;IR（nujol）3295，2920，2850，1720，1630，1530，1460，1375，1285cm ^-1.

N, N '-two (4-crosses carboxylbenzoyl)-1,4-diamino-cyclohexane (PCBHEX)

N, N '-two (4-crosses carboxylbenzoyl)-1, (1.63g 0.0037mol) is dissolved in the methylsulfonic acid (10ml) the 4-diamino-cyclohexane, and (solution of 1.26ml70% 0.0333mol) is handled with the room temperature hydrogen peroxide.Finish reaction with frozen water after 7 hours,, obtain 1.57g(95% at 25 ℃ of vacuum oven inner dryings) white powder; ℃ m.p.＞310.Iodimetric titration is designated as 79% peracid.1H NMR(200MHz, DMSO-d6) δ 8.47-8.44(m, ester), 8.03-7.91(m, peracid and ester) and, 3.88(s, ester), 3.79(br s, ester and peracid) and, 1.94-1.91(m, ester and peracid), 1.52-1.43m, ester and peracid); IR(nujol) 3295(is wide, hydroxyl), 1730(peracid carbonyl) cm ^-1

Example 5

Carbonyl oxyethyl group hexanedioyl chlorine

(25.63g, 0.147mol) (34.98g, 0.293mol) at the round-bottomed flask internal reaction, flask is equipped with condenser to hexanodioic acid-ethyl ester, is heated to 37 ℃ and keeps 3 hours with thionyl chloride.Replace condenser with the remodeling still head, under 5mmHg, remove excessive thionyl chloride.Distill out transparent liquid (59 ℃/about 0.1mmHg) products (26.84g, 95%).IR3550，3420，2950，2910，2840，1785，1715，1455，1360，1230，1170，1140，1080，1010，940cm ^-1。

N, N '-two (carbonyl oxyethyl group adipyl)-1,4-phenylenediamine

Carbonyl oxyethyl group hexanedioyl chlorine (13.74g, 0.071mol) solution in chloroform (40ml) be added into 4 ℃ 1, (3.89g, 0.036mol) (7.53ml is in solution 0.054mol) in chloroform (330ml) and triethylamine for the 4-phenylenediamine.In 5 hours reaction medium is warmed to room temperature.To its crystallization, obtain 6.30g(42% with ethyl acetate) white fluffy solid;

M.p.156-160 ℃. ¹H NMR(DMSO-d ₆) δ 9.81(2H, s, NH), 7.49(4H, s), 4.04(4H, q), 1.57(8H, m), 2.34(8H, m), 1.18(6H, t); ¹³C NMR δ 173.65,171.25,134.38,120.74,60.39,36.90,33.98,25.01,24.42,14.23; IR(nujol) 3290,2920,2840,1720,1645,1540,1455,1370,1370,1290,1255,1170cm ^-1; Low res MS(CI, Trimethylmethane) 421(MH+).

N, N '-two (crossing the carboxyl adipyl) phenylenediamine (DPAPD)

N, N '-two (carbonyl oxyethyl group adipyl)-1, (6.00g 0.0143mol) is dissolved in methylsulfonic acid (21ml) to the 4-phenylenediamine, and (solution of 4.87ml 70% 0.1287mol) is handled with the room temperature hydrogen peroxide.After 2 hours from frozen water separated product, obtain 4.97g(88%) shallow orange powder; M.p.210-212(decomposes).Iodimetric titration is designated as 87% peracid.1HNMR(200MHz, DMSO-d ₆) δ 11.97(2H, br s), 9.83(2H, s) 7.49(4H, m), and 4.10(trace, q, ester), 2.49-2.00(8H, m), and 1.57(8H, br s), 1.17trace, t, ester); IR(nujol) cm 1750(peracid carbonyl 3100(hydroxyl)) ^-1.

Embodiment 6

N, N '-(4-carbo methoxy group benzoyl)-1,4-butanediamine

(19.07g 0.096mol) is dissolved in the toluene (380ml) that places in the 1000ml round-bottomed flask that mechanical stirrer, thermometer and feed hopper are housed with 4-carbo methoxy group Benzoyl chloride.Dropwise added 1 in flask in 40 minutes, the solution (80ml) of 4-butanediamine in water keeps the temperature of reaction mixture at 25 ℃ by water-bath simultaneously.Form white solid immediately, restir reaction mixture 2 hours.Solid collection on sintered glass, is used toluene, water, 5%HCl and water washing respectively.Use the DMF recrystallize, obtain white crystal, dry under 60 ℃ in vacuum oven, product 17.91g(90%), fusing point

260-261 ℃. ¹H NMR(200MHz, DMSO-d ₆) δ 8.70(2H, m), 8.05-7.93(8H, m) 3.88(6H, s) 3.34(4H, s), 1.58(4H, s); IR(nujol) 3300,1720,1625,1530,1275,1105,860,730cm ^-1; Low res.MS(CI, Trimethylmethane) 413(MH+); ¹³C NMR(75MHz, DMSO-d ₆) δ 166.9,165.7,165.4,165.2,138.7,131.6,129.0,127.5,127.2,52.3,26.5.

N, N '-two (4-crosses carboxylbenzoyl)-1,4-butanediamine (PCBBD)

Be dissolved in the N in the methylsulfonic acid (25ml), N '-two (4-carbo methoxy group benzoyl)-1, the 4-butanediamine (3.00g, 0.007mol) (0.066mol) handle with hydrogen peroxide by aforesaid method by the solution of 2.50ml 70%.Following 5 hours of room temperature, 3 ℃ after 16 hours, make peracid in precipitation on ice, wash with water, drying obtains 1.8g(60%) white powder; M.p.180 ℃ (decomposition).Iodometric titrationiodimetry titration is indicated as 74% peracid, 5.7%a.o.(in theory: 7.7% a.o.).IR(nujol) cm 1745(peracid carbonyl 3320-3100(hydroxyl)) ^-1; 1H NMR(200MHz, DMSO-d ₆) δ 8.65(2H, m), 8.03-7.90(8H, m), and 3.87(st starting raw material, 7%), 3.29(4H, s), 1.58(4H, s).

Example 7

N, N '-two (4-carbo methoxy group benzoyl)-1,2-phenylenediamine

(18.5g 0.093mol) is dissolved in chloroform (100ml) to 4-carbo methoxy group Benzoyl chloride under nitrogen, be cooled to 0 ℃.Dropwise to wherein adding 1, and the 2-phenylenediamine (5.00g, 0.046mol) and triethylamine (12.8ml, 0.092mol) solution in chloroform (350ml).After 16 hours, remove by filter the chlorination triethyl ammonium with the sintered glass of being with filter paper.With cold 5%HCl(3 * 200ml) and saturated NaCl solution (2 * 150ml) washing organic layers, with dried over mgso it.The decompression under remove chloroform separate product.Use the ethanol recrystallize, obtain 12.19g(61%) white powder; M.p.211-216 ℃.

¹H NMR(200MHz, DMSO-d ₆) δ 10.24(2H, s), 8.09-8.07(8H, 2s), 7.69(2H, s), 7.33(2H, s), 3.90-3.88(6H, 2s); ¹³C NMR(50MHz, DMSO-d ₆) δ 165.29,164.37,138.13,131.82,130.94,128.94,127.69,125.79,125.42,52.08; IR(nujol) 3380,3280,1720,1645,1540,1290,1275,1100cm ^-1; Low res.MS(CI, Trimethylmethane) 433(MH+) 271,165.

N, N '-two (4-crosses the carboxyl benzoyl)-1, the 2-phenylenediamine (1,2-PCBPD)

N, N '-two (4-carbo methoxy group benzoyl)-1, (2.75g 0.0064mol) is dissolved in methylsulfonic acid (25ml) to the 2-phenylenediamine, is chilled to 0 ℃ again.Dropwise to wherein add hydrogen peroxide (solution of 1.57ml 90%, 0.058mol).After following 16 hours of the room temperature, as above method finishes reaction.Iodometric titrationiodimetry titration is indicated as 70% peracid, 5.2%a.o.

(theoretical value 7.3%a.o.) IR(nujol) cm 1740(peracid carbonyl 3160(hydroxyl)) ^-1; ¹H NMR(200 MHz, DMSO-d ₆) δ 10.20(2H, s), 8.09-8.07(8H 2s), 7.73-7.52(2H, m), 7.39-7.22(2H, m), 3.89(∈ ester about 7%); ¹³C NMR(50MHz, DMSO-d ₆) δ 166.58,164.76,137.95,133.37,131.19,129.30,127.76,126.01.

Example 8

N, N '-succinyl-two (4-carboxymethoxyl) aniline

Succinyl dichloride is distillation under reduced pressure earlier before use.In a 1000ml round-bottomed flask, under nitrogen, (20g, 0.132mol), (10.7ml 0.133mol) and chloroform (250ml) reaction, is chilled to 0 ℃ to piperidines then to make the 4-Methyl anthranilate.Dropwise to the chloroformic solution that wherein adds succinyl dichloride (7.5ml, 0.068mol).Can be observed the lavender precipitation after the adding.After the room temperature 2 hours, use the sintered glass filtration product, wash successively, on sintered glass, permit its dry air with 5%HCl(2 * 400ml), water (600ml)., dry in 60 ℃ of vacuum ovens with DMF to the product recrystallize, obtain 16.09g(62%) white crystal; M.p.284-285 ℃.

¹H NMR 200 MHz, DMSO-d ₆) δ 10.42(2H, s), 7.96-7.74(8H, s), 3.85(6H, s), 2.75(4H, s); IR(nujol) 3340,3320,1710,1690,1675,1610,1595,1530,1295,1270,1175,1160,1105,770 cm ^-1; Low res.MS(CI, Trimethylmethane) 385(MH+), 234,152; ¹³C NMR(75 MHz, DMSO-d ₆) δ 170.9,165.7,143.6,130.2,123.6,118.2,51.7,31.0.

N, N '-succinyl--two (4-crosses carboxyl) aniline (SDPCA)

With N, (5.02g 0.013mol) is dissolved in the methylsulfonic acid (30ml) N '-succinyl--two (4-carbo methoxy group) aniline, is chilled to 0 ℃.Dropwise add hydrogen peroxide (solution of 4.43ml 70%, 0.117mol).After following 6 hours of the room temperature, finish reaction, obtain the light brown powder product as well-established law; M.p.201 ℃.Iodimetric titration is designated as 72% peracid, the theoretical 8.2%a.o. of 6.0%a.o.().IR(nujol) cm 1750(peracid carbonyl 3200(hydroxyl)) ^-1; 1HNMR(200MHz, DMSO-d ₆) δ 10.37, each 2H of 10.34(, s, one is peracid OH, one is acid amides-NH), 7.92-7.68(8H, m), and 3.81(s, ester), 2.72(4H, s, ester and peracid).

Example 9

N, N '-two (carbonyl oxyethyl group adipyl) ethylene diamine

(1.17g, (2.5g is 0.013mol) in the solution of toluene (36ml) 0.0195mol) dropwise to be added to carbonyl oxyethyl group hexanedioyl chlorine under the room temperature for ethylene diamine in water (5ml).Behind the restir 2.5 hours, filter white solid, wash successively with toluene, water, 0.1N HCl and water, at 63 ℃ of vacuum oven inner dryings.Appear at IR spectrum (3080cm once eliminating ^-1) the exploration of impurity in, in toluene, extract this material, with removing by filter insolubles, remove toluene in a vacuum and obtain white powder (0.31g, 13%); M.p.117-120 ℃ (staying white residue after most of fusion).

¹H NMR(200MHz, DMSO-d ₆) δ 7.83(2H, br s), 4.05(4H, q) 3.37(H ₂O), 3.07(5H, br s), 2.28-2.02(10H, br s) and, 1.49(9H, br s), 1.18(6H, t); For the oxyethyl group proton, the peak is 3.07 Hes, and the integration at 1.49 places is the high proton in every place, high 2 protons at the 2.28-2.02 place.

IR（nujol）3300，2920，2850，1725，1640，1550，1460，1375，1270，1245，1180，730cm ^-1.

Because the toluene purifying fails to eliminate the impurity that does not identify, and has used to be used to prepare N the method for N '-two (4-carbo methoxy group benzoyl) piperazine.Carbonyl oxyethyl group-hexanedioyl chlorine (1.0g, 0.0052mol) in the solution of chloroform (12ml) under nitrogen, dropwise added ethylene diamine (0.16g, 0.0026mol), (0.54ml, 0.0039mol) chloroform (5ml) is in 4 ℃ solution for triethylamine.Stirred the mixture 5.5 hours, and as usually finished reaction, obtain 0.60g(62%) solid.With toluene this product recrystallize is got 0.20g(21%) still contain white powder by the impurity of IR and NMR indication; M.p.120-122 ℃.Also fail to eliminate this impurity with ethyl acetate.

¹³C NMR(200MHz, CDCl ₃/ CD ₃COCD ₃) δ 207.44,173.87,60.38,40.07,36.08,33.90,25.12,24.39,14.33,14.25; Low res.MS(CI, Trimethylmethane) 373(MH+).

N, N '-two (crossing the carboxyl hexanedioyl) ethylene diamine

N, (0.023g 0.00055mol) is dissolved in methylsulfonic acid (1.4ml) to N '-two (carbonyl oxyethyl group hexanedioyl) ethylene diamine, with the hydrogen peroxide under the room temperature (solution of 0.19ml 70%), and stirs 18 hours.This product is difficult to separate from frozen water, and it is flaky substance (0.0088g, 46%), and blackening in the time of＜220 ℃ is not melted but be lower than 350 ℃.Iodometric titrationiodimetry titration is designated as 55% peracid.1H NMR(200MHz, DMSO-d6, δ 7.81(br s, ester and peracid), 4.10(q, ester) and, 3.06(H ₂O), 2.22 and 2.19(m, ester and peracid), 1.48(m, ester and peracid) and, 1.19(t, ester).IR(nujol) cm 1755(peracid carbonyl 3200(hydroxyl)) ^-1

Example 10

N-benzoyl-4-benzaminic acid

In the 500ml Morton flask of mechanical stirrer and feed hopper is housed, add the yellow soda ash be dissolved in 200ml water (26.5g, 0.25mol).(13.71g 0.10mol), stirs the mixture until dissolving fully to add the 4-benzaminic acid by part in flask.Mixture is chilled to 0 ℃, dropwise add again Benzoyl chloride (13.92g, 11.50ml, 0.099mol).One dense white precipitate forms immediately, at room temperature stirs 2 hours, and mixture is poured on cold rare HCl.Filter solid, with rare HCl and water washing.With second alcohol and water recrystallize, 11.69g(49%) required product;

mp 284-288℃;IR（nujol）3340，1680，1665，1650，1515cm ^-1; ¹H NMR（200MHz，DMSO-d ₆）δ12.40（1H，s），10.55（1H，s），8.20-7.45（9H，m）.

The amino carboxyl phenylformic acid (BP-PABA) of crossing of N-benzoyl-4-

(5.0g 0.0207mol) is dissolved in the 20ml methylsulfonic acid N-benzoyl-4-benzaminic acid.Mixture is as cold as 0 ℃, to wherein dropwise add dense hydrogen peroxide (solution of 2.40ml 70%, 0.0634mol).Stir this mixture under the room temperature after 3 hours, it is poured on a large amount of frozen water.Filter in B, washing precipitation with water is 4.5 until the pH of filtrate.By iodometric titrationiodimetry titration indication activeconstituents is 79%(4.9%a.o., 5.22% theoretical value); M.p.140 ℃ (decomposition);

IR(nujol) 3450(hydroxyl), 3340,1740,1655,1530cm ^-1. ¹H NMR(300 MHz, DMSO) δ 8.05-7.50(9H, m).

Example 11

4-carbo methoxy group benzanilide

(11g 0.055mol) is dissolved in the chloroform (200ml), stirs with mechanical stirrer under nitrogen with 4-carbo methoxy group Benzoyl chloride.Flask is chilled to 0 ℃, to wherein dropwise being incorporated in chloroform 1(35ml) in aniline (20.64g, 0.222mol) solution.Add the back and form white precipitate.After following 2 hours of the room temperature, remove chloroform with rotary evaporation.Product washs with 10%HCl, filters with sintered glass, washes with water earlier several times, washs with chloroform again.Use the toluene recrystallize, get 5.02g(34%) white powder;

m.p.194-195℃. ¹H NMR（200 MHz，DMSO-d ₆）δ10.45（1H，s），8.09-7.34（9H，M），3.91-3.90（3H，m）;IR（nujol）3380，1720，1665，1605，1540，1330，1285，1170，1120，760，730cm ^-1; ¹³C NMR（50MHz，CDCl ₃/CD ₃COCD ₃）δ166.3，165.2，139.2，138.5，132.7，129.6，128.9，127.6，124.4，120.5.

4-crosses carboxyl benzanilide (PCBA)

(4.78g 0.0187mol) is dissolved in methylsulfonic acid (25ml) to (4-carbo methoxy group benzoyl) aniline.Dropwise add hydrogen peroxide (2.13ml 70% solution, 0.056mol).After following 5 hours of the room temperature, end reaction as usual obtains 3.86g(80%) buff powder.Iodometric titrationiodimetry titration is designated as 66% peracid, 4.1%a.o.IR(nujol) the 3320(hydroxyl), 1750(peracid carbonyl) cm ^-1, ¹H NMR(200MHz, DMSO-d ₆) δ 11.90(1H, br s), 10.42(1H, s), 8.11-7.09(9H, m), 3.90(ester 20%).

Example 12

N, N, N ', N '-1,2,4,5-tetracarboxylic benzoyl-two (6-aminocaprolc acid)

With 1,2,4,5-tetracarboxylic phthalic acid (20g, 0.0917mol) and 6-aminocaprolc acid (24.6g 0.188mol) is suspended in 200ml DMF, reheat to 120 ℃.Heating makes the solid dissolving.After 3 hours, cooling solution is poured on the frozen water, and filters.Solid is placed on to stir in the 500ml hot methanol and is purified, and makes it cooling again; Produce 30g(74%) white solid; IR

（nujol）1770，1705（br），1055cm ^-1; ¹H NMR（200MHz，DMSO-d ₆）δ12.0（2H，s），8.15（s，2H），3.61（2H，t），2.2（2H，t），1.8-1.2（6H，m）; ¹³C NMR（50MHz，DMSO-d ₆）δ175.0，166.6，137.2，118.0，38.1，33.7，27.8，26.0，24.3.

N, N, N ', N '-1,2,4,5-tetracarboxylic benzoyl-two (the amino carboxyl caproic acid of crossing of 6-) is (DIPAP)

(7.0g 0.0224mol) is dissolved in the 55ml methylsulfonic acid to the imide dicarboxylic acid, and (5.0ml 0.134mol) handles with 70% hydrogen peroxide.Short period of time afterreaction mixture becomes extremely thick, must use mechanical stirring.Room temperature was poured on mixture on the frozen water after 5 hours, separated it more as described above.Activeconstituents is 98%; IR(nujol) 3270,1760,1740,1710,1155,1055cm ^-1

Example 13

N, N '-terephthaloyl-two (the amino oxy hexanoic acid of crossing of 6-) (TPCAP)

N, N '-terephthaloyl-two (6-aminocaprolc acid) ^*(5.01g 0.0127mol) is dissolved in the 30ml methylsulfonic acid, and (4.33ml 70%, 0.114mol) handles with 0 ℃ hydrogen peroxide.Stirred the mixture under the room temperature 5.5 hours, and as usually then finished reaction.Obtain 4.91g(92%); Activeconstituents 88% 6.7%a.o., theoretical value 7.6%); IR(nujol) 3300,3200,1760,1740,1630,1545cm ^-1

^＊Zinner，H.;Sych，G.;Ludwig，W.J.Prakt.Chem.17，147-153（1962）.

Example 14

N, N '-two (4-carboxyl aniline) terephthalate

The 4-benzaminic acid (2.1eq, 14.11g, 0.103mol) and yellow soda ash (5eq, 25.92g 0.245mol) stir in 4000ml water fast.Under the room temperature broken terephthalyl chloride is added wherein by part.Stir after 72 hours, with solution to 10%HCl.Solid collected by filtration washes with water, the 16.6g(83% productive rate) white powder.A kind of impurity in this product is the affixture (＜3%) of single addition.1H

NMR（200 MHz，DMSO-d ₆）δ10.74（2H，s），8.15-7.90（12H，m），3.4（2H，br s）;IR（nujol）3360，1690，1660，1610cm ^-1.

N, N '-two (4-crosses carboxyl aniline) terephthalate (DPCAT)

N, (4.98g 0.012mol) is suspended in the 60ml methylsulfonic acid N '-two (4-carboxyl aniline) terephthalate, and (solution of 4.09ml70% 0.108mol) is handled with hydrogen peroxide.Activeconstituents 91%, the theoretical 7.3%a.o. of 6.7%a.o.().IR（nujol）3380，3200，1740，1660，1600cm ^-1。

Example 15

N, N-phthalyl-4-benzaminic acid

(10.0g, 0.0675mol) (9.35g 0.0682mol) is dissolved in the 100ml dry DMF to Tetra hydro Phthalic anhydride, is heated to 120 ℃ and keeps 4.5 hours with the 4-benzaminic acid.Cooling mixture falls on frozen water and filtration.Use the alcohol-water recrystallize, get 6.6g(37%) fluffy white solid.

mp 189-190;IR（nujol）1780-1745，1725，1695，1605cm ^-1; ¹H NMR（200MHz，DMSO-d ₆）δ13.1（1H，s），8.2-7.58（4H，aa′bb′），8.06-7.9（4H，m）; ¹³C NMR（50MHz，DMSO-d ₆）δ166.69，166.65，135.81，134.82，131.48，129.88，129.82，126.99，123.54.

N, the amino peroxybenzoic acid (phenyl PAP) of N-phthalyl-4-

To N, N-phthalyl-4-amino-phenylformic acid (4.03g, 0.0151mol) in the suspension of 60ml methylsulfonic acid, add room temperature hydrogen peroxide (2.29ml, 0.0605mol).End reaction as usual after 6 hours, and be stored as wet filter also (6.23g).Dry-eye disease contains 84% peracid; The m.p.173(decolouring); IR3305,

1785，1760，1730，1700，1600，1510，1075cm ^-1; ¹H NMR（200MHz，DCDl ₃）δ11.7（1H，s）8.4-7.55（8H，m）.

Example 16

The stability of peracid in the heavy duty scavenging solution

Used prescription contains 35% tensio-active agent in this research, obtains pH4.5 with borax/sorbyl alcohol pH transition system.The peracid consumption is 2500ppm.The table I has been listed basic recipe.Test recipe (mainly containing peracid) is stored in 40 ℃, takes out aliquots containig periodically, and the percentage ratio of peracid in the residue is measured in titration.The half life of test recipe, listed in the table II.

The table I

The basic recipe * of pH transition system

Water 38.1

Sorbyl alcohol (100%) 19.6

Borax 10aq 5.0

NaOH(100%) 2.9

The polymkeric substance (100%) 1.0 of uncoupling

Neodol 25-9 10.5

LAS acid (96%) 22.9

* initial pH=4.5

The table II

The stability of peracid in the heavy duty scavenging solution

t1/2

40 ℃ of peracid (my god)

PCBPIP 79

DPCAT 65

Phenyl PAP 48

SDPCA 43

PCBED 34

1,2-PCBPD 33

DPAPD 32

DIPAP 29

TPCAP 25

PCBBD 15

SBPB 11

PCBA 8

DPDA 5

PAP 3

All amido peracid are more stable than DPDA in heavy duty liquid.Half life of 5, was above 30 days among these.PCBPIP has tangible 79 day half life at 40 ℃.

* describe among the EP267175 4,4 '-the two benzoyl hydroperoxides of sulphonyl

For the purposes of the present invention, realize that following 40 ℃ peroxide stability half life is favourable: at least 10 days, preferably at least 15 days, more preferably at least 30 days, preferably at least 50 days.

Example 17

Solubleness in the water

Basic premise of the present invention is that the solubleness of peracid influences its stability in composition.Therefore, the solubility values of various peracid is measured, and these values are relevant with stabilization of peroxide.

The mode of carrying out of solubility experiment is, stirs the Powdered peracid of 0.2g fast in 50ml contains the Milli-Q water of phosphonic acids Dequest2041 of 0.01g/1.Heat this solution to 40 ℃ 15 minutes, bathe balance to 25.0 ℃ (± 1 ℃) with water cycle then.After 2 hours, stop to stir, allow solid settlement.Filter a aliquots containig with the instant syringe of abandoning of the polypropylene that Millex-HA 0.45 μ m filtering unit is housed.The pH of filtrate is between 4.5-5.0.Clarifying filtrate is handled with potassium terephthalate damping fluid and potassiumiodide, according to method (Davies, the D.M. of Davies; Deary, M.E.Analyst(1988), 113, the 1477-1479) concentration of spectrometry triiodide.Repeat this step after 1 hour, to guarantee to have reached equilibrium value.The reproducibility of method is found to be ± and 10%.

The results are shown in the table III.Monoperacid and diperacid are separated to list, and are different because of believing two types in the error aspect the measurement.The analysis of diperacid solubleness can be depending on the purity of measuring specimen in use, but the analysis of monoperacid solubleness should be irrelevant with purity.This is because measurement is the active oxygen of surveying.In view of pollutent such as unreacted carboxylicesters or carboxylic acid can not disturb the measurement of monoperacid, the low-purity diperacid can contain a carboxylicesters (or acid) base and a mistake acidic group.These molecules will may possess different solubility performance than desired molecule, and active o content will only be half of diperacid in each molecule.

Therefore, two kinds of concentration, the titratable concentration of crossing carboxyl and molecule is listed in the table III.

Claims (9)

1, a kind of cleaning composition comprises:

I) a kind ofly contain amido or imino-organic peroxide acid, its water solubility＜1 * 10 with what significant quantity existed, is used to bleach ^-4M,

Ii) a kind of with significant quantity exist, be used to suspend this peroxy acid tensio-active agent and

Iii) a kind of to exist, be used in storage period to keep pH with significant quantity be 3.5-8.5, can make the pH pH regulator system of 0.5pH unit at least that raises behind dilute with water.

2, according to the composition of claim 1, pH regulator system wherein comprises a kind of borate and polyvalent alcohol, and the proportional range of this borate and polyvalent alcohol is 1: 10 to about 10: 1.

3, according to the composition of claim 1, peroxy acid wherein is selected from

Wherein:

R is selected from 1-16 carbon alkyl, 1-16 carbocyclic ring alkyl and 6-12 carbon aryl;

R ¹Be selected from hydrogen, 1-16 carbon alkyl, 1-16 carbocyclic ring alkyl and 6-12 carbon aryl;

R ²Be selected from hydrogen, 1-16 carbon alkyl, 1-16 carbocyclic ring alkyl and 6-12 carbon aryl and work as R ³Can form the carbonyl of ring when being arylidene with R;

R ³Be selected from 1-16 carbon alkylidene group, 5-12 carbocyclic ring alkylidene group and 6-12 carbon arylidene;

N and m are that summation is 1 integer; With

M is selected from hydrogen, basic metal, alkaline-earth metal, ammonium and alkanol ammonium cation and group, and

Wherein:

R ⁴Be selected from the combination of 1-12 carbon alkylidene group, 5-12 carbocyclic ring alkylidene group, 6-12 carbon arylidene and these groups;

R ⁵Be selected from H, 1-16 carbon alkyl, 6-12 carbon aryl and energy and R ³Form the carbonyl of a ring together;

R ⁶Be selected from H, 1-16 carbon alkyl, 6-12 carbon aryl and and R ³Can form group of a 3-12 isocyclic together;

R ³Be selected from 1-12 carbon alkylidene group, 5-12 ring alkylidene group and 6-12 carbon arylidene;

N ' and n " integer of respectively doing for oneself, selection mode be make the two add up to 1;

M ' and m " integer of respectively doing for oneself, selection mode be make the two add up to 1; With

M is selected from H, basic metal, alkaline-earth metal, ammonium and alkanol ammonium cation and group.

4, according to the composition of claim 1, the amount of amido wherein or imino-organic peroxide acid is 0.1-40 weight %.

5, according to the composition of claim 1, the amount of pH regulator system wherein is the about 40 weight % of about 1%-.

6, according to the composition of claim 1, the amount of tensio-active agent wherein is the about 50 weight % of about 1%-.

7, according to the composition of claim 1, peroxy acid wherein is selected from

N, N '-two (4-crosses carboxylbenzoyl)-1,4-butanediamine;

N, N '-two (4-crosses carboxylbenzoyl)-1,2-phenylenediamine;

N, N '-succinyl-two (4-crosses carboxyl) aniline;

4-crosses carboxylbenzoyl aniline;

N, the amino peroxybenzoic acid of N-phthalyl-4-;

N, N '-two (4-crosses carboxylbenzoyl) ethylene diamine;

N, N '-two (4-crosses carboxyl aniline) terephthalate;

N, N, N ', N '-1,2,4,5-tetracarboxylic benzoyl-two (the amino carboxyl caproic acid of crossing of 6-);

N, N '-two (4-crosses carboxylbenzoyl) piperazine;

N, N '-two (4-crosses carboxylbenzoyl)-1,4-diamines-hexanaphthene;

N, N '-two (crossing the carboxyl adipyl) phenylenediamine; With

N, N '-two (crossing the carboxyl adipyl) ethylene diamine;

N, N '-terephthaloyl-two (the amino carboxyl caproic acid of crossing of 6-).

8, according to the composition of claim 1, wherein also comprise a kind of deflocculate polymkeric substance.

9, a kind of method of contamination with wash base-material comprises this base-material of compositions-treated with claim 1.