CN1022929C - Bleaching composition - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R1 is 1-20C alkyl, alkenyl or aryl; R2 and R3 are 1-3C alkyl, hydroxyalkyl or -(C2H4O)1-5H; X<-> is an organic or inorganic anionic ion; n is 1-3]. USE:A bleach activating agent. Useful as a component of bleaching agent composition and bleaching and cleaning agent composition. PREPARATION:For example, a tert. amine is reacted with a halide of acetonitrile as same as quaternarization reaction of a normal amine to provide the compound expressed by formula I (X<-> is halogen). The compound expressed by formula I is blended with hydrogen peroxide or a peroxide (e.g. sodium percarbonate) capable of generating hydrogen peroxide in an aqueous solution to afford the bleaching agent composition and bleaching and cleaning agent composition.

Description

Bleaching composition

The present invention relates to bleaching composition and bleaching cleaning composition.

The shortcoming of chlorine bleaching agent is that its application is limited by kinds of fibers, can not be applied to painting cloth or tprinted Fabrics and have special smell.Oxygen-bearing bleaching agent does not have these shortcomings, thereby is extensively promoted in recent years.

Specifically, because SPC-D and Sodium peroxoborate have fabulous bleaching and stability, therefore, use as oxygen-bearing bleaching agent usually.

The bleaching efficiency of oxygen-bearing bleaching agent is than chlorine bleaching agent difference, and therefore, oxygen-bearing bleaching agent will use simultaneously with various bleach-activating agents, in addition, various activators have been done research, the example of these activators comprises nitrile, as acetonitrile, propane dinitrile, phthalonitrile and benzoylimino-diacetonitrile; The O-acetic ester is as glucose penta-ethyl ester, octoacetyl sucrose, triactin, sorbitol hexaacetate, acetoxyl benzene sulfonate, triethyl cyanurate and methyl-chloroformate; The N-acylate, as N, N, N ', N ', acyl connection urea, N-benzyl imidazole, two-N-ethanoyl dimethylglyoxime, 1-phenyl-3-ethanoyl glycolylurea, N in-tetra acetyl ethylene diamine, the tetra-acetylated second, diacetanilide N,, N-ethanoyl glycol ether imines and diacetyl methylene radical diformamide; Acid anhydrides is as the mixed acid anhydride of Tetra hydro Phthalic anhydride, succinyl oxide, benzoyl oxide, Pyroglutaric acid, O-alkyl sulfide acid anhydrides and carboxylic acid and organic sulfonic acid; The sulphonyl oxime, as two (methylsulfonyl) dimethylglyoximate, acyl phosphate is as the benzoyl diethyl phosphoric acid; Benzene sulfonate; Organophosphorus triazo-compound such as diphenylphosphine trinitride; Two sulfones such as diphenyl disulfoxide; N-sulfonylimidazoles, cyanamide, halo triazole and chlorination N, N-dimethyl-N-octyl group-N-10 carbon phenoxy group dodecyl ammonium.But even oxygen-bearing bleaching agent uses with above-mentioned activator, its bleaching efficiency is still relatively poor.

Have in the molecule

The known compound of group comprises following compounds:

（J.Chem.Soc.Perkin Trans.，2，1978.No.8，pp.786～793），

In order to develop the oxygen bleach composition with stronger bleaching efficiency, the present inventor studies, and finds, and superoxide is used and can reach this purpose with specific positively charged ion organic peracid precursor.

An object of the present invention is to provide bleaching composition and bleaching cleaning composition.

Another object of the present invention provides the cation compound of the activator of the new described composition of conduct.

The invention provides a kind of bleaching composition, said composition comprises (a) a kind of superoxide and (b) has at least a being selected from (b-1) and (b-2) the organic peracid precursor of group that the present invention also provides the bleaching cleaning composition that contains detergent component in addition.

Organic peracid precursor defined above should comprise having general formula (b-3), (b-4), (b-5), (b-6) and compound (b-7) respectively and have at least one (b-1) and/or (b-2) polyalkylenepolyamines of group.

To do detailed definition to preferred precursor below.

A kind of precursor has general formula (b-3), in the formula, and R ₁Be C ₁～C ₂₄Alkyl, C ₁～C ₂₄Alkenyl, has C ₁～C ₂₄The alkaryl of alkyl, has substituent C ₁～C ₂₄Alkyl, has substituent C ₁～C ₂₄Alkenyl has C ₁-C ₂₄Alkyl and other substituent alkaryl, R ₂And R ₃Respectively be C ₁～C ₃Alkyl, have 1 to 3 carbon atom hydroxyalkyl ,-(C ₂H ₄O) nH(n is 1 to 5) ,-CH ₂CN, X are negatively charged ion.

A kind of precursor has general formula (b-4), in the formula, and R ₁Be C ₁～C ₂₀Alkyl, C ₁～C ₂₀Alkenyl, aryl, has substituent C ₁～C ₂₀Alkyl, has substituent C ₁～C ₂₀Alkenyl, have substituent aryl, R ₂And R ₃Respectively be C ₁～C ₃Alkyl, have 1 to 3 carbon atom have hydroxyalkyl or-(C ₂H ₄O) nH(n is 1 to 3).

A kind of precursor has general formula (b-5) or (b-6), in the formula, and R ₁To R ₅Respectively be hydrogen, C ₁To C ₁₀Alkyl, C ₁～C ₁₀Alkenyl, has substituent C ₁～C ₁₀Alkyl has substituent C ₁～C ₁₀Alkenyl, carboxyl, alkylsulfonyl or cyano group, X are negatively charged ion.

A kind of precursor be have be selected from (b-1) and (b-2) in the Alkylenediamine compound or the polyalkylenepolyamines compound of at least one group.

A kind of precursor has general formula (b-7), wherein R ₁, R ₂, R ₃And R ₄Respectively be C ₁～C ₆Alkyl, n are 1 to 16 integer, and X is a negatively charged ion.

(a) be preferably 99.9/0.1 to 20/80 with (b) mol ratio, component (b) with 100 parts (weight) (b) and the particle form of the adulterant of 5 to 20 parts of (weight) tackiness agents be present in the composition.

The invention provides cation compound with general formula defined above (b-7).

In the present invention, require component (b) to have

Three N cation groups.Group (b-2) has two (b-1) groups, but only contains two azonias that group is shared.

Below with reference to the preferred embodiment of component (b) to the present invention's explanation that lays down a definition, component (b-3)

In the formula, R ₁Be straight or branched C _1-24Alkyl or alkenyl or alkaryl (wherein moieties has 1 to 24 carbon atom), these groups can be substituted; R ₂And R ₃Respectively be C _1-3Alkyl or hydroxyalkyl ,-(C ₂H ₄O) _1-5H or-CH ₂-CN, X are negatively charged ion.

Adopt for example to make the method for corresponding amine and the reaction of halo nitrile can easily prepare above-mentioned ammonium salt, available following reaction formula is represented:

Component (b-4)

（b-4）

In the formula, R ₁Be straight or branched C _1-20Alkyl, alkenyl or aryl, these groups can be substituted; R ₂And R ₃Respectively for have the alkyl of 1 to 3 carbon atom or hydroxyalkyl or-(C ₂H ₄O) _1-5H; X Be the organic or inorganic negatively charged ion, n is 1 to 3 integer.

In the cation compound shown in the general formula (b-4), R in the general formula ₁Be C _1-8Alkyl or phenyl and n are that 2 compound is most preferred bleach-activating agent.

Adopt for example following manner,, can prepare the cation compound shown in the general formula (b-4) even tertiary amine and halo acetonitrile react to be similar to the method that makes amine be converted into corresponding quaternary ammonium compound.

Compound (b-5) and (b-6)

R in the formula ₁-R ₅Respectively be hydrogen atom, can substituted straight or branched C _1-10Alkyl or alkenyl, carboxyl, alkylsulfonyl or cyano group, X ^-Be the organic or inorganic negatively charged ion.

Adopt for example to make corresponding pyridine (can at random be replaced by alkyl, alkenyl, carboxyl, alkylsulfonyl or cyano group) and the reaction of halo nitrile, can easily prepare the used ammonium salt of the present invention, this reacts available following reaction formula and represents:

Can be at random replaced, comprise pyridine, 2-, 3-and 4-pyridine carboxylic acid, nicotinic acid, 3,5-pyridine carboxylic acid, 3-pyridine-sulfonic acid and 2-, 3-and 4-cyanopyridine as the pyridine of raw material by alkyl, alkenyl, carboxyl, alkylsulfonyl or cyano group.Wherein pyridine and nicotinic acid are most preferred because of effective.

Alkylenediamine and polyalkylenepolyamines compound

These compounds have at least one and are selected from above-mentioned (b-1) and group (b-2), in other words, have at least one general formula (b-1) or (b-2) shown in quaternary nitrogen atoms.

Activator of the present invention can be obtained by Alkylenediamine or polyalkylenepolyamines.Specifically, Alkylenediamine shown in the following general formula and polyalkylenepolyamines

(R in the formula ₁Be hydrogen atom or low alkyl group; R ₂Be straight or branched C _2-10Alkylidene group, n are 2 to 1,000) can be used as the raw material of activator of the present invention.The object lesson of Alkylenediamine is 1, the 2-quadrol, and the example of polyalkylenepolyamines comprises that molecular weight is at most 1000 the lower polyethylene polyamine of molecular weight, as diethylenetriamine, Triethylenetetramine (TETA) and tetren, tri propylidene tetramine, four butylidenes, five amine, two butylidene triamines, di hexylidene triamine and three hexylidene tetramines.

Make the nitrogen-atoms of Alkylenediamine or polyalkylenepolyamines and general formula X '-(CH ₂)-C ≡ N(X ' is a halogen atom) shown in compound reaction, from the cost and benefit angle preferably with the chloro acetonitrile reaction, form quaternary ammonium compound, thereby can easily introduce

Group.

Now the method that is prepared activator of the present invention by the 1 as raw material is described.

These methods only are the examples of preparation activator method of the present invention, and in addition to the above methods, also available other method prepares activator.Alkylenediamine or polyalkylenepolyamines as raw material promptly can be the primary amine classes shown in the above-mentioned example, also can be secondary amine or tertiary amine.The structure of the activator that obtains is different with the mol ratio of Alkylenediamine or polyalkylenepolyamines raw material and used chlorination acetonitrile and alkylogen, thereby can prepare various activators.

Briefly, when preparing activator of the present invention by raw material Alkylenediamine or polyalkylenepolyamines, at least one in Alkylenediamine or the polyalkylenepolyamines, preferably at least two nitrogen-atoms are converted to the group with structure shown in the following formula:

Compound (b-7)

These compounds are most preferred component (b)

R in the formula ₁, R ₂, R ₃And R ₄Respectively be C _1-6Alkyl, X

Be the organic or inorganic negatively charged ion, n is 1 to 16 integer.

In the new compound of the present invention, R in the formula (b-7) ₁, R ₂, R ₃And R ₄Respectively be C _1-3Alkyl (particularly methyl) and n are that those compounds of 1 to 9 integer are valuable especially.

Adopt for example following method can prepare the compound that the present invention has above-mentioned general formula, even the halogenide of uncle's Alkylenediamine and acetonitrile reacts by the quaternized method of common amine, can easily prepare the compound with above-mentioned general formula, available following reaction is represented:

Compound (b-7) is new, and can be used as textile softeners, static inhibitor, sterilant and bleach-activating agent.

In the present invention, component (b) is easy to attached on the bleaching thing owing to having cation group.In addition, because quaternary nitrogen atoms is electrophilic, so-carbon atom on the CN base is easily positively charged and to having bleached activation.Therefore, component (b) provides the position of bleaching action has taken place, and has strengthened the bleaching efficiency of composition.

Activator of the present invention can be made particle by usual way before adding superoxide.For example, with 5 to 20 parts (weight), preferably one or more tackiness agents of 10 to 100 parts (weight) (at 5 to 60 ℃, particularly 10 to 40 ℃ have flowability) join in the activator of 100 parts (weight), then the mixture that obtains are made particle.

Used tackiness agent can be to be selected from nonionogenic tenside, and as in polyoxyethylene glycol, polypropylene glycol, liquid paraffin and the higher alcohols one or more, these tackiness agents particularly have flowability at 10 to 40 ℃ at 5 to 60 ℃.

According to the used inorganic peracid precursor and the kind of tackiness agent, from ordinary method such as extruder grain, drum granulating or compression granulation, select suitable method to carry out granulation.For example; press the extruder grain method; it is 150 microns or littler organic peracid precursor uniform mixing in common mixing machine that fine grinding is become particle diameter; tackiness agent is progressively added in the precursor of grinding; then fully knead; then, the mixture that will knead adds in the Squeezinggranulator to obtain particle, then screening.Improve particle characteristics if desired, before screening, available average main particle diameter is that 0.1 micron or littler thin inorganic powder (as the SiO 2 powder of pulverizing) are coated on the particle.

The used superoxide of the present invention is preferably hydrogen peroxide or can produces the superoxide of hydrogen peroxide in the aqueous solution.

The example that can produce the superoxide of hydrogen peroxide in the aqueous solution comprises yellow soda ash-superoxide hydrogen adducts, Tri sodium Phosphate-hydrogen peroxide adduct, trisodium phosphate-hydrogen peroxide adduct, urea-hydrogen peroxide adduct, 4Na ₂SO ₄2H ₂O ₂NaCl, Sodium peroxoborate monohydrate, sodium perborate tetrahydrate, sodium peroxide and calcium peroxide, wherein, yellow soda ash-hydrogen peroxide adduct, Sodium peroxoborate monohydrate and sodium perborate tetrahydrate are most preferred.

According to the present invention, the mol ratio of superoxide and specific above-mentioned activator is generally 99.1/0.1 to 20/80, is preferably 99/1 to 50/50.Composition should contain 1 to 99%(weight) component (a).

Except above-mentioned SYNTHETIC OPTICAL WHITNER, bleach detergent compositions of the present invention can contain following component:

[1] tensio-active agent:

(1) straight or branched alkylbenzene sulfonate, wherein the average carbon atom number of moieties is 10-16.

(2) alkyl or alkenyl ether sulfate, wherein the average carbon atom number of straight or branched alkyl or alkenyl is 10-20, on average contain 0.5-8 moles of ethylene oxide, propylene oxide or butylene oxide ring in the molecule, the adding ratio of ethylene oxide/propylene oxide is 0.1/9.9-9.9/0.1, or the adding of ethylene oxide/butylene oxide is than being 0.1/9.9-9.9/0.1.

(3) alkyl or alkenyl sulfate, wherein the average carbon atom number of alkyl or alkenyl is 10-20.

(4) alkene sulfonate, the average carbon atom number in the molecule are 10-20.

(5) alkane sulfonate, the average carbon atom number in the molecule are 10-20.

(6) saturated or unsaturated fatty acid salt, the average carbon atom number in the molecule are 10-24.

(7) alkyl or alkenyl ether carboxylic acid salt, wherein, the average carbon atom number of alkyl or alkenyl is 10-20, on average contain 0.5-8 moles of ethylene oxide, propylene oxide or butylene oxide ring in the molecule, the adding of ethylene oxide/propylene oxide is than being 0.1/9.9-9.9/0.1, and the adding of ethylene oxide/butylene oxide is than being 0.1/9.9 to 9.9/0.1.

(8) have the alpha-sulfo-fatty acid salt or the ester of following general formula:

Wherein Y is C _1-3Alkyl or counter ion, Z are counter ion, and R is C _10-20Alkyl or alkenyl.

The example of the counter ion of anion surfactant can have basic metal (as sodium and potassium) ion, alkaline-earth metal (as calcium and magnesium) ion, ammonium ion, the alkanolamine that contains 1-3 silane alcohol base (containing 2 or 3 carbon atoms) such as the ion of monoethanolamine, diethanolamine, trolamine and tri-isopropanolamine.

(9) have the following amino acid type surfactant that passes through:

No.1

In the formula, R ₁Be C _8-24Alkyl or alkenyl, R ₂Be hydrogen or C _1-2Alkyl, R ₃For amino acid based, X is alkalimetal ion or alkaline-earth metal ions.

No.2

In the formula, R ₁, R ₂Identical with top implication with X, n is the integer of 1-5.

No.3

R in the formula ₁Identical with top implication, m is the integer of 1-8.

No.4

In the formula, R ₁, R ₃Identical with X with top implication, R ₄Represent chlorine, C _1-2Alkyl or hydroxyalkyl.

No.5

R in the formula ₂, R ₃Identical with X with top implication, R ₅Be beta-hydroxy alkyl or beta-hydroxy alkenyl with 6-28 carbon atom.

No.6

R in the formula ₃, R ₅Identical with X with top implication.

(10) phosphate ester surfactants:

№ 1 acid phosphatase alkyl (or alkenyl) ester:

R ' is for having the alkyl or the alkenyl of 8-24 carbon atom in the formula, and n '+m ' is 3, and n ' represents the number of 1-2.

№ 2 alkyl acid phosphates (or alkenyl) ester:

R ' is identical with top implication in the formula, and n "+m " is 3, n " is the number of 1-3.

№ 3 alkyl (or alkenyl) phosphoric acid salt:

R ', n in the formula " with m " are identical with top implication, and M is Na, K or Ca.

(11) the sulfonic acid type amphoterics shown in the following formula:

No.1

R in the formula ₁₁Be C _8-24Alkyl or alkenyl, R ₁₂Be C _1-4Alkylidene group, R ₁₃Be C _1-5Alkyl, R ₁₄Be C _1-4Alkylidene group or hydroxy alkylidene.

No.2

R in the formula ₁₁And R ₁₄Identical with top implication, R ₁₅And R ₁₆Respectively for having the alkyl or the alkenyl of 8-24 or 1-5 carbon atom.

No.3

R in the formula ₁₁And R ₁₄Identical with top implication, n1 is the integer of 1-20.

(12) has the Betaine type amphoterics of following general formula: No.1

No.1

R in the formula ₂₁Be alkyl, alkenyl, β-hydroxyalkyl or the beta-hydroxy alkenyl with 8-24 carbon atom, R ₂₂Be C _1-4Alkyl, R ₂₃Be alkylidene group or hydroxy alkylidene with 1-6 carbon atom.

No.2

R in the formula ₂₁And R ₂₃Identical with top implication, n2 is the integer of 1-20.

No.3

R in the formula ₂₁And R ₂₃Identical with top implication, R ₂₄Be carboxyalkyl or hydroxyalkyl with 2-5 carbon atom.

(13) polyxyethylated or alkenyl ether, wherein the average carbon atom number of alkyl or alkenyl is 10-20, the oxyethane of adding is the 1-30 mole.

(14) polyoxyethylene alkyl phenyl ether, wherein the average carbon atom number of alkyl is 6-12, the oxyethane of adding is the 1-25 mole.

(15) polyoxypropylene alkyl or alkenyl ether, wherein the average carbon atom number of alkyl or alkenyl is 10-20, the propylene oxide of adding is the 1-20 mole.

(16) polyoxy butylene alkyl or alkenyl ether, wherein the average carbon atom number of alkyl or alkenyl is 10-20, the butylene oxide ring of adding is the 1-20 mole.

(17) nonionogenic tenside, the alkyl wherein or the average carbon atom number of alkenyl are 10-20, the oxyethane that adds and the total mole number of propylene oxide or oxyethane and butylene oxide ring are the 1-30 mole, and the ratio of oxyethane and propylene oxide is 0.1/9.9 to 9.9/0.1.

(18) the higher fatty acid alkylolamide of following general formula or its alkylene oxide adduct:

R ' in the formula ₁₁Be alkyl or the alkenyl with 10-20 carbon atom, R ' ₁₂Be H or CH ₃, n3 is the integer of 1-3, m3 is the integer of 0-3.

(19) multitudinous sugar/fatty acid ester comprises that average carbon atom number is lipid acid and the sucrose of 10-20.

(20) fatty acid monoesters comprises that average carbon atom number is lipid acid and the glycerine of 10-20.

(21) has the alkyl amine oxide of following general formula: not

R in the formula ₁₃' for having the alkyl or the alkenyl of 10-20 carbon atom, R ₁₄' and R ₁₅' respectively be C _1-3Alkyl.

(22) have the cats product of following formula:

No.1

In the formula, R ₁', R ₂', R ₃' and R ₄' at least one be alkyl or alkenyl with 8-24 carbon atom, residue is C _1-5Alkyl, X ' are halogen.

No.2

In the formula, R ₁', R ₂', R ₃Identical with X ' with above-mentioned implication.

No.3

In the formula, R ₁', R ₂' identical with X ' with above-mentioned implication, R ₅' be C _2-3Alkylidene group, n are the integer of 1-20.

Composition can contain at least a above-mentioned tensio-active agent, and its content is at least 10%(weight).

Preferred surfactants is above-mentioned tensio-active agent 1), 2), 3), 4), 5), 6), 11) ,-№ 212)-№ 1,13), 14), 15), 17) and 18).

[2] divalent-metal ion sequestrant

Composition can contain 0-50%(weight) one or more are selected from an alkali metal salt of following compounds or the builder component of alkanolamine salt:

1) salt of all kinds of phosphoric acid, the example of these phosphoric acid has former phosphoric acid, tetra-sodium, triphosphoric acid, metaphosphoric acid, hexa metaphosphoric acid and phytinic acid.

2) all kinds of phosphonic salt, these phosphonic examples have ethane-1,1-di 2 ethylhexyl phosphonic acid, ethane-1,1,2-tri methylene phosphonic acid, ethane-1-hydroxyl-1,1-di 2 ethylhexyl phosphonic acid or derivatives thereof, ethane-hydroxyl-1,1,2-tri methylene phosphonic acid, ethane-1,2-dicarboxyl-1,2-di 2 ethylhexyl phosphonic acid and first hydroxyethylidene diphosphonic acid.

3) salt of phosphono-carboxylic acids, the example of these phosphono-carboxylic acids has 2-phosphinylidyne butane-1,2-dicarboxylic acid, 1-phosphinylidyne butane-2,3,4-tricarboxylic acid and Alpha-Methyl phosphonosuccinic acid.

4) amino acid whose salt, these amino acid whose examples have aspartic acid, L-glutamic acid and glycine.

5) salt of amino polyacetic acid, the example of these amino polyacetic acids have nitrilo oxalic acid, iminodiethanoic acid, ethylenediamine tetraacetic acid (EDTA), diethylene triaminepentaacetic acid(DTPA), glycoletherdiaminotetraacetic acid(GEDTA), hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid and dienkolic acid.

6) polymer electrolyte, as polyacrylic acid, poly-equisetic acid, poly-methylene-succinic acid, poly-citraconic acid, poly-fumaric acid, polymaleic acid, poly-methylfumaric acid, poly-alpha-hydroxy vinylformic acid, the polyvinyl phosphonic acids, the sulfonation polymaleic acid, maleic anhydride/diisobutylene multipolymer, maleic anhydride/styrol copolymer, maleic anhydride/methyl ethylene ether copolymer, maleic anhydride/ethylene copolymer, maleic anhydride/ethene cross-linking copolymer, maleic anhydride/vinyl-acetic ester multipolymer, maleic anhydride/acrylonitrile copolymer, maleic anhydride/acrylate copolymer, maleic anhydride/butadienecopolymer, maleic anhydride/isoprene copolymer, gather-the beta-keto carboxylic acid by maleic anhydride and carbon monoxide deutero-, methylene-succinic acid/ethylene copolymer, methylene-succinic acid/equisetic acid multipolymer, methylene-succinic acid/maleic acid, methylene-succinic acid/acrylic copolymer, propanedioic acid/methylene radical multipolymer, methylfumaric acid/fumaric acid multipolymer, ethylene glycol/ethylene terephthalate multipolymer, vinyl pyrrolidone/vinyl acetate copolymer, 1-butylene-2,3,4-tricarboxylic acid/methylene-succinic acid/acrylic copolymer, the polyester polyacetals carboxylic acid that contains ammonium, the cis-isomeride of Epoxysuccinic acid, poly-[N, N-two (carboxymethyl) acrylamide], poly-(hydroxycarboxylic acid), starch succinate, the starch maleic acid ester, the starch terephthalate, starch-phosphate, dicarboxylic acid starch, two carboxymethyl starch and cellulose hemisuccinate ester.

7) non-disassociation macromolecular compound is as polyoxyethylene glycol, polyvinyl alcohol, Polyvinylpyrolidone (PVP) be dissolved in the polyvinyl alcohol of cold water and urethaneization.

8) salt of di-carboxylic acid, the example of these di-carboxylic acid have oxalic acid, propanedioic acid, fourth diester, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, decane-1,10-dicarboxylic acid; The salt of oxyacetic acid, the salt of thioglycolic acid, the salt of the salt of the salt of oxosuccinic acid, hydroxyl disuccinic acid, the salt of carboxymethyl hydroxy succinic acid and carboxymethyl tartronic acid; The salt of hydroxycarboxylic acid, the example of these hydroxycarboxylic acids have oxyacetic acid, oxysuccinic acid, hydroxy new pentane acid, tartrate, citric acid, lactic acid, glyconic acid, glactaric acid, glucuronic acid and dialdehyde starch oxide compound; The salt of following acid: methylene-succinic acid, methylsuccinic acid, 3-methylglutaric acid, 2,2-dimethyl malonic acid, fumaric acid, L-glutamic acid, 1,2,3-propane tricarboxylic acid, equisetic acid, 3-butene-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, ethane tetracarboxylic acid, ethylene-tetracarboxylic acid, positive alkenyl equisetic acid, 1,2,3,4-pentamethylene tetracarboxylic acid, phthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4,5-pyromellitic acid, mellitic acid, tetrahydrofuran (THF)-1,2,3,4-tetracarboxylic acid and tetrahydrofuran (THF)-2,2,5, the 5-tetracarboxylic acid; The salt of sulfonation carboxylic acid, the example of these sulfonation carboxylic acids have sulfo group methylene-succinic acid, sulfo group tricarballylic acid, cysteic acid, sulfoacetic acid and sulfo-succinic acid; Condenses, organic acid salt such as the CMOS of the condenses of the multitudinous sugar of carboxymethylation, lactose and raffinose, carboxymethylated tetramethylolmethane, carboxymethylation glyconic acid, polyvalent alcohol or carbohydrate and maleic anhydride or succinyl oxide, hydroxyl carboxylic acid and maleic anhydride or succinyl oxide and Builder M.

9) silico-aluminate

№ 1 has the crystal aluminosilicate of following formula

X ¹(M ₂' O or M " O) Al ₂O ₃Y ¹(SiO ₂) W ¹(H ₂O)

In the formula, M ' is an alkali metal atom, M, and " be and the tradable alkaline earth metal atom of calcium, X ', Y ' and W ' are the mole number of each component, and be as follows usually: 0.7≤X '≤1.5,0.8≤Y '≤6, W ' is a positive number.

№ 2 has following common detergent builder compound, and this is most preferred:

Na ₂O·Al ₂O ₃·nSiO ₂·wH ₂O

N is the number between the 1.8-3.0 in the formula, and W is the number between the 1-6.

№ 3 has the amorphous silicon aluminate of following formula

x（M ₂O）·Al ₂O ₃·y（SiO ₂）·w（H ₂O）

M is sodium and/or potassium atom in the formula, X, and Y and W represent the mole number of each component respectively, and its scope is as follows: 0.7≤X≤1.2,1.6≤Y≤2.8, W comprises any positive number of zero.

№ 4 has the amorphous silicon aluminate of following formula:

X（M ₂O）·Al ₂O ₃·Y（SiO ₂）·Z（P ₂O ₅）·W（H ₂O）

M is the mole number that Na or K, X, Y, Z and W represent each component respectively in the formula, and its scope is as follows: 0.20≤X≤1.10,0.20≤Y≤4.00,0.001≤Z≤0.80, W comprises any positive number of zero.

[3] alkali or inorganic electrolyte:

Composition also can contain 1-50%(weight), be preferably 5-30%(weight) one or more an alkali metal salts, these salt are selected from the following compounds as alkali or inorganic electrolyte: silicate, carbonate and vitriol.In addition, composition can contain organic bases, as trolamine, diethanolamine, monoethanolamine and tri-isopropanolamine.

[4] anti-redeposition agent

Composition can contain 0.1-5%(weight) one or more as following compounds of anti-redeposition agent: polyoxyethylene glycol, polyvinyl alcohol, Polyvinylpyrolidone (PVP) and carboxymethyl cellulose.

[5] enzyme (this enzyme mainly has enzyme and turns usefulness into when washing).

Can use following enzyme (pressing the classification of enzyme reaction property):

Lytic enzyme, hydratase, oxydo-reductase, desmolase, transferring enzyme and isomerase.All these enzymes all can be used for the present invention.Most preferred enzyme is a lytic enzyme, as proteolytic enzyme, esterase, carbohydrase and nuclease.

Examples of proteases has stomach en-, trypsinase, Quimotrase, collagenase, M-Zyme, elastoser, subtilysin, BPN, papoid, bromeline, Carboxypeptidase A and B, aminopeptidase and Aspergillopeptidase A and B.

The example of ester ester has gastric lipase enzyme, steapsase, vegetable lipase, Phospholipid hydrolase, cholinesterase and Phosphoric acid esterase.

Carbohydrase comprises alkali cellulose enzyme, maltin, sucrase, amylase, polygalacturonase, N,O-Diacetylmuramidase, alpha-glucosidase and beta-glucosidase enzyme.

[6] bluing agent and fluorescent dye:

If desired, can in composition, add various bluing agents and fluorescent dye, for example, recommend to have the compound of following array structure:

With the bluing agent with following general formula:

D represents blueness or red-violet colour residue in the formula, the monoazo-dyes residue, disazo dyes residue or anthraquinone dye residue, each representation hydroxy of X and Y, amino, can be by hydroxyl, sulfonic group, the aliphatics amino that carboxylic acid group or alkoxyl group replace, or can be by halogen, hydroxyl, sulfo group, the carboxylic acid group, aromatics or alicyclic amino that low alkyl group or lower alkoxy replace, R represents hydrogen atom or low alkyl group, but except the following situation: (1) R represents hydrogen atom, X and Y be simultaneously representation hydroxy or alkanol amido, (2) R represents hydrogen atom, a kind of representation hydroxy among X and the Y, and another represents the alkanol amido, n is the integer more than or equal to 2

Bluing agent with following formula:

D represents blueness or red-violet colour residue in the formula, azoic dyestuff residue or anthraquinone dye residue, and X and Y can be identical or different, represent alkanol amido or hydroxyl.

[7] anti-hard caking agent:

In pulverous detergent composition, add following anti-hard caking agent: to benzene methanesulfonic acid salt, the magnesium oxide of the silicon-dioxide of xylyl sulfonate, acetate, sulfosuccinate, talcum, pulverizing, clay, Calucium Silicate powder (as Micro-Cell of Johns-Manvill CO.), lime carbonate.

[8] antioxidant:

Antioxidant comprises for example uncle's fourth hydroxytoluene, 4,4 '-butylidene two (the 6-tertiary butyl-3-cresylol), 2,2 '-butylidene two (the 6-tertiary butyl-4-methylphenol, single vinylbenzene cresols, double styrene cresols, single styrenated phenol, double styrene phenol and 1,1 '-bis(4-hydroxyphenyl) cyclohexane.

[9] adducts of stabilization of peroxide agent and hydrogen peroxide

Can use stablizer in the bleach detergent compositions, comprise magnesium salts, as sal epsom, Magnesium Silicate q-agent, magnesium chloride, magnesium silicofluoride, magnesium oxide and magnesium hydroxide, and silicate are as water glass.

[10] spices and coloured material

Preparation method with reference to component (b) and bleaching composition illustrates the present invention below.Nine kinds of compounds of preparation component (b), I-a and I-b drop in the range of definition of (b-3), II-a and II-b drop in the range of definition of (b-4), III-a and III-b drop on respectively in (b-5) and the range of definition (b-6), (IV-a) and (in the range of definition of IV-b) drop on (b-7), (IV-c) drop in the range of definition of polyalkylenepolyamines compound.

Preparation example 1

Synthesizing of following formula: compound

（Ⅰ-a）

Chloromethyl cyanide is dissolved in 20 milliliters of acetone that are contained in 100 milliliters of three-necked flasks.Do carrier gas with nitrogen and in solution, blast Trimethylamine Anhydrous, stir this solution with magnetic stirrer simultaneously.Blasting Trimethylamine 99 continuously 3 hours so that after the equivalent of Trimethylamine 99 was the normal twice of chloromethyl cyanide, sealed flask at room temperature stirred and spends the night.Cross liquid and isolate the white crystal of generation, obtain 8.93 and digest compound (I-a), productive rate is 95.3%.

Preparation example 2

Synthesizing of following formula: compound

（Ⅰ-b）

In 100 milliliters of two neck flasks that cooling tube is housed, add 20 milliliters of ethanol, 10.7 gram dimethyl octyl group amine are dissolved in this ethanol, then Dropwise 5 .42 gram chloromethyl cyanide.Dropwise, heated mixt in oil bath (temperature is 90 ℃) reacts under the alcohol reflux condition, up to confirming that with the TLC method raw material amine runs out of.The reaction mixture that distillation obtains obtains on 15.76 grams to remove ethanol, and quaternary ammonium salt, productive rate are 99.3%.

Preparation example 3

Synthesizing of following formula: compound

（Ⅱ-a）

6.0 gram acetate 2-dimethylaminoethyls are dissolved in the 20 milligrams per liter acetone that are contained in 100 milliliter of two neck flask.At room temperature in flask, drip 8.6 gram chloromethyl cyanides.The mixture that stirring obtains under this temperature 8 hours, and steaming desolventizes.With acetone thorough washing resistates, steam and remove acetone.Obtain the cation compound of 7.3 gram colorless oil, productive rate is 93%.

Physical properties:

IR（KBr，cm ^-1）

3382，3016，2968，2908，1746，1479，1377，1233，1050

¹H-NMR(CD ₃OD, TMS is as the internal reference thing, δ)

2.48（3H，s），3.83（6H，s），4.25～4.4（2H，t），4.68～4.85（2H，t），5.4（2H，s）

Preparation example 4

Synthesizing of following formula: compound

（Ⅱ-b）

5 gram phenylformic acid 2-dimethylaminoethyls are dissolved in the 20 milligrams per liter acetone that are contained in 100 milliliter of two neck flask.Dropwise 5 .9 chloromethyl cyanide in the flask at room temperature.The mixture that stirring obtains under this temperature 8 hours filters, and obtains white crystal.Use the washing with acetone crystal, drying obtains the colourless crystalline cation compound of 6.17 grams, and productive rate is 89%

Physical properties

mp177-180℃

IR（Kbr，cm ^-1）

3028，2920，1722，1488，1470，1446，1371，1314，1269，1170，1113，1065，1026，975，915，894，708

¹H-NMR(CD ₃OD, TMS is as the internal reference thing, δ)

3.9（6H，s），4.4～4.6（2H，t），5.05～5.25（2H，t），7.8～8.0（2H，d），8.35～8.55（2H，d）

Preparation example 5

Compound (III-a) synthetic

（Ⅲ-a）

10 gram pyridines are dissolved in 20 milliliters of acetone, under agitation in solution, drip 14.3 gram chloromethyl cyanides then.At room temperature the continuously stirring mixture is 8 hours.Obtain the mixture of reaction products of light brown, separating mixture obtains 18.0 and digests compound (III-a), productive rate is 92.3%.

Preparation example 6

Synthetic compound (III-b)

（Ⅲ-b）

10 gram nicotinic acid and 3.4 gram NaO are dissolved in 100 ml methanol that are contained in the flask that is equipped with cooling tube together, in solution, drip 9.2 gram chloromethyl cyanides then.With 80 ℃ oil bath reacting by heating mixture, reaction is 3 hours under the condition of methanol eddy.After steaming desolventizes, recrystallization in methyl alcohol, (III-b), productive rate is 54% to obtain 7.1 gram products.

Preparation example 7

（Ⅳ-a）

Dissolving 20 gram (172 mmole) chloromethyl cyanides at room temperature stir this solution with magnetic stirrer simultaneously in 300 milliliter of two neck flask that return line is housed in 100 milliliters of acetone, in this solution, drip 39 gram (516 mmole) N, N, N ', the solution of N '-Tetramethyl Ethylene Diamine in 100 milliliters of acetone.Dropwise,, reacted 90 minutes, then concentrate and cooling at 90 ℃ of heated mixt.The crystal that filter to collect forms obtains 39.37 and digests compound (I-a), productive rate is 85.6%.

Fusing point: 195～200 ℃ (decomposition)

νKBr（cm ^-1）：

3022，2944，1482，1455，1410，981，918，906，792。

¹H-NMR：

3.52（12H，s），4.33（4H，s），4.95（4H，brs）。

Preparation example 8

（Ⅳ-b）

Except with 57.8 gram (516 mmole) N, N, N ', N '-tetramethyl--1,6-hexanediamine replace repeating to prepare example 7 outside the 39 gram Tetramethyl Ethylene Diamines, and (IV-b), productive rate is 80.3% to obtain the white crystalline compound of 102.8 grams.

Fusing point: 210 to 203 ℃ (decomposition)

^νKBr（cm ^-1）：

2962，2920，1488，1455。

¹H-NMR：

1.05-2.25（8H，m），3.35（12H，s），

3.40-3.80（4H，m），4.75（4H，s）。

Preparation example 9

Compound (IV-c) synthetic

Restrain the amine that following formulas are represented with 100

Be dissolved in 400 milliliters of ethanol that are contained in 1000 milliliters of three-necked flasks that are equipped with cooling tube, in this solution, drip 131.3 gram chloromethyl cyanides.Dropwise, give the mixture heating up that obtains with oil bath (temperature is 90 ℃).The mixture that heating obtains under backflow alcoholic acid condition 24 hours steams and removes ethanol, obtains the quaternary amine of the above-mentioned amine of 177.3 grams, and transformation efficiency is 76.6%.

The example 1 to 8 of composition

As shown in table 1, use organic peracid precursor I-a to prepare bleaching composition 1 to 8 to IV-c, prepare Comparative composition 1 to 4 simultaneously, measure their bleaching action with bleachability or bleaching degree.The results are shown in the table I.

Dipping bleaching action (table 1)

SPC-D being dissolved in 300 milliliters 20 ℃ the water with the preparation activity keto concentration is 0.05% solution.Add promoting agent in solution, it is normal 16 times of contained hydrogen peroxide in the solution that its consumption should make the equivalent of C ≡ N group in the activator, makes bleaching composition thus.5 black tea staining cloth (8 * 8 centimetres) with following method processing were flooded 30 minutes in bleaching composition, wash drying with water.Calculate black tea staining bleaching of cloth rate with following equation:

Bleachability (%)=(reflectivity before the reflectivity-bleaching after the bleaching)/(reflectivity before the reflectivity-bleaching of calico) * 100

Reflectivity in the following formula is by NDR-101DP(Nippon Denshoku kogyo K, and K makes) adopt the colour filter of 460 sodium rice to measure.

The processing of black tea staining cloth is as follows: the black tea of 80 gram NITTOH (yellow packing) is boiled in 3 liters of deionized waters and boils about 15 minutes, filter the mixture of gained by the boil off bleached cotton cloth.#2003 is immersed in the filtrate of acquisition with cotton shirt cloth, boils to boil 15 minutes.Taking-up is immersed in the cloth in the filtrate and placed about 2 hours rapidly.Make the cloth nature airing of acquisition, wash with water to washing lotion and be colourless.The cloth that obtains is dewatered, press to be cut into test size (8 * 8 centimetres).

In table 1, the compound shown in (1) has following general formula:

(2) TAED shown in is tetra acetyl ethylene diamine (production of Hoechst company).(3) compound shown in is produced by Interox company.(4) the bleaching degree shown in is to be 0.05% measured in solution with activity keto concentration.

The example 9 and 10 of composition

Bleaching method:

In the water with 300 milliliters 20 ℃ of hydrogen peroxide addings, so that available oxygen concentration is 0.05.Again toward wherein adding 1 gram yellow soda ash.With the amount that equates with the hydrogen peroxide mole number add in the solution compound (IV-a) or (IV-b), with one as stated above the black tea staining cloth (10 * 10 centimetres) of processing in this solution, flood and bleached in 30 minutes.Wash cloth with water, drying.Calculate bleachability by above-mentioned equation.Be that 0.06% clorox is as evaluating than product with effective chlorine density.Structure is listed in table 2.

The example 11 to 18 of detergent composition

Cation compound shown in SPC-D and the table 3 added contain as the nonionogenic tenside of substrate but do not contain in the solution of heavy duty detergent (can buy from the market) of anion surfactant, contain the detergent solution of composition that table 3 is given with preparation.Down wash the 5 piece black tea staining cloth (8 * 8 centimetre) as stated above processed 10 minute at 20 ℃ with detergent solution in Terg-O-Tometer, wash with water, drying is measured bleachability as stated above.The result lists in the table 3 with the data of Comparative composition 7 to 10.

Example 19

As follows respectively preparation not phosphorous, contain carbamate additives for low phosphorus and contain three kinds of bleaching compositions of a large amount of phosphorus, percentage is by weight.

The phosphorated composition is not prepared by following component: 14% linear sodium laurylsulfonate, 6% polyoxyethylene (10 moles of EO) C _12-13The water glass of alkyl oxide, 2% hard tallow fatty acids sodium salt, 5%2go, 10% yellow soda ash, 25%4A type zeolite, 10% SPC-D, 10% cation compound (IV-a), 2% molecular weight is 6000 polyoxyethylene glycol, 2% proteolytic enzyme, 4% water, and all the other are sodium sulfate.

The composition that contains carbamate additives for low phosphorus is prepared by following component: 10% linear sodium laurylsulfonate, 2% sodium lauryl sulphate, 8% polyoxyethylene (7.7 moles of EO) C _12-13(IV-a), 1% molecular weight are 11000 polyoxyethylene glycol, 1% S-WAT, 2% proteolytic enzyme, 4% water, remaining sodium for the sodium salt of alkyl oxide, 2% hard tallow fatty acids, the water glass of 5%1go, 10% yellow soda ash, 20%4A type zeolite, 15% trisodium phosphate, 10% Sodium peroxoborate, 5% cation compound.

The composition that contains a large amount of phosphorus is prepared by following component: and the sodium salt of 20% polyoxyethylene (8.6 moles of EO) tallow alcohol ether, 2% hard tallow fatty acids, 30% Tri sodium Phosphate, 10% Sodium peroxoborate, 5% cation compound (IV-a), the water glass of 5%2go, 10% yellow soda ash, 1% S-WAT, 2% molecular weight are 6000 polyoxyethylene glycol, 2% proteolytic enzyme, 6% water, and all the other are sodium sulfate.

Table 1

The present invention's contrast

1 2 3 4 5 6 7 8 1 2 3 4

SPC-D 93 89 90 88 92.5 92 93 90 88.5 94 98 100

Ⅰ-a 7 - - - - - - - - - - -

Group

Ⅰ-b - 11 - - - - - - - - - -

Close

Ⅱ-a - - 10 - - - - - - - - -

Thing

Ⅱ-b - - - 12 - - - - - - - -

Ⅲ-a - - - - 7.5 - - - - - - -

Heavy

Ⅲ-b - - - - - 8 - - - - - -

Amount

Ⅳ-a - - - - - - 7 - - - - -

Hundred

Ⅳ-c - - - - - - - 10 - - - -

Divide

Methyl-2-cyano group-pyridine iodide ⁽¹⁾--------11.5---

Rate

TAED ^（2）- - - - - - - - - 6 - -

Single magnesium phthalate of crossing ⁽³⁾----------13-

18.3

Bleaching degree (%) ⁽⁴⁾37.0 35.7 37.3 41.6 40.0 38.7 47.3 44.1 13.2 20.3 21.4

16.3

Table 2

The present invention's contrast

9 10 5 6

H ₂O ₂0.106 0.106 0.106 -

Group is heavy

Ⅳ-a 0.417 - - -

Resultant

Ⅳ-b - 0.505 - -

Thing hundred

NaOCl - - - 0.063

Divide

Na ₂CO ₃0.333 0.333 0.333 -

Rate

NaOH - - - 0.01

The concentration of available oxygen (%) 0.05 0.05 0.05-

The concentration of available chlorine (%)---0.06

Bleaching concentration 77 73 21 63

Claims (3)

1, a kind of bleaching composition, said composition contains (a) hydrogen peroxide or a kind of superoxide that can discharge hydrogen peroxide in the aqueous solution, (b) a kind of organic peracid precursor is 99.9/0.1 to 20/80 with (b) mol ratio (a), and described peracid precursors is at least a in following one group:

X is a kind of negatively charged ion in the formula, R ₁Be C _1-24Alkyl, R ₂And R ₃Respectively be C _1-3Alkyl;

X, R in the formula ₂And R ₃As mentioned above, R ₂₁Be C _1-20Alkyl or phenyl, n are 1 to 3 integer;

X as mentioned above in the formula;

In the formula X as mentioned above, R ₃₁, R ₃₂, R ₃₃And R ₃₄Respectively be C _1-3Alkyl, n ₂It is 1 to 9 integer;

Reaction product with following compounds and chloromethyl cyanide

2, according to the described bleaching composition of claim 1, said composition also contains detergent component.

3, according to the described bleaching composition of claim 1, said composition contains 100 parts (weight) (b) and the particle of the adulterant of 5 to 20 parts of (weight) tackiness agents.