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CN1066194C - Bleach compositions comprising bleach activators and bleach catalysts - Google Patents

Bleach compositions comprising bleach activators and bleach catalysts Download PDF

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Publication number
CN1066194C
CN1066194C CN95193445A CN95193445A CN1066194C CN 1066194 C CN1066194 C CN 1066194C CN 95193445 A CN95193445 A CN 95193445A CN 95193445 A CN95193445 A CN 95193445A CN 1066194 C CN1066194 C CN 1066194C
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Prior art keywords
bleach
composition
valerolactim
bleaching
hexanolactam
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CN95193445A
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CN1149886A (en
Inventor
M·E·伯恩斯
A·D·维里
R·T·哈茨霍恩
L·F·泰勒
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Procter and Gamble Co
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Abstract

Bleaching and cleaning compositions comprising a bleaching compound, one or more bleach activators, and a bleach catalyst. Thus, laundry detergent compositions and automatic dishwashing compositions which comprise perborate, percarbonate and activators such as benzoyl caprolactam exhibit improved stain removal performance in the presence of the bleach catalyst.

Description

The bleaching composition that contains bleach-activating agent and bleaching catalyst
Invention field
The present invention relates to use manganese complex to improve the cleaning and the bleaching composition of performance.The active bleaching of oxygen bleaching, fabric washing, automatic bowl and the sanitizing compositions that have improved are provided.
Background of invention
For the formulator of cleaning combination, comprise that in such composition it is common convention that SYNTHETIC OPTICAL WHITNER such as Sodium peroxoborate or SPC-D is used for its bleaching action.Admit that widely such SYNTHETIC OPTICAL WHITNER removes the ability of various stains and dirt from fabric.With similar method, the formulator of automatic bowl composition has been found that various SYNTHETIC OPTICAL WHITNER can help to remove the tealeaves stain from the bowl dish, protein dirt or the like.Various fabric bleaching agent and/or pre-preserved material composition also comprise percarbonate or perborate bleach.The sanitizer that is used for lavatory, outfall sewer etc. also can contain various SYNTHETIC OPTICAL WHITNER.
Unfortunately, a lot of SYNTHETIC OPTICAL WHITNER can not work under all working conditionss best.As a general suggestion, perborate and percarbonate are more effective in hot water than in cold water.But at present a lot of human consumers carry out fabric washing and other cleaning operation medium to the temperature condition of cold water.For the performance of improved borate and percarbonate bleach, manufacturerss have turned to what is called " bleach-activating agent ".Such activator generally comprises to react to each other with perborate and percarbonate and discharge to produce the organic molecule of " peracid " bleaching species.Bleaching adds under wide water temperature of being combined in of activator and the working conditions works well.
This also is known, and promptly various transition-metal cations (for example manganese) have the ability as bleach-activating agent or catalyst action, supposes because the katalysis of itself and superoxide or peracid bleaching species.Unfortunately, a lot of transition metal are that reaction so easily is so that they destroy bleaching species soon under conventional cleaning condition with crossing compound.Trial with catalysis of manganese positively charged ion and improvement bleaching action has some special problems, because if improper use, ugly brown MnO 2Stain deposition can occur on the surface of being bleached.
Various manganese bleaching catalysts have been advised.United States Patent (USP) 4430243, Bragg have been instructed the bleaching catalyst that uses various sequestrants and manganese positively charged ion and on-catalytic metallic cation mixture.Manganese gluconate catalysis has been described in United States Patent (USP) 4728455.Described SYNTHETIC OPTICAL WHITNER of the prior art does not obtain accepting in commerce.Recently, a series of manganese bleaching catalysts (hereinafter quoting) that relate to the relative complex ligand have been reported.
Have now found that to comprise N-acyl lactam activator or acid amides deutero-activator and bleaching catalyst combination, especially can be used to provide effective improved bleaching action with the metal bleach catalyst combination.
Therefore, the composition of the purpose of this invention is to provide the improvement of using bleach-activating agent and catalyzer washing and bleaching.Another purpose of this paper provides a kind of method of using bleach system of the present invention to remove dirt and stain from fabric and bowl dish.From following open these and other purposes of reaching of this paper as can be seen.
Background technology
In US4634551, described and in detergent for washing clothes, used acid amides deutero-bleach-activating agent.In the people's such as Hodge of October 30 nineteen ninety promulgation US4966723, the another kind of bleach-activating agent that comprises benzoxazine type activator has been described.Reported in the following United States Patent (USP) that manganese uses to strengthen bleaching property with various complex coordination bodies: 4430243; 4728455; 5246621; 5244594; 5284944; 5194416; 5246612; 5256779; 5280117; 5274147; 5153161; 5227084; 5114606; 5114611.Referring to: EP549271A1; EP544490A1; EP549272A1; And EP544440A2.
Summary of the invention
The present invention includes bleaching composition, comprise SYNTHETIC OPTICAL WHITNER, especially a kind of H that is selected from 2O 2, perborate, percarbonate, persulphate and peracid SYNTHETIC OPTICAL WHITNER, one or more bleaching catalysts, the especially metal bleach catalyst of the bleach-activating agent of one or more selections and catalytically effective amount.Preferred compositions comprises percarbonate or perborate bleach, or its mixture and be selected from acyl lactam type activator, acid amides deutero-activator, the bleach-activating agent of benzoxazine type activator and composition thereof.In addition, bleaching composition of the present invention can also contain second bleach-activating agent or be selected from the peracid of tetra acetyl ethylene diamine (TAED), nonanoyl Oxybenzene sulfonate (NOBS) and monoperphthalic acid manganese.
Preferred bleach-activating agent is selected from following material:
A) the following amido deutero-bleach-activating agent of general formula:
Figure 9519344500081
Or its mixture, wherein R 1Be the alkyl that contains 1-14 the carbon atom of having an appointment, aryl or alkaryl, R 2Be the alkylidene group that contains 1-14 the carbon atom of having an appointment, arylidene or alkarylene, R 5Be H or the alkyl that contains 1-10 the carbon atom of having an appointment, aryl or alkaryl and L are leavings groups;
B) the following benzoxazine type bleach-activating agent of general formula:
Figure 9519344500082
R wherein 1Be H, alkyl, alkaryl, aryl, aralkyl, wherein R 2, R 3, R 4And R 5Can be identical or different H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino, the COOR of being selected from 6(R wherein 6Be H or alkyl) and carbonyl functional group's substituting group;
C) the following N-acyl lactam bleach-activating agent of general formula: Wherein n is 0-8, preferred 0-2, and R 6Be H, contain alkyl, aryl, alkoxy aromatic yl or the alkaryl of 1-12 carbon atom, perhaps contain the phenyl (seeing common pending application 08/064,562 and 08/082,270) of the replacement of 6-18 carbon atom; With
, b) and mixture c) d) a).
Preferably the mol ratio of hydrogen peroxide that is generated by peroxy bleaching compound and bleach-activating agent is greater than about 1.0, and most preferably the mol ratio of hydrogen peroxide and bleach-activating agent is at least about 1.5.
Preferred a) type bleach-activating agent is those wherein R 1For containing the alkyl of 6-12 the carbon atom of having an appointment, R 2For containing 1-8 carbon atom and R 5It is the bleach-activating agent of H or methyl.Particularly preferred bleach-activating agent is R in the top general formula 1For containing the alkyl of 7-10 the carbon atom of having an appointment, R 2Those bleach-activating agents that contain 4-5 the carbon atom of having an appointment.
Preferred b) the type bleach-activating agent is R wherein 2, R 3, R 4And R 5Be H and R 1Be those bleach-activating agents of phenyl.
Preferred described c) acyl moiety of type N-acyl lactam bleach-activating agent has formula R 6-CO-, wherein R 6Be H, contain the alkyl of 1-12 the carbon atom of having an appointment, aryl, alkoxy aromatic yl or alkaryl perhaps contain the phenyl of the replacement of 6-18 the carbon atom of having an appointment.In particularly preferred embodiments, R 6Be selected from phenyl unsubstituted or that replace, heptyl, octyl group, nonyl, 2,4,4-trimethylphenyl, decyl and its mixture.
Particularly preferred activator comprises benzoyl caprolactam; the nonanoyl hexanolactam; the benzoyl Valerolactim, nonanoyl Valerolactim, 3; 5; 5-trimethyl acetyl base hexanolactam, 3,5; 5-trimethyl acetyl base Valerolactim; the capryloyl hexanolactam, capryloyl Valerolactim, decanoyl hexanolactam; the decanoyl Valerolactim; the undecanoyl hexanolactam, undecanoyl Valerolactim, (the amino caproyl of 6-decoyl) Oxybenzene sulfonate; (the amino caproyl of 6-nonanoyl) Oxybenzene sulfonate, (the amino caproyl of 6-caprinoyl) Oxybenzene sulfonate and their mixture.The benzoyl lactan of particularly preferred replacement comprises the methyl benzoyl hexanolactam; the methyl benzoyl Valerolactim; ethylamino benzonitrile acyl group hexanolactam; ethylamino benzonitrile acyl group Valerolactim; the propyl group benzoyl caprolactam; propylbenzene formyl radical Valerolactim; the sec.-propyl benzoyl caprolactam; isopropyl benzene formyl radical Valerolactim; the butyl benzoyl caprolactam; butylbenzene formyl radical Valerolactim; tertiary butyl benzoyl caprolactam; tert.-butylbenzene formyl radical Valerolactim; the amyl group benzoyl caprolactam; amylbenzene formyl radical Valerolactim; the hexyl benzoyl caprolactam; hexyl benzene formyl radical Valerolactim; the ethoxy benzonitrile acyl caprolactam; phenetole formyl radical Valerolactim; the propoxy-benzoyl caprolactam; propoxy-benzoyl Valerolactim; isopropoxy benzoyl hexanolactam; isopropoxy benzoyl Valerolactim; the butoxy benzoyl caprolactam; butyl phenyl ether formyl radical Valerolactim; the tert.-butoxy benzoyl caprolactam; tert.-butoxy benzoyl Valerolactim; the pentyloxy benzoyl caprolactam; amyl phenyl ether formyl radical Valerolactim; the hexyloxy benzoyl caprolactam; hexyloxy benzoyl Valerolactim; 2; 4,6-trichlorine benzoyl caprolactam, 2; 4; 6-trichlorobenzene formyl radical Valerolactim, penta fluoro benzene formyl radical hexanolactam, penta fluoro benzene formyl radical Valerolactim; dichloro-benzoyl base hexanolactam; dimethoxy benzoyl hexanolactam, 4-chlorobenzene formacyl hexanolactam, 2; 4-dichloro-benzoyl base hexanolactam; the terephthaloyl dicaprolactam, penta fluoro benzene formyl radical hexanolactam, penta fluoro benzene formyl radical Valerolactim; dichloro-benzoyl base Valerolactim; dimethoxy benzoyl Valerolactim, 4-chlorobenzene formacyl Valerolactim, 2; 4-dichloro-benzoyl base Valerolactim; terephthaloyl two Valerolactims, 4-nitro benzoyl hexanolactam, 4-nitro benzoyl Valerolactim; dinitrobenzoyl hexanolactam, dinitrobenzoyl Valerolactim and its mixture.Particularly preferred bleach-activating agent is selected from benzoyl caprolactam, benzoyl Valerolactim, nonanoyl hexanolactam; the nonanoyl Valerolactim; 4-nitro benzoyl hexanolactam, 4-nitro benzoyl Valerolactim, capryloyl hexanolactam; the capryloyl Valerolactim; the decanoyl hexanolactam, decanoyl Valerolactim, undecanoyl hexanolactam; the undecanoyl Valerolactim; 3,5,5-trimethyl acetyl base hexanolactam; 3; 5,5-trimethyl acetyl base Valerolactim, dinitrobenzoyl caprolactam; the dinitrobenzoyl Valerolactim; the terephthaloyl dicaprolactam, terephthaloyl two Valerolactims, (the amino caproyl of 6-decoyl) Oxybenzene sulfonate; (the amino caproyl of 6-nonanoyl) Oxybenzene sulfonate, (the amino caproyl of 6-caprinoyl) Oxybenzene sulfonate and their mixture.
Preferred compositions is that wherein bleaching catalyst is those compositions of metal-based catalyst herein.
The present invention also comprises detergent composition, and especially detergent for washing clothes comprises conventional tensio-active agent and other the scrubbed component and the bleaching catalyst of SYNTHETIC OPTICAL WHITNER and catalytically effective amount.Have again; SYNTHETIC OPTICAL WHITNER preferably includes and bleach-activating agent in such composition, especially is selected from the N-acyl caprolactam, N-acyl group Valerolactim benzoxazine type activator, amido deutero-activator and their mixture percarbonate together, perborate and its mixture.
The present invention also comprises and contains SYNTHETIC OPTICAL WHITNER, the washing composition of the water-soluble manganese salt of bleach-activating agent and catalytically effective amount or bleaching composition.
The present invention also comprises the method for the bleachability that improves oxygen or peracid bleaching composition, comprises that the manganese positively charged ion with catalytically effective amount adds in the composition in the presence of the ligand of selecting.It provides a kind of from the method for fabric except that stain removal, comprises described fabric is contacted with the water medium that contains described composition.
In the composition and method of this paper, use bleaching catalyst with catalytically effective amount." catalytically effective amount " is meant what the comparison test condition of no matter using is, the amount that all is enough to improve bleaching and removes stain removal from target substrates.Like this, in the fabric washing operation, target substrates generally is the fabric of making dirty with for example stain of various foods.Wash for automatic bowl dishwashing, target substrates can be ceramic cup of making dirty with for example tea dirt or the polyethylene pan of making dirty with tomato soup.Test conditions changes with employed wash type and user's custom.The preceding year washing machine that uses in Europe compared with the American version washing machine of uploading like this, generally will use the less water and the washing composition of higher concentration.Some washing machine needs longer cycles of washing than other washing machines.In the fabric washing operation, some user selects to use very hot water, and other people use warm water even cold water.Certainly, the catalytic performance of bleaching catalyst will be subjected to above-mentioned consideration and the influence of the content of used bleaching catalyst in full formula, and bleaching composition can suitably be regulated.As implementation method (but being not so limited), can regulate the composition of this paper and method so that the active bleaching catalyst of the order of magnitude one of was provided 1,000 ten thousand fens at least in wash water solution, in washing liquid, preferably provide about 0.1ppm-about 700ppm, more preferably from about the catalyzer of 1-500ppm.In order to further specify this point, the order of magnitude of 3 micromolar Mn catalysts is at 40 ℃, pH10, and it is effective using peroxyboric acid and bleach-activating agent (for example benzoyl caprolactam) under the European condition.Under U.S.'s condition, reach equifinality and need improve concentration 3-5 doubly.Compare with the product that does not have Mn catalyst, the bleach-activating agent and the Mn catalyst that use with perborate can make formulator be issued to equal bleaching action at the perborate that uses lower concentration.
Unless stated otherwise, all percentage ratios, ratio and umber are all represented with weight herein.All documents of quoting at relevant portion draw at this and are reference.
Detailed Description Of The Invention
Bleaching catalyst
The bleaching catalyst material that is used for this paper can be forms such as free acid, salt.
One type bleaching catalyst is such catalyst system, it comprises the active heavy metal cation of a kind of given bleach catalyst, as copper, iron or manganese positively charged ion, a kind of have seldom or do not have an active assistant metal positively charged ion of bleach catalyst, as zinc or aluminium cations and a kind ofly have sequestrant, the especially ethylenediamine tetraacetic acid (EDTA) that catalytic metal positively charged ion and assistant metal positively charged ion is had given stability constant, ethylenediamine tetraacetic (methylene phosphonic acid) and its water-soluble salt.This catalyzer is disclosed in the United States Patent (USP) 4430243.
The bleaching catalyst of other types comprises the manganese base complex that is disclosed in United States Patent (USP) 5246621 and 5244594.The preferred example of these catalyzer comprises Mn IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(PF 6) 2, Mn III 2(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(ClO 4) 2, Mn IV 4(u-O) 6(1,4, the 7-7-triazacyclononane) 4-(ClO 4) 4, Mn IIIMn IV 4(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(ClO 4) 3And its mixture.Other description arranged in EP549272.Other the ligand herein that is applicable to comprises 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and its mixture.
The bleaching catalyst that can suitably select to be used for dishwasher composition and concentrated powder detergent composition is used for the present invention.The example of suitable bleaching catalyst is seen United States Patent (USP) 4246612 and 5227084.
Referring to United States Patent (USP) 5194416, it has instructed monokaryon manganese complex (IV) as Mn IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH 3) 3(PF 6).
As disclosed in United States Patent (USP) 5114606, another kind of bleaching catalyst is the manganese (II) of band ligand, the water soluble complex of (III) and/or (IV), and described ligand is the non-carboxylate salt polyol with at least three continuous C-OH groups.Preferred ligand comprises sorbyl alcohol, iditol, melampyrum, mannitol, Xylitol, arabitol, adonitol, meso tetrahydroxybutane, meso-inositol and lactose and its mixture.
United States Patent (USP) 5114611 has been instructed the bleaching catalyst that contains transition metal complex, comprises the Mn, Co, Fe or the Cu that have non--(greatly)-ring ligand.Described ligand as shown in the formula:
R 2?R 3
R 1-N=C-B-C=N-R 4R wherein 1, R 2, R 3And R 4Be selected from H separately, the alkyl of replacement and aryl make each R 1-N=C-R 2And R 3-C=N-R 4Formation five or six membered ring.Described ring can further be substituted.B is selected from O, S, CR 5R 6, NR 7With the bridge bond group of C=O, wherein R 5, R 6And R 7Be selected from H separately, alkyl or aryl comprises group replacement or non-replacement.Preferred ligand comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole ring.Selectable, described ring can be by for example alkyl, aryl, and alkoxyl group, halogen and nitro substituent replace.Particularly preferred ligand is 2,2 '-two pyridyl amine.Preferred bleaching catalyst comprises Co, Cu, Mn, two pyridyl methane of Fe and two pyridyl amine complex.Particularly preferred catalyzer comprises Co (2,2 '-two pyridyl amine) Cl 2, two (different sulfo-cyanato-) two pyridyl amine-cobalts (II), three (bipyridyl amine) cobalt (II) perchlorate, Co (2,2 '-two pyridyl amine) 2O 2ClO 4, two (2,2 '-two pyridyl amine) copper (II) perchlorate, three (two-2-pyridyl amine) iron (II) perchlorate and its mixture.
Other examples comprise manganese gluconate, Mn (CF 3SO 3) 2, Co (NH 3) 5Cl and have four-N-dentate and the double-core Mn complex compound of two-N-dentate ligand comprises N 4Mn III(u-O) 2Mn IVN 4) +[Bipy 2Mn III(u-O) 2Mn IVBipy 2]-(ClO 4) 3
Bleaching catalyst of the present invention also can be by mixing with water-soluble manganese salt water-soluble ligand and preparing by the resulting mixture of evaporation concentration in water medium.Can use any water-soluble manganese salt easily in this article.Manganese (II), (III), (IV) and/or (V) is easy to buy on market.In some cases, in washings, can there be enough manganese, but in general, preferably in composition, adds the Mn positively charged ion and exist with catalytically effective amount to guarantee it.Therefore, the sodium salt of ligand and be selected from MnSO 4, Mn (ClO 4) 2Or MnCl 2The salt of one of (least preferred) is dissolved in the water ligand under neutrality or slight alkalinity pH condition: the mol ratio of Mn salt is about 1: 4-4: 1.Water can be at first by boiling deoxidation and by cooling off with nitrogen-burst agitation.Evaporate resulting solution (if desired, at N 2Need not be further purified bleaching and the detergent composition that is used for herein down) and with resulting solid.
In another kind of mode, with water-soluble manganese source, for example MnSO 4, join in bleaching/cleaning combination or the aqueous bleaching/cleaner bath that comprises ligand.The complex compound of some type obviously forms on the spot, and has guaranteed improved bleachability.In such formation method on the spot, can use the molar weight of ligand to be much higher than the molar weight of manganese expediently, the mol ratio of ligand: Mn is 3: 1-15: 1.Other ligand also can be used to remove the metal ion of variation, for example iron and copper, thus prevent that SYNTHETIC OPTICAL WHITNER from decomposing.A kind of possible such system has been described in EP549271.
Although do not explain the structure of bleach catalyst manganese complex of the present invention, can infer that they comprise sequestrant or other hydration coordination compoundes that is reacted to each other and produced by the nitrogen-atoms with the cationic carboxyl of manganese and ligand.Equally, be not to know the cationic, oxidized attitude of manganese in catalytic process very definitely, it can be (+II), (+III), (+IV) or (+V) valence state.Because ligand has six points and is connected to the manganese positively charged ion, so can infer: can have multinuclear species and/or " cage " structure in the aqueous bleaching medium with having reason.No matter the form of in esse active Mn-ligand species how, thereby it all works with tangible catalytic way and provides improved bleachability to what difficulty was cleaned such as stains such as tea, tomato-sauce, coffee, blood.
Other bleaching catalyst has description in the document below, for example, EP408131 (cobalt complex catalyst), EP384503 and 306089 (catalysis of metalloporphyrin agent), US4728455 (manganese/multidentate ligand catalyzer), US4711748 and EP224952 (manganese that on silico-aluminate, adsorbs), US4601845 (aluminosilicate carrier and zinc or the manganese salt that have manganese), US4626373 (manganese/ligand catalyzer), US4119557 (positive iron complex catalyzer), DE2054019 (cobalt sequestrant catalyzer), CA866191 (salt that contains transition metal), US4430243 (having cationic sequestrant of manganese and on-catalytic metallic cation), and US4728455 (gluconic acid Mn catalyst).
Bleaching compounds and SYNTHETIC OPTICAL WHITNER-should be understood that bleaching catalyst itself does not play SYNTHETIC OPTICAL WHITNER.Or rather, it improves conventional whiteners as catalyzer, particularly as perborate, and percarbonate, the performance of oxygen bleaching agents such as persulphate especially exists under the condition of bleach-activating agent.Therefore, composition herein also contains SYNTHETIC OPTICAL WHITNER or contains the bleaching mixture of SYNTHETIC OPTICAL WHITNER and one or more bleach-activating agents, presents in an amount at least sufficient to provide stain or the bleaching of the stain be concerned about.The content that SYNTHETIC OPTICAL WHITNER is general is that about 1-of detergent composition is about 80%, and it is about 20% to be more typically about 5-, especially for fabric washing.Bleaching and preimpregnation composition can contain the SYNTHETIC OPTICAL WHITNER of the 5-99% that has an appointment.If exist, the amount of bleach-activating agent generally is that about 0.1-is about 60%, is more typically the bleaching mixture that SYNTHETIC OPTICAL WHITNER adds bleach-activating agent that contains of about 0.5-about 40%.
The SYNTHETIC OPTICAL WHITNER that is used for herein can be any fabric washing, hard surface detergent of being used for, or other are at present known or become SYNTHETIC OPTICAL WHITNER in the detergent composition of known cleaning purpose.These SYNTHETIC OPTICAL WHITNER comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Can use perborate bleach herein, for example Sodium peroxoborate (for example list or tetrahydrate).
The preferred peroxygen bleach that uses in composition.Suitable peroxy bleaching agent compound comprises yellow soda ash peroxyhydrate and " percarbonate " SYNTHETIC OPTICAL WHITNER of equal value, trisodium phosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Can use persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE, DuPont industrial production) herein.
Preferred percarbonate bleach comprises that median size is the dried particle of the about 1000mm of about 500-, the described particle that is not more than about 10% (weight) less than about 200mm be not more than the described particle of about 1O% (weight) greater than about 1250mm.Selectively, percarbonate can be used silicate, and borate or water soluble surfactant active apply.Percarbonate can be buied from various commercial source, for example FMC, Solvay and Tokai Denka.
Composition of the present invention also can contain the mixture of bleach-activating agent.
Peroxygen bleach, perborate, preferred and bleach-activating agent such as percarbonate is combined, and this causes producing on the spot the peroxy acid corresponding to bleach-activating agent in aqueous solution (promptly in washing process).
Amido deutero-bleach-activating agent-be used for the present invention's a) type bleach-activating agent is the compound that the amide group of following general formula replaces: Or its mixture, wherein R 1, R 2And R 5Definition can be any suitable leavings group with L as above.Leavings group is that conduct is by crossing any group that from bleach-activating agent be replaced of oxyhydroxide negatively charged ion to the bleach-activating agent nucleophilic attack.Cross hydrolysis reaction and caused the formation of peroxycarboxylic acid, in general, for the group that is suitable for as leavings group, must there be an electronics sucking action in it.It also should form a stable body makes reversed reaction speed to ignore.Help being crossed oxyhydroxide negatively charged ion nucleophilic attack like this.
In the time period of the best (as a cycles of washing), the L group must have enough reactivities to reacting., if the L reactivity is too big, this activator is difficult to stably be used for bleaching composition.These characteristics usually pKa with the conjugate acid of leavings group are relevant.Although known this outside routine.Usually the leavings group that demonstrates described character be the pKa of wherein each conjugate acid in about 3 scopes of about 4-, preferably about 6-is about 11, most preferably from about those groups of 8-about 11.
Preferred bleach-activating agent is those compounds that top general formula is arranged, wherein R 1, R 2And R 5The definition and the L that are same as peroxy acid are selected from following group and its mixture: R wherein 1Be the alkyl that contains about 14 carbon atoms of the 1-that has an appointment, aryl, alkaryl, R 3Be the alkyl chain that contains about 8 carbon atoms of 1-, R 4Be H or R 3Be H or dissolve group with Y.
Preferred dissolving group is-SO 3 -M +,-CO 2 -M +,-SO 4 -M +,-N +(R 3) 4X-, and O＜-N (R 3) 3, most preferably-SO 3 -M +,-CO 2 -M +, R wherein 3It is the alkyl chain that contains about 4 carbon atoms of the 1-that has an appointment, M is the positively charged ion that solubleness is provided to bleach-activating agent, X is the negatively charged ion that solubleness is provided to bleach-activating agent, and preferred, M is a basic metal, the ammonium cation of ammonium and replacement, sodium and potassium are most preferred, and X is a halogen, oxyhydroxide, methylsulfate, or acetic acid anion.It should be noted that the bleach-activating agent that has leavings group (not containing the dissolving group) should be dispersed in the liquid lime chloride well so that help its dissolving.
Preferred bleach-activating agent is that wherein L is selected from those activators of the top general formula of following group:
R wherein 3Define as above, Y is-SO 3 -M +,-CO 2 -M +, wherein the M definition as above.
The example of the bleach-activating agent of preferred above-mentioned general formula comprises (6-decoyl amido caproyl) Oxybenzene sulfonate, (6-nonanoyl amido caproyl) Oxybenzene sulfonate, (6-caprinoyl amido caproyl) Oxybenzene sulfonate and their mixture.
Another kind of important bleach-activating agent (comprising b) type and c) those activators of type) provide organic peracid, as in this article described by open loop as by crossing the result of oxyhydroxide negatively charged ion to cyclocarbonyl carbon nucleophilic attack.For example, at c) described ring-opening reaction in the type activator comprises by the attack to the lactan cyclocarbonyl of hydrogen peroxide or its negatively charged ion.Because hydrogen peroxide or its negatively charged ion preferably occur in outer cyclocarbonyl to the attack of acyl lactam, partly need catalyzer so obtain a significant open loop.The example of another open loop bleach-activating agent can be at b) find in the activator, for example disclosed in United States Patent (USP) 4966723 (people such as Hodge issues on October nineteen ninety 30).
Comprise benzoxazine type activator with following formula by the disclosed this activator compound of Hodge: The benzoxazine that comprises this type replacement R wherein 1Be H, alkyl, alkaryl, aryl, aralkyl, wherein R 2, R 3, R 4And R 5Can be identical, also can be different, be selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino, COOR 6(R wherein 6Be H or alkyl) and the carbonyl functional group.
Preferred benzoxazine type activator is:
When using activator, about 10.5 at about 8.5-with pH, the washing soln of preferred 9.5-10.5 is crossed the superficial bleaching performance that hydrolysis reaction can obtain the best with convenient.Can obtain above-mentioned pH with common known material as buffer reagent, described buffer reagent is the component selected of this paper bleach system.
Another kind of preferred bleach-activating agent comprises the acyl lactam activator, especially as shown in the formula acyl caprolactam and acyl group Valerolactim:
Figure 9519344500181
R wherein 6Be H, the alkyl of about 12 carbon atoms of 1-, aryl, alkoxy aromatic yl or alkaryl perhaps contain the phenyl of the replacement of about 18 carbon atoms of about 6-.Referring to autre action pendante U. S. application 08/064,562 and 08/082,270, this application discloses the benzoyl lactan that replaces.Referring to United States Patent (USP) 4545784 (being presented to Sanderson on October 8th, 1985) (document is incorporated herein by reference), it discloses the acyl caprolactam that is adsorbed on the Sodium peroxoborate, comprises benzoyl caprolactam.
The non-limitative example of other bleach-activating agent-other various activators (selectively containing the bleaching composition that is disclosed in herein) is included in those activators among US4915854 (being presented to people such as Mao April 10 nineteen ninety) and the US4412934.Nonanoyl Oxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activator are general commonly used, also can use its mixture.For other SYNTHETIC OPTICAL WHITNER used herein and activator referring to US4634551.
SYNTHETIC OPTICAL WHITNER-another kind of selectable, but preferred, the SYNTHETIC OPTICAL WHITNER that can unrestrictedly use comprises percarboxylic acids salt SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class reagent comprises monoperoxyphthalic acid manganese hexahydrate (INTEROX), metachloroperbenzoic acid, the manganese salt of 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and diperoxy sebacic acid.Above-mentioned SYNTHETIC OPTICAL WHITNER is disclosed in US4483781 (being presented to Hartman on November 20th, 1984), U.S. Patent application 740446 (people such as Burns applied on June 3rd, 1985), EP0133354 (people such as Banks, on February 20th, 1985 is open), and US4412934 (being presented to people such as Chung November 1 nineteen eighty-three).Particularly preferred SYNTHETIC OPTICAL WHITNER is also included within US4634551 (being presented to people such as Burns on January 6th, 1987) disclosed 6-amino in the ninth of the ten Heavenly Stems-6-oxo and crosses oxy hexanoic acid.
The present invention can also selectively comprise bleaching composition, and this bleaching composition contains the insoluble basically organic peroxide acid with following general formula of significant quantity:
Figure 9519344500191
R wherein 1, R 2, and R 5Definition as top a) type bleach-activating agent.
Bleaching/the cleanup action of excellence of the present invention can realize safely to natural rubber machine part and other natural rubber article (comprising the fabric that contains natural rubber and natural rubber elastomer).And not exclusively understand bleaching mechanism and especially superficial bleaching mechanism.Yet, believe that usually bleach-activating agent has experienced by crossing the anionic nucleophilic attack of oxyhydroxide to form percarboxylic acids, this crosses the oxyhydroxide negatively charged ion is to generate from the hydrogen peroxide of being emitted by peroxygen bleach.This reaction was referred to as hydrolytic action usually.
Acid amides deutero-herein and lactan bleach-activating agent also can with rubber safety, enzyme safety, hydrophilic activator for example TAED be used in combination, usually the weight ratio of acid amides deutero-or caprolactam activators: TAED is 1: 5-5: 1, and preferred about 1: 1.
Binder component
Composition herein can comprise selectively that one or more other detergent additives materials or other help to strengthen cleaning performance, handle the substrate that is cleaned or improve the material of detergent composition aesthetics (for example spices, tinting material, dyestuff etc.).Preferably, binder component should have and SYNTHETIC OPTICAL WHITNER satisfactory stability used herein.Preferably, washing composition herein should be a no boron and without phosphorus.In addition, bowl dish formula optimization is free from chloride.Be the illustrative example of such additive material below.
Washing assistant-detergent builders can selectively be included in herein the composition so that help to control hardness of minerals.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for fabric cleaning composition so that help to remove particulate fouling.
The variation that the content of washing assistant can have broad with end-use and its physical form that needs of composition.When it existed, composition generally contained the washing assistant at least about 1%.Liquid formulations generally contains about 50% (weight) of the 5-that has an appointment, the detergent builders of more general about 5-about 30% (weight).Granular recipe generally contains about 80% (weight) of the 10-that has an appointment, the detergent builders of more general about 15-about 50% (weight).Yet, and do not mean that the washing assistant of the lower or high level of eliminating.
The example of silicate-like builder is an alkalimetal silicate, especially SiO 2: Na 2O is 1.6: 1-3.2: those silicate and the layered silicate of 1 scope, for example lamina sodium silicate in US4664839 (being presented to H.P.Rieck on May 12nd, 1987).NaSKS-6 (being abbreviated as " SKS-6 " herein usually) is the trade mark by the crystalline layered silicate of Hoechst sale.Different with zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na 2SiO 5The layered silicate of morphological form.It can pass through such as preparing in those methods described in DE-A3417649 and the DE-A-3742043.SKS-6 is the layered silicate that highly is preferred for herein, but other such layered silicate for example has general formula NaMSi xO 2x+1YH 2O (wherein M is sodium or hydrogen, and x is 1.9-4, preferred 2 and y be 0-20, preferred 0) those layered silicates can be used for herein.Various other layered silicates that derive from Hoechst comprise as α NaSKS-5, NaSKS-7 and the NaSKS-11 of β and γ form.As mentioned above, δ-Na 2SiO 5(NaSKS-6 form) is most preferably to be used for herein.Also can use other silicate, Magnesium Silicate q-agent for example, it can be as (crispening) agent of curling in granular recipe, as the oxygen bleaching agent stablizer with as the component of foam control system.
The example of carbonate builders is disclosed alkaline-earth metal and a metal carbonate in German patent application number 2321001 (on November 15th, 1973 is open).
The silico-aluminate washing assistant is useful in the present invention.The silico-aluminate washing assistant has very big importance in most popular commercially available heavy dirty granular detergent composition, and also is the important builder component in the liquid detergent formula.The silico-aluminate washing assistant comprises having empirical formula M z(zAlO 2) y] xH 2Those silico-aluminates of O, wherein z and y are at least 6 integer, and the mol ratio of z and y is that about 1.0-about 0.5 and x are the integers of about 15-about 264.
Useful aluminosilicate ion exchange material can buy from the market.These silico-aluminates structurally can be crystalline or unbodied and can be the silico-aluminate or the synthetic of natural formation.A kind of method of producing aluminosilicate ion exchange material is disclosed in US3985669 (being presented to people such as Krummel on October 12nd, 1976).The preferred synthetic crystallization aluminosilicate ion exchange material that is used for herein can Zeolite A, Zeolite P (B), and the title of Zeolite MAP and Zeolite X obtains.In particularly preferred embodiments, the crystal aluminosilicate ion-exchange material has formula Na 12[(AlO 2) 12(SiO 2) 12] xH 2O, wherein x is about 20-about 30, particularly about 27.This material is known as Zeolite A.The zeolite (x=0-10) of dehydration also can be used for herein.Preferably, the particle diameter of silico-aluminate is about 0.1-10 micron.
The organic detergent washing assistant that is applicable to the object of the invention includes, but not limited to various multi-carboxylate's compound." multi-carboxylate " representative of using in this article has a plurality of carboxylate groups, the compound of preferred 3 carboxylate groups.The multi-carboxy acid salt washing agent generally joins in the composition with the form of acid, but form that also can neutral salt adds.When using with the form of salt, basic metal, sodium for example, potassium, and lithium, perhaps alkanol ammonium salts is preferred.
What comprise in the multi-carboxy acid salt washing agent is various types of useful materials.The important multi-carboxy acid salt washing agent of one class comprises the ethers multi-carboxylate, and it is included in disclosed oxidation disuccinate among US3128287 (being presented to Berg on April 7th, 1964) and the US3635830 (being presented to people such as Lamberti on January 18th, 1972).Referring to " TMS/TDS " washing assistant among the US4663071 (being presented to people such as Bush on May 5th, 1987).The ethers multi-carboxylate who is suitable for also comprises ring compound, alicyclic compound especially, and for example at US3923679, those disclosed compound in 3835163,4158635,4120874 and 4102903.
The Citrate trianion washing assistant, for example citric acid and its water-soluble salt (especially sodium salt) are because it is from available and its biological degradability of renewable source, so be the multi-carboxy acid salt washing agent of particularly important for detergent formulation.Citric acid can be used for liquid and granular recipe, particularly is used in combination with aerolite and/or layered silicate washing assistant.The oxidation disuccinate also is useful especially in such composition and mixture.
Lipid acid, for example C 12-C 18Monocarboxylic acid also can join in the composition, individually or with above-mentioned washing assistant, especially Citrate trianion and/or succinate washing assistant in combination so that other washing assistant activity to be provided.Use lipid acid can cause foam to reduce usually like this, this is that formulator should be considered.
Under the operable situation of phosphorus base washing assistant and particularly, can use various alkali metal phosphates, for example tripoly phosphate sodium STPP, trisodium phosphate and the sodium orthophosphate known of people at the strip prescription that is used for hand-washing.
Although sequestrant-can use washing assistant, detergent composition herein preferably do not contain those manganese sequestrants that takes out manganese from the bleaching catalyst complex compound.Especially, phosphonate, phosphoric acid salt and amino phosphonates do sequestrant (for example DEQUEST) preferably are not used in the composition.Yet, the manganese sequestrant of nitrogen base, quadrol-N for example, N '-disuccinate (EDDS) is useful.
Detergent surfactant-content comprises conventional C for the non-limitative example that is used for tensio-active agent herein of about 1-about 55% (weight) usually 11-C 18Alkylbenzene sulfonate (" LAS ") and primary, side chain and C at random 10-C 20Alkyl-sulphate (" AS "), formula CH 3(CH 2) x(CHOSO 3 -M +) CH 3And CH 3(CH 2) y(CHOSO 3 -M +) CH 2CH 3C 10-C 18Secondary (2,3) alkyl-sulphate, x and (y+1) be to be at least 7 wherein, preferably being at least 9 integer and M is water-soluble cationic (especially sodium), unsaturated vitriol is oleyl sulfate for example, C 10-C 18Alkyl alkoxy sulfate (" AE xS ", EO1-7 ethoxy sulfate especially), C 10-C 18Alkyl alkoxy carboxylate salt (especially EO1-5 ethoxy carboxylate), C 10-C 18Glyceryl ether, C 10-C 18Alkyl polyglycoside and its corresponding Sulfated many glycosides, and C 12-C 18The salt of alpha sulfonated fatty acid esters.If desired, Chang Gui nonionic and amphoterics for example comprise the C of so-called narrow peak alkylethoxylate 12-C 18Alkylethoxylate (" AE ") and C 6-C 12Alkyl phenolic alkoxy thing (especially ethoxylate and blended oxyethyl group/propoxy-), C 12-C 18Trimethyl-glycine and sulfonation trimethyl-glycine (" sultaines "), C 10-C 18Amine oxide or the like also can be included in the whole composition.Also can use C 10-C 18N-alkyl polyhydroxy fatty acid amide.General example comprises C 12-C 18N-methyl glucoside acid amides.See WO9206154.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, for example C 10-C 18N-(3-methoxy-propyl) glucose amide.The N-propyl group is to N-hexyl C 12-C 18Glucose amide can be used to reduce whipability.Also can use C 10-C 20Conventional soap class.High if desired whipability can be used the C of side chain 10-C 16Soap.The mixture of negatively charged ion and nonionogenic tenside is useful especially.Other useful tensio-active agent is listed in the standard textbook.
The suitable nonionogenic tenside that is specially adapted to bowl dish is the straight chain alcohol of low bubble or still ethoxylation, for example Plurafac that is provided by Eurane Co. TMRA series, the Lutensol that provides by BASF Co. TMLF series is by Rohm ﹠amp; The Triton that Haas Co. provides TMDF series and the Synperonic that provides by ICI Co. TMLF series.
Clay soil removal/anti deposition agent-composition of the present invention more also can selectively contain and has that clay soil is removed and the amine of the water-soluble ethoxylation of antiredeposition character.The granular detergent composition that contains these compounds generally contains the amine of the water-soluble ethoxylation of the 0.01-that has an appointment about 10.0% (weight); Liquid detergent composition generally contains about 5% (weight) of the 0.01-that has an appointment.
Most preferred soil release and anti redeposition agent are the tetrens of ethoxylation.Illustrative ethoxylated amine also has further description in US4597898 (being presented to VanderMeer on July 1st, 1986).Another organizes preferred clay soil removal-anti redeposition agent is the cation compound that is disclosed in the european patent application 111965 (Oh and Gosselink, on June 27th, 1984 is open).Other operable clay soil removal/anti deposition agent again comprises the amine polymer that is disclosed in the ethoxylation in the european patent application 111984 (Gosselink, on June 27th, 1984 is open); Be disclosed in the amphoteric ion polymer in the european patent application 112592 (Gosselink, on July 4th, 1984 is open); With the amine oxide that is disclosed in US4548744 (Connor, on October 22nd, 1985 issued).Other clay soil removals known in the art and/or anti redeposition agent also can be used for composition herein.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are known in this area.
In the composition of polymeric dispersant-in this article, when especially having zeolite and/or layered silicate washing assistant, it is very favourable using polymeric dispersant with the amount of about 7% (weight) of about 0.1-.Suitable polymeric dispersant comprises polymeric multi-carboxylate and polyoxyethylene glycol, although also can use other polymeric dispersants known in the art.Although bound by theory not, but it is believed that, when with other washing assistants (comprising the lower molecular weight multi-carboxylate) when being used in combination, by suppress crystalline growth, particulate fouling discharges peptization and antiredeposition, polymeric dispersant has strengthened the overall performance of detergent builders.
Polymeric multi-carboxylate material can preferably with its sour form, carry out polymerization or copolymerization and prepare by with suitable unsaturation monomer.The unsaturation monomer acids that can polymerization forms suitable multi-carboxylate polymer comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.There is the polymeric multi-carboxylate in this article or do not contain the monomer fragment of carboxylate groups, ethene methyl ether for example, vinylbenzene, ethene etc. are suitable, are no more than about 40% (weight) but condition is such fragment.
Specially suitable polymeric multi-carboxylate can derive from vinylformic acid.The acrylic acid based polymer that is used for herein like this is the acrylic acid water-soluble salt of polymeric.The preferably about 2000-10000 of the molecular-weight average of the polymkeric substance of sour form like this, more preferably from about 4000-7000 and most preferably from about 4000-5000.The water-soluble salt of such acrylate copolymer can comprise, for example, and basic metal, the ammonium salt of ammonium and replacement.Such water-soluble polymers is known material.For example, the such polyacrylate of use in detergent composition is disclosed in US3308067 (Diehl, on March 7th, 1967 issued).
Vinylformic acid/maleic copolymer also can be as the preferred ingredient of dispersion/anti redeposition agent.Such material comprises the water-soluble salt of vinylformic acid and maleic acid.The preferably about 2000-100000 of the molecular-weight average of the multipolymer of sour form like this, more preferably from about 5000-75000, most preferably from about 7000-65000.About 1: 1 of the segmental ratio of acrylate in such multipolymer and maleate normally about 30: 1-, more preferably from about 10: 1-2: 1.The water-soluble salt of such vinylformic acid/maleic acid can comprise, for example, and basic metal, the ammonium salt of ammonium and replacement.Such water soluble acrylate/maleate is known material, and it has description in european patent application 66915 (December 15 nineteen eighty-two is open).
Another polymeric material that can comprise is polyoxyethylene glycol (PEG).PEG can demonstrate dispersing agent performance and play clay soil removal-anti redeposition agent.The molecular weight ranges that generally is used for this purpose polyoxyethylene glycol is that about 500-is about 100000, and preferably about 1000-is about 50000, and more preferably from about 1500-about 10000.
Also can use polyaspartic acid salts and polyglutamate, especially unite use with zeolite builders.Molecular weight (on average) preferably about 10000 such as the dispersion agent of polyaspartic acid salts.
Enzyme-, for example, comprise the dirt of removing protein-based, carbohydrate-based or triglycerin ester group and prevent the dye transfer that runs off, and, can comprise enzyme in the prescription in this article for fabric recovers for various fabric washing purposes.The enzyme that can add comprises proteolytic enzyme, amylase, and lipase, cellulase, and peroxidase, with and composition thereof.The enzyme that also can comprise other types.They can be any suitable sources, for example plant, animal, bacterium, fungi and yeast source.Yet their selection is by the Several Factors decision, and for example pH is active and/or stable optimization, and thermostability is to the stability of activated detergent, washing assistant etc.In this respect, preferably bacterium and fungal enzyme, for example bacterial amylase and proteolytic enzyme, and fungal cellulase.
Usually to be enough to providing every gram composition up to about 5mg, the amount of the about 3mg of normally about 0.01mg-adds enzyme.Unless stated otherwise, it is about 5% that composition herein contains the 0.001-that has an appointment usually, the commercially available enzyme preparation of preferred 0.01-1% (weight).In described commercial articles, existing proteolytic enzyme amount is enough to provide every gram composition 0.005-0.1Anson unit (AU) activity.
The suitable example of proteolytic enzyme is the subtilysin that obtains from special subtilis and lichem bacillus strain.Another kind of suitable proteolytic enzyme obtains from Bacillus strain, in the scope of pH8-12, has maximum activity, sells by Novo Industries A/S development and with registered trademark ESPERASE.The preparation method of this enzyme and analogue enzyme has been described in the british patent specification 1,243,784 of Novo.Commercially available be applicable to that removing deproteinize is that the proteolytic ferment of main stain comprises Novo Industries A/S (Denmark) with trade name ALCALASE and SAVINASE and International Bio-Synthetics, those that Inc. (Holland) sells with MAXATASE.Other proteolytic enzyme comprise that protease A (sees european patent application 130756, on January 9th, 1985 is open) and proteolytic enzyme B (see that european patent application applied for and european patent application 130756 on April 28th, 87303761.8,1987, people such as Bott, on January 9th, 1985 is open).
Amylase for example comprises the α-Dian Fenmei of describing in british patent specification 1296839 (Novo), and RAPIDASE (International Bio-synthetics, Inc.) and TERMAMYL (Novo Industries).
The plain enzyme of useful fiber comprises bacterium or fungal cellulase in the present invention.Preferably, their best pH is between 5-9.5.
The suitable lipase that is used for the washing composition purposes comprises as disclosed in English Patent 1372034, by the microorganism of pseudomonas, as those lipase of Situ Ci Shi aeruginosa atcc 19.154 productions.Also can be referring to the lipase in Japanese patent application 53,20487 (on February 24th, 1987, special permission was open).Described lipase can be from Amano PharmaceuticalCo.Ltd.Nagoya, and Japan obtains with trade name Lipase P " Amano " (this paper is called " Amano-P ").Other commercially available lipase comprise Amano-CES, and ex Chromobacterviscosum (can be from Toyo Jozo Co., Tagata, Japan as the lipase of Chromobacter viscosum var.lipolyticum NRRLB 3673; Buy); With from US BiochemicalCorp., USA and Disoynth Co., the Chromobacter viscosum lipase that Holland obtains and do not have the lipase of gladiolus pseudomonas.LIPOLASE enzyme that obtain from Humicola lanuginosa and that buy from Novo (can referring to EPO 341947) is to be used for preferred lipase herein.
Peroxidase uses with oxygen source (for example percarbonate, perborate, persulphate, hydrogen peroxide etc.).They are used for " solution bleaching ", promptly prevent to transfer to another substrate from a substrate at dyestuff of removing during the washing operation or pigment in solution.Peroxidase is known in this area, and comprises, for example, horseradish peroxidase, lignoenzyme and halo peroxidase be chloro and bromoperoxidase for example.The detergent composition that contains peroxidase is disclosed in, for example in the PCT International Application No. WO 89/099813 (on October 19th, 1989 is open, and contriver O.Kirk assigns in Novo Industries A/S).
Various enzymes and the method that they are joined in the synthetic detergent composition also are disclosed among the US3553139 (being presented to people such as McCarty on January 5th, 1971).Enzyme also is disclosed among the US4101457 (being presented to people such as Place on July 18th, 1978) and among the US4507219 (being presented to people such as Hughes on March 26th, 1985).Be applicable to that enzyme and its adding in filling a prescription like this in the liquid detergent formula are disclosed among the US4261868 (being presented to people such as Hora on April 14th, 1981).The enzyme that is used for washing composition can be with various consistent.The enzyme stabilization technique open and be illustrated among the US3600319 (being presented to people such as Gedge on August 17th, 1971) and european patent application 0199405 (on October 29th, 1986 is open for application number 86200586.5, Venegas) in.The enzyme stabilising system also is disclosed in, for example among the US3519570.
Enzyme stabilizers-be used for enzyme herein can come stable by the water-soluble sources (it offers enzyme with above-mentioned ion) that has calcium and/or magnesium ion in end formulation.(calcium ion is more effective a little and be preferred in this article than magnesium ion usually, if only use one type of cationic word.) by there being various other stablizer, the especially borates of public technology, can provide other stable: see Severson US4537706.General washing composition, especially liquid washing agent, every liter of final composition comprise that about 1-is about 30, and preferably about 2-is about 20, more preferably from about 5-about 15 and the most preferably from about calcium ion of the about 12mmol of 8-.The amount that this can exist with enzyme and its change a little to calcium or magnesium ion susceptibility.Should select the content of calcium or magnesium ion like this, it makes at the washing assistant that allows in the composition after the complexings such as lipid acid, more a spot of enzyme that can be used for is always arranged.Can use any water miscible calcium or magnesium salts as calcium or magnesium ion source, include, but not limited to calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formiate, and lime acetate, and corresponding magnesium salts.Because the calcium in enzyme slurry and prescription water, so a spot of calcium ion, the about 0.4mmol/l of about usually 0.05-often is present in the composition.In solid detergent composition, prescription can comprise that the water-soluble calcium ion source of q.s is to provide above-mentioned amount in washing liquid.In another selectable method, natural water hardness is just enough.
Should be appreciated that above-mentioned calcium or magnesium ion are enough to provide enzyme stability.More calcium and/or magnesium ion can be joined in the composition so that the greasy other method of removing to be provided.Therefore, as a general suggestion, composition herein generally includes water-soluble calcium or the magnesium ion source of about 0.05-about 2% (weight), perhaps both.Certainly, its amount can change with the type and the amount of the enzyme that uses in composition.
Composition herein also can be selectively, but preferably contain various other stablizers, especially borate type stablizer.Usually, the amount that such stablizer uses in composition is about 0.25-about 10%, preferred about 0.5-is about 5%, and more preferably from about the boric acid of 0.75-about 3% (weight) or other can form the borate compound (is benchmark calculating with boric acid) of boric acid in composition.Boric acid is preferred, although other compounds boron oxide for example, borax and other alkali metal borate (for example just-, partially-and sodium pyroborate, and sodium pentaborate) be suitable for.Also can use the boric acid (for example phenyl-boron dihydroxide, butane boric acid and right-bromophenylboronic acid) of replacement in the place of boric acid.
Gorgeous or the whitening agent of white dyes-any white dyes known in the art or other can be increased joins in herein the detergent composition, and its amount generally is about 1.2% (weight) of about 0.05-.Can be used for commercially available white dyes of the present invention and can be divided into subgroup, it comprises, but is not necessarily limited to stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiophene-5, the 5-dioxide, pyrroles, the derivative of 5-and 6-element heterocycle and other all ingredients.The example of such whitening agent is disclosed in " The Production and Application ofFluorescent Brightening Agent ", M.Zahradnik, Published by Jone Wiley ﹠amp; Sons, New York (1982).
The specific examples that is used for the white dyes of the present composition is those that determine in US4790856 (being presented to Wixon on December 13rd, 1988).These whitening agent comprise the PHORWHITE series whitening agent of Verona.Other whitening agent that are disclosed in the reference comprise: from the Tinopal UNPA that Ciba-Geigy buys, Tinopal CBS, and Tinopal5BM; Artic White CC and Artic WhiteCWD from gondola Hilton-Davis purchase; 2-(4-stryl-phenyl)-2H-naphthols [1,2-d] triazole; 4,4 ' two-(1,2,3-triazoles-2-yl)-stilbenes; 4,4 '-two (stryl) biphenyl; And aminocoumarin.The specific examples of these whitening agent comprises 4-methyl-7-diethyl amino coumarin; 1, two (venz imidazoles-2-yl) ethene of 2-; 1,3-phenylbenzene-phrazolines; 2, the two (benzoxazoles of 5--2-yl) thiophene; The 2-stryl-naphthalene-[1,2-d] oxazole; And 2-(stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.Referring to US3646015 (being presented to Hamilton on February 29th, 1972).The negatively charged ion whitening agent is preferred in this article.
Froth suppressor-the compound that reduces or the inhibition foam forms can be joined in the composition of the present invention.Foam inhibition is particularly important in so-called " high density cleaning process " and in the Europe class washing machine at preceding year.
Can use various materials as froth suppressor, and froth suppressor is known for those skilled in the art.For example, see Kirk Othmer Encyclopedia of ChemicalTechnology, Third Edition, Volume7, pages 430-447 (Jone Wiley ﹠amp; Sons, Inc.1979).The significant especially froth suppressor of one class comprises monocarboxylic acid lipid acid and its water-soluble salt.See US2954347 (being presented to Wayne St.John September 27 nineteen sixty).Monocarboxylic acid lipid acid and its salt as froth suppressor generally have about 24 carbon atoms of 10-, the alkyl of preferred 12-18 carbon atom.The salt that is suitable for comprises an alkali metal salt for example sodium, potassium and lithium salts and ammonium and alkanol ammonium salts.
Detergent composition herein also can contain the nonsurfactant froth suppressor.They comprise, for example, high-molecular-weight hydrocarbons, as paraffin, fatty acid ester (for example, fatty acid glyceryl ester), the fatty acid ester of monovalent alcohol, the C of ester family 18-C 40Ketone (as stearone) or the like.Other froth suppressor comprises the alkylating aminotriazine of N-, for example three-to six-alkyl melanocyte or two-to four-alkyl diamine chlorination triazine, the latter is as the uncle of containing 1-24 carbon atom or the secondary amine of cyanogen muriate and 2 or 3 moles, propylene oxide, with the mono phosphoric acid ester stearate stearic alcohol ester of mono phosphoric acid ester and single stearyl di(2-ethylhexyl)phosphate an alkali metal salt (K for example for example, Na, and Li) and the product that forms of phosphoric acid ester.Can use hydrocarbon for example paraffin and halo paraffin with liquid form.Liquid hydrocarbon is a liquid under room temperature and normal atmosphere, and pour point is-40 ℃ to about 50 ℃ approximately, minimum boiling point low and 110 ℃ (under normal atmosphere).It also is known using wax shape hydrocarbon, and preferably its fusing point is lower than about 100 ℃.Hydrocarbon has constituted the froth suppressor of the preferred detergent composition of a class.For example, the hydrocarbon froth suppressor has description in US4265779 (being presented to people such as Gandolfo on May 5th, 1981).Above-mentioned hydrocarbon comprises saturated and undersaturated aliphatics with about 70 carbon atoms of about 12-, alicyclic, aromatic series and heterocyclic hydrocarbon.The term " paraffin " that is used for this froth suppressor discussion often comprises real paraffin and cyclic hydrocarbon mixture.
Another kind of preferred nonsurfactant froth suppressor comprises the siloxane foams inhibitor.Such comprises the dispersion liquid that uses organopolysiloxane oil (for example polydimethylsiloxane), organopolysiloxane oil or resin or emulsion and organopolysiloxane and organopolysiloxane chemisorption or be melted in the composition of the silica granule on the silica wherein.The siloxane foams inhibitor in this area be know and be disclosed in, for example in US4265779 (being presented to people such as Gandolfo on May 5th, 1981) and the european patent application 893078519 (Starch, M.S.1990 February 7 open).
Other siloxane foams inhibitor is disclosed among the US3455839, and it relates to by adding a spot of polydimethylsiloxane liquid and is used for the composition and the method for aqueous solution froth breaking.
The mixture of siloxanes and silanization silica is disclosed in, for example among the German patent application DOS2124526.Silicone antifoam agent in granular detergent composition and Foam Control are disclosed among US3933672 (people such as Bartolotta) and the US4652392 (people such as Baginski, on March 24th, 1987 issued).
The froth suppressor that is used for illustrative siloxanes herein is the Foam Control of foam inhibition amount, and it is made up of following material substantially:
(ⅰ) viscosity is the polydimethylsiloxane fluid of the about 1500cs of about 20-(25 ℃);
(ⅱ) silicone resin of per 100 parts (i) about 5-about 50 parts (weight), this resin is by (CH 3) 3SiO 1/2Unit and SiO 2The unit is formed, (CH 3) 3SiO 1/2Unit and SiO 2Unitary ratio is about 0.6: about 1.2: 1 of 1-and
(ⅲ) solid silicone of per 100 parts (i) about 1-about 20 parts (weight).
At the preferred siloxane foams inhibitor that is used for herein, with specific polyoxyethylene glycol or polyethylene-polypropylene divalent alcohol copolymers or its mixture (preferably), perhaps polypropylene glycol is made the solvent that is used for external phase.Basic siloxane foams inhibitor is side chain/crosslinked and preferably is non-straight chain.
In order to further specify this point, the general liquid laundry detergent compositions with control foam comprises about 1% (weight) of about 0.001-, preferred about 0.7% (weight) of about 0.01-, the more preferably from about described siloxane foams inhibitor of about 0.5% (weight) of 0.05-; This siloxane foams inhibitor comprises: the nonaqueous emulsion of (1) basic foam reducing composition, it is (a) organopolysiloxane, (b) silicone compounds of arborescens siloxanes or generation silicone resin, (c) finely divided packing material, (d) promote component of mixture (a), (b) with the catalyzer that (c) reacts formation siliconization thing; (2) at least a nonionic siloxane tensio-active agent; (3) polyoxyethylene glycol or at room temperature the solubleness in water greater than about 2% (weight) and polyethylene glycol-propylene glycol copolymers that do not have polypropylene glycol.At particulate composition, can use similar amount in the gel etc.Referring to US4978471 (Starch, issue December 18 nineteen ninety), and US4983316 (Starch, on January 8th, 1991 issued), US5288431 (people such as Huber, on February 22nd, 1994 issued), with US4639489 and US4749740 people such as (, 46 row-4 hurdles, 1 hurdle, 35 row) Aizawa.
Siloxane foams inhibitor herein preferably includes the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, its molecular-weight average all be lower than about 1000, preferably between about 100-800.The polyoxyethylene glycol herein and the multipolymer of the polyethylene/polypropylene glycol at room temperature solubleness in water are greater than about 2%, are preferably greater than about 5% (weight).
Preferred solvent herein is a molecular-weight average less than about 1000, more preferably between about 100-800, and the multipolymer of polyoxyethylene glycol between about 200-400 and polyethylene/polypropylene glycol most preferably, preferred PPG200/PEG300.Polyoxyethylene glycol preferably: the weight ratio of the multipolymer of polyethylene/polypropylene glycol is 1: 1-1: between 10, most preferably 1: 3-1: between 6.
The preferred siloxane foams inhibitor that is used for does not herein contain polypropylene glycol, and especially molecular weight is 4000 polypropylene glycol.They preferably do not contain the segmented copolymer of oxyethane and propylene oxide yet yet, as PLURONICL101.
Other be used for herein froth suppressor comprise secondary alcohol (for example 2-alkyl alcohol) and above-mentioned alcohol and silicone oil (for example be disclosed in US4798679,4075118 and EP150872 in siloxanes) mixture.Secondary alcohol comprises having C like this 1-C 16The C of chain 6-C 16Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and it can obtain with trade name ISOFOL12 from Condea.The mixture of secondary alcohol obtains with trade name ISALCHEM123 from Enichem.The blended froth suppressor generally comprises the mixture of alcohol+siloxanes, and its weight ratio is 1: 5-5: 1.
For the detergent composition that is used for automatic washing machine, should not form and make it overflow the foam of washing machine degree.When it used, froth suppressor preferably existed with " foam inhibition amount "." foam inhibition amount " is meant that the formulator of composition can select the amount of Foam Control to make and be enough to the low foam laundry washing composition that the control foam result is formed for automatic washing machine.
Composition herein generally includes the froth suppressor of 0-about 5%.When monocarboxylic acid lipid acid and salt thereof during as froth suppressor, 5% (weight) of the general as many as detergent composition of the amount of its existence.The preferred fatty monocarboxylate froth suppressor that uses about 0.5-about 3%.The usage quantity of siloxane foams inhibitor generally is 2.0% (weight) of as many as composition, although also can use higher amount.This upper limit is that nature exists, basically because relevant with the efficient that keeps the minimum and low amount of cost to control whipability effectively.The preferably about 0.01-of amount of the siloxane foams inhibitor that uses is about 1%, and more preferably from about 0.25-about 0.5%.As employed in this article, these weight percent numerical value comprise any silica that can be used in combination with organopolysiloxane, and operable any additives.The amount of normally used mono phosphoric acid ester stearyl ester froth suppressor is between about 2% (weight) of about 0.1-of composition.The amount of the general hydrocarbon froth suppressor that uses is that about 0.01-is about 5.0%, although can use higher amount.The amount of the general pure froth suppressor that uses is about 3% (weight) of about 0.2-of the finished product composition.
Fabric softener-in composition of the present invention, can selectively use various fabric softeners by washing, especially US4062647 (Storm and Nirschl, on December 13rd, 1977 issued) in the particulate montmorillonitic clay, and other softening agent clays known in the art, general its amount is about 10% (weight) of about 0.5-, so that the fabric softener that has fabric washing at present benefit to be provided.The clay softening agent can be disclosed in, for example amine and the cationic softener of US4375416 (people such as Crisp, issue March 1 nineteen eighty-three) and US4291071 (people such as Harris, on September 22nd, 1981 issued) are used in combination.
Dye transfer inhibitor-composition of the present invention can comprise that also one or more transfer to the effective material of another kind of fabric to suppressing dyestuff from a kind of fabric in washing process.Usually, such dye transfer inhibitor comprises polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, magnesium phthalocyanine, peroxidase and its mixture.If you are using, the amount of these reagent generally is about 10% (weight) of about 0.01-of composition, about 5% (weight) of preferably about 0.01-and about 2% (weight) of 0.05-more preferably from about.
More specifically, be preferred for the structural unit that herein polyamine N-oxide pllymers contains following formula: R-A x-P; Wherein P is a polymerizable unit, and the N-O group can be connected on the polymerizable unit or the N-O group can form polymerizable unit a part or N-O group can be connected on both; A is one of following structure :-NC (O)-and ,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; With R be aliphatic series, the aliphatic series of ethoxylation, aromatic series, heterocycle or alicyclic group or its combination, the nitrogen-atoms of N-O group can be connected thereto or the N-O group is the part of these groups.Preferred polyamine N-oxide polymer is that wherein R is a heterocyclic group, pyridine for example, pyrroles, imidazoles, pyrroline, piperidines and its derivative.
The N-O group can be represented by following general formula: R wherein 1, R 2, R 3Be aliphatic series, aromatic series, heterocycle or alicyclic group or its combination, x, y and z are 0 or 1; The nitrogen-atoms of N-O group can connect or form the part of any above-mentioned group.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferred pKa＜7, more preferably pKa＜6.
Can use any polymer backbone, as long as the amine oxide polymers that forms is water miscible and has the dyestuff inhibition activity.The example of suitable polymeric skeleton is a polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and its mixture.These polymkeric substance comprise that wherein a kind of monomer type is that amine n-oxide and other monomer types are random or block polymers of N-oxide compound.The amine of amine n-oxide polymkeric substance and the ratio of amine n-oxide are 10: 1-1: 1000000.Yet the quantity that is present in the amine oxide group in the polyamine oxide polymer can change by suitable copolymerization or by suitable N-oxidisability.Can obtain polyoxygenated amine with almost any polymerization degree.Usually, molecular-weight average is in the scope of 500-1000000; More preferably 1000-500000; 5000-100000 most preferably.
The most preferred polyamine N-oxide that is used for this paper detergent composition is poly-(4-vinylpridine-N-oxide compound), its molecular-weight average be about 50000 and the ratio of amine and amine n-oxide be about 1: 4.
The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being referred to as " PVPVI " class) also is preferred for herein.Preferably, the average molecular weight range of PVPVI is about 5000-1000000, more preferably 5000-200000 and most preferably 10000-20000.(average molecular weight range is by as people such as Barth, Chemicai Analysis, Vol113 " Modern Methods of Polymer Characterization ", described in scattering of light determine.The disclosed content of this article is incorporated herein by reference.) the N-vinyl imidazole of PVPVI multipolymer and the mol ratio of N-vinyl pyrrolidone generally be 1: 1-0.2: 1, more preferably 0.8: 1-0.3: 1, most preferably 0.6: 1-0.4: 1.These multipolymers can be straight chain also can be side chain.
The present composition also can use molecular-weight average about 400000 for about 5000-, preferably about 5000-about 200000 and the Polyvinylpyrolidone (PVP) of 5000-about 50000 (" PVP ") more preferably from about.PVP is known for the technician of detergent applications; See, for example, EP-A-262897 and EP-A-256696 (being incorporated herein by reference).It is about 100000 for about 500-that the composition that contains PVP also can contain molecular-weight average, the polyoxyethylene glycol of preferably about 1000-about 10000 (" PEG ").Preferably, the ratio of PEG and PVP (to be released in the ppm in the washings) is about 2: about 50: 1 of 1-, more preferably from about 3: about 10: 1 of 1-.
Detergent composition herein also can selectively contain the 0.005-5% that has an appointment (weight) particular type also provide dye transfer inhibiting hydrophilic white dyes.If you are using, composition herein preferably includes the white dyes of about 0.01-1% (weight).
The hydrophilic white dyes that is used for the present invention is those compounds with following structural formula:
Figure 9519344500331
R wherein 1Be selected from anilino, N-2-pair-hydroxyethyl and NH-2-hydroxyethyl; R 2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; With M be for example sodium or potassium of the salifiable positively charged ion of shape.
As the R in following formula 1Be anilino, R 2Be N-2-two-hydroxyethyl and M are during such as the positively charged ion of sodium, this whitening agent is 4,4 ' ,-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 ' stilbene disulfonic acid and disodium salt.This specific whitening agent is sold by Ciba-Geigy Corporation with trade name Tinopal-UNPA-GX.Tinopal-UNPA-GX is the hydrophilic white dyes that is preferred for detergent composition herein.
As the R in following formula 1Be anilino, R 2Be N-2-hydroxyethyl-N-2-methylamino and M when being positively charged ion such as sodium, this whitening agent is 4,4 ' two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 ' stilbene disulfonic acid disodium salt.This specific whitening agent is sold by Ciba-Geigy Corporation with trade name Tinopal-5BM-GX.
As the R in following formula 1Be anilino, R 2Be morpholino and M when being positively charged ion such as sodium, this whitening agent is 4,4 ', and-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino] 2,2 ' stilbene disulfonic acid, sodium salt.This specific whitening agent is sold by Ciba-Geigy Corporation with trade name Tinopal-AMS-GX.
Specific selection is used for white dyes of the present invention when being used in combination with the previously described polymeric dye transfer inhibitor of selecting, and special dye transfer rejection effect is provided.Compare with these the two kinds of detergent composition components when using separately, the polymeric material of above-mentioned selection (for example, PVNO and/or PVPVI) with the white dyes of above-mentioned selection (for example, TinopalUNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) be combined in and provide in the aqueous cleaning solution obviously preferably that dye transfer suppresses.Bound by theory not, we believe that above-mentioned whitening agent works by this way, promptly because they have high affinity to fabric in washings, so they are deposited on these fabrics relatively soon.The degree that whitening agent is deposited on the fabric in the aqueous solution can be with the parameter-definition that is referred to as " consumption coefficient ".In general consumption coefficient is whitening agent material and the b that a) is deposited on the fabric) ratio of initial whitening agent concentration in washings.The whitening agent that has high relatively consumption coefficient in the context of the present invention is suitable for most being used for suppressing dye transfer.
Certainly, should be appreciated that, in the present composition, also can optionally use the compound of other conventional white dyes types " to brighten " benefit so that conventional fabric to be provided, rather than the effect that provides real dye transfer to suppress.Such use is conventional with known for detergent formulation.
Can contain various other components that are used for detergent composition in the composition of other components-in this article, comprise other active ingredients, carrier, hydrotropic agent, processing aid, dyestuff or pigment, the solvent that is used for liquid formulations is used for the filler of bar compositions, or the like.High if desired whipability can be with foam secondary accelerator C for example 10-C 16Alkanolamide joins in the composition, and its amount generally is 1-10%.C 10-C 14Monoethanolamine and diglycollic amide have illustrated the foam secondary accelerator of this typical types.It also is very favourable that the additive tensio-active agent of above-mentioned foam secondary accelerator and high whipability (for example above-mentioned amine oxide, trimethyl-glycine and sulfonation trimethyl-glycine) uses together.If desired, can add its amount generally is the solubility magnesium salts of 0.1-2%, for example MgCl 2, MgSO 4, or the like, remove greasy performance other foam to be provided and to strengthen.
The various scrubbed component that are used for this composition can apply described matrix with hydrophobic coating and further stablize then by described component is adsorbed on porous hydrophobic matrix.Preferably, scrubbed component is mixed with tensio-active agent before being adsorbed porous matrix into.In use, scrubbed component is discharged into the aqueous washings from matrix, finishes its predetermined washing function in the aqueous solution.
In order to illustrate in greater detail this technology, with the porous hydrophobic silex (trade name SIPERNATD10, Degussa) with contain 3-5%C 13-15The protein enzyme solution of ethoxylated alcohol (EO7) nonionogenic tenside mixes.Usually, enzyme/surfactant soln is 2.5 times (weight) of silica.The powder dispersed with stirring of gained is in silicone oil (can use the various silicone oil of range of viscosities as 500-12500).Gained the silicone oil dispersion liquid emulsified or be added in addition in the last washing composition matrix.By this method, such as above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent; bleaching catalyst, light activating agent, dyestuff; fluorescent agent, the component of fabric conditioner and hydrolyzable tensio-active agent can be " protected " and be used for washing composition, comprise liquid laundry detergent compositions.
Liquid detergent composition can contain water and other solvents as carrier.Low-molecular-weight uncle or secondary alcohol (use methyl alcohol, ethanol, propyl alcohol and Virahol illustrate) be suitable for.Single hydroxy alcohol is preferred for the dissolving tensio-active agent, but also can use polyvalent alcohol, for example contains those alcohol (for example 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol) of about 6 carbon atoms of 2-and about 6 hydroxyls of 2-.Said composition can contain 5-90%, the above-mentioned carrier of general 10-50%.
The preferred preparation like this of detergent composition herein, it makes that the pH of during moisture cleaning operation washings is about 11 at about 6.5-, between preferably about 7.5-about 10.5.Automatically wash the preferred pH of dish formula for a product between about 8-about 11.Laundry product generally is pH9-11.The technology that pH is controlled at the recommendation usage quantity comprises the use buffer reagent, alkali, and acid or the like, and those skilled in the art know.
The following examples illustrate according to composition of the present invention, but do not plan to be limited to these examples.
Embodiment 1
A kind of dry-cleaning clothing SYNTHETIC OPTICAL WHITNER is as follows: component % (weight) SPC-D 20.0 benzoyl caprolactam activator 10.0Mn-catalyzer *0.1 water soluble filler *Equal amount
*As US5246621 and 5244594 described Mn IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(PF 6) 2
*Yellow soda ash, sodium silicate mixture (1: 1).
In above-mentioned composition, SPC-D can be replaced by the perborate of equivalent.
In above-mentioned composition, bleaching catalyst can be replaced by the following catalyzer of equivalent:
Mn III 2(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(ClO 4) 2, Mn IV 4(u-O) 6(1,4, the 7-7-triazacyclononane) 4-(ClO 4) 4, Mn IIIMn IV 4(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(ClO 4) 3, Mn IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(OCH 3) 3(PF 6) 2Co (2,2 '-two pyridyl amine) Cl 2, two (different sulfo-cyanato-) two pyridyl amine-cobalts (II), three (bipyridyl amine)-cobalt (II) perchlorate, Co (2,2 ' two pyridyl amine) 2O 2ClO 4, two (2,2 ' two pyridyl amine) are with (II) perchlorate, three (two-2-pyridyl amine) iron (II) perchlorate, manganese gluconate, Mn (CF 3SO 3) 2, Co (NH 3) 5Cl has the double-core Mn complex compound of four-N-dentate and two-N-dentate, comprises N 4Mn III(u-O) 2Mn IVN 4) +[Bipy 2Mn III(u-O) 2Mn IVBipy 2]-(CiO 4) 3With its mixture.
In addition, in above-mentioned composition, bleach-activating agent can be replaced by the following bleach-activating agent of equivalent:
The benzoyl Valerolactim; the nonanoyl hexanolactam, nonanoyl Valerolactim, 4-nitro benzoyl hexanolactam; 4-nitro benzoyl Valerolactim; the capryloyl hexanolactam, capryloyl Valerolactim, decanoyl hexanolactam; the decanoyl Valerolactim; the undecanoyl hexanolactam, undecanoyl Valerolactim, 3; 5; 5-trimethyl acetyl base Valerolactim, 3,5; 5-trimethyl acetyl base Valerolactim; the dinitrobenzoyl hexanolactam, dinitrobenzoyl Valerolactim, terephthaloyl dicaprolactam; terephthaloyl two Valerolactims; (the amino caproyl of 6-decoyl) Oxybenzene sulfonate, (the amino caproyl of 6-nonanoyl) Oxybenzene sulfonate, (the amino caproyl of 6-caprinoyl) Oxybenzene sulfonate and their mixture.
The composition self that can use embodiment 1 is as SYNTHETIC OPTICAL WHITNER, perhaps it can be joined the preimpregnation composition or contains in the detergent composition of tensio-active agent to give its bleaching benefit.
In the laundry detergent composition hereinafter, abbreviation component symbol has following meaning:
LAS-C 12Sodium alkyl benzene sulfonate
TAS-tallow alkyl sodium sulfate
TAE n-with the tallow alcohol of the oxyethane ethoxylation of every mol of alcohol n mole
The 25EY-C of the ethylene oxide condensation of average out to Y mole 12-15It mainly is the primary alconol of straight chain
The TAED-tetra acetyl ethylene diamine
NOBS-nonanoyl Oxybenzene sulfonate
Silicate-unbodied water glass (is followed SiO usually 2: Na 2The O ratio)
The NaSKS-6-crystalline layered silicate
Carbonate-unbodied yellow soda ash
The CMC-Xylo-Mucine
Zeolite A-primary particle diameter scope is the sodium silicoaluminate of the hydration of 1-10 micron
Polyacrylic acid-Mw tIt is 4000 acrylate homopolymer
Citrate trianion-citrate trisodium dihydrate
Ma/AA-1: toxilic acid/acrylic copolymer of 4, molecular-weight average about 80000
The mixing protease and the amylase of enzyme-sell by Novo Industries AS
Whitening agent-4,4 ' ,-two (2-morpholino-4-anilino-S-triazine-6-base is amino) stilbene-2,2 '-disulfonic acid disodium
Froth suppressor-25% paraffin (Mpt50 ℃), 17% hydrophobic silex, 58% paraffin oil vitriol-anhydrous sodium sulphate
When being used for the fabric cleaning, use said composition with the mode of routine and conventional concentration.Therefore, in typical method, put into said composition liquid, aqueous and stir dirty fabric, its concentration can be the about 10000ppm scope of about 100-, depends on the soil loading amount.
The embodiment II
Prepare following detergent composition (parts by weight)
A B C D ELAS 7.71 7.71 7.71 7.71--AS--------6.80N-glucose amides--------1.50TAS 2.43 2.43 2.43 2.43 2.43TAE11 1.10 1.10 1.10 1.10 1.1025E3 3.26 3.26 3.26 3.26 3.26 Wessalith CSs 19.50 19.50 19.50 13.00 13.00 citrates 6.50 6.50 6.50----MA/AA 4.25 4.25 4.25 4.25 4.25NaSKS-6------10.01,10.01 citric acids------2.73 2.73TEA50------0.26 0.26 carbonate 11.14 11.14 6.00 9.84 4.00 perborate 16.00 16.00 18.00 16.00 16.00 benzoyl caprolactams 10.00 3.00 10.00 5.00 15.00TAED----0.00 5.00 0.00NOBS--3.00------Mn catalyst*0.50 1.00 0.22 0.02 0.22CMC, 0.48 0.48 0.48 0.48 0.48 froth suppressor 0.5 0.5 0.5 0.5 0.5 whitening agent, 0.24 0.24 0.24 0.24 0.24 enzyme, 1.4 1.4 1.4 1.4 1.4 silicate (2.0 ratio) 4.38 4.38 4.38----MgSO 40.43 0.43 0.43 0.43 0.43 spices, 0.43 0.43 0.43 0.43 0.43 vitriol 4.10 4.10 4.10 11.67 11.67
Water and various other material are to balance
*Mn IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(PF 6) 2,
Above-mentioned composition can obtain modification by adding lipase.
Above-mentioned composition can be by substituting further modification with this bleaching catalyst with the bleaching catalyst of pointing out of equivalent in the embodiment I.
Above-mentioned composition also can be by substituting further modification with benzoyl caprolactam with the bleach-activating agent of pointing out of equivalent in the embodiment I.
Above-mentioned composition also can substitute or pass through the further modification of removal TAED in prescription by the NOBS that TAED is used equivalent.
Above-mentioned composition also can substitute further modification by perborate being used the percarbonate of equivalent.
The embodiment III
The laundry bars that has SYNTHETIC OPTICAL WHITNER be by standard the pressing method preparation and comprise: C 12-13LAS (20%); Tripoly phosphate sodium STPP (20%); Water glass (7%); SPC-D monohydrate (10%); (the amino caproyl of 6-caprinoyl) Oxybenzene sulfonate (10); Mn IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(PF 6) 2(1.0%), MgSO 4Or talc filler; And water (5%).
Above-mentioned composition can obtain modification by adding lipase.
Above-mentioned composition can be by substituting further modification with this bleaching catalyst with the bleaching catalyst of pointing out of equivalent in the embodiment I.
Above-mentioned composition also can be by substituting further modification with (the amino caproyl of 6-caprinoyl) Oxybenzene sulfonate bleach-activating agent with the bleach-activating agent of pointing out of equivalent in the embodiment I.
Above-mentioned composition also can substitute further modification by perborate being used the percarbonate of equivalent.The embodiment IV
A kind of automatic bowl composition is as follows: component % (weight) trisodium citrate 15 yellow soda ash 20 silicate 19 nonionogenic tensides 23 sodium polyacrylates (m.w. 4000) 35Termamyl enzyme (60T) 1.1Savinase enzyme (12T) 3.0 Sodium peroxoborate monohydrates 10 benzoyl caprolactam 2Mn catalyzer 40.03 small powder equal amount
1BRITESIL，PQ?Corporation
2Polyethylene/polypropylene oxides is hanged down pore forming material
3ACCUSOL,Rohm?and?Haas
4The Mn positively charged ion of 1: 1 mol ratio and ligand are to form Mn on the spot IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(PF 6) 2
In above-mentioned composition, perborate can substitute with the percarbonate of equivalent.
In above-mentioned composition, bleaching catalyst can substitute to be formed on the bleaching catalyst of pointing out in the embodiment I with the bleaching catalyst that works (as pointing out in the embodiment I) of equivalent or with metallic cation and ligand.
In above-mentioned composition, also can be by benzoyl caprolactam is substituted further modification with the bleach-activating agent of pointing out of equivalent in the embodiment I.
In above-mentioned composition, what tensio-active agent also can be by equivalent is any low foaming, and nonionogenic tenside replaces.The straight chain alcohol of low bubble or still ethoxylation, for example P1urafac that is provided by Eurane Co. are provided example TMRA series, the Lutensol that provides by BASF Co. TMLF series is by Rohm ﹠amp; The Triton that Haas Co. provides TMDF series and the Synperonic that provides by ICI Co. TMLF series.
The automatic bowl composition can be a particle, sheet, bar, or the form of rinse aid.Make particle, sheet, bar, or the method for rinse aid is known in the art.Referring to, for example the United States Patent (USP) sequence number 08/106022,08/147222, and 08/147224,08/147219,08/052860,07/867941.
All above-mentioned particulate compositions can be used as spray-dired particle or high-density (greater than 600g/1) particle or agglomerate and provide.If desired, the Mn catalyzer can be adsorbed on the water-soluble granular and among keeping the catalyzer and the equilibrium composition of composition to be separated, stablizing in addition when storage is provided like this.Such particle (it should not contain oxidable component) can comprise, for example, and water-soluble silicate, carbonate or the like.
Although above-mentioned composition is the typical case who is used for herein, most preferably: (1) said composition does not contain the STPP washing assistant; (2) nonionogenic tenside: the ratio of anion surfactant is greater than 1: 1, preferably is 15: 1 at least; (3) in composition, there are 1% perborate or other chlorine scavenger at least so that the MnO that forms in using 2Minimum.
Although the foregoing description illustrated present technique and has been used in laundry and the application of the cleaning/bleaching composition that uses of washing the dishes,, herein the catalytically bleaching system of the it should be appreciated by those skilled in the art that occasion that will improve oxygen bleaching of can in officely what is the need for is used.Therefore, occasion is used technology of the present invention, for example bleached pulp below, the bleaching hair, the utensil of the cleaning and the non-protein-based of sterilizing is artificial tooth for example, and in dentifrice composition, clean tooth and kill oral cavity bacterium, and can be in any other occasion of bleaching benefit to the user.

Claims (8)

1. detergent composition, one or more that comprise catalytically effective amount contain the bleaching catalyst of transition metal, a kind of bleaching compounds and one or more bleach-activating agents that can in liquid, aqueous, produce hydrogen peroxide, wherein said bleach-activating agent is selected from:
A) the following acid amides deutero-bleach-activating agent of general formula: Or its mixture, wherein R 1Be the alkyl that contains 1-14 carbon atom, aryl or alkaryl, R 2Be alkylidene group, arylidene or the alkarylene that contains 1-14 carbon atom, R 5Be H or the alkyl that contains 1-10 carbon atom, aryl or alkaryl and L are leavings groups;
B) the following benzoxazine type bleach-activating agent of general formula:
Figure 9519344500022
R wherein 1Be H, alkyl, alkaryl, aryl, aralkyl, wherein R 2, R 3, R 4And R 5Be can be identical or different substituting group, be selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino and-COOR 6, R wherein 6Be H or alkyl, and the carbonyl functional group;
C) the following N-acyl lactam bleach-activating agent of general formula:
Figure 9519344500023
Wherein n is 0-8, and R 6Be H, contain alkyl, aryl, alkoxy aromatic yl or the alkaryl of 1-12 carbon atom, or contain the phenyl of the replacement of 6-18 carbon atom; With
, b) and mixture c) d) a).
2. according to the composition of claim 1; it comprises percarbonate or perborate bleaching compound, or its mixture, and bleach-activating agent is selected from: benzoyl caprolactam; the benzoyl Valerolactim; the nonanoyl hexanolactam, nonanoyl Valerolactim, 4-nitro benzoyl hexanolactam; 4-nitro benzoyl Valerolactim; the capryloyl hexanolactam, capryloyl Valerolactim, decanoyl hexanolactam; the decanoyl Valerolactim; the undecanoyl hexanolactam, undecanoyl Valerolactim, 3; 5; 5-trimethyl acetyl base hexanolactam, 3,5; 5-trimethyl acetyl base Valerolactim; the dinitrobenzoyl hexanolactam, dinitrobenzoyl Valerolactim, terephthaloyl dicaprolactam; terephthaloyl two Valerolactims; (the amino caproyl of 6-decoyl) Oxybenzene sulfonate, (the amino caproyl of 6-nonanoyl) Oxybenzene sulfonate, (the amino caproyl of 6-caprinoyl) Oxybenzene sulfonate and their mixture.
3. according to the composition of claim 2, the bleaching catalyst that wherein contains transition metal is selected from: Mn IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(PF 6) 2, Mn III 2(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 2Mn IV 4(u-O) 6(1,4, the 7-7-triazacyclononane) 4(ClO 4) 4Mn IIIMn IV 4(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 3, Mn IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (OCH 3) 3(PF 6); Co (2,2 '-two pyridyl amine) Cl 2, two (different sulfo-cyanato-) two pyridyl amine-cobalts (II), three (bipyridyl amine) cobalt (II) perchlorate, Co (2,2 '-two pyridyl amine) 2O 2ClO 4, two (2,2 pairs of pyridyl amine) copper (II) perchlorate, three (two-2-pyridyl amine) iron (II) perchlorate, manganese gluconate, Mn (CF 3SO 3) 2, Co (NH 3) 5Cl has the double-core Mn complex compound of four-N-dentate and two-N-dentate ligand, comprises N 4Mn III(u-O) 2Mn IVN 4) +[Bipy 2Mn III(u-O) 2Mn IVBipy 2]-(ClO 4) 3With its mixture.
4. one kind comprises conventional surfactants, other scrubbed component and according to the laundry detergent composition of the bleaching composition of claim 1.
5. according to the composition of claim 4; wherein bleaching compounds is selected from: percarbonate; perborate and composition thereof; bleach-activating agent is selected from: benzoyl caprolactam, benzoyl Valerolactim, nonanoyl hexanolactam; the nonanoyl Valerolactim; 4-nitro benzoyl caprolactam, 4-nitro benzoyl Valerolactim, capryloyl hexanolactam; the capryloyl Valerolactim; the decanoyl hexanolactam, decanoyl Valerolactim, undecanoyl hexanolactam; the undecanoyl Valerolactim; 3,5,5-trimethyl acetyl base hexanolactam; 3; 5,5-trimethyl acetyl base Valerolactim, dinitrobenzoyl hexanolactam; the dinitrobenzoyl Valerolactim; the terephthaloyl dicaprolactam, terephthaloyl two Valerolactims, (the amino caproyl of 6-decoyl) Oxybenzene sulfonate; (the amino caproyl of 6-nonanoyl) Oxybenzene sulfonate, (the amino caproyl of 6-caprinoyl) Oxybenzene sulfonate and their mixture.
6. method of improving the bleachability of bleaching composition, this bleaching composition comprises oxygen or peracid SYNTHETIC OPTICAL WHITNER or can produce bleaching compounds and a kind of or many bleach-activating agent of hydrogen peroxide that in liquid, aqueous wherein said bleach-activating agent is selected from:
A) the following acid amides deutero-bleach-activating agent of general formula:
Figure 9519344500041
Or its mixture, wherein R 1Be the alkyl that contains 1-14 carbon atom, aryl or alkaryl, R 2Be alkylidene group, arylidene or the alkarylene that contains 1-14 carbon atom, R 5Be H or the alkyl that contains 1-10 carbon atom, aryl or alkaryl and L are leavings groups;
B) the following benzoxazine type bleach-activating agent of general formula:
Figure 9519344500042
R wherein 1Be H or alkyl, alkaryl, aryl, aralkyl, R wherein 2, R 3, R 4And R 5Be can be identical or different substituting group, be selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino ,-COOR 6, R wherein 6Be H or alkyl, and the carbonyl functional group;
C) the following N-acyl lactam bleach-activating agent of general formula: Wherein n is 0-8, and R 6Be H, contain alkyl, aryl, alkoxy aromatic yl, the alkaryl of 1-12 carbon atom or contain the phenyl of the replacement of 6-18 carbon atom; With
, b) and mixture c) d) a).
Wherein said improvement is included in water-soluble ligand existence adds catalytically effective amount down to it manganese positively charged ion.
7. one kind from fabric, crust, or the bowl dish removes the method for stain, comprises described fabric, and crust, or the bowl dish contacts with the water-bearing media that contains according to the bleaching composition of claim 1.
8. automatic bowl composition comprises low bubble nonionogenic tenside and according to the bleaching composition of claim 1.
CN95193445A 1994-04-07 1995-03-20 Bleach compositions comprising bleach activators and bleach catalysts Expired - Fee Related CN1066194C (en)

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