CN1151158A - Cationic bleach activators - Google Patents
Cationic bleach activators Download PDFInfo
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- CN1151158A CN1151158A CN 95193687 CN95193687A CN1151158A CN 1151158 A CN1151158 A CN 1151158A CN 95193687 CN95193687 CN 95193687 CN 95193687 A CN95193687 A CN 95193687A CN 1151158 A CN1151158 A CN 1151158A
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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
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
- C11D3/3927—Quarternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D211/74—Oxygen atoms
- C07D211/76—Oxygen atoms attached in position 2 or 6
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
Abstract
Cationic bleach activators are prepared from caprolactam or valerolactam. Compounds of formula (I), wherein R, R' and R'' are alkyl, hydroxyalkyl or polyalkanoxy groups and x is 0 or 1 are provided. The activators are used with perborate or percarbonate in bleaches, laundry detergents and automatic dishwashing detergents.
Description
Field of the present invention
The present invention relates to a kind of cationic activation immunomodulator compounds that is used to strengthen as SYNTHETIC OPTICAL WHITNER performances such as perborate and percarbonate.The cationic activation agent is applicable to fabric washing and bleaching composition, wash dining set is with composition etc. automatically.
Background of the present invention
Seek a kind of effective laundry detergent composition prescription of under various working conditionss, from fabric, removing multiple dirt and mottling that is enough to improve, this industrial remain one quite the difficulty problem.The formulator of automatic dishwashing detergent composition will be designed composition and can clean effectively and sterilize and normal long-pending have the vessel of thick especially dust also to face similar difficulty.The rules that effective phosphate builders uses are limited in many zones owing to set up in the world, make that these problems relevant with the preparation of real effective cleaning combination are more complicated.
The most common cleaning combination contains various cleansing tensio-active agents, so that remove all dirts and mottling from the surface.The various detergency enzymes of also more common in addition adding, soil-suspending agent, non-phosphorus Cleaning Aid Agent, optical brightener or the like is to strengthen total cleaning performance, and the cleaning combination of many full preparations also contains SYNTHETIC OPTICAL WHITNER, typical SYNTHETIC OPTICAL WHITNER is the perborate compound, uses the percarbonate compound recently.Though perborate and percarbonate are very effective when high temperature, to be willing in the low temperature that uses to the moderate temperature scope the certain user, they can lose most bleaching function.Therefore, various bleach-activating agents such as tetra acetyl ethylene diamine (TAED) and nonanoyl oxygen base benzene sulfonate (NOBS) have now been developed so that perborate and percarbonate all have bleaching action at wide temperature range.
Although oneself and SYNTHETIC OPTICAL WHITNER of TAED and NOBS used altogether in various cleanings and bleaching composition, but still continuing to seek more effective activator species.In general, improved activator species should be safe and effective and preferably should be able to be deposited on firm dirt and the mottling and can interact with it.That for example, has delivered on document variously is with cationic activator.Because they have improved the magnetism to band negatively charged ion dirt surface, so have preferable performance, unfortunately, many cationic activation agent of being mentioned are that maintain secrecy and expensive often material.And some cationic activation agent is not as fine compatible with anion surfactant, so be difficult to they are mixed with the detergent composition that contains real effective tensio-active agent+activated bleaching system.
The invention provides a kind of cationic activation agent that can make with the raw material of easily buying on the market, it can not only remove dirt and mottling on the fabric effectively, and is used in the automatic dishwashing compositions and also can removes dirt and mottling from vessel.This activator that newly is designed to is all very effective in the washing or the dipping temperature scope of broadness.Especially this activator is to very safe as rubber surfaces such as rubber groove flexible pipes, and rubber hose is normal the use in some European forward type washing machine.And preferred cation activator of the present invention is to the formulator particularly advantageous, because they are all compatible with many conventional cats products.Therefore, as seeing in the disclosure of back, this cationic activation agent activator more known than prior art is a great progress.
Background technology
At United States Patent (USP) 4,904,406,4,751,015,4,988,451,4,397,757,5,269,962,5,127,852,5,093,022,5,106,528.English Patent 1,382 discloses polytype cationic bleach agent and bleach-activating agent in the patents such as 594, European patent 475,512,458,396,284,292 and Japanese Patent 87-318,332.
The invention summary
The present invention relates to the bleach activating immunomodulator compounds of tool following formula:
Substituent R, R ' and R " can be C separately
1-C
10Alkyl, C
2-C
4Hydroxyalkyl or [(C
yH
2y) O]
n-R , y=2-4 wherein, n=1-20 and R are C
1-C
4Alkyl or hydrogen.Preferred compound is R, R ' and the R C that respectively does for oneself wherein
1-C
3Alkyl or hydroxyalkyl, especially all substituted radicals are those compounds of methyl, ethyl or hydroxyethyl.When x=0, this compound is produced by Valerolactim.When x=1, it is produced by hexanolactam.Negatively charged ion X kind in the compound is particularly important not.For example, X can be other desired any suitable negatively charged ion of chlorion, methylsulfate, bromide anion or formulator.Shown in molecular structural formula, the relative carbonyl substituted base location of its quaternary ammonium group can be ortho position, a position or contraposition (preferably).
The present invention also relates to bleaching composition, it comprise be at least composition 0.25%, preferably the following formula of 0.5%-10% cationic bleach activators and generally be at least composition 5%, preferably SYNTHETIC OPTICAL WHITNER, particularly perborate and the percarbonate bleach of 10%-60%.
The present invention also relates to a kind of laundry detergent composition, it comprises:
(a) be generally the bleach activating immunomodulator compounds of 0.5%-10% as above-mentioned molecular formula;
The SYNTHETIC OPTICAL WHITNER of described amount is disclosed (b);
(c) as following described cleansing tensio-active agent disclosed; With
(d) the cleansing additive of Ren Xuan one or more.
The present invention also relates to a kind of automatic dishwashing compositions, it comprises:
(a) be generally the bleach activating immunomodulator compounds of 0.5%-10% as above-mentioned molecular formula;
(b) SYNTHETIC OPTICAL WHITNER;
(c) one or more decontamination lotion promoters;
(d) Ren Xuan low foaming surfactant; With
(e) the cleansing additive of Ren Xuan one or more.(b)-(e) described in the consumption of component such as following the disclosing.
The present invention also relates on fabric or the crust especially that vessel get on except that the method for spot, it is included in water and exists to be preferably under the stirring down described spot is contacted with the cationic activation immunomodulator compounds with SYNTHETIC OPTICAL WHITNER.The content of activator in water generally is at least about 10ppm.And the general 50ppm at least of the content of SYNTHETIC OPTICAL WHITNER.
All percentages herein, ratio and ratio, except as otherwise noted, all by weight, the relevant portion of all documents that drawn is all with reference in being incorporated herein.
The detailed description of invention
The invention provides a kind of cationic bleach activators compound of type as mentioned above.Described compound can be synthetic with following general reaction:
It is synthetic to be described in more detail it below.
Example I N-(4-(triethyl aminomethyl) benzoyl) hexanolactam, the preparation of chloride salt
4-chloromethyl benzoic acid chlorides-load onto feed hopper, inlet pipe and a magnetic stirrer for a single neck round-bottomed flask adds 4-chloromethyl benzoic acid (0.5mol), toluene (1.0mol acid/350ml) and zeolite again under argon shield.Be added dropwise to thionyl chloride (1.0mol) by separating funnel, change feed hopper into reflux exchanger then, under argon shield, reactant is heated to refluxing toluene and refluxed 4 hours, again with reactant cool to room temperature, solvent evaporated.
4-chloromethyl benzoyl caprolactam-load onto mechanical stirrer, reflux exchanger, feed hopper and inlet pipe for one three neck round-bottomed flask.Under argon shield, add hexanolactam (0.5mol), triethylamine (0.75mol) and aequum 75% toluene (1.0ml hexanolactam/1.5L) then.Reaction solution is heated to refluxing toluene.The 4-chloromethyl benzoic acid chlorides that will be suspended in again in the residual toluene adds under low flow velocity.Argon shield and under refluxing toluene reaction stirred 6 hours, cool off a little and filter.Collecting the solids Triethylammonium chloride abandons.The freezing product precipitation that makes of filtrate is separated out, collected product with vacuum filtration, washing is also dry.
N-(4-(triethyl aminomethyl) benzoyl) hexanolactam; chloride salt-load onto magnetic stirrer, feed hopper and inlet pipe for a single neck round-bottomed flask; under argon shield, add 4-chloromethyl benzoyl caprolactam (0.5mol) and acetonitrile (1mol hexanolactam/1.5L), be added dropwise to triethylamine (1.0mol) again.Feed hopper changed into reflux exchanger and reactant is heated to acetonitrile under argon shield reflux and refluxed 4 hours.Cool to room temperature and solvent evaporated then.Add excessive acetone in the flask again and blend product, mixture heating up is refluxed to acetone with magnetic stirrer, cool to room temperature then, through vacuum filtration, washing and drying obtain product.
The synthetic of embodiment 1 can carry out with the alternative hexanolactam of Valerolactim, also can synthesize with substituting triethylamine as Trimethylamine 99, can obtain corresponding cationic bleach activators under every kind of situation.
This cationic activation agent can not be used itself, but as using with " peroxide " SYNTHETIC OPTICAL WHITNER described in following the disclosing.
Among SYNTHETIC OPTICAL WHITNER-the present invention, washing composition, automatic dishwashing and bleaching composition all contain SYNTHETIC OPTICAL WHITNER, and content generally is about 1%-60% (weight), more usually are about 10%-35% (weight).
The used SYNTHETIC OPTICAL WHITNER of the present invention can be any SYNTHETIC OPTICAL WHITNER that is used in detergent composition used in textiles cleaning, the hard surface cleaning, automatic dishwashing compositions, clothing SYNTHETIC OPTICAL WHITNER or the like or other cleaning purpose.For example, the present invention can use perborate bleach.As Sodium peroxoborate (one or tetrahydrate), yellow soda ash peroxidation hydrate (sodium carbonateperoxyhydrate) and " percarbonate " SYNTHETIC OPTICAL WHITNER of equal value, trisodium phosphate peroxidation hydrate, urea peroxidation hydrate and sodium peroxide.Persulphate SYNTHETIC OPTICAL WHITNER (for example OXONE of Dupont company manufacturing) also can be used, and also can use the mixture of such SYNTHETIC OPTICAL WHITNER.
Preferred percarbonate bleach, its dried particulate median size are not higher than 10% of described particle weight less than about 200 microns particle with greater than 1250 microns particle between 500 microns to 1000 microns.Optional is that this percarbonate available silicon hydrochlorate, borate or water soluble surfactant active apply.Percarbonate can be from FMC, and the various commercial channel of company such as Solvay and Jokai Denka are buied.
If need, SYNTHETIC OPTICAL WHITNER can be carried out catalysis with manganic compound.Such compound is to know in this area, for example comprises at United States Patent (USP) 5,246 621,5,244,594,5,194,416,5,114,606 and european patent application disclose the 549th, 271A1,549,272A1,544,440A2 and 544, disclosed manganese-based catalyst in 490A1 number.Preferred example includes Mn in these catalyzer
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)
3, Mn
IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH
3)
3(PF
6) and their mixture.Other metal matrix bleaching catalyst is included in United States Patent (USP) 4,430, those disclosed in 243 and 5,114,611.Use manganese and various compound ligand improving bleaching action, report is arranged in 455,5,284,944,5,246,612,5,256,779,5,280,117,5,274,147,5,153,161 and 5,227,084 also at United States Patent (USP) 4,728.
According to practical situation, composition among the present invention and method can be regulated to reach and contain the active bleaching catalyst of 0.1ppm at least in water lotion, reach the about 700ppm of about 0.1ppm-and preferably in washing liquid, contain described catalyzer, be more preferably the about 500ppm of about 1ppm-, but not limit by these.
Though effectively bleaching composition can only contain cationic activation agent of the present invention and SYNTHETIC OPTICAL WHITNER in the present invention, but for improving or improve cleaning performance, (fully-formulated) of full preparation is washed generally also to comprise other additive component with automatic dishwashing compositions.The non-limiting example of these components is disclosed in following to provide convenience to formulator.
Additive component
The general consumption of the tensio-active agent of cleansing tensio-active agent-available indefiniteness is about about 55% (weight) of 1%-, and example comprises conventional C
11-C
18Alkylbenzene sulfonate (" LAS ") and primary, side chain and random C
10-C
20Alkyl-sulphate (" AS "); Molecular formula is 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 about 7 integer in the formula, preferably being at least about 9 integer and M is especially sodium of a kind of water-soluble cationic, undersaturated vitriol such as oleoyl vitriol, C
10-C
18Alkyl alkoxy sulfate (" AE
xS ", EO 1-7 ethoxy sulfate particularly), C
10-C
18Alkyl alkoxy carboxylate salt (particularly EO 1-5 ethoxy carboxylate), C
10-C
18Glyceryl ether, C
10-C
18APG (polyglycosides) and their corresponding sulfated polysaccharides glycosides and C
12-C
18α-sulfonated fatty acid ester.If requirement is arranged, in total composition, also can comprise conventional nonionic and amphoterics, for example C
12-C
18Alkylethoxylate (" AE ") comprises so-called narrow peak (narrow peaked) alkylethoxylate and C
6-C
12Alkyl phenolic alkoxy thing (particularly ethoxylate and blended ethoxy/propoxylated glycerine), C
12-C
18Betaine and sulfo group betaine (" sultone (sultaines) "), C
10-C
18Amine oxide or the like.Also can use C
10-C
18N-alkyl polyhydroxy fatty acid amide, typical example comprises C
12-C
18N-methyl glucose amide (glucamide) is seen WO 9,206,154.Other comprises N-alkoxyl group polyhydroxy fatty acid amide by sugared deutero-tensio-active agent, as C
10-C
18N-(3-methoxy-propyl) glucamide.The N-propyl group is to N-hexyl C
12-C
18Glucamide can be used for low foaming.C
10-C
20Conventional soap also can use.If wish high foaming, can use the C of side chain
10-C
16Soap, the mixture of negatively charged ion and nonionogenic tenside is particularly useful.The automatic dishwashing composition generally is to adopt low foaming surfactant, for example blended vinyloxy group/propenyloxy group nonionogenic tenside.Other conventional useful tensio-active agent is listed in the standard textbook.
Washing assistant-detergent builders can randomly be contained in the composition of the present invention to help the adjusting hardness of minerals.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used in automatic dishwashing and the fabric cleaning composition to help the removing of particulate dirt.
The washing assistant consumption can change in wide region, depends on the end-use and the desired physical form thereof of composition.If contain washing assistant, composition generally contains about 1% washing assistant at least.The high-performance composition generally contains the detergent use washing assistant and is about 10%-80% (weight), more usually is about 15%-50% (weight).Yet this does not mean and gets rid of with the lower or washing assistant of a large amount more.
Inorganic or contain polyphosphate (for example tri-polyphosphate, pyrophosphate salt and glassy polymer metaphosphate), phosphonate, phytinic acid, silicate, carbonate (comprising supercarbonate, sesquicarbonate), vitriol and the aluminosilicate that P detergent use washing assistant comprises basic metal, ammonium and alkanol ammonium, but be not limited to these, yet need nonphosphate builders in some place.Importantly, even so-called " weak " washing assistant (with phosphate ratio) as Citrate trianion in the presence of or what is called " owing composite (underbuilt) " situation (with zeolite or layered silicate washing assistant time may produce), it is very effective uncannily that the present composition makes us.
The example of silicate-like builder is alkali-metal silicate, particularly SiO
2With Na
2The ratio of O is 1.6: 1-3.2: those silicate and layered silicate in 1 scope, the United States Patent (USP) of announcing on May 12nd, 1987 of H.P.Rieck 4,664 for example, the lamina sodium silicate described in 839.NaSKS-6 (writing a Chinese character in simplified form " SKS-6 " in this article usually) is the trade mark of a kind of crystal type lamina sodium silicate of Hoechst company sale.Different with zeolite builders, the NaSKS-6 sodium silicate drug builder does not contain aluminium.NaSKS-6 has the δ-Na of layered silicate
2SiO
5Form.It can be with as German Patent A-3, and 417,649 and A-3,742,043 described those methods are produced.SKS-6 is with being very preferred layered silicate in the present invention, but other this type of layered silicate also can use in the present invention.As general formula is NaMSi
xO
2x+1YH
2The layered silicate of O, wherein M is sodium or hydrogen, and x is 1.9-4, and is preferred 2, and y is 0-20, preferably 0.The various layered silicates of other of Hoechst company comprise NaSKS-5, NaSKS-7 and the NaSKS-11 of α, β and γ type.As described above, that override is selected for use among the present invention is δ-Na
2SiO
5(NaSKS-6 type).Other silicate such as Magnesium Silicate q-agent also can use, and can play the fluffy powder effect in granular prescription, and oxygen bleaching agent is played stabilizer function and the component of the regulation system of doing to foam.
Alkaline-earth metal and the alkali-metal carbonate of the example of carbonate builders described on November 15th, 1973 No. the 2nd, 321,001, disclosed German patent application.
The silico-aluminate washing assistant can be with in the present invention.Silico-aluminate is very important in the heavy duty type granular detergent composition of last sale, and it also is a kind of effective washing assistant composition in the liquid detergent prescription simultaneously.The silico-aluminate washing assistant comprises that empirical formula is Mz (zAlO
2) y] xH
2Those compounds of O, wherein z and y are at least 6 integer, and the mole ratio of z and y is that 1.0-is about 0.5, and x is one from about 15 to about 264 a integer.
The available aluminosilicate ion exchange material can be bought on market.These silico-aluminates can be crystallization or amorphous structure, and they can be obtained by natural silico-aluminate or synthetic.A kind of method of making aluminosilicate ion exchange material is disclosed in the people's such as Krummel that on October 12nd, 1976 announced the United States Patent (USP) 3,985,669.Used preferred synthetic crystallization type aluminosilicate ion exchange material can be purchased the Zeolite A on the market, Zeolite P (B), Zeolite MAP and the Zeolite X trade mark among the present invention.In a particularly preferred embodiment, crystal type aluminosilicate ion exchange material molecular formula is Na
12[(AlO
2)
12(SiO
2)
12] xH
2O, wherein x is about 20-30, and especially about 27.This material is called as Zeolite A.Also can use the Zeolite (x=0-10) of dehydration among the present invention.The aluminosilicate particle diameter is preferably about 0.1-10 micron.
The organic detergent that is applicable to the object of the invention comprises (but being not limited to) various polycarboxylic acid salt compounds with washing assistant.Described polycarboxylate is meant the compound of a plurality of carboxylate groups, preferably has 3 carboxylate salts at least.The polycarboxylate washing assistant can sour form be added in the composition usually, but also can the neutral salt form add in the composition.When using, preferably such as an alkali metal salt or alkanol ammonium salts such as sodium, potassium and lithiums with salt form.
The polycarboxylate washing assistant comprises multiple useful material.The important polycarboxylate of one class is the ether polycarboxylate, the United States Patent (USP) 3 that comprises the Berg that announces as on April 7th, 1964,128, the people's such as Lamberti that on January 18th, 287 and 1972 announced United States Patent (USP) 3, disclosed oxygen di-succinate (oxydisuccinate) in 635,830, the people's such as Bush that on May 5th, also visible announced United States Patent (USP) 4,663,071 described " TMS/TDS " washing assistant.Suitable ether polycarboxylate also comprises ring compound, alicyclic compound especially, and as at United States Patent (USP) 3,923,679,3,835,163,4,158,635,4,120,874 and 4,102, those compounds described in 903.
Other available detergent use washing assistant comprises the ether hydroxy-polycarboxylate; The multipolymer of maleic anhydride and ethene or vinyl methyl ether; 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid; The carboxyl dimethyoxy succinic acid; Various basic metal, ammonium and substituted ammonium salt such as polyacetic acids such as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA); And polycarboxylate, as mellitic acid, Succinic Acid, oxygen di-Succinic Acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxyl dimethyoxy succinic acid and their soluble salt.
The Citrate trianion washing assistant, owing to can make and reclaim that resource obtains utilizing and they have biodegradability, therefore they are polycarboxylate washing assistants of particularly important in the dirt-cleaning agent prescription as the soluble salt (particularly sodium salt) of citric acid and it.Citrate trianion also can be used in the dishwashing compositions, especially uses with zeolite and/or layered silicate washing assistant.Oxygen di-succinate is also effective especially in such composition or when shared.
What be applicable to detergent composition of the present invention also has 3,3-dicarboxyl-4-oxa--1, disclosed related compound in the United States Patent (USP) 4,566,984 of the Bush that 6-adipate and on January 28th, 1986 announce.Available Succinic Acid class washing assistant comprises C
5-C
20Alkyl and alkenyl succinic acid and their salt.Particularly preferred this compounds is the dodecenyl succinic Succinic Acid.The specific examples of Succinic Acid salt washing assistant comprises dodecyl succinate, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The dodecyl succinate is wherein preferred washing assistant, in the disclosed european patent application 86200690.5/0,200,263 argumentation is arranged on November 5th, 1986.
Open in the United States Patent (USP) 3,308,067 of the people's such as Crutchfield that other polycarboxylate that is suitable for has been announced on March 13rd, 1979 United States Patent (USP) 4,144,226 and the Diehl that announced on March 7th, 1967.The United States Patent (USP) 3,723,322 of also visible Diehl.
Lipid acid is C for example
12-C
18Monocarboxylic acid also can be added into separately in the composition or with above-mentioned washing assistant and use, and is particularly shared with Citrate trianion and/or Succinic Acid salt washing assistant, to improve the activity of washing assistant.So use lipid acid generally will cause bubbling and reduce, formulator should be taken into account this point.
Under the situation of available phosphorus base washing assistant, especially in the prescription of the used strip and block of hand washing operation, can use various alkali metal phosphates, for example well-known tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate.Also can use such as ethane-1-hydroxyl-1 phosphonate washing assistants (for example seeing United States Patent (USP) 3,159,581,3,213,030,3,422,021,3,400,148 and 3,422,137) such as 1-diphosphonate and other known phosphonate.
Sequestrant-present composition also can randomly contain one or more iron and/or manganese sequestrant.The optional aminocarboxylate described below freely of such sequestrant, amino phosphonates do, the aromatic chelating agent of multifunctional replacement and their mixture.Though to prove in theory, the benefit that it is believed that these materials partly is not because they have the special ability of removing de-iron and mn ion by forming the soluble chelating thing from washing soln.
The aminocarboxylate that can be used as optional sequestrant comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate, ethanol Diglycocol, their basic metal, ammonium and substituted ammonium salt and their mixture.
When allowing to contain carbamate additives for low phosphorus in detergent composition, the sequestrant that amino phosphonates do also is fit to do in the present composition uses, and they comprise ethylenediamine tetraacetic (methylene phosphonic acid salt) DEQUEST.Preferred amino phosphonates do does not contain the alkyl or alkenyl group that is higher than about 6 carbon atoms.
The aromatic chelating agent of multifunctional replacement also can use in the present composition, sees the people's such as Connor that on May 21st, 1974 announced United States Patent (USP) 3,812,044.The compound of the preferred sour form of this kind is the dihydroxy disulfobenzene, as 1, and 2-dihydroxyl-3,5-disulfobenzene.
A kind of preferred biodegradable sequestrant of Shi Yonging is quadrol two succinates (" EDDS ") in the present invention, its (S, S) isomer particularly, and as authorizing the United States Patent (USP) 4,704 of Hartman and Perkins on November 3rd, 1987, described in 233.
If be used, generally these amount of chelant are about the 0.1%-10% of detergent composition weight, and preferably, amount of chelant should be the 0.1%-3.0% of this kind composition weight approximately.
Enzyme-for reaching various cleaning purposes comprises the mottling of, saccharide-based protein-based as removing and triglyceride level base and for to prevent the transfer of bright-coloured dyestuff and to be the recovery of fabric, can comprise enzyme in prescription of the present invention.The enzyme that is added comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase and their mixture.The enzyme that also can comprise other type.They can have any suitable source, as plant, animal, bacterium, fungi and yeast source.And their selection is arranged by several factors, as pH activity and/or optimal stability point, thermostability, to the stability of activated detergent, washing assistant etc.In this respect, preferably bacterium or fungal enzyme are as bacterial amylase and proteolytic enzyme and fungal cellulase.
Usually organized enzyme more usually is that the heavy amount of about 0.01mg-3mg adds up to about 5mg to enzyme in every gram composition to be enough to make.In other words, the present composition generally contains the 0.001%-5% that has an appointment, the commercial enzyme preparation of preferred 0.01%-1% (weight).Usually the proteolytic enzyme that contains in this commodity preparation is being enough to provide every gram composition 0.005-0.1Anson unit (AU) active level.
The examples of proteases that is fit to is a subtilysin, and it is that specific bacterial strain from B.subtilis and B.licheniforms obtains.Another useful proteases is that the bacterial strain from genus bacillus obtains, and it all has maximum activity in the pH8-12 scope, and this enzyme is sold by Novo IndustriesA/S exploitation and with the ESPERASE registrar name of an article.The preparation of this enzyme and similar enzyme has argumentation in the british patent specification 1,243,784 of Novo.Proteolytic ferment is suitable for removing the protein-based spot, this kind enzyme can be bought from the market, comprises those enzymes of being sold with the MAXATASE trade(brand)name of ALCALASE and SAVINASE trade(brand)name and Imernational Bio-Synthetics Inc (Netherlands) by Novo Industries A/S (Denmark).Other proteolytic enzyme comprises that protease A is (referring to the european patent application of announcing on January 9th, 1,985 130,756) and proteolytic enzyme B (seeing european patent application sequence number 87303761.8 that proposed on April 28th, 1987 and people's european patent applications 130,756 such as Bett of announcing on January 9th, 1985).
Amylase comprises α-Dian Fenmei, the RAPIDASE of International Bio-Synthetics Inc. company and the TERMAMYL of Novo Industries company that for example discusses in british patent specification 1,296.839 (Novo).
Spendable cellulase comprises bacterium and fungal cellulase among the present invention.Preferably, they preferably should have the pH optimum value between 5-9.5.The cellulase that is fit to has been disclosed in the United States Patent (USP) 4 of authorizing people such as Barbesgoard on March 6th, 1984,435, in 307, this patent disclosure from Humicola insolens and Humicola bacterial classification DSM1800 or belong to that Aeromonas belongs to fungal cellulase that cellulase 212 that fungi generates produces and from the cellulase of the hepatopancreas extraction of sea mollusk (Dolabella Auricula Solander).The cellulase that is fit to also is disclosed in GB-A-2, and in 075,028, GB-A-2,095,275 and DE-OS-2,247,832, CAREZYME (Novo company) is effective especially.
The lipase that is suitable in the washing composition comprises those enzymes of producing with the pseudomonas quasi-microorganism, for example is disclosed in English Patent 1,372, the pseudomonas Pseudomonas Stutzeri ATCC19 in 034,154.Also see the lipase in the disclosed Japanese patent application 53,20487 on February 24th, 1978.This enzyme can be from Japan Nagoya Amano phamaceutical Co, and Ltd. buys, and product is called lipase P " Amano ", below is called " Amano-P ".Other commercial lipases comprises Amano-CES; Lipase from Chromobacter viscosum, as Chromobacter viscosum var.lipolyticum NRRLB 3673, can be from Japanese Toyo Jozo Co., Tagata buys, can also buy Chromobacter viscosum lipase and from the lipase of Rhodopseudomonas Pseudomonas gladioli from U.S. U.S.Biochemical Corp and Dutch Disoynth Co..The LIPOLASE (also seeing EPO 341,947) that obtains and can buy from Novo company from Humicola Lanuginosa is the preferred lipase that uses among the present invention.
For example percarbonate, perborate, persulphate and hydrogen peroxide etc. are used in combination peroxidase with oxygen source.They are used to " solution bleaching ", prevent promptly that in washing operation pigment or dyestuff transfer on the other substrate from a kind of substrate in washing lotion.Peroxidase is being known in the art, and for example comprises horseradish peroxidase, this quality enzyme and haloperoxidase for example chlorine and bromine peroxide enzyme.The detergent composition that contains peroxidase for example has been disclosed in the PCT International Application No. WO 89/099813 of the O.Kirk that announced on October 19th, 1989, has transferred NovoIndustries A/S.
The scope of enzyme material and the method that they are added in the synthetic detergent composition also have been disclosed in the United States Patent (USP) 3,553,139 of authorizing people such as McCarty on January 5th, 1971.Enzyme also is disclosed in to be authorized in the United States Patent (USP) 4,507,219 of Hughes in United States Patent (USP) 4,101,457 and on March 26th, 1985 of authorizing people such as Place on July 18th, 1978.Be used for the enzyme of detergent formulation and they added such prescription method being disclosed in the United States Patent (USP) 4,261,868 of authorizing people such as Hora on April 14th, 1981.The enzyme that is used for washing composition can be stablized with various technology.The enzyme stabilization technology is disclosed in the european patent application publication number 0,199,405 of the United States Patent (USP) 3,600,319 of for example authorizing people such as Gedge on August 17th, 1971 and the Venegas that announced on October 29th, 1986, in the application number 86200586.5.For example also discussing the enzyme stabilising system in the United States Patent (USP) 3,519,570.
Can add in suds suppressor-present composition and can reduce or suppress the compound that foam forms.In European washing machine of forward type and automatic dishwashing machine,, in 455 and 4,489,574 what is called of discussing " high density washing out method ", press down bubble effect particularly important at United States Patent (USP) 4,489.
Multiple material all can be used as suds suppressor, those skilled in the art have known these defoamers, referring to for example Kirk Othmer chemical technology encyclopaedia (Kirk Othmer Encyclopediaof Chemical Technology), the third edition, the 7th volume is (John Wiley﹠amp p.430-447; Sons, Inc., 1979).A significant especially class suds suppressor is monobasic aliphatic carboxylic acid and their soluble salt, sees and authorizes the United States Patent (USP) 2,954,347 of Wayne St.John September 27 nineteen sixty.Monobasic aliphatic carboxylic acid that uses as suds suppressor and their salt generally have about 24 carbon atoms of 10-, the hydrocarbyl chain of 12-18 carbon atom preferably.Suitable salt comprises an alkali metal salt such as sodium, potassium and lithium salts, ammonium and alkanol ammonium salts.
Also can contain the on-surface-active suds suppressor in the detergent composition of the present invention.They comprise high-molecular-weight hydrocarbons for example paraffin, fatty acid ester (as fatty acid triglycercide), the fatty acid ester of monohydroxy-alcohol, aliphatic C
18-C
40Ketone (as stearone) etc.Other froth suppressor comprise the alkylating aminotriazine of N-as three to six alkyl melamines or two to tetraalkyl diammonium chloride triazine etc., they are to contain the primary amine of 1-24 carbon atom or the product that the secondary amine reaction generates by cyanuryl chloride and two or three mol; 1,2 propylene oxide and a stearyl phosphoric acid ester (salt) are as phosphoric acid one stearyl ester and stearyl di(2-ethylhexyl)phosphate basic metal (as K, Na and Li) salt and phosphoric acid ester.Hydro carbons such as paraffinic hydrocarbons and halogenated paraffin can liquidly use, and liquid hydrocarbon is liquid under room temperature and atmosphere, and in-40 ℃ of-50 ℃ of scopes yield point are being arranged approximately, and minimum boiling point is not less than about 110 ℃ (under normal atmosphere).Wax shape hydrocarbon also is used, preferably has to be lower than about 100 ℃ fusing point.Hydro carbons is the preferred class suds suppressor of detergent composition.The hydro carbons suds suppressor is authorized existing argumentation the in people's such as Gandolfo the United States Patent (USP) 4,265,779 in for example on May 5th, 1981.Hydro carbons comprises the aliphatic series that contains 12-70 the carbon atom of having an appointment, alicyclic, aromatic series and heterocycle is saturated or unsaturated hydrocarbons.The term of using in the suds suppressor " paraffinic hydrocarbons " is discussed here to be meant and to comprise the real paraffinic hydrocarbons and the mixture of cyclic hydrocarbon.
Other preferred on-surface-active formulation suds suppressor comprises (gathering) silicone suds suppressor.This class suds suppressor comprises that use is as the organopolysiloxane oil of polydimethylsiloxane, dispersion liquid or the emulsion or the resin of organopolysiloxane oil, and organopolysiloxane combines usefulness with silica dioxide granule, with the silica bound time spent, organopolysiloxane by chemisorption or consolidation on silicon-dioxide.The polysiloxane suds suppressor is known in this area.For example be disclosed in the United States Patent (USP) 4,265,779 of authorizing people such as Gandolfo on May 5th, 1981 and February 7 nineteen ninety disclosed Starch, in the European Patent Application No. 89307851.9 of M.S..
Other polysiloxane suds suppressor is disclosed in United States Patent (USP) 3,455, and in 839, it relates to by adding a small amount of polydimethylsiloxane liquid therein and reaches the composition and the method for aqueous solution froth breaking.
The mixture of the silicon-dioxide of polysiloxane and silanization is at for example German patent application DOS2,124, discuss in 526, polysiloxane defoamers and Foam Control have been disclosed in people's such as Bartolotta United States Patent (USP) 3 in granular detergent composition, 933, authorized on March 24th, 672 and 1987 in people's such as Baginski the United States Patent (USP) 4,652,392.
The example of the polysiloxane group suds suppressor of Shi Yonging is the Foam Control that presses down the bubble amount in the present invention, and it basic composition is:
(i) at 25 ℃ of 20cs.-1500cs that have an appointment, the polydimethylsiloxane liquid of viscosity;
(ii) per 100 weight parts (i) contain by (Ct
3)
3SiO
1/2Unit and SiO
2About 5-50 part of polyorganosiloxane resin that the unit is formed, wherein (CH
3)
3SiO
1/2Unit and SiO
2The ratio of unit is about 0.6: 1-1.2: 1; With
(iii) per 100 weight parts (i) contain the solid silicone of about 1-20 part.
In the present invention in the preferred polysiloxane suds suppressor of Shi Yonging, be by some polyoxyethylene glycol or polyoxyethylene glycol polypropylene glycol multipolymer or their mixture (preferably), or polypropylene glycol is formed as the solvent of external phase.Main polysiloxane suds suppressor is a side chain/crosslinked, preferably nonlinear.
For further specifying this point, adopt the typical laundry detergent composition of control foaming randomly to comprise about 0.001%-1%, preferred about 0.01%-0.7%, the above-mentioned polysiloxane suds suppressor of 0.05%-0.5% (weight) more preferably from about, it comprises the antifoams nonaqueous emulsion that (1) is main, antifoams is the mixture of following (a)-(d): (a) organopolysiloxane, (b) resinousness siloxanes or become the silicone compounds of polyorganosiloxane resin, (c) packing material of fine dispersion and (d) can promote (a), (b) and (c) the constituents of a mixture reaction generates the catalyzer of silane hydrochlorate (silanolates); (2) at least a nonionic siloxane tensio-active agent; (3) under polyoxyethylene glycol or the room temperature in water solubleness greater than the ethylene glycol and the propylene glycol copolymers of about 2% (weight); And do not contain polypropylene glycol.Also see and authorize the United States Patent (USP) 4 of Starch December 18 nineteen ninety, 978,471, the United States Patent (USP) of authorizing Starch on January 8th, 1991 was authorized people's such as Huber United States Patent (USP) 5 on February 22nd, 4,983,316,1994,288,431 and people's such as Aizawa United States Patent (USP) 4,639,483 and 4,46 row-Di, 4 hurdles, first hurdle, 35 row in 749,740.
Polysiloxane suds suppressor among the present invention preferably comprises polyoxyethylene glycol and ethylene glycol/propylene glycol copolymers.It is about 1000 that their molecular-weight average all is lower than, preferably between 100-800.Polyoxyethylene glycol that the present invention is used and the ethylene glycol/propylene glycol copolymers at room temperature solubleness in the water are higher than about 2% (weight), preferably are higher than about 5% (weight).
Among the present invention preferred solvent be have molecular-weight average less than about 1000, more preferably from about between 100-800, most preferably polyoxyethylene glycol between 200-400 and ethylene glycol/propylene glycol copolymers, preferred PPG 200/PEG 300.Preferably the weight ratio of polyoxyethylene glycol and ethylene glycol/propylene glycol copolymers is about 1: 1-1: between 10, most preferably 1: 3-1: between 6.
It is 4000 polypropylene glycol that the preferred polysiloxane suds suppressor that uses among the present invention does not contain polypropylene glycol, particularly molecular weight.They preferably do not contain oxyethane and propylene oxide block copolymer as PLURONIC L101 and so on yet.
Among the present invention other suds suppressor of available comprise secondary alcohol (as the 2-alkyl alcohol) and alcohol with such as at United States Patent (USP) 4,798,679,4,075,118 and EP 150,872 in the mixture of silicone oil of disclosed siloxanes and so on.Secondary alcohol includes C
1-C
16The C of chain
6-16Alkyl alcohol.A kind of preferred alcohol is 2-butyl octanol, can buy with ISOFOL 12 trade marks from Condea company.The secondary alcohol mixture can be buied with ISALCHEM 123 trade marks from Enichem company.The weight ratio that the blended suds suppressor generally comprises alcohol and polysiloxane is 1: 5-5: 1 mixture.
To being used for any detergent composition of automatic washing machine, the foam that is generated should not make it overflow washing machine.When using suds suppressor, suds suppressor preferably exists with " pressing down the bubble amount "." press down bubble amount " is the amount that the formulator that means composition can be selected this Foam Control, this amount be enough to can control foam to be met the low foaming laundry detergent that automatic washing machine uses.
Composition of the present invention generally contains the suds suppressor of 0%-about 5%.When being used as the suds suppressor use, the consumption of monobasic aliphatic carboxylic acid and salt thereof generally is about 5% (weight) of detergent composition at the most.Preferably use the monobasic fat carboxylate suds suppressor of about 0.5%-3%.The consumption of polysiloxane suds suppressor generally is about 2.0% (weight) of detergent composition at the most, though also can use higher amount.This upper limit determines it is actual needs, bubbles mainly due to relating to making cost keep minimum and reaching effective control with effective low consumption.The preferred polysiloxane suds suppressor that uses about 0.01%-1%, more preferably from about 0.25%-0.5%.When using in the present invention, these weight percent numerical value comprise can with common any silicon-dioxide and the spendable any subsidiary material that use of organopolysiloxane.The common usage quantity scope of one stearyl phosphoric acid ester (salt) suds suppressor is about 0.1%-2% (weight) of composition.Hydrocarbon suds suppressor typical amounts scope is about 0.01%-5.0%, but also available higher amount.The general consumption of alcohol suds suppressor is the 0.2%-3% (weight) of final composition.
Also can randomly contain water-soluble ethoxylated amine in soil dirt removing/anti redeposition agent-composition of the present invention with the removing of soil dirt and antiredeposition performance.The detergent composition that contains this compound generally contains the about 0.01%-10.0% of water-soluble ethoxylated amine (weight).
Most preferred soil dirt removes and anti redeposition agent is the ethoxylation tetren.The example of ethoxylated amine is authorized on July 1st, 1986 in the United States Patent (USP) 4,597,898 of VanderMeer further argumentation.Another kind of preferred soil dirt removing-anti redeposition agent is a disclosed cation compound in the european patent application 111,965 of the Oh of announcement on June 27th, 1984 and Gosselink.Other available soil dirt removing/anti redeposition agent comprises the ethoxylated amine polymkeric substance in the european patent application 111,984 that is disclosed in the Gosselink that announced on June 27th, 1984; Be disclosed in the amphoteric ion polymer in the european patent application 112,592 of the Gosselink that announced on July 4th, 1984 and be disclosed in amine oxide in the United States Patent (USP) 4,548,744 of authorizing Connor on October 22nd, 1985.Other soil dirt that is known in the art removes and/or anti redeposition agent also can be used in the present composition.The preferred anti redeposition agent of another type comprises carboxymethyl cellulose (CMC) material, and they are well known in the art.
Polymeric dispersant-the favourable usage quantity of polymeric dispersant is about 0.1%～7% (weight) in the present composition, when especially having zeolite and/or layered silicate washing assistant to exist.The suitable polymers dispersion agent comprises polycarboxylate and polyoxyethylene glycol, and also can use other dispersion agent as known in the art.Though not accepting opinion limits, but it is believed that when polymeric dispersant and other washing assistant (comprising the lower molecular weight polycarboxylate) are shared, thereby owing to suppress the performance that crystal growth, dirt particles release peptization and anti-redeposition have strengthened whole detergent use washing assistant.
Polymer poly carboxylate salt material can be by suitable unsaturated monomer, preferably carries out polymerization with their acid type or copolymerization is produced.The unsaturated monomer acid that can aggregate into suitable polycarboxylate comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.Polycarboxylate or the existence that contains just like non-carboxylate salt free radical monomer chain links such as vinyl methyl ether, vinylbenzene, ethene are suitable among the present invention, as long as the formation of these chain links is not more than about 40% (weight).
Specially suitable polycarboxylate can be obtained by vinylformic acid.The polymkeric substance of available this kind acrylic in the present invention is a polymeric vinylformic acid water-soluble salt.The preferable range of the polymkeric substance molecular-weight average of this acid type is about 2,000～10,000, is more preferably about 4,000～7,000, most preferably about 4,000～5,000.The water-soluble salt of this acrylate copolymer can comprise as basic metal, ammonium and substituted ammonium salt.This type soluble polymer is a material known.Using this type polyacrylate for example to be disclosed in detergent composition authorized in the United States Patent (USP) 3,308,067 of Diehl on March 7th, 1967.
The multipolymer of vinylformic acid/maleic also can be done to disperse, a preferred component of anti redeposition agent uses.This material comprises the water-soluble salt of vinylformic acid and maleic acid.The preferable range of this average molecular weight of copolymer of acid type is about 2,000～100,000, more preferably about 5,000～75,000, most preferably about 7,000～65,000.The acrylate chain link was generally 30: 1～1: 1 the ratio ranges of maleate chain link in this multipolymer, more preferably about 10: 1～2: 1.The water-soluble salt of this vinylformic acid/maleic acid comprises as basic metal, ammonium and substituted ammonium salt.Known such solubility acrylate/maleate copolymer material is discussed in the european patent application No.66915 that announces December 15 nineteen eighty-two.Also discussed this base polymer of forming by the hydroxypropyl acrylate among the EP 193,360 that on September 3rd, 1986 announced.Other available dispersion agent comprises toxilic acid/vinylformic acid/vinyl alcohol terpolymer.This material also has been disclosed among the EP 193,360, comprises for example vinylformic acid/toxilic acid/vinyl alcohol (45/45/10) terpolymer.
The another kind of polymer materials that can comprise is polyoxyethylene glycol (PEG), PEG has dispersing agent performance and can play the effect of soil dirt removing-anti redeposition agent, the typical molecular weight scope that is used for these purposes is about 500～100,000, preferably be about 1,000～50,000, be more preferably 1,500～10,000.
Also can use poly aspartic acid and polyglutamic acid dispersion agent, particularly be used in combination with zeolite builders.This poly aspartic acid dispersion agent preferably has about 10,000 molecular-weight average.
Any polymkeric substance stain remover known to polymkeric substance stain remover-those skilled in the art all can randomly be used for the compositions and methods of the invention.Polymkeric substance stain remover feature is that existing hydrophilic chain link has hydrophobic chain link again, the former can make for example surface hydrophilic of hydrophobic fabric such as polyester and nylon, and energy-conservation being deposited on of hydrophobic chain also keeps on the hydrophobic fabric adhering to thereon up to finishing whole washing and rinse cycle, so play a kind of fixing hydrophilic chain link effect.Can make like this in the spot washing process afterwards of appearance to go to clean and become easier with stain remover.
Spendable in the present invention polymkeric substance stain remover comprises that especially those have the following component (a) or (b) or (a) and (b) stain remover of combination: (a) the hydrophilic component of one or more nonionics, it is substantially by (i)-(iii) form: (i) polymerization degree is at least 2 polyoxyethylene chain link, or (ii) oxypropylene or the polymerization degree are 2～10 polyoxypropylene chain link, it is bonded to neighbouring part with ehter bond at each end unless wherein said hydrophilic chain link does not comprise any oxypropylene unit, or (iii) comprise the mixture of oxygen ethene and the unitary oxyalkylene units of about 30 oxypropylenes of 1-, wherein said mixture includes the oxygen ethylene unit of q.s so that hydrophilic component has very big wetting ability, be enough to when stain remover is deposited on the conventional polyester synthon surface, improve the wetting ability on such surface, described hydrophilic chain link preferably contains at least about 25% oxygen ethylene unit, particularly, more preferably contain at least about 50% oxygen ethylene unit for containing the unitary this component of about 20～30 oxypropylenes; (b) one or more hydrophobic components, it comprises (i) C
3Oxyalkylene terephthalate chain link, wherein if described hydrophobic component also comprises the oxygen ethylene terephthalate, then oxygen ethylene terephthalate unit is to C
3The ratio of oxyalkylene terephthalate unit is about 2: 1 or lower, (ii) C
4～C
6Alkylene or oxygen C
4～C
6Alkylene chain link or their mixture, (iii) the polymerization degree is at least poly-(vinyl acetate) chain link of 2, (preferably polyvinyl acetate), or (iv) C
1～C
4Alkyl oxide or C
4Hydroxyalkyl ether substituent or their mixture, wherein said substituent is with C
1～C
4Alkyl oxide or C
4Hydroxyalkyl ether derivatived cellulose or their form of mixtures occur, and this derivatived cellulose is amphipathic, thereby they have the C of q.s
1～C
4Alkyl oxide and/or C
4The hydroxyalkyl ether unit in case adhere to this common synthon surface, just can improve the wetting ability of fiber surface to be deposited on conventional polyester synthon surfaces and to keep the hydroxyl of q.s.
(a) (i) generally should have an appointment 200 the polymerization degree of polyoxyethylene chain link, also available more high-polymerization degree, preferably 3～about 150, more preferably 6～about 100.Suitable oxygen base C
4-C
6The hydrophobic chain link of alkylene comprises that (but being not limited to these) is as MO
3S (CH
2)
nOCH
2CH
2The end capped polymkeric substance stain remover of O-, wherein M is a sodium, and n is the integer of 4-6, and as authorizing the United States Patent (USP) 4,721 of Gosselink on January 26th, 1988,580 is described.
Available polymkeric substance stain remover also comprises the derivatived cellulose as the hydroxy ethers cellulose polymer compound in the present invention, the segmented copolymer of ethylene terephthalate or terephthalic acid propylene glycol ester and terephthalic acid epoxy ethyl ester or epoxy propyl ester etc.This stain remover that can buy on the market comprises the hydroxy ethers Mierocrystalline cellulose as METHOCEL (DOW company).The Mierocrystalline cellulose stain remover of Shi Yonging comprises that also those are selected from C in the present invention
1～C
4Alkyl and C
4Hydroxy alkyl cellulose, see the United States Patent (USP) 4,000,093 of authorizing people such as Nicol on December 28th, 1976.
There is the stain remover of poly-(vinyl acetate) hydrophobic chain link feature to comprise as C
1～C
6Poly-(vinyl acetate) graft copolymer of vinyl acetate, preferably poly-(vinyl-acetic ester) is grafted to as on the polyalkylene oxide skeletons such as polyethylene oxide.European patent application 0,219,048 referring to the people such as Kud that announced on April 22nd, 1987.This class stain remover that can buy on the market comprises SOKALAN section bar material, as the SOKALAN HP-22 that can buy from BASF AG (Germany).
The preferred polymkeric substance stain remover of one class is the statistic copolymer of ethylene terephthalate and polyethylene oxide (PED) terephthalate.The molecular weight of this polymkeric substance stain remover was authorized the United States Patent (USP) 3,893,929 of Basadur on July 8th, 3,959,230 and 1975 referring to the United States Patent (USP) of authorizing Hays on May 25th, 1976 in about 2,500～55,000 scope.
Another kind of preferred polymkeric substance stain remover is to have the unitary polyester of repetition ethylene terephthalate, contain the polyoxyethylene terephthalate unit of the ethylene terephthalate unit and 90～80% (weight) of 10～15% (weight), it is produced by the polyoxygenated ethylidene glycol of molecular-weight average 300～5000.The example of this polymkeric substance comprises the ZELCON 5126 (from Dupont company) that can buy on the market and MILEASE T (from ICI company) authorize Gosselink referring on October 27th, 1987 United States Patent (USP) 4,712,857.
The sulfonated products that another kind of preferred polymkeric substance stain remover is the ester oligomer of substantial linear, this oligopolymer are linked by terephthaloyl oligomer ester skeleton and oxyalkylene oxygen repeating unit and end group part covalency that skeleton forms.This stain remover is authorized in November 6 nineteen ninety in the United States Patent (USP) 4,968,451 of J.J.Scheibel and E.P.Gosselink and is expounded adequately.Other suitable polymers stain remover comprises the United States Patent (USP) 4 of authorizing people such as Gosselink on December 8th, 1987,711, terephthalate kind polyester in 730, authorized the United States Patent (USP) 4 of Gosselink on January 26th, 1988,721, negatively charged ion end-blocking oligomer ester in 580 and authorized block polyester oligomeric compound in the United States Patent (USP) 4,702,857 of Gosselink on October 27th, 1987.
Preferred polymkeric substance stain remover also comprises the stain remover of the United States Patent (USP) 4,877,896 of authorizing people such as Maldonado on October 31st, 1989, this Patent publish the end capped terephthalate of negatively charged ion, especially Sulfoarolyl.
If use, the content of stain remover in detergent composition of the present invention is about 0.01%-10% (weight) usually, generally is about 0.1%-5%, preferably is about 0.2%-3.0%.
Also having another kind of preferred stain remover is to have terephthaloyl unit, the different terephthaloyl of sulfo group unit, ethylene oxide oxygen unit and oxygen-1, the oligopolymer of 2-propylene units repeating unit.These repeating units constitute the skeleton and the preferred isethionic acid alkali end-blocking with modification of this oligopolymer.Particularly preferred this stain remover comprises about 1 the different terephthaloyl of sulfo group unit, 5 terephthaloyl unit, approximately with the ethylene oxide oxygen and the oxygen-1 of 1.7-1.8 ratio, 2-propylene oxygen unit and 2 2-(2-hydroxy ethoxy)-ethane sulfonic acid sodium end-blocking unit.Described stain remover also comprises the brilliant stability of falling of the 0.5%-20% that is about oligopolymer weight, preferably is selected from xylenesulfonate, cumene sulfonate, tosylate and their mixture.
Dye transfer inhibitor-present composition also can contain one or more and can effectively be suppressed at dyestuff in the cleaning process and be transferred to material on the another kind of fabric from a kind of fabric.Usually, this kind dye transfer inhibitor comprises polyvinylpyrrolidone, polyamine N-oxide, N-V-Pyrol RC and N-ethene imidazoles multipolymer, manganese phthalocyanine, peroxidase and their mixture.If use, typical consumption is about the heavy 0.01%-10% (weight) of composition.Be preferably about 0.01%-5%, more preferably about 0.05%-2%.
More particularly, the polyamine N-oxide that the present invention preferably uses contains the unit with R-Ax-P structural formula, wherein P is that a kind of polymerisable unit and N-O group can be connected on this unit or the N-O group can form the part of this polymerizable unit, and perhaps the N-O group can be connected on Unit two; One of A is-NC (O)-,-C (O) O-,-S-,-O-,-the N=group; X is 0 or 1; R is aliphatic group, ethoxyquin aliphatic group, aryl, heterocyclic radical or alicyclic radical, or their combination, and the nitrogen of N-O group can be connected on it or the N-O group is the part of these groups.Preferred polyamine N-oxide compound is that wherein R is those polymkeric substance such as heterocyclic groups such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and their derivatives.
The N-O group can be represented with following general structure:
R wherein
1, R
2, R
3Be aliphatic group, aryl, heterocyclic radical, alicyclic radical or their combination; X, y and z are 0 or 1; And the nitrogen of N-O group can be connected or form the part of above-mentioned any group, and there are pKa＜10 the amine oxide unit of polyamine N-oxide, preferred pKa＜7, more preferably pKa＜6.
Can use any polymer backbone, as long as the polyamine oxide compound that forms is water miscible and has the dye transfer rejection.The example of the polymer backbone that is fit to has polyethylene, poly-alkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and their mixture.These polymkeric substance comprise random or segmented copolymer, and one of them monomer is that the amine n-oxide type is the N-oxide type with another.The ratio that polyamine N-oxide generally contains amine and amine n-oxide is 10: 1-1: 1,000,000.Yet the amine oxide group number in the polyamine oxide compound can change with appropriate copolymerization or with appropriate N-oxidisability.Almost can any polymerization degree obtain the polyamine oxide compound.Molecular-weight average is generally at 500-1, in 000,000 scope, and more preferably 1,000-500,000, most preferably 5,000-100,000.This class preferable material can be described as " PVNO ".
The polyamine N-oxide of most preferably using in detergent composition of the present invention is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is about 50,000, and amine is about 1: 4 to the ratio of amine n-oxide.
N-V-Pyrol RC and N-ethene imidazoles multipolymer (being called " PVPVI " class) also are preferably used among the present invention.Preferred PVPVI has 5,000-1, molecular-weight average in 000,000 scope is more preferably 5,000～200,000, most preferred is 10,000-20,000 (light scattering method measuring that average molecular weight range employing Barth etc. describes in " chemical analysis (Chemical Analysis) " Vol.113 " identifies the modernism (Modern Methods of PolymerCharacterization) of polymkeric substance ", the disclosure content is incorporated herein by reference).The N-ethene imidazoles of PVPVI multipolymer is generally 1 to the mole ratio of N-V-Pyrol RC: 1-0.2: 1, be more preferably 0.8: 1-0.3: and 1, most preferred is 0.6: 1-0.4: 1.These multipolymers can be multipolymers straight chain or branching.
Composition of the present invention can also use molecular-weight average to be about 5,000-400,000 polyvinylpyrrolidone (" PVP "), preferably about 5,000-200.000, be more preferably about 5,000-50,000.PVP is that the detergent applications personnel are known, referring to for example EP-A-262897 and EP-A-256, and 696, its content is hereby incorporated by.The composition that contains PVP also can contain molecular-weight average and be about 500-100,000 polyoxyethylene glycol (" PEG "), preferably about 1,000-10,000.Preferably, throw in PEG in the washings, by ppm, be about 2: 1-50 the ratio of PVP: 1, preferredly be about 3: 1-10: 1.
Detergent composition of the present invention also can randomly contain the wetting ability optical brightener with inhibiting some type of dye transfer of the 0.005%-5% that has an appointment (weight).If use, the present composition preferably contains the such optical brightener of about 0.01%-1% (weight).
Available wetting ability optical brightener in the present invention is those compounds with following structural formula:
R wherein
1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R
2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; M is for example sodium or a potassium of salt-forming cation.
In the said structure formula, work as R
1Be anilino, R
2Be N-2-two-hydroxyethyl and M are for example during positively charged ion sodium, then brightener be 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-S-triazine-2-yl) amino]-2,2 '-the stilbene disulfonic acid disodium salt.This brightener by Ciba-Geigy company with trade(brand)name Tinopal-UNPA-GX in market sale.Tinopal-UNPA-GX is the preferred wetting ability optical brightener that can be used in the detergent composition of the present invention.
In the said structure formula, work as R
1Be anilino, R
2Be that N-2-hydroxyethyl-N-2-methylamino-and M are for example during positively charged ion sodium, then brightener be 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-S-triazine-2-yl) amino]-2,2 '-the stilbene disulfonic acid disodium salt.This brightener by Ciba-Geigy company with trade(brand)name Tinopal5BM-GX in market sale.
In the said structure formula, work as R
1Be anilino, R
2Be that morpholino and M are for example during positively charged ion sodium, then brightener be 4,4 '-two [(4-anilino-6-morpholino-S-triazine-2-yl) amino]-2,2 '-the stilbene disulfonic acid sodium salt.This brightener by Ciba-Geigy company with trade(brand)name Tinopal AMS-GX in market sale.
The specific optical brightener of selecting for use among the present invention is when when shared, especially effectively dye transfer rejection being arranged then with selected polymeric dye transfer inhibitor noted earlier.Selected polymer materials (as PVNO and/or PVPVI) share can provide in rinsing solution than these two kinds of detergent composition components with selected optical brightener (as TinopalUNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) and uses much better dye transfer restraining effect separately.Do not accept opinion and limit, it is believed that such brightener effect is because they have the avidity very high to fabric in washings, therefore can be deposited on these fabrics quickly.The degree that brightener is deposited on the fabric in washings can be determined with being called " consumption coefficient " (" exhaustion coefficient ") parameter.Consumption coefficient is generally brightener material and the b that a) is deposited on the fabric) ratio of the initial concentration of brightener in washing lotion.Brightener with higher consumption coefficient is to be suitable for the dye transfer inhibitor that the present invention uses most.
Certainly, people know that also other conventional optical brightener also can randomly be used for the present composition so that " blast " effect of fabrics in general to be provided, and are not to be a kind of real dye transfer restraining effect.This usage is routine and known by the production of detergents field.
Brightener-any can add in the detergent composition of the present invention by about 0.05%-1.2% (weight) in optical brightener known in the art or other blast or whitening agent.Can be used for commercialization optical brightener of the present invention and can be divided into several groups, comprise (but not necessarily being limited to) stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiphene-5, derivative and other brightener of 5-dioxide, pyrroles, 5-and 6-joint ring heterocyclic compound.The example of such brightener has been disclosed in New York, John Wiley ﹠amp; In the M.Zahradnik work " production of brightener and application (The production andApplication of Fluorescent Brightening Agents) " that Sons company publishes nineteen eighty-two.
The specific examples that can be used on the optical brightener in the present composition is authorized on December 13rd, 1988 in the United States Patent (USP) 4,790,856 of Wixon and is proposed.These brighteners comprise the PHORWHITE series brightener of Verona company.Other brightener that discloses in this piece document comprises: Tinopal UNPA, Tinopal CBS and the Tinopal 5BM that can buy from Ciba-Geigy company; The Arlic WhiteCC and the Artic White CWD that can buy from Hilton-Davis (Italy) company; 2-(4-Strvl-phenyl)-2H-naphthols [1,2-d] triazole species; 4,4 '-two-(1,2,3-triazoles-2-yl) stilbene class; 4,4 '-two (stryl) biphenyl class and aminocoumarin class.The specific examples of these brighteners comprises 4-methyl-7-diethyl-aminocoumarin; 1, two (Venzimidazol-2-yl) ethene of 2-; 1,3-phenylbenzene-phrazolines; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-stryl-napth-[1,2-d] oxazole and 2-(stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.Authorize the United States Patent (USP) 3,646,015 of Hamilton referring on February 29th, 1972.The negatively charged ion brightener is preferred in the present invention.
The softening agent of fabric softener-various perforation washing (through-the-wash) fabrics, especially authorized the United States Patent (USP) 4 of Storm and Nirschl on December 13rd, 1977,062, disclosed particulate smectic structure potter's clay in 647, and other potter's clay softening agent known in the art all can randomly be used for composition of the present invention, typical consumption is about 0.5%-10% (weight), so that fabric favourable its softness when cleaning.The potter's clay softening agent can and authorize also that disclosed amine and cationic softener share in people's such as Harris the United States Patent (USP) 4,291,071 with the United States Patent (USP) 4,375,416 of for example authorizing people such as Crisp March 1 nineteen eighty-three on September 22nd, 1981.
Other all composition of other composition-can be used in the detergent composition all can be included in the composition of the present invention, comprises the solvent of other activeconstituents, carrier, hydrotropic agent, processing aid, dyestuff or pigment, liquid formulations, the solid weighting agent of bar compositions etc.As when requiring high foaming, suds booster is C for example
10～C
16Alkanolamide can be added in the composition, and general content is 1%-10%.C
10～C
14Monohydroxy-alcohol acid amides and two alcohol amide are suds boosters of a quasi-representative.Such suds booster with as above-mentioned amine oxide, betaine and sulfo group betaine to help foaming surfactant to use also favourable.If need, generally can add for example MgCl of 0.1%～2% solubility magnesium salts
2, MgSO
4Deng to increase foam and to strengthen greasy removing performance.
The various decontamination compositions that are used for the present composition can apply described matrix with hydrophobic coating and reach further stabilization then randomly by they being adsorbed in the porous hydrophobic matrix.Preferably, the decontamination composition mixes with tensio-active agent earlier before in being adsorbed into porous matrix.In use, the decontamination composition discharges from above-mentioned matrix and enters in the water lotion, thereby finishes the dirt-removing functions of its expection.
For illustrating in greater detail this technology, with porous hydrophobic silicon-dioxide (trade(brand)name SIPERNATD10, DeGussa) with contain 3%-5%C
13-C
15The proteolysis enzyme solution of ethoxylated alcohol (EO7) nonionogenic tenside mixes.Typically, enzyme/surfactant soln is generally 2.5X silicon-dioxide heavily.The gained powder under agitation is scattered in the silicone oil and (can uses range of viscosities to be 500-12,500 various silicone oils).Again with the silicone oil dispersion liquid emulsification that obtains or add in to the end the washing composition matrix.In this way; for example above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, photosensitizer, dyestuff, fluorescent agent, fabric conditioner and the hydrolyzable tensio-active agent of each composition all in addition " protection " be used for washing composition, comprise being used for liquid laundry detergent composition.
Liquid or gelatinous composition can contain some water and other fluid is made carrier.Suitable is lower molecular weight uncle or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol, solubilizing surfactant is preferably used monohydroxy-alcohol, but for example also can use those polyvalent alcohols that contain about 6 carbon atoms of 2-and about 6 hydroxyls of 2-(as 1, ammediol, ethylene glycol, glycerol and 1, the 2-propylene glycol).Composition can contain 5%-90% and be generally the such carrier of 10%-50%.
Detergent composition of the present invention preferably should be prepared to be become: during being used for the water cleaning operation, washing water should have the pH value between about 6.5-about 11.5, preferably between about 7.5-10.5.Washed and automatic dishwashing product is generally at pH9-11.PH being controlled at the technology of recommending usage level comprising use buffer reagent, alkali, acid etc., is well-known to those skilled in the art.For various cleanings and bleaching operation, composition can use under about 5 ℃-boiling temperature.The consumption of composition is generally 50ppm-10 in water lotion, in the 000ppm scope, but is not limited to this scope.
The composition that the following examples explanations can be produced with cationic bleach activators of the present invention, but be not limited thereto.Such composition is the general activator that discharges at least about 10ppm in washing lotion, is preferably about 50ppm～700ppm.This can be regulated according to the requirement of formulator.Example II
Earlier water-soluble a kind of simple and effectively the fabric bleaching agent is composed as follows before using:
Component % (weight)
The cationic activation agent
*7.0
Sodium peroxoborate (monohydrate) 50.0
Water glass 5.0
The sodium sulfate surplus
*The caprolactam activators of producing by embodiment 1
In another embodiment, the example I composition changes with the alternative Sodium peroxoborate of SPC-D.EXAMPLE III
A kind of particulate laundry detergent that bleaching activity is promoted comprises following component:
Component % (weight)
The cationic activation agent
15.5
Sodium peroxoborate
2(monohydrate) 17.0
C
12Alkylbenzene sulfonate 10.0
C
14-C
15Alkyl-sulphate 10.0
ZeoliteA (1-10 micron) 30.0
Polyoxyethylene glycol (4000) 1.5
Sodium sulfate 11.0
Lipolase 0.20
Savinase enzyme 0.75
Termamyl enzyme 0.30
Diethylentriamine pentacetate 0.6
Water glass 3.0
Yellow soda ash 6.0
Other and moisture content surplus
1Produce by example I
2Available percarbonate substitutes Sodium peroxoborate.
The composition of EXAMPLE III is used for the ordinary method laundering of textile fabrics, and it has excellent elimination mottling performance, especially to the removing of tea and drinks mottling.
If need, the composition that is equivalent to EXAMPLE III usually can be processed slivering (piece) shape washing soap with conventional compacting and extrusion method.EXAMPLE IV
A kind of automatic dishwashing compositions is composed as follows:
Component % (joint)
The cationic activation agent
13.0
SPC-D
215.0
Trisodium Citrate 15.0
Yellow soda ash 20.0
Water glass 9.0
Nonionogenic tenside
32.0
Dispersion agent
46.0
Savinase enzyme 2.0
Termamyl enzyme 1.5
Diethylentriamine pentacetate 0.15
Sodium sulfate, moisture content, auxiliary material surplus
1Produce by example I.
2Can be substituted by perborate.
3Preferred low whipping agent.
4The polyacrylate type.
The EXAMPLE IV composition has the excellent properties that can remove various mottlings from vessel.Persistent mottlings such as tea can be removed from dish surface effectively.
Claims (8)
1. following formula bleach activating immunomodulator compounds:
Wherein x is 0 or 1, substituent R, R ' and R, and " C respectively does for oneself
1-C
10Alkyl, C
2-C
4Hydroxyalkyl or [C
yH
2y) O]
n-R , y=2-4 wherein, n=1-20 and R are C
1-C
4Alkyl or hydrogen and X are negatively charged ion.
2. according to the hexanolactam compound of claim 1, wherein X is 1, and each substituent R, R ' and R " are selected from methyl, ethyl or hydroxyethyl.
3. according to the Valerolactim compound of claim 1, wherein x is 0, and each substituent R, R ' and R " are selected from methyl, ethyl or hydroxyethyl.
4. bleaching composition, it comprises each bleach-activating agent and the SYNTHETIC OPTICAL WHITNER by claim 1-3.
5. according to the composition of claim 4, wherein SYNTHETIC OPTICAL WHITNER is selected from perborate and percarbonate bleach.
6. washed detergent composition of using, it comprises: (a) by the bleach activating immunomodulator compounds of claim 1; (b) SYNTHETIC OPTICAL WHITNER; (c) detersive surfactant; (d) optional one or more detergent additives.
7. automatic dishwashing compositions, it comprises: (a) according to the bleach activating immunomodulator compounds of claim 1; (b) SYNTHETIC OPTICAL WHITNER; (c) one or more decontamination lotion promoters; (d) optional low-foaming surfactant; (e) optional one or more detergent additives.
8. remove the method for spot from fabric or crust for one kind, comprise described spot is contacted with SYNTHETIC OPTICAL WHITNER with according to the bleach activating immunomodulator compounds of claim 1 in water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9407944.9 | 1994-04-21 | ||
| GB9407944A GB9407944D0 (en) | 1994-04-21 | 1994-04-21 | Cationic bleach activators |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1151158A true CN1151158A (en) | 1997-06-04 |
Family
ID=10753912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95193687 Pending CN1151158A (en) | 1994-04-21 | 1995-04-04 | Cationic bleach activators |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH09512531A (en) |
| CN (1) | CN1151158A (en) |
| GB (1) | GB9407944D0 (en) |
| WO (1) | WO1995029160A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093291A (en) * | 2010-12-10 | 2011-06-15 | 上海应用技术学院 | Preparation method of N-[4-(triethyl aminomethyl) benzoyl] caprolactam bromide |
| CN103225199A (en) * | 2013-05-07 | 2013-07-31 | 江南大学 | Preparation and application method of fabric normal-temperature rinsing system |
| CN103554024A (en) * | 2013-11-22 | 2014-02-05 | 江南大学 | Synthesis method for cationic bleaching activating agents with surface activity |
| CN104151310A (en) * | 2014-07-11 | 2014-11-19 | 江南大学 | Dicationic bleaching activator and synthesis method and application thereof |
| CN107130425A (en) * | 2017-05-09 | 2017-09-05 | 南京鞋局信息技术有限公司 | A kind of fabric normal temperature rinse reagent of non-aqueous solution system |
| CN110320354A (en) * | 2019-07-24 | 2019-10-11 | 无锡市妇幼保健院 | A kind of antigen retrieval buffers and application method |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5755992A (en) * | 1994-04-13 | 1998-05-26 | The Procter & Gamble Company | Detergents containing a surfactant and a delayed release peroxyacid bleach system |
| US5578136A (en) * | 1994-08-31 | 1996-11-26 | The Procter & Gamble Company | Automatic dishwashing compositions comprising quaternary substituted bleach activators |
| MX9703718A (en) * | 1994-11-18 | 1998-02-28 | Procter & Gamble | Bleaching compositions and bleach-additives comprising bleach activators effective at low perhydroxyl concentrations. |
| US5599781A (en) * | 1995-07-27 | 1997-02-04 | Haeggberg; Donna J. | Automatic dishwashing detergent having bleach system comprising monopersulfate, cationic bleach activator and perborate or percarbonate |
| DE19616770A1 (en) * | 1996-04-26 | 1997-11-06 | Henkel Kgaa | Acyl lactams as bleach activators for detergents and cleaning agents |
| US8252122B2 (en) | 2009-03-17 | 2012-08-28 | Bbt Bergedorfer Biotechnik Gmbh | Use of an agent that contains carbamide and/or at least a derivative thereof as a cleaning agent |
| EP3191572A1 (en) | 2014-09-10 | 2017-07-19 | Basf Se | Encapsulated cleaning composition |
| US20190085273A1 (en) | 2016-03-09 | 2019-03-21 | Basf Se | Encapsulated laundry cleaning composition |
| GB202014070D0 (en) | 2020-09-08 | 2020-10-21 | Alborz Chemicals Ltd | Polymorph |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3332939A (en) * | 1967-07-25 | Acylated lactams |
-
1994
- 1994-04-21 GB GB9407944A patent/GB9407944D0/en active Pending
-
1995
- 1995-04-04 JP JP7527653A patent/JPH09512531A/en not_active Ceased
- 1995-04-04 CN CN 95193687 patent/CN1151158A/en active Pending
- 1995-04-04 WO PCT/US1995/004154 patent/WO1995029160A1/en active Application Filing
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093291A (en) * | 2010-12-10 | 2011-06-15 | 上海应用技术学院 | Preparation method of N-[4-(triethyl aminomethyl) benzoyl] caprolactam bromide |
| CN102093291B (en) * | 2010-12-10 | 2012-10-24 | 上海应用技术学院 | Preparation method of N-[4-(triethyl aminomethyl) benzoyl] caprolactam bromide |
| CN103225199A (en) * | 2013-05-07 | 2013-07-31 | 江南大学 | Preparation and application method of fabric normal-temperature rinsing system |
| CN103554024A (en) * | 2013-11-22 | 2014-02-05 | 江南大学 | Synthesis method for cationic bleaching activating agents with surface activity |
| CN104151310A (en) * | 2014-07-11 | 2014-11-19 | 江南大学 | Dicationic bleaching activator and synthesis method and application thereof |
| CN107130425A (en) * | 2017-05-09 | 2017-09-05 | 南京鞋局信息技术有限公司 | A kind of fabric normal temperature rinse reagent of non-aqueous solution system |
| CN110320354A (en) * | 2019-07-24 | 2019-10-11 | 无锡市妇幼保健院 | A kind of antigen retrieval buffers and application method |
| CN110320354B (en) * | 2019-07-24 | 2022-04-08 | 无锡市妇幼保健院 | Antigen repairing liquid and using method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09512531A (en) | 1997-12-16 |
| WO1995029160A1 (en) | 1995-11-02 |
| GB9407944D0 (en) | 1994-06-15 |
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