CN1124977A - Bleach activation via anhydrides and lipase - Google Patents
Bleach activation via anhydrides and lipase Download PDFInfo
- Publication number
- CN1124977A CN1124977A CN 94192284 CN94192284A CN1124977A CN 1124977 A CN1124977 A CN 1124977A CN 94192284 CN94192284 CN 94192284 CN 94192284 A CN94192284 A CN 94192284A CN 1124977 A CN1124977 A CN 1124977A
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- CN
- China
- Prior art keywords
- additive
- detergent composition
- composition
- lipase
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000004367 Lipase Substances 0.000 title claims abstract description 49
- 108090001060 Lipase Proteins 0.000 title claims abstract description 49
- 102000004882 Lipase Human genes 0.000 title claims abstract description 49
- 235000019421 lipase Nutrition 0.000 title claims abstract description 49
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 20
- 230000004913 activation Effects 0.000 title claims abstract description 14
- 150000008064 anhydrides Chemical class 0.000 title abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 108
- 239000003599 detergent Substances 0.000 claims abstract description 43
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 102000004190 Enzymes Human genes 0.000 claims abstract description 28
- 108090000790 Enzymes Proteins 0.000 claims abstract description 28
- 230000000694 effects Effects 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 108090000371 Esterases Proteins 0.000 claims abstract description 6
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
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- 235000010233 benzoic acid Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
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- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
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- 235000015165 citric acid Nutrition 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
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- 238000005202 decontamination Methods 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 239000002270 dispersing agent Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
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- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical class OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 235000019626 lipase activity Nutrition 0.000 description 1
- 230000002366 lipolytic effect Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- HPEUEJRPDGMIMY-IFQPEPLCSA-N molybdopterin Chemical class O([C@H]1N2)[C@H](COP(O)(O)=O)C(S)=C(S)[C@@H]1NC1=C2N=C(N)NC1=O HPEUEJRPDGMIMY-IFQPEPLCSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- JOZQZNSZHRGPIO-UHFFFAOYSA-N n,n-dimethylmethanamine;toluene Chemical compound CN(C)C.CC1=CC=CC=C1 JOZQZNSZHRGPIO-UHFFFAOYSA-N 0.000 description 1
- GHLZUHZBBNDWHW-UHFFFAOYSA-N nonanamide Chemical compound CCCCCCCCC(N)=O GHLZUHZBBNDWHW-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical class [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Classifications
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
-
- 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
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
-
- 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
- C11D3/3942—Inorganic per-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
- C11D3/3947—Liquid compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
The invention concerns a detergent composition or additive containing a lipase and/or enzyme having esterase activity, an anhydride and a source of hydrogen peroxide, wherein said composition has a bleach activation effect. The use of said composition or additive in washing laundry to remove especially triglyceride or grease in addition to bleachable soils is also disclosed in this invention.
Description
SYNTHETIC OPTICAL WHITNER is used for laundry detergent for a long time to strengthen comprehensive cleaning action of laundry detergent.Various SYNTHETIC OPTICAL WHITNER are used for many-sided washing purposes for a long time, and comprising the washing and the pre-wash of fabric, and hard table cleaning (hard surface cleaning) waits other purposes.
The effect of SYNTHETIC OPTICAL WHITNER is with color spot on fabric, yarn fabric and the stiff dough and dirt oxidation.And peroxy bleaching compounds such as hydrogen peroxide, Sodium peroxoborate or SPC-D have the oxidation vigor, so these compounds often use in bleaching preparations.
Some organic compound is added in the SYNTHETIC OPTICAL WHITNER as perborate can generates peracid, thereby improve bleachability.Such organic compound comprises such as tetraacetyl ethylene diamine activators such as (TAED).
Also replenish various enzymes in the detergent composition of having developed and be used to remove some color spot and dirt.
For example, proteolytic enzyme color spot of protein hydrolysate matrix especially effectively in the cleaning of fabric.
Amylase can be used for removing the carbohydrate matrix color spot that is produced by food etc., and lipase is in prewashing or very effective to the hydrolysis of lipid substrate color spot in soaking again.
The EP-A-130 of Novo Industry A/S application has described enzyme as a kind of application of improved additives in washing or detergent composition that substantially improves scourability in 064.Can affirm that people need a kind of improved bleaching or activatory oxidizer system, in the aqueous solution, this system also can keep this performance under hot conditions except have the ability of improving bleaching effect under the cold washing condition.
Clorox?Comp。The EP-B-268 of application has described a kind of like this activatory oxidizer system in 465, with under a kind of hydrogen peroxide cource, reaches enzymatic hydrogen peroxide hydrolysis (enzymatic perhydrolysis) substrate generation peracid.The substrate for enzymatic activity reaction causes the formation of peracid.
The substrate of the enzyme effect of using in above-mentioned patent, more definite substrate of saying so the lipase effect is the ester class.Yet ester is highly stable and reactive behavior is low in normal conditions, unless they have especially effectively leavings group when synthetic.Though ester can generate peracid in the presence of lipase and superoxide, this reaction efficiency is very low.Therefore known to the inventor, the practical application in washing composition never of ester and lipase.The invention solves the problems referred to above.And relate to a kind of high-efficient washing system.The present invention relates to a kind of detergent composition or additive, comprise lipase and/or have the enzyme of esterase activity, a kind of acid anhydrides and a kind of hydrogen peroxide cource, described composition has bleach activation.Found acid anhydrides in containing the environment of hydrogen peroxide, both having made does not have lipase to exist, and is very active effective molecule yet, can react the generation peracid.The adding of lipase further promotes reaction surprisingly and strengthens the hydrogen peroxide hydrolysis of acid anhydrides, thereby becomes more effective bleach system.
Therefore, of the present invention comprise a kind of acid anhydrides, a kind of lipase and/or have the enzyme of esterase activity and a kind of composition of hydrogen peroxide cource efficient and very big magnetism is arranged with it for scourability.
Thus, the invention provides a kind of new hydrogen peroxide activation method, adopted acid anhydrides and lipase and/or had the enzyme of esterase activity.Find that sufficient bleach activating phenomenon takes place for lipase and acid anhydrides in superoxol.This phenomenon is more much better than than add acid anhydrides or lipase separately in superoxol, thereby the generation of this phenomenon and the acid anhydrides that adds in bleaching environment and lipase and the synergy that causes is relevant.
In the solution that contains acid anhydrides and hydrogen peroxide, add lipase can obviously quicken corresponding to the generation of the peracid of acid anhydrides.This effect is novel, because in traditional theory, lipase only helps the hydrolysis of ester class (particularly triglyceride level).According to the present invention, any lipase all is novel in unexpected to the effect of acid anhydrides or hydrolytic action.
This activation system will replenish the effect of known bleach-activating agent, and these activators comprise TAED, NOBS, BOBS, different BOBS, PAG, TAGU, SULFONIMINES, metalloporphyrin, Organic Manganese complex compound, quaternary ammonium or quaternary phosphine bleaching precursor (as trimethyl ammonium toluene acyloxy benzene sulfonate) or acetylated glycerol fatty acid esters.This activation system also will replenish the effect that is pre-formed peracid, and the example of these peracid has DPDA, NAPAA, PAP (N, the N-phthaloyl imino is crossed caproic acid), single brassylic acid and two of crossing to cross brassylic acid.In fact, the acid anhydrides of the overwhelming majority with ring-type or straight chain skeleton structure all can be used for the present invention; Mixed acid anhydride also is fit to the present invention, because it can generate different hydrophobic performances and surface-active peracid simultaneously, thereby the dirt that removal has different avidity is had special efficacy.
Comprise a kind of hydrogen peroxide cource (perborate, percarbonate etc.) if drying composition or the liquid composition that comprises hydrogen peroxide itself also contain acid anhydrides and lipase, so this composition can have the bleach activation of remarkable reinforcement.The present invention also can be used for the liquid product that those pH values, composition and diluted state three can reach the stability of permission applicable to the many products from granulated detergent to the granular bleaching agent.
Should suitably select the pH value of solution when in wash(ing)cycle, using detergent composition of the present invention or additive, so that the alkalescence conversion that acid anhydrides (polymkeric substance) is become carboxylate salt minimizes.Therefore for instance, 1% solution of pH value between 7 to 11 is suitable.
The commercially available acid anhydrides that is similar to succinyl oxide and maleic anhydride can be included in a kind of anhydrous bleaching composition and be used in combination with lipase.The acid anhydrides that certainly, also can comprise other no ring-type structures or symmetrical structure.
Polymeric anhydride and comprise that the copolymerization acid anhydrides of anhydride monomers is also very suitable.The multipolymer of preferred in this respect vinylformic acid and maleic anhydride.
For acid anhydrides is added in the anhydrous substrate, available solid phase as cyclodextrin absorbs anhydrous material (as succinyl oxide or maleic anhydride) and liquid material.Condense or the finished product of coating can improve the stability of acid anhydrides in finished product with suitable protection material (as CMC weighting material etc.).Use bleach activating system of the present invention, can outside the decontamination advantage of performance lipase uniqueness, TAED, NOBS or other well-known activators can effectively be replaced or combination.By utilizing system of the present invention, acid anhydrides can produce organic acid, and according to employed specific molecular, these organic acids can be in the suds and have good synergy ability.
As with flocculation agent or the coating-forming agent of above-mentioned acid anhydrides (polymkeric substance), can make bleach precursor in alkalis, have better stability as bleach precursor.Better fabric consistency and unexpected collaborative bleach activation appear subsequently.
A kind of representative formulations of the present invention comprises:
SPC-D 3～80%
Acid anhydrides or source of anhydride 0.1～10%
Lipase 0.1～10%
TAED 0～20％
Cushion/weighting material 0～90%
Washing assistant 0～90%
Tensio-active agent 0～20%
Other enzymes 0～5%
Other are 0～10% years old
Illustrate that specific examples of the present invention is representational clothing SYNTHETIC OPTICAL WHITNER preparation (A) and representational laundry detergent formulations (B):
A B
Other enzymes of % % SODIUM PERCARBONATE 40 20TAED 12 5 maleic anhydrides/acrylic acid granular polymer 5 buffers 38 20 lipase (Lipolase Novo100T) 0.5 0.5 builders-30 surfactant-15 0.5 1.5 other-4
Illustrate that more specifically example of the present invention is a representational granular automatic dishwasher preparation (C) and (D):
Granular automatic dishwasher detergent formulations (C) and (D) in, the meaning of used shortenings is explained as follows:
Perborate: anhydrous sodium perborate monohydrate
Percarbonate: anhydrous SPC-D
TAED: tetra acetyl ethylene diamine
Citrate trianion: citrate trisodium dihydrate
MA/AA:1: toxilic acid/acrylic copolymer of 4, molecular-weight average is about
Be 80,000.
Silicate: amorphous sodium silicate (common SiO
2: Na
2The O ratio)
Proteolytic enzyme: the protease of commodity Savinase by name, Novo Industry
A/S sells.
Amylase: the amylolytic enzyme of commodity Termamyl by name, Novo Industry
A/S sells.
Lipase: the lipolytic enzyme of commodity lipolase by name, Novo Industry
A/S sells
Non-ionic type: the C of commodity Plurfac LF404 by name
13～C
15Mix oxyethyl group
Change/propenoxylated Fatty Alcohol(C12-C14 and C12-C18), average degree of ethoxylation 3.8, average third
Oxygen base degree 4.5.BASF GMbH sells.
PVP: molecular-weight average is 12,000 Polyvinylpyrolidone (PVP).
Vitriol: anhydrous sodium sulphate prepares the preparation (parts by weight) of following dishwasher washing agent of the present invention: the composition weight umber
Before C D citrate 38.0 35.0 perborate 3.5-percarbonate-3.5 TAED, 2.0 2.0 MA/AA, 4.0 6.0 silicate (ratio is 2) 26.0 30.0 paraffin oils (1) 0.5 0.5 protease 2.0 2.5 amylase 1.5 0.5 lipase 2.0 2.0 nonionics (2) 1.5 1.5 lime soap dispersant (3) 2.0-PVP-0.5 sulfate are added to 100 pH values 10.7 10.7 10.7 (1) and add available from the WINOG 70 (2) of Wintershall with the Lutensol AOI2 of paraffin oil premixed (3) available from BASF
Lipase
The used lipase of the present invention is included in washing composition and the bleaching composition, and its consumption makes the steatolysis enzymic activity that has 10～0.005LU/mg in the final composition, preferred 5～0.05LU/mg composition.
It is a kind of 13mmol of containing Ca that one lipase unit (LU) is defined as at 30 ℃ of temperature, pH=9.0, substrate
++The 3.3wt% sweet oil and the emulsion of 3.3% Sudan Gum-arabic, 5mmol/l Tris-buffer reagent in contain under the condition of 20mmol/l NaCl, stablize the amount that pH value system per minute generates 1/ little used lipase of titratable lipid acid that rubs.EP0258068 (Novo) is seen in the another kind definition of lipase unit, and this patent (inter alia) is mentioned operable lipase in actually operating of the present invention, quotes for referencial use herein.
Certainly can use the mixture of above-mentioned lipase and other known lipase.Can use the not purified lipase or the lipase of purifying, purification process can adopt similar phenyl sepharose adsorption technology variously knows adsorption method.
Detergent composition of the present invention or additive can be mixed with any form easily, wherein preferred powder form.Composition has various purposes and can be used in anhydrous bleaching preparation and the detergent formulations, comprising clothing and automatic dishwasher detergent formulations.
The machinery that composition of the present invention the can be used for general types process that washes the dishes, used dishwasher can be selected from market.More particularly, this machinery process of washing the dishes comprises with the dissolving or the aqueous solution that is dispersed with the said detergent composition of significant quantity and handles the article that dirt is arranged, for example pottery, glassware, hollow ware and cutter etc.The significant quantity of detergent composition is as the wash the dishes dosage of process product commonly used of standard machinery, and each washing adds 8g～16g detergent composition, makes it dissolving or is dispersed in 3 to 10 liters of washing solns.The washing process temperature is generally in 40～65 ℃ of scopes.Also can add the rinse aid composition if desired.
Can contain other used components of aforementioned present technique field in detergent composition of the present invention or the additive; Deposition agent, flavouring agent, tensio-active agent, anti-pigment shift component, white dyes, other enzymes (as proteolytic enzyme and amylase) etc. again as washing assistant, anti-soil dirt.
In addition, detergent composition also can comprise tensio-active agent, they can be anion surfactant, nonionogenic tenside, amphoterics, cats product or zwitterionics, also can be these surfactant mixtures.
These commonly used tensio-active agents are authorized on May 23rd, 1972 in the United States Patent (USP) 3,664,961 of Norris and are listed.
The mixture of anion surfactant is particularly suitable in this, the mixture of sulfosalt surfactant and sulfate surfactant especially, and wherein the weight ratio of the two was generally 5: 1 to 1: 2, was preferably 3: 1 to 2: 3, more preferably 3: 1 to 1: 1.Preferred sulfonate comprises alkylbenzene sulfonate and α-sulfonation fatty acid methyl ester, and the alkyl chain carbon number of alkylbenzene sulfonate is from 9 to 15, and the alkyl chain that contains 11 to 13 carbon atoms is more suitable, and α-the used lipid acid of sulfonation fatty acid methyl ester can be from C
12～C
18Fat source is derived, wherein C
16～C
18Fat source more preferably.Negatively charged ion separately all is a basic metal, wherein preferred sodium.Preferred sulfate surfactant is the alkyl-sulphate of alkyl chain carbon number from 12 to 18, optionally mixes ethoxy sulfate during use, and the alkyl chain carbon number of ethoxy sulfate is 10 to 20, more preferably 10 to 16, and average degree of ethoxylation from 1 to 6.The example of preferred alkyl-sulphate has tallow alkyl sulfate, coconut palm fat alkyl-sulphate and C
14～15Alkyl-sulphate.The example of preferred ethoxy sulfate is usually said AE3S (C
12～15The vitriol of 3 ethoxylations of alkyl), the positively charged ion under the various situations is alkali metal cation, preferred sodium.
Can be used for a class nonionogenic tenside of the present invention is the condenses of oxyethane and hydrophobic part, is 8-17 to form average hydrophile-lipophile balance value (HLB), preferred 9.5-13.5, the more preferably tensio-active agent of 10-12.5.Hydrophobic (oleophylic) part can be aliphatic or aromatic with regard to character, can regulate easily with the length of the polyoxyethylene group of specific hydrophobic group condensation, to generate the water-soluble cpds of required hydrophile-lipophile balance value.For bringing into play the activity of lipase to greatest extent, the present invention preferably uses a kind of so-called mil-LAS that contains detergent composition or additive.
Particularly preferred this class nonionogenic tenside is the C that every mol of alcohol contains the 3-8 moles of ethylene oxide
9-C
15Primary alcohol ethoxylate, especially those every mol of alcohol contain the C of 6～8 moles of ethylene oxide
14～C
15Primary alconol and every mol of alcohol contain the C of 3-5 moles of ethylene oxide
12～C
14Primary alconol.
Another kind of ionic surfactant pack is drawn together alkyl polyglucoside (alkyl polyglucoside) compound of following general formula,
RO (C
nH
2nO)
tZ
xWherein the Z representative is by glucose deutero-part; R is the saturated hydrophobic alkyl group that contains 12 to 18 carbon atoms; T represents 0 to 10; N represents 2 or 3; X represents 1.3 to 4.Also comprise unreacted Fatty Alcohol(C12-C14 and C12-C18) that is less than 10% and the short-chain alkyl polyglucoside that is less than 50% in this compound.This compounds is open being applied among the EP-B0070077,0075996 and 0094118 of washing composition with them.
Suc as formula
Polyhydroxy fatty acid amide surfactant also be suitable for and make nonionogenic tenside, wherein R
1Represent H, C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture; R
2Represent C
5-31Alkyl, Z representative comprise one and bring to few 3 polyhydroxy alkyls that directly are connected to the linear alkyl of the hydroxyl on the chain, or its alkoxy derivative; Wherein preferential is R
1Represent methylidene, R
2Represent straight chain C
11～17Alkyl or alkenyl chain, for example coconut alkyl or their mixture, Z is derived from the reducing sugar in the reductive amination process, for example glucose, fructose, maltose and lactose.
According to the present invention, it is anion surfactant and nonionogenic tenside between 1: 1 to 10: 1 that detergent composition or additive preferably comprise ratio.
Another kind of tensio-active agent is the semi-polarity tensio-active agent as amine oxide.The amine oxide that is suitable for is selected from single C
8～C
20(preferred C
10～C
14) N-alkyl or alkenyl amine oxide compound and 1.3-propylene diamine dioxide, wherein remaining nitrogen bonding position can be replaced by methyl, hydroxyethyl or hydroxypropyl.
Another kind of tensio-active agent is an amphoterics, as being the tensio-active agent of principal constituent with the polyamine.
Cats product also can be used in the detergent composition of the present invention, and the quaternary surfactant that is fit to is selected from single C
8～C
16(preferred C
10～C
14) N-alkyl or alkenyl ammonium surfactant, wherein residual nitrogen bonding position can be replaced by methyl, hydroxyethyl or hydroxypropyl group.
The mixture of various surfactants, particularly cloudy release-non-ionic type and anionic-non-ionic type-cationic mixture are preferred.Particularly preferred surfactant mixture is described in British Patent NO.2040987 and EuropeanPublished Application NO.0087914.The tensio-active agent that can contain 1%～70% weight in the detergent composition, but the content of tensio-active agent is generally 1%～30% (weight) in detergent composition of the present invention, more preferably 10～25%.Too much tensio-active agent is harmful to lipase activity.
Washing assistant
Help washing matter content in detergent composition of the present invention to be generally 0%～90%; Preferred 0%～30%.
Detergent composition of the present invention should preferably not contain or not phosphatic substantially washing assistant (herein do not contain substantially mean help at total washing composition its content is less than 1% in the system of washing).The system of washing that helps of the present invention can be made up of water soluble detergency promoter, water-insoluble washing assistant or their mixture.Certainly, when detergent composition was same as the automatic bowl process, washing assistant was preferably water miscible.
Water-insoluble washing assistant can be an a kind of mineral ion exchange material, selects the inorganic silicon-aluminum hydrochloride hydrates usually for use, especially as the synthetic zeolite hydrate of hydrated zeolite A, X, B, P, MAP or HS.
Preferred silico-aluminate ion exchange material has following structure cell formula:
M
z[(AlO
2)
z(SiO
2)
y]
xH
2O wherein M represents the calcium exchange cation; Z and Y are at least 6, and the mol ratio of Z and Y is 1.0 to 0.5; X is at least 5, and is preferred 7.5～276, and more preferably 10～264.The silico-aluminate material is a hydrated form, and the crystal of preferably moisture 10%～28% (more preferably 18%～22%).
The feature of above-mentioned silico-aluminate ion exchange material is that also its particle diameter is between 0.1 to 10 micron, preferred 0.2～4 micron; " particle diameter " vocabulary shows the average particle diameter of the given ion exchange material that the analysis means commonly used such as microscopy that adopt scanning electronic microscope are for example measured herein.The feature of silico-aluminate ion exchange material is that also its calcium ion-exchanged capacity should be at least the normal CaCO of 200mg in anhydride
3The water hardness/g silico-aluminate, generally at the 300mg equivalent between 352mg equivalent/g.The feature of silico-aluminate ion exchange material of the present invention also is their calcium ion exchange rate, sees GB-l for details, 429,143.
The silico-aluminate ion exchange material that the present invention can actual use is commercially available product, can be natural goods, but synthetics preferably., discussed in 985,669 at US Patent NO.3 about the method for preparing the silico-aluminate ion exchange material.The synthetic crystallization shape silico-aluminate ion exchange material that can preferably use can Zeolite A, with ZeoliteB, with ZeoliteX, buy with the trades mark such as Zeolite HS and their mixtures.In a particularly preferred embodiment, the crystal aluminosilicate ion exchange material is Zeolite A, and molecular formula is:
Na
12[(AlO
2)
12(SiO
2)
12] xH
2O wherein X is 20～30, especially 27.Molecular formula is
Na
86: (AlO
2)
86(SiO
2)
106]-10.276H
2Zeolite X and the molecular formula of O are
Na6[(AlO
2)
6(SiO
2)
6] 7.5H
2O). Zeolite HS also is fit to.
The another kind of water-insoluble no machine aided washing matter that is fit to is stratification silicate (Layeredsilicate), as SKS-6 (Hoechst).SKS-6 is a kind of by water glass (Na
2Si
2O
5) the crystallization stratification silicate formed.High Ca
++/ mg
++Binding ability mainly is a cationic exchange mechanism.This substance dissolves improves in hot water.
Water soluble detergency promoter can be monomer or oligomeric carboxylate sequestrant.
The carboxylate that contains a carboxyl that is fit to comprises lactic acid, glycolic acid and their ether derivant, and this is open in Belgian Patent Nos.831 368,821369 and 821370.The many carboxylates that contain two carboxyls comprise the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) diacetic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid, and German Offenlegen Schrift 2,446,686 and 2,446,687 and U.S.Patent NO.3,935, the ether carboxylate of describing in 257, Belgian PatentNO.840, the sulfinyl carboxylate of describing in 623.The many carboxylates that contain three carboxyls comprise water-soluble citrate, aconitate and citraconate, and succinate derivative, as British Patent NO.1,379, the newborn oxygen base succinate (lactoxysuccinate) and the British Patent NO.1 that describe among the carboxy methoxy-succinic acid salt of describing in 241, the Netherlands Application 7205873, the oxygen Quito carboxylate such as the 2-oxa--1 of description in 387,447,1,3-tricarballylic acid thing.
The many carboxylates that contain four carboxyls comprise British Patent NO.1, disclosed oxygen base disuccinate, 1,1,2 in 261,829,2-ethane tetracarboxylic acid thing, 1,1,3,3-propane tetramethyl acidulants and 1,1,2,3-propane tetramethyl acidulants.Contain the substituent many carboxylates of sulfo group and comprise British Patent Nos.1,398,421,1,398, disclosed sulfo-succinic acid salt derivative in 422 and U.S.PatentN0.3,936,448, with British PatentNO.1, the sulfonation pyrolysis Citrate trianion of describing in 082,179, and contain the substituent many carboxylates of phosphine at British Patent NO.1, open in 439,000.
The many carboxylates of alicyclic ring and heterocycle comprise pentamethylene-suitable, suitable, suitable-tetramethyl acidulants, cyclopentadiene five first acidulants, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetramethyl acidulants, 2,5-tetrahydrofuran (THF)-suitable-diformazan acidulants, 2,2,5,5-tetrahydrofuran (THF)-tetramethyl acidulants, 1,2,3,4,5, the carboxymethyl derivant of 6-hexane-pregnancy acidulants and polyhydroxy-alcohol, these polyvalent alcohol examples such as sorbyl alcohol, mannitol and Xylitol.The many carboxylates of fragrance comprise mellitic acid, 1,2,4,5-pyromellitic acid and British Patent NO.1, disclosed phthalic acid derivative in 425,343.
In above-mentioned many carboxylates, preferred many carboxylates are the hydroxyl carboxylate, particularly Citrate trianion that per molecule contains three carboxyls at the most.Used preferred builder system comprises as water-insoluble silico-aluminate washing assistant such as Zeolite A or stratification silicate (SKS/6) and mixture as water-soluble carboxylation thing sequestrants such as citric acids in the present composition.
Other washings that help that can be configured for builder system of the present invention comprise inorganics as alkaline carbonate, supercarbonate and silicate.
Other water-soluble organic salts that are fit to are homopolymerization or co-polymeric acids or their salt.Wherein poly carboxylic acid comprises at least two each other for the carboxyl of no more than two carbon atoms separate.
This base polymer is at GB-A-1, and is open in 596,756.The example of this class salt is that molecular weight is the multipolymer of the polyacrylate of 2000-5000 and it and maleic anhydride, the molecular weight of this analog copolymer in 20,000 to 70,00 scopes, especially about 40,000.
Composition of the present invention can fully contain and accounts in the composition weight 0.05% to 5% sequestrant (heavy metal sequestering agent), and is preferred 0.05%～1%, and most preferably 0.1%～0.5%.
The sequestrant that can suit to comprise in the detergent composition of the present invention is quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or its an alkali metal salt, alkaline earth salt, ammonium salt, replacement or their mixture.Preferred EDDS compound is free acid and its sodium salt or magnesium salts.The example of these preferred EDDS sodium salts comprises Na
2EDDDS and Na
4EDDS.The example of these preferred EDDS magnesium salts comprises MgEDDS and Mg
2EDDS.Most preferably contain the EDDS magnesium salts in the detergent composition of the present invention.
Other sequestrants include organic phosphonates, and amino alkylidenyl many (alkylene phosphonic acids salt), basic metal ethane 1-hydroxy-diphosphonic acid salt, WSI 3310 salt, ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt are wherein arranged.Phosphonate compounds can they sour form or exist with the form of the title complex of alkalimetal ion or alkaline metal ions, the molar ratio of described metal ion and described phosphonate compounds was at least 1: 1.These title complexs are at US-A-4, describe in 259,200.
Be preferably the magnesium salts form in the organic phospho acid compound that exists.The content of phosphorated chelating agent should be the least possible in the detergent composition of the present invention, gets rid of them fully in the most preferred group compound.The suitable sequestrant of other that can comprise comprises the amino many carboxylates sequestrant as EDTA and HEDTA.
Optional components
Generally also comprise optional components in the composition of the present invention, these components often constitute the part of detergent composition.The for example anti-redeposition of these optional compositions and soil-suspending agent, white dyes, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, suds suppressor, anti-hard caking agent, dyestuff and pigment, they can add different amounts as required.
Suitable anti-redeposition and soil-suspending agent comprise as derivatived celluloses such as methylcellulose gum, carboxymethyl cellulose and Natvosols, and homopolymerization or copolymerization poly carboxylic acid or their salt.Such polymkeric substance comprises that the front mentions polyacrylate and the copolymer of maleic anhydride and acrylic acid as washing assistant, also have the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, the maleic anhydride composition accounts for 20% (mole) at least in the multipolymer.The consumption of these materials is generally 0.5～10% of composition weight, and is preferred 0.75～8%, and most preferably 1%～6%.
Preferred white dyes is an anionic property, these examples have 4,4 '-two-(2-diethanolamino-4-anilino-S-triazine-6-base is amino) Stilbene-2,2 ' disulfonic acid disodium, 4-4 '-two-(2-morpholino-4-anilino-S-triazine-6-base is amino) Stilbene-2: 2 '-disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-S-triazine-6-base is amino) Stilbene-2: 2 '-the disulfonic acid disodium, 4 ', 4 " two-(2; 4-hexichol amido-S-triazine-6-base is amino) Stilbene-2-sodium sulfonate; 4,4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-S-triazine-6-base is amino) Stilbene-2,2 '-the disulfonic acid disodium; 4; 4 '-two-(4-phenyl-2; 1,3-triazole-2-yl)-Stilbene-2,2 ' disulfonic acid disodium, 4,4 ' two (2-anilino-4-(1-methyl-2-hydroxyethylamino)-S-triazine-6-base is amino) Stilbene-2,2 " disulfonic acid disodium and 2 (Stilbene base-4 "-(naphtho--1 ', 2 ': 4,5)-1,2,3-triazole-2 " sodium sulfonate.
The inorganic perhydrate SYNTHETIC OPTICAL WHITNER of any particulate (perhydrate bleach) all can be used.Inorganic perhydrate is 3%～80% of bleaching weight of additive at the consumption of bleaching in the additive, and is preferred 8%～60%, more preferably 12%～50%; As when being used for full formula (fully formulated) washing composition of European washing machine, its consumption is 3%～80% of a washing composition weight, and is preferred 12%～40%, more preferably 8%～30%; As when being same as in the full formula washing composition of American and Japanese washing machine, its consumption is 3%～80% of a washing composition weight, and is preferred 3%～15%, more preferably 3%～10%.The preferred example of these SYNTHETIC OPTICAL WHITNER is the monohydrate and the tetrahydrate of Sodium peroxoborate, SPC-D and their mixture.
The component of another kind of preferred additionally mixed is a kind of peroxycarboxylic acid SYNTHETIC OPTICAL WHITNER and its salt, preferably adds with form granular or as a form of gel during use.
Peroxygen bleach preferably mixes use with bleach-activating agent, (just in the washing process corresponding to the peroxy acid of bleach-activating agent) can produce resultant on the spot in the aqueous solution like this.Disclose the suitable example of this compounds among the British Patent Nos.1586769 and 2143231, in European PublishedPatent Application NO.0062 523, be described about making them generate globular method.The preferred example of these compounds is tetra acetyl ethylene diamines, 3; 5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt, diperoxy dodecylic acid, peroxide adipic acid pelargonamide, positive nonanoly acyloxy benzene sulfonate (NOBS) and acetyl triethyl Citrate trianion (ATC) as describing among the EuropeanPatent Application 91870207.7 as describing among the US 4 259 201 as in US 4 818 425, describing.
The consumption of bleach-activating agent be generally for instance composition heavy 1%～24%, more commonly used 1%～18%, preferred 2%～14%.
Another kind of optional components is a suds suppressor, for example siloxanes and silicon-dioxide one mixture of siloxanes.Siloxanes is generally the alkylation polysiloxane, and silicon-dioxide is generally selected its chip form for use, as aerosil and xerogel and dissimilar hydrophobic silicas.These materials can fine-grained form add, but wherein suds suppressor advantageously is added on a kind of non-surface active basically washing composition opacity carrier of water-soluble or water dispersible with releasing pattern.In addition, suds suppressor also solubilized or be dispersed in a kind of liquid vehicle and with spray method it is added on one or more other components.
As described above, the silicone foam control agent that is suitable for can comprise above the alkylation siloxanes of the kind of carrying and a kind of mixture of silica solid.This mixture is by making the method for siloxanes attached to the surface of solid silica.A kind of preferred silicone foam control agent be a kind of size of particles between 10 millimicrons to 20 millimicrons, specific surface area is greater than 50m
2The hydrophobic silaneization of/g (most preferably trimethylammonium-silanization) silicon-dioxide and molecular weight be the intimately admixing thing of the dimethyl silicone fluids between 500～2000 greatly, wherein siloxanes to the weight ratio of silanized silica greatly between 1: 1 to 1: 2.
A kind of preferred silicone foam control agent is disclosed among the U.S.Patent 3,933,672 of Bartollota etc.Other useful especially froth suppressor are self-emulsifying siloxane foams inhibitor, and this described in the German Patent ApplicationDTOS 2,646,126 that published on April 28th, 1977.An example of this compound is the DC-544 that commercially available DowCorning makes, and it is a kind of siloxanes/glycol multipolymer.
The consumption of above-mentioned suds suppressor is generally 0.001%～2% of composition weight, and preferred 0.01%～1%.Independent particle is preferably made in the adding of foam properties-correcting agent, so just can make wherein including other foam inhibition things, as C
20～C
24The high molecular weight copolymer of lipid acid, Microcrystalline Wax and oxyethane and propylene oxide, if not so, then these materials will have a negative impact to the dispersiveness of substrate.The U.S.Patent NO.3 for preparing Bartolotta that the technology of this foam modified particle formerly mentions etc., open in 933,672.
Other useful polymkeric substance are polyoxyethylene glycol, and particularly molecular weight is at 1000～10000 polyoxyethylene glycol, wherein molecular weight 2000～8000 more preferred, molecular weight be approximately 4000 the most preferred.The consumption of polyoxyethylene glycol be composition heavy 0.2% to 5%, preferred 0.25% to 2.5%.These polymkeric substance and previously mentioned homopolymerization or copolymerization multi-carboxylate are for promoting whiteness to keep in the presence of transition metal impurity, and fabric dust deposition and the scourability that improves clay, protein and oxidable dirt all are favourable.
Used soil releasing agent is the conventional terephthalic acid and ethylene glycol and/or the unitary multipolymer of propylene glycol or the terpolymer of different arrangements in the present composition.The example of these polymkeric substance is in the common US Patent Nos 4116885 that transfers the possession of and 4711730 and European Published Patent Application NO.0, and is open in 272,033.The expression formula of a kind of special preferred polymers of EP-A-0 272 033 is: (CH
3(PEG)
43)
0.75(POH)
0.25[T-PO)
2.8(T-PEG)
0.4] T (PO-H) 0.25 ((PEG)
43CH
3)
0.75PEG is-(OC in the formula
2H
4) O-, PO is (OC
3H
6O) and T be (pcOC
6H
4CO)
Modified poly ester also is well-adapted, this modified poly ester is dimethyl terephthalate, dimethyl sulfo group isophthalic ester, ethylene glycol and 1, the random copolymers of 2-propylene glycol, and its end group mainly is made up of the sulfosalicylic acid ester, secondly is made up of ethylene glycol and/or propylene glycol monoester.Target be obtain two ends all " mainly " by the polymkeric substance of sulfo group benzene methyl group end capping, be among the present invention most of multipolymers all by sulfosalicylic acid ester end-blocking, but the inwhole end-blockings of some multipolymer, so the end group of these multipolymers just may be by ethylene glycol and/or 1, the monoesters group of 2-propylene glycol is formed, and therefore " secondly " is just by these species compositions.
The dimethyl terephthalic acid that contains about 46% (weight) herein in the selected polyester, about 16% (weight) 1, the 2-propylene glycol, the ethylene glycol of about 10% (weight), the dimethyl methyl yl benzoic acid of about 13% (weight), with the sulfoisophthalic acid of about 15% (weight), and molecular weight is about 3,000.About polyester and preparation method thereof, in EPA 311 342, be explained in detail.
5000 to 20,000, some polymkeric substance such as polyvinylpyrrolidone of preferred 10000-15000 also can be used as effective auxiliary agent and are used for the transfer that washing process stops unstable tinting material between fabric as molecular weight.
Also can add fabric softener in the detergent composition of the present invention.These auxiliary agents can be inorganic or organic on kind.The example of inorganic softening agent has GB-A-1, disclosed montmorillonitic clay in 400,898.The organic fabric softening agent is included among GB-A-1514276 and the EP-B-0011340 disclosed water-insoluble tertiary amine and disclosed these water-insoluble tertiary amines and single C in EP-B-0 026 527 and EP-B-0 026 528
12～C
14Disclosed pair of long-chain acid amides among the mixture of quaternary ammonium salt and the EP-B-0 242 919.The useful organic constituent of other of fabric sofetening system comprises as EP-A-0 299 575 and 0,313, disclosed high molecular weight polyethylene oxide material in 146.
When montmorillonitic clay was added to the rest part of preparation as a kind of dry blending component, consumption was 5% to 20% of a composition weight, preferred 8% to 15%.The consumption of organic fabric softening agent such as water-insoluble tertiary amine or two long-chain acid amides be composition heavy 0.5% to 5%, be generally 1% to 3%; And the add-on of high molecular weight epoxy ethane class and water-soluble cationic material is 0.1% to 2% (weight), is generally 0.15% to 1.5%.Though can the dry mixed particulate forms add easily at these materials of some occasions, these materials are to be added in the spray-dired part of composition generally speaking, perhaps their liquid forms with fusing are sprayed onto in other solid ingredients of composition.
Manufacture method
Composition of the present invention can do mix by comprising, the whole bag of tricks manufacturing in being combined in of spraying drying, agglomeration and granulating and these technology.Composition of the present invention can be made into the product with different stacking densities, from the plain particles product to so-called " concentrating " product (being that the product tap density is greater than 600g/l).Example
Example 1
Contain two parts of 10ml superoxol (containing 35% (weight) effective ingredient), 50ml water and 5ml solution vinous, 1 part adds the 1g succinyl oxide, and another part adds 1g succinyl oxide and 1ml lipase suspension., filter after 3 hours Deng the marquis, measure the absorption value of two parts of test solutions at the 300nm place respectively with spectrophotometer, measurement result is as follows:
The not fatty enzyme of fatty enzyme
Absorption value (300nm place) 1.781 2.944
Above-mentioned data are for carrying out four experiment gained results' mean value separately, between each time test-results only behind radix point second minor swing appears, this shows that all experimental results are all quite accurate.
The existence that experimental result shows lipase has very strong promoter action (absorption value reduces 40%) to the decolouring of grape wine solution.There is a kind of great activation phenomenon in this indirect proof.
Example 2
2 parts of solution that contain 5ml grape wine, 10ml superoxol (effective ingredient that contains 35% (weight)) and 50ml water, 1 part adds another part of 1g succinyl oxide face and adds 1g succinyl oxide and the granular lipase of 0.3g., filter after 14 hours Deng the marquis, measure the absorption value (with absorption peak corresponding) of two parts of test solutions respectively at the 310nm place with spectrophotometer.Measurement result is as follows:
The not fatty enzyme of fatty enzyme
Absorption value (310nm place) 1.055 1.624
Above-mentioned data are for carrying out four experiment gained results' mean value separately.The accuracy of experimental result with last time tested identical.
The result shows that lipase has very strong promoter action (absorption value reduces 35%) to the decolouring of grape wine solution, and a kind of great activation phenomenon of this indirect proof exists.
Example 3
2 parts of solution that contain 10ml grape wine, 10ml superoxol (effective constituent that contains 35% (weight)) and 50ml water, 1 part adds the 1g succinyl oxide and another part adds 1g succinyl oxide and the granular lipase of 0.3g.After 14 hours, filter test solution Deng the marquis, measure the absorption value (with absorption peak corresponding) of two parts of test solutions respectively at the 317nm place with spectrophotometer.Measurement result is as follows:
The not fatty enzyme absorption value of fatty enzyme (317nm place) 1.793 2.387
Above-mentioned data are the mean value that carries out secondary experiment gained result separately.The accuracy of experimental result is identical with the front experiment.
Experimental result shows the stronger grape wine solution decolorization (absorption value reduces 25%) of generation when lipase exists once more, and this confirms that indirectly a kind of great activation phenomenon exists.
Example 4
2 parts of solution that contain 5ml grape wine, 10ml superoxol (effective ingredient that contains 35% (weight)) and 50ml water aly add the 1g maleic anhydride and another part adds 1g maleic anhydride and the granular lipase of 0.3g.Deng the marquis after 14 hours, filter test solution, measure near two parts of test solutions absorption value of (corresponding) 312nm respectively with spectrophotometer with absorption peak.Measurement result is as follows:
The not fatty enzyme of fatty enzyme
Absorption value (312mm place) 1.864 2.050
Above-mentioned data are the mean value that carries out secondary experiment gained result separately, between each time result only behind radix point the 3rd minor swing appears, this shows that all experimental results are all quite accurate.
Experimental result shows that grape wine solution has stronger decolorization (absorption value reduces 10%) when lipase exists.A kind of activation phenomenon of this indirect proof exists.
Example 5
Two parts of solution that contain 10ml grape wine, 10ml superoxol (activeconstituents that contains 35% (weight)) and 50ml water aly add the 1g maleic anhydride and another part adds 1g maleic anhydride and the granular lipase of 0.3g.Deng the marquis after 14 hours, filter test solution, measure near two kinds of test solutions absorption value of (corresponding) 318nm respectively with spectrophotometer with absorption peak.Measurement result is as follows:
The not fatty enzyme of fatty enzyme
Absorption value (318nm place) 2.41 2.67
Above-mentioned data are the mean value that carries out secondary experiment gained result separately, between each time result only behind radix point the 3rd minor swing appears, this shows that all experimental results are all quite accurate.
Experimental result shows that grape wine solution has stronger decolorization (absorption value reduces 10%) when lipase exists.A kind of activation phenomenon of this indirect proof exists.
Carry out the color spot of grape wine, coffee ﹠ tea with different preparations and remove test, the gained result confirms top conclusion too.
In fact these results preparation of all fully having given prominence to fatty enzyme and source of anhydride has the remarkable effect that promotes to remove color spot.
Example 6
The detergent compositions that contains a kind of source of anhydride and lipase with containing a kind of source of anhydride not the detergent compositions of fatty enzyme carry out the laundry test of unitary variant.
A is to A " forenamed prescription among removal-0.9A=the application of the removal of the color spot that the cleaning of collar and cuff-0.8 can be bleached (grape wine, the mean value of coffee ﹠ tea)-1.5 grease stains; A "=same recipe but not fatty enzyme; Test method: test is carried out in the washing machine that 40 ℃ of medium hardness (14g/us gallon) water is housed, and adds 170g ordinary granular washing composition and 50g A or A each wash(ing)cycle ".Each specimen test result is the mean value of 8 revision tests, but warranty test has good tolerance range and accuracy like this.
According to this test method, result between 0～0.5 unit represents that two removal effects that test products produced do not have observable difference, 0.6 the result between～1.0 units represents that two removal effects that test products produced have little but the visible difference, 1.1 the result between～2.0 represents that two kinds of removal effects that test products produced are obviously different, and range estimation can be judged easily.Positive result shows that first test kind has better removing effect.
Claims (10)
1, contain a kind of lipase and/or have the detergent composition or the additive of the enzyme of esterase activity, a kind of acid anhydrides and a kind of hydrogen peroxide cource, described composition has bleach activation.
2, according to the detergent composition or the additive of claim 1, wherein acid anhydrides is a kind of highly reactive polymer that contains the acid anhydrides residue.
3, according to the detergent composition or the additive of claim 2, wherein polymkeric substance is a kind of multipolymer that contains maleic anhydride and vinylformic acid residue.
4, according to each detergent composition or additive of aforementioned claim, wherein the amount of enzyme makes and has 10 to 0.005LU/mg steatolysis enzymic activity in the final product composition having, the amount of acid anhydrides is 0.1～10%, and the amount of hydrogen peroxide cource is 5%～80%.
5, according to each detergent composition or additive of aforementioned claim, wherein anion surfactant is 1: 1 to 10: 1 to the ratio of nonionogenic tenside.
6, each detergent composition or the additive application that is used for bleach activating of aforementioned claim.
7, each detergent composition or additive are used for removing and can bleach dirt among the claim 1-5, and triglyceride level or greasy application.
8, each detergent composition or Application of Additives among the claim 1-5, wherein composition or additive are 1% solution of a kind of pH value between 7.0 and 11.0 in wash(ing)cycle.
9, contain a kind of lipase and/or have the detergent composition or the additive of the enzyme of esterase activity, a kind of hydrogen peroxide cource and a kind of bleach precursor particle, described bleach precursor particle contains a kind of as tackiness agent and/or as the highly reactive polymer of the band acid anhydrides residue of coating-forming agent.
10, according to the detergent composition or the additive of claim 9, wherein bleach precursor is TAEDE
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP93201107 | 1993-04-16 | ||
| EP93201107.5 | 1993-04-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1124977A true CN1124977A (en) | 1996-06-19 |
Family
ID=8213768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94192284 Pending CN1124977A (en) | 1993-04-16 | 1994-04-13 | Bleach activation via anhydrides and lipase |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0693118A4 (en) |
| JP (1) | JPH08509257A (en) |
| CN (1) | CN1124977A (en) |
| AU (2) | AU7136894A (en) |
| SG (1) | SG63573A1 (en) |
| WO (1) | WO1994024257A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8514707D0 (en) * | 1985-06-11 | 1985-07-10 | Unilever Plc | Enzymatic detergent composition |
| GB8716219D0 (en) * | 1987-07-09 | 1987-08-12 | Unilever Plc | Perfume compositions |
| US5264142A (en) * | 1991-11-25 | 1993-11-23 | Lever Brothers Company, Division Of Conopco, Inc. | Stabilization of peroxygen bleach in enzyme-containing heavy duty liquids |
-
1994
- 1994-04-13 JP JP6523428A patent/JPH08509257A/en active Pending
- 1994-04-13 SG SG1996003391A patent/SG63573A1/en unknown
- 1994-04-13 AU AU71368/94A patent/AU7136894A/en not_active Abandoned
- 1994-04-13 EP EP94920658A patent/EP0693118A4/en not_active Withdrawn
- 1994-04-13 WO PCT/US1994/004076 patent/WO1994024257A1/en not_active Application Discontinuation
- 1994-04-13 CN CN 94192284 patent/CN1124977A/en active Pending
-
1997
- 1997-10-10 AU AU40032/97A patent/AU4003297A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08509257A (en) | 1996-10-01 |
| EP0693118A4 (en) | 1998-11-25 |
| EP0693118A1 (en) | 1996-01-24 |
| AU7136894A (en) | 1994-11-08 |
| WO1994024257A1 (en) | 1994-10-27 |
| SG63573A1 (en) | 1999-03-30 |
| AU4003297A (en) | 1997-12-18 |
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