CN1070223A - The purging compound that contains polyhydroxy fatty acid amide surfactant and clay softening system - Google Patents

The purging compound that contains polyhydroxy fatty acid amide surfactant and clay softening system Download PDF

Info

Publication number
CN1070223A
CN1070223A CN 92109294 CN92109294A CN1070223A CN 1070223 A CN1070223 A CN 1070223A CN 92109294 CN92109294 CN 92109294 CN 92109294 A CN92109294 A CN 92109294A CN 1070223 A CN1070223 A CN 1070223A
Authority
CN
China
Prior art keywords
alkyl
mentioned
clay
cleaning composition
salt
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.)
Granted
Application number
CN 92109294
Other languages
Chinese (zh)
Other versions
CN1037452C (en
Inventor
A·C·康文斯
A·布什
A·J·普雷蒂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of CN1070223A publication Critical patent/CN1070223A/en
Application granted granted Critical
Publication of CN1037452C publication Critical patent/CN1037452C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

The application discloses a class cleaning composition, and it comprises polyhydroxy fatty acid amide surfactant, and its molecular formula is:
R wherein 1Be hydrogen, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or their mixture, R 2Be C 5-C 31Alkyl, Z are the polyhydroxy alkyls with straight-chain alkyl, are at least directly connecting 3 hydroxyls, perhaps ethoxylated derivatives on the above-mentioned straight chain.
Also has a clay softening system.

Description

The purging compound that contains polyhydroxy fatty acid amide surfactant and clay softening system
The present invention and contain purging compound softening of clay softening system by employing.
Clay, particularly terre verte class clay is known fabric softener, their using in the fabric-softening process of being undertaken by washing are disclosed as prior art, wherein the GB-B-1400898 patent is an example in this prior art, but people clearly realize that very that the precipitation of above-mentioned clay is far from fully.In fact, under typical European wash conditions, only the available clay less than half is deposited on the fabric, and remaining then is flushed away along with washings in the flushing process of back.
Have been found that causing the incomplete reason of precipitation is that disadvantageous interaction can take place for employed clay and the general tween of large usage quantity (promptly more than 4%).
So be necessary the content of the nonionogenic tenside in the argillaceous that carries out via purging compound is softening is limited,, or add the clay flocculating agent described in EP-A-299575 so that obtain the good softening performance of clay.
It is found that at present some polyhydroxy fatty acid amide and fabric softening clay as nonionogenic tenside have good consistency.
And above-mentioned discovery just can cause developing by softening that purging compound carries out, available higher non-ionic surface activator content has better cleaning performance to said purging compound owing to having now under the condition that need not the clay flocculating agent, has better softening performance owing to the clay precipitation capacity increases in addition.
Multiple polyhydroxy fatty acid amide is disclosed in the prior art.No. 2965576 patents of US and No. 809060 patents of GB relate to a kind of purging compound that includes anion surfactant and some acidamide surfactant, this mixture can comprise the N-methylglucosamine, it can be added as a kind of low temperature profoamer.
No. 2703798 patents of US relate to a kind of water-soluble purging compound, and it comprises the aliphatic ester in the lipid acid and the polycondensation product of N-alkylated glucamine, and it is useful that this polycondensation product is considered in water-soluble purging compound, and further do not purify.
Pct international patent application WO 83/04412 relates to a kind of amphipathic compound of poly-hydroxy aliphatic group, and this compound serves many purposes, as the tensio-active agent as makeup, medicine, shampoo, lotion and spongaion.
No. 2982737 patents of US relate to a kind of detergent block, it comprises that urea, sodium lauryl sulphate anion surfactant, N-methylglucosamine nonionogenic tenside, this last a kind of promoting agent can be N-methyl, N-sorb glycosyl lauramide, and the N-methyl, N-sorb glycosyl myristamide.
Known other glycosamine tensio-active agent also has, and as the purging compound described in the DT2226872 patent, it comprises one or more tensio-active agents and builder salt, and this salt can be polymeric phosphate, sequestrant, washing soda.
Propose in No. 745036 patents of GB heterocycleamide and carboxylicesters are used as chemical intermediates, emulsifying agent, moistening and dispersion agent, washing composition, fabric softener etc.
The invention provides a kind of purging compound, it comprises:
(a) at least 1% polyhydroxy fatty acid amide surfactant by weight percentage, its structural formula is:
Figure 921092946_IMG4
R wherein 1Be hydrogen, C 2-C 4Alkyl, the 2-hydroxyethyl, 2-hydroxypropyl, or above-mentioned mixture,
R 2Be C 5-C 31Alkyl;
Z is polyhydroxy alkyl or its alkoxy derivative, and above-mentioned poly-hydroxy has the alkyl straight chain, and above-mentioned straight chain directly links to each other with at least 3 hydroxyls.
(b) clay softening system
The polyhydroxy fatty acid amide surfactant that will describe below the present composition comprises, this surfactant content is at least 1%, is preferably 3%～50%, is the best with 3%～30% wherein.
Polyhydroxy fatty acid amide surfactant of the present invention comprises the compound of following structural formula:
Figure 921092946_IMG5
R wherein 1Be hydrogen, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or above-mentioned mixture are wherein preferably selected C for use 1-C 4Alkyl is selected C for use 1Or C 2Alkyl is then better, selects C for use 1Alkyl (being methyl) is for best;
R 2Be C 5-C 31Alkyl is preferably selected straight chain C certainly for use 7-C 19The mixture of alkyl or alkenyl or above-mentioned base is selected straight chain C for use 9-C 17The mixture of alkyl or alkenyl or above-mentioned base is then better, and selects C for use 11-C 17The mixture of alkyl or alkenyl or above-mentioned base is best;
Z is polyhydroxy alkyl or its alkoxy derivative (being preferably ethoxylated derivative or propoxylated derivative), and above-mentioned polyhydroxy alkyl has the alkyl straight chain, and this straight chain directly links to each other with at least 3 hydroxyls.Z is preferably derived by reducing sugar with the reductive amination reaction and makes, and Z is preferably a kind of glycosyl (glycityl).The reducing sugar that is fit to has glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As raw material, except top listed various sugar, can also use high glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle.Should be understood that above-mentioned several maize treacle can be sugar component mixture of Z-shaped one-tenth.Z preferably selects base described below for use, promptly-and CH 2-(CHOH) n-CH 2-OH ,-CH(CH 2OH)-(CHOH) N-1-CH 2OH ,-CH 2-(CHOH) 2-(CHOR ')-(CHOH)-CH 2OH and their oxidation alkyl derivative, wherein n is an integer 3～5, comprises that here 3 and 5 is own, R ' is hydrogen, ring or aliphatic monose.Preferably selecting n for use is 4 glycosyl, particularly selects for use-CH 2-(CHOH) 4-CH 2OH.
In the structure formula I, R 1Can for, as N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl, N-2-hydroxypropyl.
R 2-CO-N＜can for, as coconut oleoyl amine (Cocamide), stearylamide, oleylamide, lauramide, myristamide, decyl amide, palmitamide, suet acid amides etc.
Z can be 1-deoxyglucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl etc.
From prior art, can learn the method for making polyhydroxy fatty acid amide.In general, above-mentioned polyhydroxy fatty acid amide can prepare by following manner, being alkylamine and reducing sugar generates the corresponding N-alkyl polyhydroxy amine in the reductive amination reaction, then in polycondensation/amidation step with this N-alkyl polyhydroxy amine and fatty aliphatic ester or triglyceride level reaction with generation N-alkyl, N-polyhydroxy fatty acid amide product.In No. 809060 patents of GB, No. 2965576 patents of US, No. 2703798 patents of US have been described the method for compositions that preparation comprises polyhydroxy fatty acid amide in No. 1985424 patents of US.
At preparation N-alkyl, the N-hydroxyalkyl, in the preferred method of N-deoxidation glycosyl fatty acid amide, wherein the glycosyl composition is the derivative of glucose, above-mentioned N-alkyl or N-hydroxyalkyl functionality then are the N-methyl, the N-ethyl, the N-propyl group, the N-butyl, N-hydroxyethyl or N-hydroxypropyl, the above-mentioned product that will prepare can by with the N-alkyl-or N-hydroxyalkyl glycosamine and fatty ester obtain having to react under the condition of catalyzer, above-mentioned fatty ester can be fatty methyl ester, the fat ethyl ester, triglyceride fat ester, above-mentioned catalyzer can be the tricresyl phosphate lithium, tertiary sodium phosphate, Tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, disodium tartrate, di-potassium tartrate, sodium-potassium tartrate, trisodium citrate, citric acid tri potassium, alkaline sodium silicate, alkaline potassium silicate, alkaline sodium aluminosilicate, the mixture of alkalescence potassium aluminosilicate and above-claimed cpd.About 0.5～50 mole of % of relative N-alkyl of above-mentioned catalyst levels or N-hydroxyalkyl glycosamine molar weight, preferably about 2.0～10 moles of %.Above-mentioned reaction is preferably under about 138 ℃～170 ℃ temperature to be carried out, general about 20～90 minutes of its reaction times.When using triglyceride level as fatty ester, carry out above-mentioned reaction and then preferably will add consisting of phase-transferring agent, this agent accounts for about 1～10% of complete reaction mixture by weight percentage, above-mentioned consisting of phase-transferring agent is selected from the saturated fatty alcohol polyethoxylated, alkylpolyglycosides, straight chain sugar acidamide surfactant, or the mixture of mentioned component.
Aforesaid method is preferably undertaken by following mode:
(a) fatty ester is heated in advance about 138 ℃～170 ℃;
(b) in the fatty acid ester of heating, add N-alkyl or N-hydroxyalkyl glycosamine, mix required degree, thereby form the two-phase liquid/liquid mixture;
(c) in above-mentioned reaction mixture, sneak into catalyzer;
(d) stir by the reaction times of defined.
In addition when fatty ester is triglyceride level, also preferably add preformed straight chain N-alkyl/N-hydroxyalkyl as consisting of phase-transferring agent, N-straight chain glucosyl fatty acid acyl amine product, its content accounts for about 2～20% of reactant by weight percentage, this will be to having reacted the seed effect, thus accelerated reaction speed.
The poly-hydroxy of above-mentioned use " lipid acid " acid amides material also has following advantage for the detergent formulation person: this material can be all or mainly by nature, renewable non-petroleum chemistry raw material is made, and degradable.This material toxicity concerning hydrobiont is very little in addition.
Should be realized that along with the generation of the polyhydroxy fatty acid amide in the structure formula I, the above-mentioned method that is used for preparing this material generally also can form a large amount of non-volatile byproducts, as esteramides and ring-type polyhydroxy fatty acid amide.Above-mentioned byproduct how much depend on specific reactant and method condition.The polyhydroxy fatty acid amide that is added in the cleaning composition preferably provides with following form, promptly when providing by this mode, add the composition that contains polyhydroxy fatty acid amide in the washing composition and contain, preferably less than about 4% ring-type polyhydroxy fatty acid amide less than about 10%.The amount that the advantage of above-mentioned preferred method is the byproduct that comprises cyclic amide that this method produces seldom.
Clay softening system comprises fabric softening clay, also comprises clay flocculating agent and/or wetting agent in addition, although above-mentioned clay flocculating agent and/or wetting agent are not very necessary compositions.
Said herein clay softening system will comprise fabric softening clay, and its content accounts for 0.5% of cleaning composition by weight percentage at least, is preferably 4～30%.And above-mentioned clay is preferably selected terre verte class clay for use.
Terre verte class clay (Smectite clays) is widely used as the fabric-softening composition in cleaning composition, the cation exchange capacity that is had in such clay of great majority is at least 50meq/100g.
Terre verte class clay can be described as three layers of expandable material, and it comprises aluminium-silicate or Magnesium Silicate q-agent.
Have two kinds of different terre verte class clays.In first kind, in lattice silicate, have aluminum oxide, in second kind, in lattice silicate, have magnesium oxide.
For aluminum oxide and magnesium oxide class clay, the general formula of above-mentioned terre verte class clay is respectively Al 2(Si 2O 5) 2(OH) and Mg 3(Si 2O 5) 2(OH) 2The amount of water of hydration can be along with to the carrying out of clay-treated method and change.In addition, in the lattice of terre verte, can take place, and in water of hydration, can occur metallic cation such as Na simultaneously by the phenomenon of iron and magnesium substitution atoms +And Ca 2+And H +Thereby, form electric neutrality.
Generally can be according to the kind of being distinguished clay by absorbed a kind of positively charged ion that mainly absorb or unique.Such as, the sodium clay is the clay that a kind of absorbed positively charged ion is mainly sodium ion.Above-mentioned absorbed positively charged ion can react with the positively charged ion generation balanced exchange in the aqueous solution, and for example in this balanced exchange reaction, the positively charged ion of monovalent can be replaced the sodium of monovalent in the solution.General cation exchange capacity of clay is measured with the unit of milliequivalent/100 gram clays (meq/100g).
Cation exchange capacity of clay can be measured with several different methods, comprising electrodialytic method, this method can by with ammonium ion exchange, carry out titration afterwards, or adopt methylene blue method to realize, and aforesaid method all is published in " the The Chemistry and Physics of Clays " of Grimshaw work, and Interscience Publishers Inc is on the 264th～265 page (1971 years).Factors such as the cation exchange capacity in the clay mineral and the expansion characteristics of clay, clay institute are electrically charged are relevant, decided by factors such as crystalline networks to small part and above-mentioned clay institute is electrically charged.The ion exchange capacity variation range of clay is very big, for the kaolin families clay, and the about 2meq/100g of its ion exchange capacity, until some clay in the polynite class, the about 150meq/100g of its ion exchange capacity and bigger.The ion exchange capacity of illite class clay then is in the interior lower region of the above-mentioned variation range that provides, for general illite class clay, the about 26meq/100g of its ion exchange capacity.
Because the ion exchange capacity of illite class clay and high mountain range class clay is lower, so their quilt identification in composition of the present invention are otiose.And in fact, the most of composition in the clay soil is exactly above-mentioned illite and kaolin families clay.Yet, terre verte class clay, as the nontronite of the about 50meq/100g of ion exchange capacity, ion exchange capacity surpasses the talcum powder of 70meq/100g in addition, all is found to be useful fabric softener.
Generally being used for above-mentioned purpose terre verte class clay all can buy on market.This class clay is montmorillonite, volchonskoite, nontronite, hectorite, talcum powder, sauconite and vermiculite for example.The trade name of above-mentioned clay on market be " fooler clay " (promptly being arranged in geographic wilkinite of Black Hills or the clay than narrow vein above the montmorillonite mineral ore) for example.Above-mentioned in addition clay also has multiple trade(brand)name, as Thixogel #1(also is " Thixo-jell ") and Gelwhite G P, above-mentioned trade(brand)name is that the geographic Georgia Kaolin of the Elizabeth company ore deposit that is positioned at the New Jersey has; Be positioned at Volclay B C and Volclay that the geographic American Colloid of Illinois Skokie company is had #325; The Black Hills Bentonite BH450 that International Minerals and Chemicals company is had; The Veegum.Pro and VeegumF that R.T.Vanderbilt company is had.Can know that the terre verte quasi-mineral that obtains according to above-mentioned trade name and trade(brand)name can comprise the mixture of various discrete mineral bodies, the mixture of this smectite minerals matter then is to be fit to material of the present invention.
The ion exchange capacity that proposes the preferred smectites clay that adopts above is 50～100meq/100g, and this is equivalent to about 0.2～0.6 layer charge.
The present invention is particularly suitable for the hectorite that adopts granulous to form naturally, and its general formula is:
〔 ( M g 3 - x L i x ) S i 4 - y M e y Ⅲ O 10 ( O H 2 - z F z ) 〕 - ( x + y ) ( x + y ) n M n +
Me wherein IIIBe aluminium, iron or boron; Or y=0; M N+Be unit price (n=1) or two valency (n=2) metal ion, it can be sodium ion, potassium ion, magnesium ion, calcium ion, strontium ion.
In above-mentioned chemical formula, value (x+y) is the layer charge of hectorite class clay.
Above-mentioned hectorite clay is preferably selected according to its layer charge character, and promptly at least 50% layer charge is in 0.23～0.31 scope.
It is to be only at 0.23 to 0.31 the hectorite clay that forms naturally that its layer charge is distributed to rare 65%.
The hectorite class clay that is suitable for the present composition is preferably and contains the sodium clay, so that obtain better softening active.
The sodium clay can be that nature forms, and also can be the calcic clay that nature forms, thereby these calcic clays are handled to convert it into contains the sodium clay.If in composition of the present invention, use the calcic clay, then can in said composition, add sodium salt, contain the sodium clay so that the calcic clay changed into.Above-mentioned salt is preferably yellow soda ash, and its add-on generally can be high to accounting for 5% of clay total amount.
The example that is suitable for the hectorite class clay of the present composition comprises the Bentone E W of the N L Chemicals company production that is positioned at NJ USA and the hectorite of Macaloid and the production of Industrial Mineral Vertures company.
If the flocculating agent molecule amount is 150000～800000 o'clock, composition of the present invention can comprise that also content is 0.05%～20% flocculation agent of clay by weight percentage, if its molecular weight is 80000～500 ten thousand, then above-mentioned flocculation agent content is 0.005～2% of clay.Major part in the above-mentioned materials is polymkeric substance and the multipolymer with very long chain, and this polymkeric substance and multipolymer are following monomeric derivatives, i.e. oxyethane, acrylamide, vinylformic acid, dimethylamino-ethyl ester isobutene, vinyl alcohol, vinyl pyrrolidone, ethylene imine.Resembling this natural gum of guar gum (guar gum) in addition also is fit to adopt.
Preferably adopt oxyethane, acrylamide or polymerizing acrylic acid thing.In order to carry out suitable interaction with clay particle, this polymkeric substance should have very long chain, and promptly its weight-average molecular weight is at least 100000.For can be fully soluble in water, the weight-average molecular weight of polymkeric substance should not surpass 10,000,000.Preferably the weight-average molecular weight of polymkeric substance is 150000～500 ten thousand
Can be the various water-soluble materials that are used for moistening purpose by the optional organic wetting agent that is used for clay agglomerates.This organic wetting agent is preferably following ingredients: a). have the aliphatic hydrocarbon polyvalent alcohol of 2～9 carbon atoms; B). the alcohol ester that obtains by the polyol derivative a); C). the alcohol ester that obtains by the polyol derivative a); D). monose and oligose, and the mixture of mentioned component.
Above-mentioned wetting agent is preferably glycerine, ethylene glycol, propylene glycol, glycerine dipolymer and trimer, ethylene glycol bisthioglycolate polymers and trimer, propylene glycol dipolymer and trimer.
The wetting agent that clay softening system can comprise accounts for 0.5%～30% of clay by weight percentage, is preferably 2%～15%.
Except that polyhydroxy fatty acid amide, composition of the present invention also can comprise one or more additional surfactant, and this promoting agent can be cationic, anionic and non-ionic type.In general this surfactant system can also comprise one or more negatively charged ion and/or nonionogenic tenside except that polyhydroxy fatty ester amine, especially preferably adopt anion surfactant, effectively comprehensively clean so that under various wash conditions, can carry out.Particularly, when composition comprises hardness responsive type tensio-active agent, as alkyl-sulphate, alkyl ester group sulfonate (as methyl ester group sulfonate), alkyl alkoxylates sulfonate (as alkylethoxylate sulfonate) and alkylbenzene sulfonate (as linear alkylbenzene sulfonate), then especially can show benefit of the present invention.Also following general nonionogenic tenside is adopted in suggestion in addition, and as alkylethoxylate or alkylpolyglycosides, mentioned component will be described below.But, consider that above-mentioned nonionogenic tenside can disadvantageous interaction take place with clay, therefore to the content of this general nonionogenic tenside in the cleaning composition argillaceous be limited (by weight percentage, general non-ionic surfactant concentration should less than the cleaning composition total amount 4%).Additional detergent surfactant content is 1～50% of cleaning composition by weight percentage, is preferably 3～40%, is the best with 5～30% wherein.
The anion surfactant that is fit to comprises alkyl ester group sulfonate, and its structural formula is as follows:
Figure 921092946_IMG6
R wherein 3Be C 8-C 20Alkyl is preferably the mixture of alkyl or above-mentioned base, R 4Be C 1-C 6Alkyl is preferably the mixture of alkyl or above-mentioned base, and M is a positively charged ion, it and alkyl ester group sulfonic acid generate water-soluble salt, and suitable salt comprises metal-salt (Salts), as sodium salt, sylvite and lithium salts, and ammonium salt that replace or non-replacement, as ammonium methyl, dimethylammonium, TMA (TriMethylAmine) and quaternary ammonium cation, as tetramethylammonium and lutidine drone, also have the positively charged ion of deriving and obtaining from alkanolamine, as monoethanolamine, diethanolamine, trolamine, preferably R 3Be C 10-C 16Alkyl, R 4Be methyl, ethyl or sec.-propyl, here ad hoc proposal adopts methyl ester group sulfonate, wherein R 3Be C 14-C 16Alkyl.
The structural formula of alkyl sulfate surfactant is RoSO 3M, wherein R is C 10-C 24Alkyl is preferably alkyl or has C 10-C 20The hydroxyalkyl of alkyl composition is wherein with C 12-C 18Alkyl or hydroxyalkyl are best, M is hydrogen or positively charged ion, as alkali metal cation (as sodium, potassium, lithium ion), ammonium ion replacement or non-replacement, this ammonium ion can be ammonium methyl, dimethylammonium, TMA (TriMethylAmine) and quaternary ammonium cation, as tetramethylammonium and lutidine, the positively charged ion that obtains etc. of deriving from the mixture of alkanolamine such as thanomin, diethanolamine, trolamine or mentioned component.For low wash temperature (as below 50 ℃), generally preferably adopt C 12-C 16Alkyl chain, for higher wash temperature (as more than 50 ℃), preferably adopt C 16-C 18Alkyl chain.
The structural formula of alkyl alkoxylates sulfate surfactant is
RO(A) mSO 3M, wherein R is the C of non-replacement 10-C 34Alkyl or include C 10-C 24The hydroxyalkyl of alkyl composition is preferably C 12-C 20Alkyl or hydroxyalkyl are wherein with C 12-C 18Alkyl or hydroxyalkyl are best, and A is oxyethyl group or propoxy-unit, and m should be greater than zero, between 0.5～6, be the best with 0.5～3 wherein generally, M is hydrogen or positively charged ion, this positively charged ion can be for as metallic cation (as sodium, potassium, lithium, calcium, magnesium plasma), ammonium or replace ammonium cation.Here not only can consider to adopt alkyl propoxylated compound vitriol, the specific example that it is also conceivable that the substituted ammonium cation of alkyl ethoxylate sulfate comprises ammonium methyl, dimethylammonium, TMA (TriMethylAmine) positively charged ion and quaternary ammonium cation, as tetramethyl-ammonium, lutidine, and by alkanolamine, the positively charged ion and the above-mentioned ionic mixture of deriving and obtaining as monoethanolamine, diethanolamine, trolamine etc.Above-mentioned tensio-active agent for example is C 12-C 18Alkyl polyethoxylated (1.0) vitriol, C 12-C 18Alkyl polyethoxylated (2.25) vitriol, C 12-C 18Alkyl polyethoxylated (3.0) vitriol, C 12-C 18Alkyl polyethoxylated (4.0) vitriol, here M is generally sodium and potassium.
Above-mentioned soap salt (Salts of soap) (comprising as sodium, potassium, ammonium and substituted ammonium such as list, two, triethanolamine salt) can be C 9-C 20Linear alkylbenzene sulfonate, C 18-C 22Uncle or secondary sulfonated alkane, C 8-C 24Ethylenic sulfonate, the sulfonation poly carboxylic acid, this acid is carried out sulfonation reaction by the pyrolysis product to alkaline earth metal citrate and is made; as described in No. 1082179 patents of GB; alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oleoyl glycerine vitriol, alkylphenol oxyethane ether sulfate; paraffin sulfonate; alkyl phosphate, isethionate such as N-acyl isethinate, acyl taurine salt; N-methyltaurine ester fatty acid amide, amber alkyl amide salts.And sulfosuccinate, sulfosuccinate monoesters, sulfosuccinic acid diesters (the particularly saturated and non-full C that closes 6-C 14Diester); the N-acyl sarcosinate; alkyl polysaccharide vitriol such as alkyl polyglucoside vitriol (non-ionic non-sulfuric acid compound will be described below), chain primary alkyl sulfate, alkyl polyethoxye carboxylate salt is as having the alkyl polyethoxye carboxylate salt of following structural formula: RO(CH 2CH 2O) kCH 2COO -M +, wherein R is C 8-C 22Alkyl, k are 0～10 integer, and M is the salifiable positively charged ion of solubility shape, and the lipid acid of esterification, and it gets for reaching the neutralization reaction that takes place with sodium hydroxide with isethionic acid generation esterification.Also can be resinous acid and hydrogenated resin acid such as rosin, hydrogenated rosins, resinous acid and derived by oil slick obtains or resinous acid and hydrogenated resin acid in oil slick.In " Surface Active Agents and Detergents " (Shwartz, Perry and Berch work I and II volume) article, also describe other example that is fit to, in the US3929678 patent, also described multiple above-mentioned tensio-active agent.
Also described the GENERAL TYPE nonionic detergent surfactant that is fit in No. 3929678 patents of US, as an example, this ionic surfactant pack that is fit to is drawn together but is not limited to:
The alkylphenol polyoxyethylene, polyoxy propylidene, polyoxy butylidene condenses.Draw together the Igepal that produces by CAF company in commercially available this ionic surfactant pack TMCO-630 and by Rohm ﹠amp; The Triton that Haas company is sold TMX-45, X-114, X-100, X-102.Above-mentioned tensio-active agent is commonly referred to as the alkylphenol alcoxylates, as alkyl phenol ethoxylate.
Above-mentioned polycondensate can be for having the C of 1-25 mole epoxy second ring 12-C 22Fatty alcohol.Commercially available this ionic surfactant pack is drawn together Tergitol in market TM15-S-9 (the C that promptly has the oxyethane of 9 moles 11-C 15The pure polycondensate of linear secondary (Linear Secondary)), Tergitol TM24-L-6NMW(is the C of the narrower oxyethane that has 6 moles of molecular weight distribution 12-C 14The primary alconol polycondensate), above-mentioned two kinds of materials are Union Carbide company and sell Neodol TM45-9(promptly has the C of the oxyethane of 9 moles 14-C 15The straight chain alcohol polycondensate), Neodol TM23-6.5(promptly have the C of the oxyethane of 6.5 moles 12-C 13The straight chain alcohol polycondensate), Neodol TM45-7(promptly has the oxyethane of 7 moles, C 14-C 15The straight chain alcohol polycondensate), Neodol TM45-4(promptly has the C of the oxyethane of 4 moles 14-C 15The straight chain alcohol polycondensate), above-mentioned four kinds of materials are Shell Chemical company and sell; Kyro TMEOB(promptly has the C of the oxyethane of 9 moles 13-C 15The alcohol polycondensate) The Procter﹠amp; Gamble company sells.Above-mentioned tensio-active agent generally all is called alkylethoxylate.
Polycondensate can be for having the oxyethane polycondensate of such hydrophobic group, and described hydrophobic group forms by propylene glycol and propylene oxide polycondensation.The example of this polycondensate comprises that the trade name of being sold by BASF AG is Pluronic TMSome tensio-active agent.
Polycondensate also can for the oxyethane polycondensate of following reactant, this reactant obtains by propylene oxide and reacting ethylenediamine.The example of this nonionogenic tenside comprises that some trade name of being sold by BASF AG is Tetronic TMProduct.
Ammonium oxide, its structural formula is:
Figure 921092946_IMG7
R wherein 3Mixture for the alkyl, hydroxyalkyl, alkyl phenyl or the above-mentioned base that contain 8～22 carbon atoms; R 4Be alkylidene group or the hydroxyl alkylidene group that contains 2～3 carbon atoms, or the mixture of above-mentioned base; X is 0～3; Each R 5For containing 1～3 carbon former alkyl or hydroxyalkyl or containing the polyethylene oxide base of 1～3 Oxyranyle.Each R 5Base can be connected with each other to form ring texture by oxygen or nitrogen-atoms.
Above-mentioned amine oxide is preferably C 10-C 13Alkyl dimethyl amine oxide and C 8-C 12Alkoxyethyl dihydroxy ethyl amine oxide.
In the US4565647 patent of the Llenado that announces on January 21st, 1986 alkyl polysaccharide is described.
Preferred alkyl polysaccharide structural formula is:
R 2O(CnH 2nO) t(glycosyl) X
R wherein 2Can be the mixture of alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and above-mentioned base, wherein alkyl comprises 10～18, preferably 12～14 carbon atom; N is 2 or 3, is preferably 2; T is 0～10, is preferably 0; X is 1.3～10, is preferably 1.3～3, is the best with 1.3～2.7 wherein.Glycosyl is preferably derived from glucose and is obtained.In order to prepare above-claimed cpd, can prepare alcohol or alkyl polyethoxylated alcohols earlier, then with itself and glucose or source of glucose reaction, thereby form glucoside (go up connect at the 1st position (1-position))).Again with other glycosyl they the 1st position and the 2nd, 3,4 and/or 6 positions of aforesaid glycosyl on link to each other, preferably based on the 2nd position.
In cleaning composition of the present invention, also can comprise the cationic detersive tensio-active agent.Cats product comprises ammonium surfactant, and as alkyl dimethyl ammonium halogenide, and those have the tensio-active agent of following structural formula:
R wherein 2For having the alkyl or the alkyl benzyl of about 8～18 carbon atoms, each R on the alkane chain 3Can be-CH 2CH 2-,-CH 2CH(CH 3)-,
-CH 2CH(CH 2OH)-,-CH 2CH 2CH 2-and above-mentioned several mixture; Each R 4Be C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, benzyl is by two R 4The ring texture that base connects into,
-CH 2CHOH-CHOHCOR 6CHOHCH 2OH, wherein R 6For any molecular weight less than about 1000 hexose or hexose polymkeric substance, y is not 0 o'clock in addition, R 6Also can be hydrogen; R 5With R 4Identical or be alkane chain, here R 2With R 5In the total number of carbon atoms be no more than about 18; Each y is 0～10, and y value summation is between 0～about 15; X is any negatively charged ion that is complementary.
The cats product of useful other of the present invention has also been described in No. 4228044 patents of US.
In cleaning composition, can add amphoterics.This tensio-active agent can be the aliphatic derivatives of the second month in a season or tertiary amine, the aliphatic derivatives of the heterocycle second month in a season and tertiary amine, and wherein aliphatic group can be straight or branched.One of above-mentioned aliphatic substituting group (aliphatic Substituents) contains at least about 8 carbon atoms, general about 8～18 carbon atoms, and wherein at least one contains the anionic water-soluble base, as carboxyl, and sulfonate radical, sulphate groups.Can be about examples of amphoteric surfactants referring to No. 3929678 patents of US.
In said detergent composition, can also mix zwitterionics, these tensio-active agents can be the derivative of secondary amine and tertiary amine, the derivative of heterocyclic secondary and tertiary amine, the derivative quaternary phosphonium compound of quaternary ammonium or season sulfonium compound, referring to United States Patent (USP) the 3rd, 929, the example of No. 678 described zwitterionicss.
Usually, amphoteric and zwitterionics and one or more anionic and/or non-ionic tensio-active agents are combined use.
Mixture of the present invention can be a particle form, the clay particles disperse form in perhaps a kind of water, and this depends on required behaviour in service.No matter, in the rinse cycle in main washing stage or washing process, can add composition of the present invention with any form.
Particle form both comprised " routine ", also comprised highdensity " closely knit " mode (" Compact " execution).
Cleaning composition of the present invention can comprise inorganic or organic detergent builder compound (builders), to help the mineral substance Hardness Control.
The amount of washing assistant can be in very wide scope, according to the last application target of this mixture, and desirable physical aspect and changing.Fluid composition, detergent builder compound generally account for 1% by weight at least, account for 5%～50% usually, preferably account for 5～30%.
For granular composition, the weight of detergent builder compound will account for 1% at least, accounts for 10～80% usually, preferably accounts for 15%～50%, does not contain lower or more a high proportion of washing assistant but do not get rid of.
Inorganic detergent builder compound comprises phosphonate, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and the silico-aluminate of basic metal, ammonium and alkanol ammonium, but is not limited to above these salts.
The example of silicate-like builder is alkali-metal silicate, especially those SiO 2: Na 2O is than in 1.6: 1～3.2: 1 scopes and be lamellated silicate, as: at United States Patent (USP) 4,664, described in 839 and be lamellated water glass.But other silicate is also useful, and as Magnesium Silicate q-agent, it can be used as a kind of crisp dose in particulate composition, as the stablizer of oxygen bleaching agent, and as a composition of foam control system.
The example of carbonate builders is alkaline earth and alkaline carbonate, comprises yellow soda ash and concentrated crystal soda, and the mixture of they and super fine calcium carbonate, as German patent application the 2nd, 321,001 described like that.
The silico-aluminate washing assistant is that very useful, best silico-aluminate is a zeolite builders in the present invention, and its molecular formula is
Wherein z and y are at least 6 integer, and the mol ratio of z and y is in 1.0～0.5 scope, and X is the integer from 15～264.
Practical aluminosilicate ion exchange material can have been bought on market, and these silico-aluminates can be crystalline or non-crystal structure, can be natural silico-aluminates, also can be the silico-aluminates of synthetic.At United States Patent (USP) the 3rd, 985, a kind of method of making aluminosilicate ion exchange material is disclosed in 669, in a most preferred embodiment, the molecular formula of the aluminosilicate ion exchange material of lenticular is:
Wherein X is about 20～30, preferably 27, and this material is exactly well-known zeolite A.The granular size of silico-aluminate is preferably in about 0.1～10 micron scope of diameter.
The example of phosphonate washing assistant is water miscible ethane 1-hydroxyl-1 1-diphosphonate, preferably its sodium salt and sylvite, also has water miscible methylene diphosphonate, as trisodium salt and tripotassium salt, and water miscible substituted methylene diphosphonate, as the phosphonic acids trisodium salt and the tripotassium salt of ethylidene, isopropylidene, benzyl methylene radical and halogenated methylene.At US 3,159,581 and US3,213,030, US3 discloses above-mentioned phosphonate washing assistant in 422,021 and US3,400,148 and US3,422,137.
Be applicable to that the organic detergent builder compound of the object of the invention comprises many kinds of polycarboxylic acids (salt) compound, but be not limited to these compounds, said here " polycarboxylic acid (salt) " has been meant a plurality of carboxyls, preferably has the compound of 3 carboxyls at least.
Usually the form of polycarboxylate washing assistant with acid is added in the mixture, but also can be added to the form of neutral salt in the mixture, when using with the form of salt, the form of an alkali metal salt preferably, as sodium salt, sylvite and lithium salts, especially best is sodium salt, or the ammonium salt of ammonium salt and replacement (as the alkanol ammonium).
Comprised the material that many kinds are useful in polycarboxylic acid (salt) washing assistant, a kind of important polycarboxylic acid (salt) washing assistant is an ether type polycarboxylic acid (salt), and the many ether type polycarboxylic acids (salt) that are used as detergent builder compound have been disclosed.As U.S. Pat 3,128,287 and US3 at Berg, the example of disclosed available ether type polycarboxylic acid (salt) in 635,830, it comprises oxygen two Succinic Acid (salt).
The ether type polycarboxylic acid (salt) of a specific type that can be used as the application's washing assistant includes the material of following general formula:
Wherein A is hydrogen or hydroxyl, B be hydrogen or-O-CH(COOX)-CH 2(COOX); X is hydrogen or salifiable positively charged ion.For example, if A and B are hydrogen in the above-mentioned general formula, so above-claimed cpd is exactly oxygen two Succinic Acid and its water miscible salt.If A is a hydroxyl, B is a hydrogen, so above-claimed cpd is exactly tartrate monobutane diacid (TMS) and water-soluble salt thereof.If A is a hydrogen, B is-O-CH(COOX)-CH 2(COOX), so above-claimed cpd is exactly tartrate two Succinic Acid (TDS) and water-soluble salt thereof.The mixture of above-mentioned these washing assistants is particularly useful in this application, and the most preferred embodiment of mixture is that its weight ratio is 97: 3～20: 80 TMS and the mixture of TDS, and these washing assistants are in U.S. Pat 4,663, discloses in 071.
The ether polycarboxylic acid (salt) that is suitable for also comprises ring compound, alicyclic compound especially, and as at US 3,923,679, US 3,835,163, US 4,158, and 635, US 4,120, and 874 and US 4,102, those described in 903.
Other practical detergent builder compound comprises the ether type hydroxyl polycarboxylic acid (salt) who is expressed from the next:
Wherein M is hydrogen or a kind of positively charged ion, is water miscible by the salt that is generated in this positively charged ion, basic metal preferably, the ammonium cation of ammonium or replacement.N is the number (preferably n is 2～10, especially is 2～4) from 2～15, and each R can be identical, also can be different, and R is selected from hydrogen, C 1-4Alkyl or C 1-4The alkyl that replaces (preferably R is a hydrogen).
Other ether polycarboxylic acid (salt) comprises maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyl oxygen Succinic Acid.
Organic polycarboxylic acid (salt) washing assistant also comprises the polyacetic acid salt of various basic metal, ammonium and replacement ammonium, and the embodiment of polyacetic acid salt washing assistant comprises the edetate and the nitrilotriacetic acid(NTA) salt of sodium, potassium, lithium, ammonium and replacement ammonium.
Also include polycarboxylic acid (salt), as mellitic acid, Succinic Acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, benzene pentacarboxylic acid and carboxymethyl oxygen Succinic Acid, and soluble salt.
Citric acid (salt) washing assistant comprises citric acid and its soluble salt, be a kind of very important polycarboxylic acid (salt) washing assistant to the liquid detergent composition of heavy type, but it also can be used in the granular composition.The salt that is suitable for comprises its metal-salt, as sodium salt, lithium salts and sylvite, and the ammonium salt of ammonium salt and replacement.
Other carboxylate salt washing assistant is included in the carbohydrate of the disclosed carboxylic acid group of having among the US-3723322 of Diehl.
In cleaning composition of the present invention, following compound also is suitable, and they are 3.3-dicarboxyl-4-oxa-s-1,6-hexanodioic acid (salt) and disclosed relevant compound in US-4566984.Suitable Succinic Acid washing assistant comprises C 5-C 20Dialkyl succinylsuccinate and salt thereof, especially dodecenyl succinic Succinic Acid.The general formula of dialkyl succinylsuccinate is R-CH(COOH) CH 2(COOH), i.e. the derivative of Succinic Acid, wherein R is an alkyl, for example C 10～C 20Alkyl or alkenyl, preferably C 12～C 16, or wherein R can be replaced by hydroxyl, sulfo group, sulphur oxygen base (Sulfoxyl) or sulfone (Sulfone) substituting group, and all these all have description in above-mentioned patent.
The form of the most handy their water-soluble salts of Succinic Acid (salt) washing assistant comprises sodium salt, sylvite, ammonium salt and alkanol ammonium salts.
The example of concrete succsinic acid (salt) washing assistant comprises: dodecyl succinate salt, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinic succinate (best) 2-15 carbene base succinate and analogues.In above-mentioned these washing assistants, dodecyl succinate salt is best, and this washing assistant is at EP86200690.5/0, has been described in 200,263.
The example of useful washing assistant also comprises carboxymethyl oxygen malonate, carboxymethyl oxygen succinate, suitable-hexanaphthene hexacarboxylic acid salt, the water miscible polyacrylic ester (salt) (molecular weight can be used as effective dispersion agent at these the poly-propionic esters (salt) more than 2000) of sodium and potassium, and the multipolymer of maleic anhydride and vinyl methyl ether or ethene.
Other polycarboxylate (salt) that is suitable for is polyacetal carboxylic acid ester's (salt), at US 4,144, has described this material in 226.Can prepare this polyacetal carboxylic acid ester by under polymerizing condition, the ester of Glyoxylic acid hydrate and initiators for polymerization being mixed, the polyacetal carboxylic acid ester who obtains is connected on the stable end group of chemical property then, the polyacetal carboxylic acid ester can be stablized and not depolymerization rapidly in basic solution, convert it into corresponding salt, be added in the tensio-active agent again.
At US 3,308, also disclose poly carboxylic acid (salt) washing assistant in 067, this material comprises the water-soluble salt of aliphatic carboxylic acid superpolymer and multipolymer, used carboxylic acid such as toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid.
In prior art, known other organic washing-assisting detergent also can use, and for example, can use the monocarboxylic acid and the solvability salt thereof of long chain hydrocarbon groups, and these should comprise the material that is " soap " usually.Usually use C 10-C 20Chain length.Alkyl can be saturated, also can be undersaturated.
It is because various purposes that enzyme can be selected in the component of washing composition, and these purposes comprise as removing protein-based, the pollutent of carbohydrate-based or triglyceride level base, and the transfer of the dyestuff that prevents to come off.The enzyme that can add comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, and their mixture.They can be from any suitable source thing, as plant, animal, bacterium, fungi and yeast source thing.Be applicable to that the proteolytic ferment of removing the protein-based pollutent can buy on market, as by Novo Industries A/S(Denmark) to sell, trade mark is ALCALASE TMAnd SAVINASE TMProduct, by International Bio-Synthetics, Inc, (Holland) sells, trade mark is MAXATASE TMProduct.
Starch decomposing protein comprises the Bio-Synthetics as International, the RAPIDASE that Inc. sells TM, and the TERMAMYL of Novo Industries sale TM
The available cellulase had both comprised the bacteria cellulose enzyme among the application, comprised fungal cellulase again.
Suitable fat enzyme as the washing composition purposes comprises that those are Lipolase by the trade mark that Novo Industries sells RProduct.
In composition of the present invention, the usage quantity that the merchant sells detergent enzyme also can be higher usually in 0.001%～2% scope.
Cleaning composition of the present invention can comprise SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach-activating agents.
A kind of SYNTHETIC OPTICAL WHITNER that can be used had both comprised peroxy acid itself, also comprised the system that can produce peroxy acid on the spot.
Peroxy acid " " the connotation here own is an alkali metal salt and the alkaline earth salt that comprises it.Usually use peroxy acid or diperoxy acid, as diperoxy dodecylic acid (DPDA) or peroxide phthalic acid.
The system that can discharge peracid on the spot is peroxygen bleach and its activator.
Peroxygen bleach is that those can produce hydrogen peroxide in the aqueous solution, its compound is well-known material in prior art, it comprises hydrogen peroxide, alkali-metal superoxide, organo-peroxide SYNTHETIC OPTICAL WHITNER such as carbamide peroxide, inorganic persalt SYNTHETIC OPTICAL WHITNER such as alkali-metal perborate, percarbonate, superphosphate, persilicate and analogue thereof.
Preferably Sodium peroxoborate can have been bought with monohydrate and tetrahydrate form, yellow soda ash peroxyhydrate, trisodium phosphate peroxyhydrate, urea peroxyhydrate.
Free hydrogen peroxide and bleach-activating agent reaction generate peroxyacid bleach.The kind of bleach-activating agent comprises ester class, acid imide, imidazoles, oximes and carbonate.In two class materials, best material comprises that o-acetoxy-benzoic acid methyl esters, p-acetoxyl benzene sulfonic acid sodium salt are as 4-acyloxy in ninth of the ten Heavenly Stems benzene sulfonic acid sodium salt; Hot acyloxy benzene sulfonic acid sodium salt of 4-and 4-acyloxy in last of the ten Heavenly stems benzene sulfonic acid sodium salt; The dihydroxyphenyl propane diacetate esters, tetraacetyl ethylene diamine, tetrem acyl 1,6-hexanediamine, and tetrem acyl methanediamine.
At US 4,483,778 and US4,539, disclose other best peroxide bleaching activator in 130, they are α substituted alkyls, or alkenyl ester, as the hot acyloxy of 4(2-chlorine) benzene sulfonic acid sodium salt, 4-(3,5,5, trimethyl acetyl oxygen base) benzene sulfonic acid sodium salt, suitable peroxy acid also is the peroxide bleaching activator, as EP 0,166,571 is described, be that general formula is the compound of RXAOOH and RXAL, wherein R is the hydroxyl bivalent hydrocarbon radical, and X is a heteroatoms, and A is carbonyl abutment group (carbonyl bribging group), L is a leavings group, especially the oxygen benzene sulfonate.
The application's composition can comprise other component, and these components help the washing effect of said composition, and they comprise that the polymeric dirt releases out agent, sequestrant, the agent of clay soil removal/anti redeposition.
Polymeric dispersant is a based copolymers as vinylformic acid/toxilic acid, also can be used as best dispersion/anti-redeposition agent component.This material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of the multipolymer of this form with acid is 2000～100, between 000, better be 5000～75,000, preferably 7,000～65,000, in this analog copolymer, acrylate to the ratio of maleate part (maleate segments) normally in 30: 1～1: 1 scope, preferably in 10: 1～2: 1 scope.The water-soluble salt of this class vinylformic acid-maleic acid can comprise the ammonium salt as alkali-metal salt, ammonium salt and replacement.Water miscible acrylate/the maleate copolymer of this class all is a known substance, in the application of EP 66915 it is described.
Other polymkeric substance that can comprise also has polyoxyethylene glycol (PEG).Polyoxyethylene glycol can not only can also present dispersing agent performance as clay soil remover/anti-redeposition agent.Being used for the common molecular weight of these purposes is 500～100, in the scope between 000, be preferably in 1,000～50,000 the scope, and 1,500～10, the scope between 000 is best.
Composition of the present invention can also comprise white dyes and suds suppressor.
Liquid cleaning composition can also comprise water and other solvent as carrier.Low-molecular-weight primary alconol or secondary alcohol, all be suitable for as methyl alcohol, ethanol, propyl alcohol and Virahol, the most handy monohydroxy-alcohol comes solubilization to separate tensio-active agent, but polyvalent alcohol, also can use as those polyvalent alcohols with 2～6 carbon atoms and 2～6 hydroxyls (as propylene glycol, ethylene glycol, glycerine, 1,2-propylene glycol).
Cleaning composition of the present invention promptly cleans in the use at the aqueous solution preferably by following prescription manufacturing, and the pH value of washing water (wash water) will be in 6.5～11 scope, is preferably in 7.5～10.5 the scope.The pH value of liquid product composition is preferably in 7.5～9.5 the scope, and 7.5～9.0 scope is best.Be used for the technology that pH value is controlled in the usage level of being advised is comprised the use buffer reagent alkali, acid or the like.These all are known to one skilled in the art.
Here lift one and make the N-methyl that the application will use, although the example of 1-deoxyglucose base laurylamide tensio-active agent is the structure that experienced chemist can modifier.But the application's employed one suitable device comprises one 3 liters, four neck flasks (four-necked flask), and the paddle stirrer of motor driving and the thermometer of sufficient length are installed on it, and the length of this thermometer can touch reaction medium.A nitrogen purging (nitrogen sweep) is installed two other neck of this bottle and a wide-aperture collateral branch pipe (is noted: when methyl alcohol is emitted rapidly, wide-aperture collateral branch pipe (wide-bore side-arm) is very important), the condenser that can effectively collect and vacuum outlet are connected on this arm.Vacuum outlet is connected on a nitrogen bleed and the vacuumometer, and then is connected on a respiratory organ and the collection trap.Be 500 watts of reaction heating with one, the heating mantles that has variable transformer temperature regulator (" Variac ") is placed on the laboratory upholder, and this upholder can allow this heating mantles raise easily or reduce, thus the further temperature of control reaction.
With the N-methylglucosamine (195 grams, 1.0 moles, Aldrich, M4700-0) and Laurate methyl (Procter ﹠amp; Gamble CE 1270,220.9 grams, 1.0 moles) put into a bottle, under the situation of nitrogen purging, limit heating solid/liquid mixture, stir on the limit, to form a melt (about 25 minutes).When the temperature of melt reaches 145 ℃, and the adding catalyzer (the anhydrous sodium carbonate powder, 10.5 grams, 0.1 mole, J.T.Baker).Turn off nitrogen purging, and regulate respiratory organ and nitrogen bleed, to produce the vacuum tightness (16343 handkerchief) of 5 inches (5/31 normal atmosphere) mercury column.From this time, make temperature of reaction remain on 150 ℃ by regulating Variac and/or rising or reducing this heating mantles.
In 7 minutes, on the liquid level of reaction mixture, at first can see the bubble of methyl alcohol, just begin vigorous reaction soon, methyl alcohol constantly distills out, till its speed reduces.Regulate vacuum tightness, making vacuum tightness is about 10 inches of mercury (10/31 normal atmosphere), subsequently vacuum tightness will increase to some extent (in minute the inch of mercury): 10 inches of mercury in the time of 3 minutes (32686 handkerchief), 20 inches of mercury in the time of 7 minutes (65372 handkerchief), 25 inches of mercury in the time of 10 minutes (81715 handkerchief).From the 11st minute of methyl alcohol release, stop heating and stirring, some foams have appearred simultaneously, then with product cooling and curing.
The following examples are used for specifying composition of the present invention, but the present invention never only limits to this, neither limit scope of the present invention, and scope of the present invention is determined by claims subsequently.
Embodiment 1
Testing sequence: the clean fabric washing article of 3.5 kilogram weights are placed in the automatic drum barrel washing machine Miele 423, wash under 60 ℃.Water hardness is that the concentration of 2.5mM calcium and said composition is 0.7% in washings.Detect in order to carry out pliability, before estimating pliability with HEAVY FLANNELETTE towel sample aline and make its drying.Used from 0～4 evaluation group marking system (PSU) by special judge to compare pliability, 0 expression does not have difference, 4 expression difference maximums.Experiencing one and 4 its pliabilitys of postevaluation wash(ing)cycle.Test with following composition:
Weight percent
Composition reference 1 embodiment 1
Tensio-active agent:
Linear alkylbenzene sulfonate 88
Suet alkyl-sulphate 22
Alkyltrimethylammonium chloride 1.5 1.5
Ethoxyquin fatty alcohol (C 12-C 15) 5-
N-methyl N-1-deoxy-glucose base C 12
Alkylamide-5
Washing assistant/sequestrant:
Zeolite A 23 23
Toxilic acid and acrylic acid multipolymer sodium salt 55
SYNTHETIC OPTICAL WHITNER:
Sodium peroxoborate 12 12
N, N, N', N'-tetraacetyl ethylene diamine 44
Spices: 0.5 0.5
Enzyme--
Sarinase (Savinase) 1.6 1.6
The softening agent system:
Terre verte/montmorillonitic clay 10.5 10.5
Glycerine 0.5 0.5
Polyethylene oxide 00
The composition weight percent
Reference 1 embodiment 1
Buffer reagent:
Carbonate 10.6 10.6
Silicate (2.0) 55
Mixing and spraying of material (suds suppressor, other) equilibrate to 100
Embodiment 1(is with 5% C 22Alkylamide for the basis) softening performance compare with reference I (with 5% oxyethyl group nonionic surface active agent).
Four wash(ing)cycles an of wash(ing)cycle
Example I is to reference I 0.4s 0.8s
Can see that its softness of product with the product (embodiment I) that contains alkylamide can obtain statistical obvious improvement.
The embodiment II
In addition, prepare composition with the clay flocculating agent, the softness that will have the product (embodiment II) of 5% alkylamide is compared with the softness of the same product with 5% oxyethyl group nonionic surface active agent (reference II), and test conditions is identical with the condition described in the embodiment I.
After a wash(ing)cycle and four wash(ing)cycles, estimate their softness:
We can observe once more contain alkylamide product than the product that contains the oxyethyl group nonionic surface active agent, have statistical more obviously good softness.
Figure 921092946_IMG8
Figure 921092946_IMG9

Claims (9)

1, a class cleaning composition is characterized in that it comprises polyhydroxy fatty acid amide surfactant, and molecular formula is:
Figure 921092946_IMG2
R wherein 1Be hydrogen, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or the mixture of above-mentioned these materials; R 2Be C 5～C 31Alkyl, Z are polyhydroxy alkyl or its alkoxy derivative, and above-mentioned polyhydroxy alkyl is a straight-chain alkyl, have at least directly connected three hydroxyls on the above-mentioned straight chain;
Also has a clay softening system.
2, a kind of cleaning composition as claimed in claim 1 is characterized in that wherein the weight percent content of above-mentioned polyhydroxy fatty acid amide is at least 1%.
3, a kind of cleaning composition as claimed in claim 1 is characterized in that having in the above-mentioned polyhydroxy fatty acid amide surfactant of molecule formula I, wherein R 1Be methyl, R 2Be C-C alkyl group or alkenyl, Z is the glycosyl of deriving and obtaining by reducing sugar, or its ethoxylated derivative.
4, a kind of cleaning composition as claimed in claim 1 is characterized in that above-mentioned clay softening system comprises a kind of clay, and its amount accounts for cleaning composition gross weight 0.5% at least.
5, cleaning composition as claimed in claim 4, wherein said clay are terre verte class clays.
6, a kind of cleaning composition as claimed in claim 1 is characterized in that above-mentioned clay softening system comprises a kind of clay flocculating agent.
7, a kind of cleaning composition as claimed in claim 1 is characterized in that above-mentioned clay softening system comprises a kind of wetting agent.
8, a kind of cleaning composition as claimed in claim 1 is characterized in that also comprising one or more cosurfactants,
Figure 921092946_IMG3
This auxiliary is anionic, cationic, nonionic detergent surfactant, or its mixture.
9, a kind of cleaning composition as claimed in claim 8 is characterized in that the amount of above-mentioned nonionic detergent surfactant equals 4% of this cleaning composition gross weight at least.
CN92109294A 1991-07-08 1992-07-08 Detergent compositions containing polyhydroxy fatty acid amide surfactants and clay softening system Expired - Fee Related CN1037452C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP91201773.8 1991-07-08
EP19910201773 EP0522206B1 (en) 1991-07-08 1991-07-08 Detergent compositions containing polyhydroxy fatty acid amide surfactants and a clay softening system

Publications (2)

Publication Number Publication Date
CN1070223A true CN1070223A (en) 1993-03-24
CN1037452C CN1037452C (en) 1998-02-18

Family

ID=8207767

Family Applications (1)

Application Number Title Priority Date Filing Date
CN92109294A Expired - Fee Related CN1037452C (en) 1991-07-08 1992-07-08 Detergent compositions containing polyhydroxy fatty acid amide surfactants and clay softening system

Country Status (15)

Country Link
EP (1) EP0522206B1 (en)
JP (1) JPH06508876A (en)
CN (1) CN1037452C (en)
CA (1) CA2113067C (en)
DE (1) DE69113259T2 (en)
ES (1) ES2077154T3 (en)
HU (1) HUT66853A (en)
IE (1) IE922133A1 (en)
IN (1) IN186294B (en)
MA (1) MA22585A1 (en)
MX (1) MX9203995A (en)
PT (1) PT100644A (en)
TR (1) TR26835A (en)
TW (1) TW216802B (en)
WO (1) WO1993001267A1 (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0593406A1 (en) * 1992-10-13 1994-04-20 The Procter & Gamble Company Non-aqueous liquid detergent compositions
GB9303721D0 (en) * 1993-02-24 1993-04-14 Unilever Plc Detergent composition
EP0628624A1 (en) 1993-06-09 1994-12-14 The Procter & Gamble Company Protease containing dye transfer inhibiting compositions
AU7244594A (en) * 1993-06-25 1995-01-17 Procter & Gamble Company, The Granular laundry detergent compositions containing lipase and sodium nonanoyloxybenzene sulfonate
US5604197A (en) * 1993-07-22 1997-02-18 The Procter & Gamble Company Softening through the wash compositions
EP0635563A1 (en) * 1993-07-22 1995-01-25 The Procter & Gamble Company Dye-transfer-inhibiting compositions containing fabric-softening agent
EP0635565B1 (en) * 1993-07-23 1997-11-12 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
DE69319237T2 (en) * 1993-07-23 1999-02-25 Procter & Gamble Dye transfer inhibiting detergent compositions
WO1995033038A1 (en) * 1994-06-01 1995-12-07 The Procter & Gamble Company Sarcosinate with clay softeners in laundry compositions
DE4430085C2 (en) * 1994-08-25 1997-02-27 Henkel Kgaa Hair shampoos
DE69431561T2 (en) * 1994-12-29 2003-08-07 Procter & Gamble Detergent compositions softening during washing
EP0919608A1 (en) * 1997-11-25 1999-06-02 The Procter & Gamble Company Use of a polyhydroxyfatty acid amide compound as a softening compound
GB2352245A (en) * 1999-07-22 2001-01-24 Procter & Gamble Detergent compositions
DE19948671A1 (en) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh laundry detergent
JP6085454B2 (en) * 2012-11-29 2017-02-22 株式会社ミルボン Washing soap
EP3085761A1 (en) * 2015-04-20 2016-10-26 Hayata Kimya Sanayi Anonim Sirketi Laundry detergent for use in washing of white and coloured fabrics together

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2703798A (en) * 1950-05-25 1955-03-08 Commercial Solvents Corp Detergents from nu-monoalkyl-glucamines
US2662073A (en) * 1951-04-27 1953-12-08 Charles L Mehltretter Gluconamides
NL217218A (en) * 1956-05-14
US2982737A (en) * 1957-05-27 1961-05-02 Rohm & Haas Detergent bars
SE319156B (en) * 1966-08-01 1970-01-12 Henkel & Cie Gmbh
DK130418A (en) * 1967-07-19
ZA734721B (en) * 1972-07-14 1974-03-27 Procter & Gamble Detergent compositions
US3852211A (en) * 1972-08-09 1974-12-03 Procter & Gamble Detergent compositions
US3915882A (en) * 1972-11-10 1975-10-28 Procter & Gamble Soap compositions
EP0112344A1 (en) * 1982-06-11 1984-07-04 National Research Development Corporation Amphipathic compounds
DE3538451A1 (en) * 1985-10-29 1987-05-07 Sueddeutsche Zucker Ag Fatty acid amides of amino polyols as non-ionic surfactants
DE3711776A1 (en) * 1987-04-08 1988-10-27 Huels Chemische Werke Ag USE OF N-POLYHYDROXYALKYL Fatty Acid Amides As Thickeners For Liquid Aqueous Surfactant Systems
EP0299575B1 (en) * 1987-07-14 1994-01-12 The Procter & Gamble Company Detergent compositions
US4844821A (en) * 1988-02-10 1989-07-04 The Procter & Gamble Company Stable liquid laundry detergent/fabric conditioning composition
DE68927290T2 (en) * 1988-12-21 1997-04-24 Procter & Gamble Textile fabric softener containing natural hector rides

Also Published As

Publication number Publication date
MX9203995A (en) 1993-04-30
PT100644A (en) 1993-09-30
EP0522206A1 (en) 1993-01-13
MA22585A1 (en) 1993-04-01
TW216802B (en) 1993-12-01
HU9400051D0 (en) 1994-05-30
ES2077154T3 (en) 1995-11-16
DE69113259D1 (en) 1995-10-26
DE69113259T2 (en) 1996-05-15
CA2113067A1 (en) 1993-01-21
CN1037452C (en) 1998-02-18
IE922133A1 (en) 1993-01-13
WO1993001267A1 (en) 1993-01-21
JPH06508876A (en) 1994-10-06
TR26835A (en) 1994-08-12
IN186294B (en) 2001-07-28
EP0522206B1 (en) 1995-09-20
CA2113067C (en) 1997-12-16
HUT66853A (en) 1995-01-30

Similar Documents

Publication Publication Date Title
CN1037452C (en) Detergent compositions containing polyhydroxy fatty acid amide surfactants and clay softening system
CN1086732C (en) Compositions comprising ethoxylated/propoxylated polyalkyleneamine polymers as soil dispersing agents
CN1037521C (en) Detergent compositions
CN1065563C (en) Bleaching compounds comprising N-acyl caprolactam for use in hand-wash or other low-water cleaning systems
CN1117611C (en) Method for preparing fatty acid amide surfactants
CN1094517C (en) Detergent composition containing efficient enduring perfume
CN1101464C (en) Detergent compositions comprising multiperacid-foaming bleach activators
CN1105174C (en) Color-safe bleach boosters, compositions and laundry methods employing same
CN1083007C (en) Perfumes for laundry and cleaning composition
CN1292062C (en) Bleaching detergent compositions
CN1090879A (en) Low sudsing polyhydroxy fatty acid amide detergents
CN1104489C (en) Detergent composition
CN1270622A (en) Improved alkylbenzenesulfonate surfactants
CN1159824A (en) Handwash laundry detergent compositions
CN1270621A (en) Improved alkylbenzenesulfonate surfactants
CN1035067C (en) Detergent compositions
CN1202197A (en) High efficiency delivery system comprising zeolites
CN87101761A (en) Detergent builder compound containing ether carboxylate and polycarbexylate
CN1090887A (en) The high-sudsers composition that contains specially selected soap
JPH06501731A (en) A detergent composition comprising a polyhydroxy fatty acid amide and an alkyl alkoxylated sulfate
CN1025870C (en) Detergent compositions
CN1133612A (en) Bar composition with N-alkoxy or N-aryloxy polyhydroxy fatty acid amide surfactant
CN1047624C (en) Detergent compositions
CN1150452A (en) Detergents with reduced peroxygen bleach levels containing chelant and enzymes
CN1322242A (en) Detergent compositions

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C15 Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993)
OR01 Other related matters
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee