CN1323342A - Detergent and descaling composition tablets and use in dish washer and washing machine - Google Patents
Detergent and descaling composition tablets and use in dish washer and washing machine Download PDFInfo
- Publication number
- CN1323342A CN1323342A CN99811953A CN99811953A CN1323342A CN 1323342 A CN1323342 A CN 1323342A CN 99811953 A CN99811953 A CN 99811953A CN 99811953 A CN99811953 A CN 99811953A CN 1323342 A CN1323342 A CN 1323342A
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- CN
- China
- Prior art keywords
- tablet
- water
- phosphate sodium
- tripoly phosphate
- sodium stpp
- Prior art date
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0086—Laundry tablets
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0091—Dishwashing tablets
-
- 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
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
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- 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 detergent and descaling composition tablets comprising compacted sodium tripolyphosphate particles with a high phase I content and water homogeneously distributed in said sodium tripolyphosphate, said tablets being characterised in that said sodium tripolyphosphate present in the tablet or in a region of the tablet contains: 70 % to 100 % wt.%, preferably 80 % to 98 wt.% of phase I relative to all the anhydrous tripolyphosphate phases; 7 % to 16 % of its weight in water, at least 50 %, preferably 70 % to 90 % of said water being in the form of crystallisation water.
Description
The present invention relates to the detergency of densification or remove calcareous sedimentary particulate composition tablet, this tablet can be used for the washing operation that carries out at washing machine or dishwasher.
The sheet cleaning composition that has fast disintegration and dissolution rate by the particle densification preparation that will contain tripoly phosphate sodium STPP (NaTPP) in water medium is known, described NaTPP is by at least 40% I phase composite and contain the water of hydration (EP-A-839,906) that 0.5～5wt% distributes in even mode.
The applicant finds, the water that exists in having relatively large water to exist in main NaTPP by the I phase composite can to avoid tablet is transferred on this NaTPP, has so just prevented the danger of sensitive ingredients (as enzyme) disintegration when this tablet is heated.
In addition, the existence of volume water makes has increased the number of hydration NaTPP seed, makes easy disintegration of this tablet and dissolving.
First purpose of the present invention is to contain based on the washing of tripoly phosphate sodium STPP densification particulate or except that calcareous precipitated composition tablet, this tripoly phosphate sodium STPP has high I phase content, with equally distributed water in described tripoly phosphate sodium STPP, described tablet is characterised in that, described tripoly phosphate sodium STPP is in this tablet or in this tablet section
* with respect to the whole phase of anhydrous sodium tripolyphosphate, contain 70～100, preferred 80～98% weight I phases
* contain its weight 7～16%, preferred 8～12% water, in these water at least 50%, preferred 70～90% are the form of crystal water.
The described tripoly phosphate sodium STPP that contains 70～100wt% I phase and 7～16% water accounts for 5～100wt% of its residing this tablet (dry weight) or this tablet section weight, preferred about 10～90wt% (butt is represented).
Be used for making at least mainly can obtaining by the method for three steps of tablet of the present invention by the NaTPP of I phase composite, promptly by sodium orthophosphate solution atomization drying, be sintered into anhydrous I phase NaTPP and hydration.
The step of atomization drying can be carried out continuously, such as by nozzle atomization device or turbine mixed aerosol device, use dry matter content to be approximately 50～70wt%, sodium orthophosphate solution about preferred 60wt% and be injected into swelling agent element, particularly volatile salt in the orthophosphate solution at the first bruss in atomizing; The injection rate of volatile salt can be (butt) about 0.1～0.6 weight part for 100 parts of orthophosphoric acid salt (butt).
The temperature of working gas inlet is relevant with the fluidic flow with the spraying gun size, can be about 500～600 ℃.
Gas outlet temperature can be 120～200 ℃, preferred 140～160 ℃.
The orthophosphoric acid salt particle that so obtains generally presents residual humidity and is lower than 5wt%; Its density is about 0.25～0.45g/cm
3, preferably at 0.35g/cm
3About; Its median diameter generally is 200～400 μ m, preferably about 300 μ m.
Sintering operation can carry out continuously, such as carrying out in the middle of the converter that provides and flow direct flame at, directly is cooled at the sintering after product.
The sodium orthophosphate that adds can be until 450～600 ℃, the about 30min to 1hr of preferred 490～530 ℃ sintering temperature.
The product that so obtains is approximately to be 250～450 μ m by its granularity of NaTPP powder of (about 70～100%) I phase composite mainly, and about preferred 350 μ m, its density is about 0.4～0.65g/cm
3, preferred 0.55g/cm
3About.
By for example being atomized, water carries out the hydration of NaTPP powder then in cylinder, flash mixer or fluidized-bed, double flowing nozzle type spraying gun is housed in these equipment, can produce about 20～300 μ m, drop about preferred 100 μ m, the water of NaTPP (water of hydration) content reaches till about 7～16% in obtaining particle.This water-content preferably about 8～12%.
Density≤the 0.8g/cm of this product
3, be preferably 0.45～0.65g/cm
3
According to first embodiment of the present invention, this hydration step is atomized by the aqueous solution based on the aqueous solution of alkali or subsalt such as yellow soda ash, salt of wormwood, alkalimetal silicate, tripoly phosphate sodium STPP and carries out.Can enumerate the atomizing that preferably contains the NaTPP aqueous solution that is less than 20ppmCa or Mg especially, these materials have formed NaTPP6H
2" nuclear " of O.
Second embodiment comprises by pore forming material such as nonionogenic tenside, carry out the step of hydration as polyethoxylated Fatty Alcohol(C12-C14 and C12-C18) or sequestrant such as polyacetic acid salt (edetate etc.), polyphosphonate (ethane 1-hydroxyl-1,1-diphosphonate, the methylene diphosphonate etc.) atomizing of the aqueous solution.
According to a selection scheme of the present invention, described tablet also contains other tripoly phosphate sodium STPP at least, is lower than 70% tripoly phosphate sodium STPP or main or all by the tri-polyphosphate of II phase composite such as the I phase content.
Particularly, described other tripoly phosphate sodium STPP is the whole no water with respect to tripoly phosphate sodium STPP, and the II phase content is 70% tripoly phosphate sodium STPP at least, and water-content can be 0～15%, preferably approximately 5～10%.
Content at other tripoly phosphate sodium STPP described in the tablet of the present invention is that the total amount of NaTPP is not all about 5～100%, preferred 10～90% by the purposes of being studied in this tablet.
Tablet as the object of the invention can be the detergent tablet that is used for washing machine or dishwasher, also can be to remove calcareous precipitation tablet.
This tablet can comprise one or two, even a plurality of zone.
When relating to the tablet that comprises two districts, described tripoly phosphate sodium STPP contains 70～100wt% I phase and 7～16% water, and it is preferably placed in two districts of this sheet.
When relating to the tablet of use in washing machine, described contain 70～100wt% I mutually and the amount of the tripoly phosphate sodium STPP of 7～16% water can account for this tablet (dry weight) or the tablet section weight that is positioned at 5～80%, be preferably about 10～60wt% (butt).
In other additive in can being present in the use in washing machine tablet, can enumerate:
The I phase content is lower than 70%, and is perhaps main or all by the tripoly phosphate sodium STPP of II phase composite, particularly with respect to whole no water, contains at least 70% II phase, and water-content is 0～15%, the tri-polyphosphate of preferably approximately 5～10%; Its content can be so that the total amount of NaTPP be about 5～60%, preferred 10～50% in the tablet in tablet.
Other inorganic or organic washing auxiliary detergent (washing assistant), its consumption can be until 50wt%, and these auxiliary agents are such as being:
The hempa hydrochlorate of-basic metal, ammonium or alkanolamine
-tetraborate or borate precursor
-amorphous or crystalline alkalimetal silicate
-alkaline carbonate
-at EP-A-488, Q2 or Q3 form Siliciumatom are rich in narration in 868, are used for the basic metal hydrosilicate of powder cleaning composition and the symbiosis particle of basic metal (Na or K) carbonate
The silico-aluminate of-amorphous or crystalline basic metal (Na or K) or ammonium is as zeolite A, P, X etc.
-water-soluble poly phosphonate (ethane 1-hydroxyl-1,1-diphosphonate, methylene diphosphonate etc.)
-water-soluble carboxyl acid polymer or copolymer salt, as molecular weight greatly about 2,000～100,000 pass through the water soluble polycarboxylic acid salt that alkene class unsaturated carboxylic acid such as vinylformic acid, toxilic acid or maleic anhydride, fumaric acid, methylene-succinic acid, methylfumaric acid, citraconic acid, the polymerization of methylene radical propanedioic acid or copolymerization obtain, particularly molecular weight about 2,000～10,000 polyacrylate (US-A-3,308,067), molecular weight is approximately 5,000～75,000 vinylformic acid and copolymer-maleic anhydride (EP-A-66,915)
-polycarboxylate (oxygen di-succsinic acid and salt thereof, tartrate monosuccinic acid and salt thereof, tartrate disuccinic acid and salt thereof)
-hydroxyl polycarboxylate
-citric acid and salt thereof, mellitic acid, succsinic acid and salt thereof
-polyacetic acid salt (edetate, nitrilotriacetic acid(NTA) salt, N-(2-hydroxyethyl)-nitrilo diacetin)
-C
5～C
20Alkyl succinic acid and salt thereof (2-12 alkenyl succinic salt, lauryl succinate etc.)
-polyacetal carboxylic acid ester
-poly-aspartic-acid, polyglutamic acid and their salt
-the polyimide that obtains by aspartic acid and/or L-glutamic acid polycondensation
The poly-carboxyl methylation derivant of-L-glutamic acid [such as N, N-two (carboxymethyl) L-glutamic acid and salt, particularly sodium salt] or other amino acid
Tensio-active agent, negatively charged ion or non-ionic, consumption are about 5～40wt%, as:
Anion surfactant, (consumption about 0～20%) as:
General formula is R-CH (SO
3M)-and the alkyl ester sulfonate of COOR ', wherein R represents C
8～C
20Alkyl, preferred C
10～C
16Alkyl, R ' represents C
1～C
6Alkyl, preferred C
1～C
3Alkyl, and M be basic metal (Na, K, Li), replace or unsubstituted ammonium (ammonium methyl, Dimethyl Ammonium, trimethyl ammonium, tetramethyl-ammonium, lupetidine) or alkanolamine (monoethanolamine, diethanolamine, trolamine etc.) deutero-positively charged ion;
General formula is ROSO
3The alkyl-sulphate of M and their ethoxylation (EO) and/or propoxylation (PO) derivative, average EO and/or PO chain number are 0.5～30, and be preferred 0.5～10, wherein R represents C
5～C
24Preferred C
10～C
18Alkyl or hydroxyalkyl, M are represented hydrogen atom or positively charged ion as defined above
General formula is RCONHR ' OSO
3The alkylamide vitriol of M and their ethoxylation (OE) and/propoxylation (OP) derivative, wherein R represents C
2～22, preferred C
6～20Alkyl, R ' are C
2-3Alkyl, M are represented hydrogen atom or positively charged ion as defined above, and average EO and/or OP chain number are 0.5～60;
C
8～C
24, preferred C
14～C
20Saturated or unsaturated fatty acid salt, C
9～C
20Alkylbenzene sulfonate, C
8～C
22Primary alkyl or secondary alkyl sulfonate, alkyl glycerol sulfonate, as at GB-A-1; sulfonation poly carboxylic acid described in 082,179, paraffin sulfonate, N-acyl group N-alkyl tauride, alkylphosphonic, isethionate, amber alkyl amide salts, alkyl sulfo succinate, sulfosuccinic acid monoesters or diester, N-acyl sarcosinate, alkyl glycoside vitriol and polyethoxye carboxylate salt
Positively charged ion is basic metal (Na, K, Li), replace or unsubstituted ammonium residue (ammonium methyl, Dimethyl Ammonium, trimethyl ammonium, tetramethyl-ammonium, lupetidine) or alkanolamine (monoethanolamine, diethanolamine, trolamine etc.) deutero-positively charged ion;
Sophorolipid is as the acid that obtained by 17-hydroxyl octadecenic acid or the form of lactone;
Nonionogenic tenside, (consumption about 0～30%) as:
Polyoxy alkylidene (polyethoxye ethylidene, polyoxy propylidene, polyoxy butylidene) alkylphenol, wherein the alkyl of Qu Daiing is C
6～C
12Alkyl, and contain 5～25 oxyalkylene chain links, can enumerate Rohm﹠amp as an example; Triton X-45, X-114, X-100 or X-102 that Haas company sells, the Rh ne-Poulenc Igepal NP2～NP17 of company;
The C that contains 1～25 oxyalkylene (oxygen ethylidene, oxygen propylidene) chain link
8～22The Fatty Alcohol(C12-C14 and C12-C18) of polyoxy alkylidene; Can enumerate Tergitol 15-S-9, the Tergitol 24-L-6 NMW of Union Carbide company sale, Neodol 45-9, Neodol 23-65, Neodol 45-7, Neodol 45-4, the Procter﹠amp that Shell Chemical company sells as an example; The Plurafac LF403 that Rhodasurf IT, the DB of the Kyro EOB that Gamble company sells, the Synperonic A3～A9 of ICI company, Rh nePoulenc company and B, BASF AG sell;
The product that oxyethane or propylene oxide and propylene glycol, ethylene glycol polycondensation obtain, weight-average molecular weight are about 2,000～10,000, the Pluronic that sells as BASF AG;
The product of oxyethane or propylene oxide and quadrol polycondensation is as the Tetronic of BASF AG's sale;
The C that contains 5～25 oxyethyl groups and/or propoxy-chain link
8～C
18Ethoxylation or propenoxylated lipid acid;
The C that contains 5～30 oxyethyl group chain links
8～C
20Aliphatic amide;
The ethoxylated amine that contains 5～30 oxyethyl group chain links;
Contain 1～50, preferred 1～25, the alkoxylate amido amine of preferred especially 2～20 oxyalkylenes (preferred oxygen ethylidene) chain link;
Amine oxide is as C
10～C
18The oxide compound of alkyl dimethyl amine, C
8～C
22The oxide compound of alkoxyethyl dihydroxyl ethamine;
Oxyalkylated terpene hydrocarbon, as contain the ethoxylation of 1～30 oxygen ethylidene and/or oxygen propylidene chain link and/or propenoxylated α-or beta-pinene;
By such as the available alkyl poly glucoside of acid catalyzed polycondensation (US-A-3,598,865, US-A-4,565,647, EP-A-132,043, EP-A-132,046), it has C by glucose and aliphatic primary alcohol
4～20Alkyl, preferred C
8～18The mean number of glucose chain link is about 0.5～3, preferred 1.1～1.8 in the alkyl, every mole of alkyl poly glucoside (APG); Can enumerate especially and to have following chain link:
* C
8～C
14Alkyl, every mole of average 1.4 glucose chain links
* C
12～C
14Alkyl, every mole of average 1.4 glucose chain links
* C
8～C
14Alkyl, every mole of average 1.5 glucose chain links
* C
8～C
10Alkyl, every mole of average 1.6 glucose chain links
They are all sold by Henkel company, and trade(brand)name is respectively Glucopon 600 EC
, Glucopon 600 CSUP
, Glucopon 650 EC
, Glucopon 225 CSUP
The agent of anti-soil dirt, quantity is about 0.01～10wt%, preferably approximately 0.1～5wt%, special preferably approximately 0.2～3wt%, such as:
-derivatived cellulose is as the hydroxy ethers of Mierocrystalline cellulose, methylcellulose gum, ethyl cellulose, Vltra tears, hydroxy butyl methyl cellulose
-be grafted on the polyvinylesters on the polyalkylene trunk, as be grafted on the polyvinyl acetate (PVA) (EP-A-219,048) on the polyoxyethylene trunk
-polyvinyl alcohol
-based on the polyester copolymer of ethylene glycol terephthalate and/or propylene glycol ester terephthalate's chain link and poly terephthalic acid oxygen ethylidene ester chain link, ethylene glycol terephthalate and/or propylene glycol ester terephthalate (chain number)/poly terephthalic acid oxygen ethylidene ester (chain number) mol ratio is about 1/10～10/1, the unitary molecular weight of polyoxyethylene is about 300～10 in the poly terephthalic acid oxygen ethylidene ester chain link, 000, the molecular weight of multipolymer is about 1,000～100,000
-based on the polyester copolymer of ethylene glycol terephthalate and/or propylene glycol ester terephthalate and polyoxyethylene and/or polyoxy propylidene chain link, the mol ratio of its ethylene glycol terephthalate and/or propylene glycol ester terephthalate (chain number)/polyoxyethylene and/or polyoxy propylidene (chain number) is about 1/10～10/1, the molecular weight of polyoxyethylene and/or polyoxy propylidene chain link is about 250～10,000, the molecular weight of copolyesters is about 1,000～100,000 (US-A-3,959,230, US-A-3,962,152, US-A-3,893,929, US-A-4,116,896, US-A-4,702,857, US-A-4,770,666, EP-A-253,567, EP-A-201,124)
-in its chain, contain the ethylene glycol terephthalate of sulfo group isophthaloyl chain link or the multipolymer of propylene glycol ester/poly terephthalic acid oxygen ethylidene ester (US-A-4,711,730, US-A-4,702,857, US-A-4,713,194)
-have sulfonation, sulfo group aroylation polyalkylene oxide is alkyl-blocked, chooses oligomeric copolyesters (US-A-4,721 of the terephthalic acid that contains sulfo group isophthaloyl chain link in its chain wantonly; 580, US-A-5,415,807, US-A-4; 877,896, US-A-5,182; 043, US-A-5; 599,782, US-A-4,764; 289, EP-A-311,342, WO92/04433, WO97/42293)
-the molecular weight that obtained by the diester such as diester, sulfoisophthalic acid and the dibasic alcohol, particularly ethylene glycol of terephthalic acid, m-phthalic acid is lower than 20,000 sulfonation terephthalic acid copolyesters (WO95/32997)
-by the bis--terephthalate, randomly the number-average molecular weight of the diester of sulfoisophthalic acid and dibasic alcohol acquisition is 300～4,000 polyester and be 600～4 by molecular weight, polyester-polyurethane (the US-A-4 that the prepolymer reaction that has isocyanate end that 000 polyoxyethylene glycol and isocyanic ester obtain obtains, 201,824)
-have 1～4 sulfo group by from ethoxylated allyl, dimethyl terephthalate (DMT) and 1, the sulfonated polyester oligopolymer (US-A-4,968,451) that 2-propylene glycol deutero-oligopolymer obtains through sulfonation.
Anti redeposition agent, to the dry powder cleaning composition, consumption is about 0.01～10wt%, this reagent just like:
The monoamine of-ethoxylation or polyamines, the amine polymer of ethoxylation (US-A-4,597,898, EP-A-11,984)
-carboxymethyl cellulose
-sulfonated polyester the oligopolymer (FR-A-2,236,926) that obtains by m-phthalic acid, sulfosuccinic dimethyl phthalate and Diethylene Glycol polycondensation
-Polyvinylpyrolidone (PVP)
It is about 0.1～20% that SYNTHETIC OPTICAL WHITNER, consumption account for described cleaning composition weight, is preferably 1～10%, as:
-perborate is as single hydration or four hydrated sodium perborates
-peralcohol is such as yellow soda ash peroxidation hydrate, pyrophosphate salt peroxidation hydrate, urea peroxidation hydrate, sodium peroxide, Sodium Persulfate
-peroxycarboxylic acid and salt thereof (being called percarbonate) are crossed oxy hexanoic acid, diperoxy 12 carbon alkyl acids, are crossed oxydisuccinic acid pelargonamide, decyl diperoxy succsinic acid as six hydration monoperphthalic acid magnesium, metachloroperbenzoic acid magnesium, 4-nonyl amino-4-oxo Perbutyric Acid, 6-nonyl amino-6-oxo
Preferably use with the bleach-activating agent that in washing medium, produces peroxycarboxylic acid on the spot; In these bleach-activating agents, can mention tetra acetyl ethylene diamine, tetra-acetylated methanediamine, tetra-acetylated glycoluril, to acetoxyl group benzene sulfonic acid sodium salt, penta-acetyl glucose, octoacetyl lactose etc.,
Fluorescent agent, consumption are about 0.05～1.2wt%, such as the derivative of stilbene, pyrazoline, tonka bean camphor, fumaric acid, styracin, pyrroles, methyne cyanine, thiophene etc.;
Froth suppressor, consumption can be until 5wt%, such as:
-C
10～C
24Aliphatic monocarboxylic acid or their an alkali metal salt, ammonium salt or alkanol amine salt, fatty acid glyceryl ester
-saturated or unsaturated aliphatic, alicyclic, aromatics or heterocyclic hydrocarbon such as paraffin, wax
-N-alkylamino triazine
-mono phosphoric acid ester stearyl ester, the stearic alcohol ester of mono phosphoric acid ester
-organopolysiloxane oil or resin are chosen wantonly and are used with silica dioxide granule
Tenderizer, consumption is approximately 0.5～10wt%, such as clay
Enzyme, consumption can be until 5mg, preferably approximately 0.05～3mg organized enzyme/g cleaning composition, enzyme is just like proteolytic enzyme, amylase, lipase, cellulase, peroxidase (US-A-3,553,139, US-A-4,101,457, US-A-4,507,219, US-A-4,261,868)
With other additive, such as:
-alcohols (methyl alcohol, ethanol, propyl alcohol, Virahol, propylene glycol, ethylene glycol, glycerine)
-buffer reagent or resemble materials such as sodium sulfate, alkaline earth metal carbonate or supercarbonate
-pigment
-disintegrating agent
-closely agent is as polyoxyethylene glycol.
When relating to the use in dishwasher tablet, described contain 70～100wt% I mutually and the tripoly phosphate sodium STPP consumption of 7～16wt% water can account for the 10～90wt% (representing) of the tablet section weight that this tablet (butt) and tablet be positioned at butt.
In the middle of other additive that in the use in dishwasher tablet, can exist, can mention:
-I phase content is lower than the tripoly phosphate sodium STPP of 70wt%, and is perhaps main or account for no water integral body 70wt% mutually at least by the tri-polyphosphate, particularly II of II phase composite fully, and water-content is 0～15wt%, is preferably the tri-polyphosphate of about 5～10wt%; It is about 20～80wt% that its consumption in tablet can make the total amount of NaTPP in the tablet.
-be dissolved in other alkalization additive or sequestrant in the washing medium, such as:
The hempa hydrochlorate of basic metal, ammonium or alkanolamine
Tetraborate or boratory precursor
Alkalimetal silicate (0～30wt%)
Alkaline carbonate (0～30wt%)
Be rich in the alkali metal silicate salt hydrate of Q2 or Q3 type Siliciumatom and the blended particles of basic metal (sodium or potassium) carbonate,, described in 868, be used for the powder cleaning composition as EP-A-488
The silico-aluminate of crystalline or unbodied basic metal (sodium or potassium) or ammonium, as zeolite A, P, X etc.,
Water-soluble poly phosphonate (ethane 1-hydroxyl-1,1-diphosphonate, methylene diphosphonate)
The water-soluble salt of carboxylic acid polyalcohol or multipolymer, as the molecular weight that obtains by alkene class unsaturated carboxylic acid such as vinylformic acid, toxilic acid or maleic anhydride, fumaric acid, methylene-succinic acid, methylfumaric acid, citraconic acid, the polymerization of methylene radical propanedioic acid or copolymerization is about 2,000～100,000 water soluble polycarboxylic acid salt, particularly molecular weight is approximately 2,000～10,000 polyacrylate (US-A-3,308,067), molecular weight is approximately 5,000～75,000 the vinylformic acid and the multipolymer of maleic anhydride (EP-A-66,915)
Polycarboxylate (polycarboxylate ether) (oxygen di-succsinic acid and salt thereof, tartrate monosuccinic acid and salt thereof, tartrate disuccinic acid and salt thereof)
The hydroxyl polycarboxylate
Citric acid and salt thereof, mellitic acid, succsinic acid and salt thereof
Polyacetic acid salt (edetate, nitrilotriacetic acid(NTA) salt, N-(2-hydroxyethyl)-nitrilo diacetin)
C
5～C
20Alkyl succinic acid and salt thereof (2-dodecenyl succinic succinate, lauryl succinate etc.)
The polyacetal carboxylic acid ester
Poly-aspartic-acid, polyglutamic acid and their salt
The polyimide that obtains by aspartic acid and/or L-glutamic acid polycondensation
Many carboxyl methylation derivants of L-glutamic acid [as N, N-two (carboxymethyl) L-glutamic acid and salt, particularly sodium salt] or other amino acid
-alkali-metal supercarbonate and sesquicarbonate
-SYNTHETIC OPTICAL WHITNER is used with bleach-activating agent (tetra acetyl ethylene diamine) (until 10%) as alkali metal perborate and percarbonate (0～20%), randomly and bleaching catalyst (metallo-organic complexs such as manganese, cobalt) (0～1%) use together
-nonionogenic tenside (0.2～5%) such as:
Polyoxy alkylidene (polyethoxye ethylidene, polyoxy propylidene, polyoxy butylidene) is changed alkylphenol, and wherein alkyl substituent is C
6～12Alkyl, and contain 5～25 oxyalkylene chain links, can enumerate Rhom﹠amp as an example; Igepal NP2～NP17 that Triton X-45, X-114, X-100 or the X-102 that Haas company sells, Rh ne-Poulenc company sell;
The polyoxy alkylidene C that contains 1～25 oxyalkylene (oxygen ethylidene, oxygen propylidene) chain link
8～C
22Fatty Alcohol(C12-C14 and C12-C18); Can enumerate Tergitol 15-S-9, the Tergitol 24-L-6 NMW of Union Carbide company sale, Neodol 45-9, Neodol 23-65, Neodol 45-7, Neodol 45-4, the TheProcter﹠amp that Shell Chemical company sells as an example; The Kyro EOB that Gamble company sells, SynperonicA3～A9 that ICI company sells, Rhodasurf IT, the DB of Rh ne-Poulenc company and the Plurafac LF403 that B, BASF AG sell;
By the product that oxyethane or propylene oxide and propylene glycol, ethylene glycol polycondensation obtain, weight-average molecular weight is about 2000～10000, the Pluronic that sells as BASF AG;
The product that obtains by propylene oxide or oxyethane and quadrol polycondensation, the Tetronic that sells as BASF AG;
The ethoxylation and/or the propoxylation C that contain 5～25 oxyethyl groups and/or propoxy-chain link
8～C
18Lipid acid;
The C that contains 5～30 oxyethyl group chain links
8～C
20Fatty acid amide;
The ethoxylated amine that contains 5～30 oxyethyl group chain links;
Contain 1～50, preferred 1～25, the alkoxylate amido amine (amidoamine) of preferred especially 2～20 oxyalkylenes (preferred oxygen ethylidene) chain link;
The oxide compound of amine is as C
10～C
18The oxide compound of alkyl dimethyl amine, C
8～C
22The oxide compound of alkoxyethyl dihydroxyl ethamine;
Oxyalkylated terpene hydrocarbon, as contain the ethoxylation of 1～30 oxygen ethylidene and/or oxygen propylidene chain link and/or propoxylation α-or beta-pinene;
-anion surfactant (0～5%)
-enzyme (0～4%)
-tinting material, essence
-close mode auxiliary agent, as polyoxyethylene glycol, the perhaps disintegration auxiliary agent of tablet.
When relating to when removing calcareous precipitation tablet, described contain 70～100wt% I mutually and 7～16wt% water tripoly phosphate sodium STPP can account for the tablet weight (in base) that wherein has tripoly phosphate sodium STPP or 10～100wt% of this tablet section weight, preferably account for 20～90wt% (representing) with butt.
Can enumerate in other additive that in removing calcareous precipitation tablet, can exist:
-I phase content is lower than the tripoly phosphate sodium STPP of 70wt%, perhaps main or complete tri-polyphosphate by the II phase composite, particularly by the II phase composite that accounts for the whole 70wt% of no water at least and wherein water-content be 0～15wt%, be preferably the tri-polyphosphate of about 5～10wt%; It is about 30～99wt% that its consumption in tablet can make the total amount of NaTPP in the tablet, preferred 50～90wt%.
-hexamethyl phosphoric acid (herametaphosphate) sodium (0～10%)
-amorphous or crystalline alkalimetal silicate (0～30%)
-alkaline carbonate (0～30%)
The silico-aluminate of-crystalline or unbodied basic metal or ammonium (0～30%)
-water-soluble poly phosphonate (ethane 1-hydroxyl-1,1-diphosphonate, methylene diphosphonate etc.) (0～5%)
The water-soluble salt of-carboxylic acid polyalcohol or multipolymer (0～20%), as the molecular weight that obtains by alkene class unsaturated carboxylic acid such as vinylformic acid, toxilic acid or maleic anhydride, fumaric acid, methylene-succinic acid, methylfumaric acid, citraconic acid, the polymerization of methylene radical propanedioic acid or copolymerization is about 2,000～100,000 water soluble polycarboxylic acid salt, particularly polyacrylate, vinylformic acid and copolymer-maleic anhydride
-tensio-active agent (0～10%)
Can be with traditional method as the tablet of the object of the invention, the compacting aequum contains the granular composition of the various components of described tablet and obtains in mould.According to the purposes of being studied, the density of this tablet can be about 0.9～2g/cm
3
Provide the following examples as example.
Embodiment 1～10
In being housed, the Niro industry spraying gun of turbine adds:
* the 3m3/h temperature is 90 ℃, and dry matter content is the sodium orthophosphate solution of 61wt%
* 0.3 part of (dry weight) volatile salt of per 100 parts of (dry weight) sodium orthophosphates
The gas inlet temperature is 500 ℃, and temperature out is 150 ℃.The product density that obtains is 0.35g/cm
3, sintering in the directly flame and the stove that circulates then is until 520 ℃.
The NaTPP that obtains has following feature:
* to account for the ratio of whole no water mutually be 87% to I
* density is 0.55g/cm
3
In industrial rotary drum by atomized water with a part of product hydration, obtain the having difference NaTPP of " hydrauture ":
* 3.3% water, 54% is crystal water in these water
* 4.4% water, 62% is crystal water in these water
* 8% water, 74% is crystal water in these water
Be respectively embodiment 1, embodiment 2 and embodiment 3.
Another part does not have hydration (embodiment 4).
Third part hydration in water atomization at intermittence L dige flash mixer, obtain the having difference NaTPP of " hydrauture ":
* 4% water, 63% is crystal water in these water
* 8% water, 75% is crystal water in these water
* 10% water, 78% is crystal water in these water
Be respectively embodiment 5, embodiment 6 and embodiment 7.
The 4th part in Comessa (Comessa company) fluidized-bed by continuous water atomization by hydration, wherein powder mass flow is 50～100kg/hr, obtain the having difference NaTPP of " hydrauture ":
* 4% water
* 8% water
* 10% water
Be respectively embodiment 8, embodiment 9 and embodiment 10.
Test 1
By means of the NaTPP close mode of Zwick 147800/01 swaging machine with not hydration or the hydration of 31.5g embodiment 4～7, reactive force is 2.4kN, and forming diameter is the cylindric tablet of 41mm.
Each tablet is placed on the sieve (mesh 2mm), in the 9L de-salted water that (200rpm) immersion under agitation is 22 ℃.
Determine the dissolution rate (VD) of every kind of tablet by the monitoring electrical conductivity of water.So record the dissolving required time of 90% tablet.
The results are shown in the table 1.
Test 2
30 parts of NaTPP of embodiment 1～3,5～6 and 8～10 are mixed with 70 parts of washing basestocks that contain following material:
* 11% alkylbenzene sulfonate
* 5% nonionogenic tenside
* the I phase NaTPP of 30% embodiment 1～3,5～6,8～10
* the trade mark of 10%Europhos company sale is the NaTPP of LV
* 7% atomizing and particle are than being the silicate of R2
* 6% yellow soda ash
* 15% SPC-D
*4％TAED
* 2% defoamer (particle)
* the Sokalan CP5 of 2%BASF company
* 4% enzyme and essence
With every kind of 31.5g mixture close mode, the power that applies is 1.6kN or 2.4kN, and forming diameter is the cylindrical tablet of 41mm.
Measure the dissolution rate and the longitudinal break stress t of each tablet, unit is Pa.
Provide longitudinal break stress t with formula t=2F/ π De, here
* F is the power that applies, and unit is N
* D is a tablet diameters, and unit is m
* e is the thickness of tablet, and unit is m
Table 1
| The NaTPP of embodiment | " hydrauture " % | The power kN that applies | ???VD90 ????Min |
| ?????4 | ???～0 | ????2.4 | ????16 |
| ?????5 | ????4 | ????2.4 | ?????4 |
| ?????6 | ????8 | ????2.4 | ?????2 |
| ?????7 | ????10 | ????2.4 | ????0.6 |
Table 2
| The NaTPP of embodiment | " hydrauture " % | The power kN that applies | ???VD90 ????Min | ?????t ????kPa |
| ?????1 | ????3.3 | ????1.6 ????2.4 | ????6.7 ????9.3 | ????9.9 ???15.2 |
| ?????2 | ????4.4 | ????1.6 ????2.4 | ?????4 ????5.2 | ????9.9 ???15.3 |
| ?????3 | ?????8 | ????1.6 ????2.4 | ????2.6 ????4.2 | ???10.3 ????23 |
| ?????5 | ?????4 | ????1.6 ????2.4 | ????3.7 ????5.6 | ???19.0 ???32.4 |
| ?????6 | ?????8 | ????1.6 ????2.4 | ????2.7 ????3.9 | ???19.2 ???33.1 |
| ?????8 | ?????4 | ????2.4 | ????4.4 | ???25.7 |
| ?????9 | ?????8 | ????2.4 | ?????3 | ???25.5 |
| ????10 | ????10 | ????2.4 | ????3.2 | ???27.3 |
Claims (15)
1. washing or remove calcareous precipitated composition tablet, this tablet contain based on having the high I phase content and the close mode particle of the tripoly phosphate sodium STPP of equally distributed water therein, and described tablet is characterised in that at this tablet or at tripoly phosphate sodium STPP described in the tablet section
* with respect to the whole phase of anhydrous sodium tripolyphosphate, contain 70～100wt%, preferred 80～98wt% I phase
* contain 7～16wt% water, in these water at least 50%, preferred 70～90% are the form of crystal water.
2. the tablet of claim 1, it is characterized in that with respect to the butt weight of the tablet that wherein has tripoly phosphate sodium STPP or the weight of this tablet section, the described tripoly phosphate sodium STPP that contains 70～100wt% I phase and 7～16wt% water accounts for 5～100wt%, preferably account for about 10～90wt%, dry matter content.
3. claim 1 or 2 tablet is characterized in that the described tripoly phosphate sodium STPP that contains 70～100wt% I phase contains about 8～12wt% water.
4. each tablet in the claim 1～3 is characterized in that the described density that contains the tripoly phosphate sodium STPP of 70～100wt% I phase is less than or equal to 0.8g/cm
3, preferred 0.45～0.65g/cm
3
5. each tablet in the claim 1～4 is characterized in that this tablet also contains at least a other tripoly phosphate sodium STPP, preferably has the tripoly phosphate sodium STPP and/or the main or complete tri-polyphosphate by the II phase composite that are lower than 70wt% I phase content.
6. the tablet of claim 5 is characterized in that the no water integral body with respect to this tripoly phosphate sodium STPP, and described other tripoly phosphate sodium STPP is at least 70wt% for the II phase content, and water-content can be 0～15%, the tripoly phosphate sodium STPP of preferably approximately 5～10%.
7. the tablet of claim 6 is characterized in that content at other tripoly phosphate sodium STPP described in this tablet will make that the NaTPP total amount is about 5～100%, preferred 10～90% in this tablet.
8. each tablet in the claim 1～7 is characterized in that this tablet is use in washing machine or use in dishwasher detergent tablet, or removes calcareous precipitation tablet.
9. each tablet in the claim 1～8, it is characterized in that this tablet is the use in washing machine detergent tablet, the amount that wherein contains the described tripoly phosphate sodium STPP of 70～100wt% I phase and 7～16wt% water accounts for 5～80wt% with respect to butt tablet that wherein has tripoly phosphate sodium STPP or tablet zone weight, preferably account for about 10～60wt%, in dry-matter.
10. 9 tablets of claim, it is characterized in that this tablet also contains with respect to no water integral body by at least 70% II phase composite, and its water-content is 0～15wt%, a kind of tripoly phosphate sodium STPP of preferably approximately 5～10wt%, its quantity makes that the total amount of NaTPP is about 5～60wt% in this tablet, is preferably 10～50wt%.
11. claim 1～8 in each tablet, it is characterized in that this tablet is the use in dishwasher detergent tablet, wherein contain 70～100wt% I mutually and the amount of the described tripoly phosphate sodium STPP of 7～16wt% water account for 10～90wt% with respect to what wherein have a tripoly phosphate sodium STPP in substrate agent or the regional weight of tablet, in dry-matter.
12. the tablet of claim 11, it is characterized in that this tablet also contains with respect to no water integral body by at least 70% II phase composite, and its water-content is 0～15wt%, a kind of tripoly phosphate sodium STPP of preferably approximately 5～10wt%, its quantity make that the total amount of NaTPP is about 20～80wt% in this tablet.
13. each tablet in the claim 1～8, it is characterized in that this tablet is the use in dishwasher detergent tablet, the amount that wherein contains the described tripoly phosphate sodium STPP of 70～100wt% I phase and 7～16wt% water accounts for 10～100wt% with respect to butt tablet that wherein has tripoly phosphate sodium STPP or tablet zone weight, preferably account for 20～90wt%, in dry-matter.
14. the tablet of claim 13, it is characterized in that this tablet also contains with respect to no water integral body by at least 70% II phase composite, and its water-content is 0～15wt%, a kind of tripoly phosphate sodium STPP of preferably approximately 5～10wt%, its quantity makes that the total amount of NaTPP is about 30～99wt% in this tablet, preferred 50～90wt%.
15. the preparation method of each tablet during aforesaid right requires is comprising suppress the granular composition that aequum contains each component that constitutes described tablet in a mould.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9812682A FR2784392B1 (en) | 1998-10-09 | 1998-10-09 | DETERGENT OR ANTI-CALCIUM COMPOSITION TABLETS AND THEIR IMPLEMENTATION IN DISHWASHER OR WASHING MACHINE |
| FR98/12682 | 1998-10-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1323342A true CN1323342A (en) | 2001-11-21 |
Family
ID=9531384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99811953A Pending CN1323342A (en) | 1998-10-09 | 1999-10-01 | Detergent and descaling composition tablets and use in dish washer and washing machine |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1119606A1 (en) |
| CN (1) | CN1323342A (en) |
| AU (1) | AU754500B2 (en) |
| FR (1) | FR2784392B1 (en) |
| HK (1) | HK1042109A1 (en) |
| RU (1) | RU2213132C2 (en) |
| WO (1) | WO2000022090A1 (en) |
| ZA (1) | ZA200102369B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1466964A1 (en) * | 2003-02-11 | 2004-10-13 | Unilever N.V. | Cleaning compositions |
| EP1466965A1 (en) * | 2003-02-11 | 2004-10-13 | Unilever N.V. | Cleaning compositions |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE632423A (en) * | 1962-05-17 | |||
| CH471891A (en) * | 1963-12-31 | 1969-04-30 | Unilever Nv | Process for the manufacture of a detergent tablet |
| ZA663029B (en) * | 1965-06-25 | |||
| DE19502774A1 (en) * | 1995-01-27 | 1996-08-01 | Henkel Kgaa | Process for the manufacture of break-resistant cleaning tablets |
| GB2318800A (en) * | 1996-11-01 | 1998-05-06 | Unilever Plc | Detergent composition |
| DE69824564T2 (en) * | 1997-03-24 | 2005-06-09 | Unilever N.V. | DETERGENT COMPOSITIONS |
-
1998
- 1998-10-09 FR FR9812682A patent/FR2784392B1/en not_active Expired - Fee Related
-
1999
- 1999-10-01 AU AU58697/99A patent/AU754500B2/en not_active Ceased
- 1999-10-01 EP EP99946276A patent/EP1119606A1/en not_active Withdrawn
- 1999-10-01 RU RU2001112111/04A patent/RU2213132C2/en not_active IP Right Cessation
- 1999-10-01 WO PCT/FR1999/002343 patent/WO2000022090A1/en not_active Application Discontinuation
- 1999-10-01 CN CN99811953A patent/CN1323342A/en active Pending
-
2001
- 2001-03-22 ZA ZA200102369A patent/ZA200102369B/en unknown
-
2002
- 2002-05-17 HK HK02103731.6A patent/HK1042109A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| RU2213132C2 (en) | 2003-09-27 |
| WO2000022090A1 (en) | 2000-04-20 |
| FR2784392A1 (en) | 2000-04-14 |
| HK1042109A1 (en) | 2002-08-02 |
| FR2784392B1 (en) | 2000-11-17 |
| EP1119606A1 (en) | 2001-08-01 |
| AU5869799A (en) | 2000-05-01 |
| ZA200102369B (en) | 2001-11-14 |
| AU754500B2 (en) | 2002-11-21 |
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