[go: up one dir, main page]

CN1077135C - Detergent compositions comprising dye transfer inhibitors, and process for making them - Google Patents

Detergent compositions comprising dye transfer inhibitors, and process for making them Download PDF

Info

Publication number
CN1077135C
CN1077135C CN95193437A CN95193437A CN1077135C CN 1077135 C CN1077135 C CN 1077135C CN 95193437 A CN95193437 A CN 95193437A CN 95193437 A CN95193437 A CN 95193437A CN 1077135 C CN1077135 C CN 1077135C
Authority
CN
China
Prior art keywords
composition
weight
powder
polyamines
free flowing
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.)
Expired - Lifetime
Application number
CN95193437A
Other languages
Chinese (zh)
Other versions
CN1149885A (en
Inventor
S·J·唐诺休
K·M·A·尚普
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 CN1149885A publication Critical patent/CN1149885A/en
Application granted granted Critical
Publication of CN1077135C publication Critical patent/CN1077135C/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/08—Silicates
    • 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
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers

Landscapes

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

Abstract

The present invention provides a free-flowing powder having a bulk density of at least 600 g/l comprising: (a) from 20 % to 95 % by weight (on anhydrous basis) of a detergent ingredient selected from the group consisting of aluminosilicate, citrate, silica, carbonate, bicarbonate, silicate, sulphate, phosphate, water-soluble polymer and mixtures thereof; and (b) from 5 % to 50 % by weight of a copolymer of N-vinylpyrrolidone and N-vinylimidazole. A process for making the free-flowing granules is also provided.

Description

The detergent composition and the production method thereof that comprise dye transfer inhibitor
The present invention relates to have the free flowing powder of high-bulk-density, this powder comprises some can make for example polymkeric substance of the clothing cleaning of washing as dye transfer inhibitor.
The invention still further relates to the method for producing this free flowing powder.
In detergent composition, use various polymkeric substance to do introduction in the prior art as dye transfer inhibitor.A kind of method that polymkeric substance is mixed granular detergent composition must be mixed powdery polymer and other granular dry component.
Yet notice, adopt this method can produce the problem of granulated detergent caking and knot cake along with using the hygroscopic polymer powder.In addition, these powder of storing in bulk also have many difficulties.
US5259994 has been devoted to address the above problem, promptly by polyvinylpyrrolidone is mixed to prepare free-pouring detergent additives with zeolite, salt hydrate (for example carbonate) and tackiness agent.Yet this tiny no water additive absorbs moisture easily when contacting with water.The gel that is generated has adverse influence to the preparation of product.
That US4414130 discloses is a kind of, and " easy disintegrating, the granular agglomerate of insoluble detergent builders wherein comprise with water-soluble binder bonded [aluminosilicate]." mentioned this tackiness agent is Polyclar (PVP of GAF supply).The method of producing agglomerate comprises that the employing atomized water spray is to promote adhesion.Embodiment 2 (B) discloses solution a kind of and agglomerant polyvinylpyrrolidone of zeolite and polyvinyl alcohol.Yet this patent does not relate to the problem of preparation and processing dye transfer inhibitor.
Though polyvinylpyrrolidone can be used as dye transfer inhibitor, yet still seeking other more effective polymkeric substance.More effective polymkeric substance is that a kind of amount ratio polyvinylpyrrolidone is few, low price and can reach the polymkeric substance of effect same.
In current granulated detergent market, particularly importantly seek a kind of dye transfer inhibiting polymers efficiently (or some mixture of polymers), this polymkeric substance should be high packing density of particles and be easy to storing, and can add to slightly in the fine and close product and can the preparation of product not had a negative impact.
The invention provides a kind of highdensity agglomerate, this agglomerate comprises the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, and its content is generally 5%-50% (weight).
The present invention also provides a kind of method, wherein, prepares the specific water absorbability dye transfer inhibiting polymers and the pre-composition of zeolite (or other powder) earlier before agglomeration.
Summary of the invention
First aspect the invention provides the free flowing powder that a kind of tap density is at least 600g/l, and this powder comprises:
(a) detergent ingredients that is selected from aluminosilicate, Citrate trianion, silicon-dioxide, carbonate, supercarbonate, silicate, vitriol, phosphoric acid salt, water-soluble polymers and composition thereof of 20%-95% (weight is by anhydrous); With
(b) multipolymer of the N-vinyl pyrrolidone of 5%-50% (weight) and N-vinyl imidazole.
Though free-pouring powder can comprise other component, yet the content of preferred surfactant is lower than 2% of this powder weight.
This free-pouring powder preferably comprises (a) 50%-75% (weight, by anhydrous) the aluminosilicate and (b) mixture of polyamines N-oxide compound and N-vinyl pyrrolidone and N-vinyl imidazole multipolymer, the total content of this polymkeric substance is the 10%-30% of powder weight.
The mixture of polyamines N-oxide compound and N-vinyl pyrrolidone and N-vinyl imidazole multipolymer, its ratio is generally 5: 1 to 1: 5, and preferred about 1: 1.
Second aspect the invention provides the method that a kind of production comprises the free flowing powder of hygroscopic polymer powder, and this method may further comprise the steps:
(a) will comprise polyamines N-oxide compound and/or N-vinyl pyrrolidone and the powder of N-vinyl imidazole multipolymer and other powder mixes, to form the powder pre-composition, described other powder is selected from aluminosilicate, Citrate trianion, silicon-dioxide, carbonate, supercarbonate, silicate, vitriol, phosphoric acid salt, water-soluble polymers and composition thereof; With
(b) this pre-composition and aqueous binder are mixed in high shear mixer to form free flowing granule.
The aqueous solution of the preferred polyamines N-of the aqueous binder oxide compound in the step (b).
A kind of preferable methods may further comprise the steps:
(a) copolymer powder of the N-vinyl pyrrolidone of 5%-25% (weight) and N-vinyl imidazole and the sodium aluminium silicate of 50%-75% (weight is by anhydrous) are mixed, with form pre-composition and
(b) aqueous solution with the polyamines N-oxide compound of this pre-composition and 5%-25% (weight is by effective constituent) mixes in high shear mixer to form free flowing granule.
Also can choose the mixture that comprises dry pre-composition and binder aqueous solution in the method wantonly to form the step (c) of free flowing powder.
The salt of aluminosilicate and any other existence usually before entering high shear mixer with its abundant hydration.
Detailed Description Of The Invention
Except as otherwise noted, all herein percentage number average is in the weight of free flowing powder.
The main component of free flowing powder of the present invention is the polymeric dye transfer inhibitor.Normally the polymeric dye transfer inhibitor is mixed in the detergent composition, be transferred to on this fabric that washs from colored fabric so that suppress dyestuff.Before dyestuff has an opportunity to be attached to other clothings in the washing, these polymkeric substance have cooperate or the absorption DYED FABRICS on the ability of the fugitive dye that washes out.
Shi Yi polymeric dye transfer inhibitor is multipolymer, polyvinylpyrrolidonepolymers polymers, Ju Yi Xi oxazolidinone and polyvinyl imidazol or its mixture of polymkeric substance, N-vinyl pyrrolidone and the N-vinyl imidazole of polyamines N-oxide compound especially.
A) polymkeric substance of polyamines N-hydride
The polymkeric substance of the polyamines N-oxide compound that is suitable for contains the unit of following structural formula:
Figure C9519343700061
In the formula, P be can be connected on the R-N-O group the polymerizability unit or wherein the R-N-O group can form the unitary part of this polymerizability or both combinations, O O OA be NC, CO, C ,-O-,-S-,-N-; X is 0 or 1; R is aliphatic series, aromatics, heterocycle family or alicyclic group or its any combination of aliphatic series, ethoxylation, these groups can be connected on the nitrogen of N-O group or wherein the nitrogen of N-O group be the part of these groups.
The N-O group can be represented by following formula:
Figure C9519343700071
In the formula, R1, R2 and R3 are aliphatic series, aromatics, heterocycle family or alicyclic group or its combinations, x or/and y or/and z is 0 or 1 and part that wherein nitrogen of N-O group can be connected or wherein the nitrogen of N-O group forms above-mentioned group.
The N-O group can be that the part of polymerizability unit (P) maybe can be connected on the polymer backbone or the two combination.
Wherein the N-O group suitable polyamines N-oxide compound that forms the unitary part of polymerizability comprises the polyamines N-oxide compound that R wherein is selected from aliphatic series, aromatics, alicyclic or heterocyclic group group.
It is oxide-based that a class in the described polyamines N-oxide compound, the nitrogen that comprises N-O group wherein form the polyamines N-of part of R-group.Preferred polyamines N-oxide compound is that wherein R is that heterocyclic group is rolled into a ball for example polyamines N-oxide compound of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and derivative thereof.
Another kind of described polyamines N-oxide compound comprises the nitrogen of N-O group wherein, and to be connected to the polyamines N-of R-group oxide-based.
Other suitable polyamines N-oxide compound is that wherein the N-O group is connected to the unitary polyamine oxidase thing of polymerizability.
Preferred polyamines N-oxide compound is the polyamines N-oxide compound with general formula (I), wherein, R be aromatics, heterocycle family or alicyclic group and wherein the nitrogen of N-O functional group be the part of described R group.
The example of above-mentioned several classes is that wherein R is for example polyamine oxidase thing of pyridine, pyrroles, imidazoles and derivative thereof of heterogeneous ring compound.
Another kind of preferred polyamines N-oxide compound is the polyamine oxidase thing with general formula (I), wherein, R be aromatics, heterocycle family or alicyclic group and wherein the nitrogen of N-O functional group be connected on the described R-group.
These examples of types are that wherein the R group can be for example polyamine oxidase thing of phenyl of aromatics.
As long as the polymkeric substance of formed amine oxide is water miscible and has the dye transfer of inhibition performance, just can adopt any polymer backbone.The example of suitable polymer blend skeleton is polyethylene kind, polyalkylene class, polyester, polyethers, polyamide-based, polyimide, polyacrylate(s) and composition thereof.
The amine that the polymkeric substance of amine n-oxide of the present invention has usually is 10: 1 to 1: 1000000 with the ratio of amine n-oxide.Yet the quantity of the amine oxide group that exists in the polyamine oxidase thing polymkeric substance can change according to suitable copolymerization or suitable N-degree of oxidation.Preferred amines is 2: 3 to 1: 1000000, more preferably 1: 4 to 1: 1000000, most preferably 1: 7 to 1: 1000000 with the ratio of amine n-oxide.In fact polymkeric substance of the present invention comprises that a kind of monomer type is amine n-oxide and other the monomer type or the random or segmented copolymer of yes or no amine n-oxide.The amine oxide unit of polyamines N-oxide compound has pKa＜10, preferred pKa＜7, more preferably pKa＜6.
The polyamine oxidase thing almost can make by the polymerization degree arbitrarily.If this material has the ability of desired water-soluble and suspension dyestuff, then the polymerization degree is not crucial.
Usually, molecular-weight average is 500-1,000,000, and preferred 1,000-50,000, more preferably 2,000-30,000, most preferably 3,000-20,000.
B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole
Being used for the molecular-weight average that N-vinyl imidazole N-vinyl pyrrolidone polymer of the present invention has is 5,000-1, and 000,000, preferred 20,000-200,000.The polymkeric substance that very preferably is used for detergent composition of the present invention comprises the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, and the molecular-weight average of wherein said polymkeric substance is 5,000-50,000, more preferably 8,000-30,000, most preferably 10,000-20,000.The scope of molecular-weight average adopts light scattering determining, this method is described in Barth H.G. and Mays J.W. chemical analysis (ChemicalAnalysis) Vol113, " identifying the modernism (Modern Methods ofPolymer Characterization) of polymkeric substance ".
The molecular-weight average of N-vinyl imidazole N-vinylpyrrolidone copolymer very preferably is 5,000-50,000, more preferably 8,000-30,000, most preferably 10,000-20,000.
N-vinyl imidazole N-vinylpyrrolidone copolymer is characterised in that to have the scope of described molecular-weight average, the performance of fabulous inhibition dye transfer can be provided and can not produce adverse influence to the cleaning performance with the detergent composition of its preparation.
The mol ratio that N-vinyl imidazole N-vinylpyrrolidone copolymer of the present invention has N-vinyl imidazole and N-vinyl pyrrolidone is 1 to 0.2, more preferably 0.8 to 0.3, most preferably 0.6 to 0.4.
C) polyvinylpyrrolidone
Detergent composition of the present invention also can use polyvinylpyrrolidone (" PVP " has molecular-weight average and be about 2, and 500-is about 400,000, and be preferred about 5, and 000-is about 200,000, more preferably from about 5,000-is about 50,000, most preferably from about 5,000-about 15,000).Suitable polyvinylpyrrolidone can be from ISP Corporation on market, New York, NY and Montreal, (viscosity molecular weight is 10 to Carnada by ProductName PVPK-15,000), (molecular-weight average is 40 to PVPK-30,000), PVPK-60 (molecular-weight average is 160,000) and PVPK-90 (molecular-weight average is 360,000) have bought.PVPK-15 also can buy from ISP Corporation.Other the suitable polyvinylpyrrolidones that can buy from BASF Cooperation on market comprise Sokalan HP165 and Sokalan HP12.Polyvinylpyrrolidone is that the technician of detergent applications is known; Referring to for example EP-A-262,897 and EP-A-256,696.D) Ju Yi Xi oxazolidone:
Detergent composition of the present invention also can use polyvinylpyrrolidone, and (" PVP " has molecular-weight average to be
Detergent composition of the present invention also can use Ju Yi Xi oxazolidone as the polymeric dye transfer inhibitor.It is about 2 that described Ju Yi Xi oxazolidone has molecular-weight average, and 500-is about 400,000, preferred about 5, and 000-is about 200,000, more preferably from about 5, and 000-is about 50,000, and most preferably from about 5,000-about 15,000.E) polyvinyl imidazol:
Detergent composition of the present invention also can use polyvinylpyrrolidone, and (" PVP " has molecular-weight average to be
Detergent composition of the present invention also can use polyvinyl imidazol as the polymeric dye transfer inhibitor.It is about 2 that described polyvinyl imidazol has molecular-weight average, and 500-is about 400,000, preferred about 5, and 000-is about 200,000, more preferably from about 5, and 000-is about 50,000, and most preferably from about 5,000-about 15,000.
The composition very preferably of free flowing powder of the present invention is an aluminosilicate.
Sodium aluminium silicate can adopt various ways.One of example is the crystalline aluminosilicate ion-exchange material of following formula
Na z[(AlO 2) 2(SiO 2) y] xH 2In the O formula, it is about 6 that z and y are at least, and the mol ratio of z and y is about 0.4 for about 1.0-, and z is about 10-about 264.Available non-crystalline state hydrated aluminum silicate material of the present invention has following empirical formula
M 2(zAlO 2YSiO 2) wherein M be sodium, potassium, ammonium or replace ammonium, z is about 2 for about 0.5-, y is 1, it is that the anhydrous aluminosilicate of every gram is at least about 50 milligramequivalent CaCO that described material has the magnesium ion exchange capacity 3Hardness.Granularity is preferred for the hydration sodium Zeolite A of about 1-10 micron.
Aluminosilicate ion-exchange washing assistant material of the present invention is hydrated form, if the then water content of crystalline state is about 28% (weight) of about 5%-, if amorphous then water content may be higher.
Crystalline aluminosilicate ion-exchange material very preferably contains the water of about 15%-about 22% in its crystalline matrix.The feature of this crystalline aluminosilicate ion-exchange material is that also its particle diameter is about 0.1 micron to about 10 microns.Amorphous material is littler usually, for example little arriving less than about 0.01 micron.The particle diameter that preferred ion-exchange material has is about 0.2 micron to about 4 microns.The median size that term used herein " particle diameter " expression is a benchmark with given ion-exchange material weight, it is to adopt conventional analytical procedure for example to utilize the microscopic examination method of scanning electronic microscope to measure.The feature of crystalline aluminosilicate ion-exchange material of the present invention also is their calcium ion-exchanged capacity usually, is that benchmark calculates this exchange capacity and is at least about 200 milligramequivalent CaCO with anhydrous 3The water hardness/gram aluminosilicate, and be generally about 300 to about 352 milligramequivalent/grams.The feature of aluminosilicate ion exchange material of the present invention also is their calcium ion exchange rate, and this speed is at least about 2 grain Ca ++/ gpm/gram/gallon aluminosilicate (in anhydrous), and be in about 2 usually to about 6 grains/gpm/gram/gallon (with the calcium ion sclerometer) scope.The calcium ion exchange rate that can demonstrate as the best aluminosilicate of washing assistant be at least about 4 grains/as logical sequence/minute/gram/as logical sequence.
The Mg that amorphous aluminosilicate ion exchange material has usually ++Exchange capacity is at least about 50 milligramequivalent CaCO 3/ gram (12 milligrams of Mg ++/ restrain) and Mg ++Rate of exchange be at least about 1 grain/gpm/gram/gallon.When adopting Cu radiation (1.54 atomic meter) check, amorphous material does not show observable diffraction pattern.
Being used to implement aluminosilicate ion exchange material of the present invention can buy on market.Be used for aluminosilicate of the present invention and structurally can be crystalline state or amorphous and can naturally occurring aluminosilicate or be synthesized into.In the United States Patent (USP) of issuing on October 12nd, 1,976 3,985,669 (people such as Krummel) a kind of method of producing aluminosilicate ion exchange material has been discussed, this patent is incorporated herein by reference.Being preferred for synthetic crystalline aluminosilicate ion-exchange material of the present invention can buy by trade mark Zeolite A, Zeolite B, Zeolite MAP and Zeolite X.In an especially preferred embodiment, the crystalline aluminosilicate ion-exchange material has the following formula structure
Na 12[(AlO 2) 12(SiO 2) 12] xH 2X is about 20 to about 30, particularly about 27 in the O formula, and the granularity that has is generally less than about 5 microns.
Aluminosilicate of the present invention can randomly for example Citrate trianion, silicate, carbonate, supercarbonate, vitriol, phosphoric acid salt, silicon-dioxide and composition thereof replace by other particulate material wholly or in part.
Except above-listed polymeric dye transfer inhibitor, water-soluble polymers can be mixed in the free flowing powder of the present invention.The representative instance of this base polymer is rudimentary carboxyalkyl cellulose sodium, low alkyl group sodium cellulosate and rudimentary hydroxy alkyl cellulose sodium, for example Xylo-Mucine, sodium carboxymethylcellulose pyce and HPMC, polyvinyl alcohol (also comprising some polyvinyl acetate usually), polyacrylamide, polyacrylate(s) and various multipolymer, for example toxilic acid and acrylic acid multipolymer.The molecular weight of this base polymer is very wide, but great majority are 2,000-100,000.
Multi-carboxylate polymer's washing assistant is presented on March 7th, 1967 in the United States Patent (USP) 3,308,067 of Diehl and is described.The carboxylic acid that this class material comprises aliphatic series is the homopolymer of toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, aconic acid, citraconic acid and methylene radical propanedioic acid and the water-soluble salt of multipolymer for example.
Free flowing powder of the present invention preferably comprises the tensio-active agent that is lower than 2% (weight), and does not preferably contain any tensio-active agent.Yet, mixing the occasion of tensio-active agent, can use negatively charged ion, nonionic, positively charged ion, amphoteric and zwitterionic tensio-active agent.Method
Preferable methods of the present invention may further comprise the steps:
(a) will comprise N-vinyl pyrrolidone and the powder of N-vinyl imidazole multipolymer and other powder mixes, to form the powder pre-composition; With
(b) this pre-composition and aqueous binder are mixed in high shear mixer to form free flowing granule.
The aqueous solution of the preferred polyamines N-of the aqueous binder oxide polymer in the step (b), the aqueous solution of preferred poly-(4-vinylpridine N-oxide compound).
Be applicable to that high shear mixer of the present invention comprises Fukae Powtech Kogyo Co., the FukaeR FS-G series that Japan produces; This device is the bowl shaped container form basically, can near its bottom basic vertical axes agitator be housed by the open top charging, at sidewall cutting tool has been installed.Agitator and cutting tool can be operated under friction-motion speed independently of one another and respectively.This container can be installed cooling jacket, or if desired cryogenic unit can be installed.
Other similar mixing tanks that are applicable to the inventive method comprise Dierks﹠amp; Sohne, the Diosna of Germany RV series; And Pharma Matrix R, by TKFielder Ltd., England produces.Other think that the mixing tank that is applicable to the inventive method is Fuji Sangyo Co., the Fuji of Japan RVG-C series; And Roto R, by Zanchena﹠amp; Co srl, Italy produces.
Other preferably suitable devices comprise Eirich RRV series (Gustau EirichHardheim, Germany produces); Lodige R, be used for intermittently blended FM series, be used for continuous mixing/agglomerant Baud KM series (Lodige Machinenbau GmbH PaderbornGermany production); Drais RT160 series (Drais Werke GmbH, MannheimGermany produces); And Winkworth RRT25 series (England produces for Winkworth Machinery Ltd., Berkshire).Particularly preferred mixing tank combination is back series connection Lodige RThe Lodige of KM mixing tank RThe CB mixing tank.
The #FM-130-D-12 type Littleford mixing tank of chopping scraper is two kinds of suitable mixing tank examples with the #DCX-Plus type Cuisinart Food Processor that 7.75 inches (19.7 centimetres) scrapers are housed in being equipped with.Other any have finely divided mixing and granulation ability and have a residence time and all can adopt for about 0.1-10 minute mixing tank." turbine type " impeller mixing tank that some scrapers are housed on turning axle is preferred.The present invention can or work continuously and implement by intermittence.
After mixing step, can adopt additional drying step.Continuous fluidized bed moisture eliminator is applicable to this operation.
The granularity of free flowing powder of the present invention also is important, and the trend that forms gel is arranged when particularly contacting with water, can produce adverse influence to the preparation of product.Preferably avoid using small-particle, particularly " fines ".Preferred average particle size greater than 300 microns, more preferably greater than 450 microns, most preferably greater than about 550 microns.The sizing screen that successively decreases by sieve aperture is measured the weight of each grade then with a series of grade of production sharing, can calculate mean particle size easily.Final product composition having
Can expect, make final product composition having thereby free flowing powder of the present invention adds in other the granular composition surely.Other granular compositions can be by any suitable method preparation, and these methods comprise spraying drying, spray cooling and agglomeration.Compact detergent compositions of the present invention (that is, its tap density is at least 600g/l) comprises 0.001%-10%, preferred 0.01%-2%, the more preferably polymeric dye transfer inhibitor of 0.05%-1% (weight) usually.Tap density
All tap densities that the present invention relates to all are to adopt non-densification heavily to irritate cup (non-compacted repour cup) densimetry to measure.This method adopts a kind of device of being made up of the funnel that is contained in 500ml cup top, and the distance from funnel bottom to the cup top is 50mm.Being used for product from funnel (by the hole of 40mm diameter) is filled in cup and overflows.Do not knock the cup and with the top of stragith edge excessive product is scraped off along cup.Measure the net weight of product then and note down, according to the volume calculation tap density of cup.
Embodiment
Adopt following abbreviation in an embodiment: the PVPVI molecular weight is 10000 the N-vinyl pyrrolidone and the copolymerization of N-vinyl imidazole
Thing.The PVNO molecular weight is 10000 poly-(4-vinylpridine N-oxide compound).
Embodiment 1
The following pre-composition of preparation in vertical mixing (vertomix) at intermittence mixer:
80 parts of Zeolite 4A (weight)
10.5 parts of PVPVI (weight)
Adopt screw feeder that this pre-composition is transported to Loedige continuously The import of CB high shear mixer (under 1700rpm, moving).The aqueous solution of PVNO (active constituent content is 35%) is pumped into nozzle place in the mixing machine.Simultaneously water pump is delivered to another nozzle place in the mixing machine.Add following ingredients in following ratio:
90.5 parts of pre-compositions (weight)
30 parts of PVNO solution (weight)
8 parts in water (weight)
The wet powder of high shear mixer outlet is delivered directly to Loedige The import of KM mixing machine (under 140rpm, moving).
Further this wet powder of agglomeration is to form wet agglomerate in second mixing machine.The port strobe that goes out of second mixing machine is opened fully, be transported to the fluidized-bed (being provided with 120 ℃ air) of operate continuously by the vibrating tube agglomerate that will wet.
The tap density that the free flowing powder that generates has is 700g/l, and it is composed as follows:
Zeolite (in anhydrous) 65%
PVPVI 10.5％
PVNO 10.5％
Water 9%
Other are 5% years old
( *Other: mainly be the impurity that zeolite is brought this process into).
Embodiment 2
Except preparing the pre-composition in the helical-ribbon type mixer continuously, repeat the method for embodiment 1, then adopt pneumatic conveyor system and screw feeder to be transported to Loedige The import of CB mixing machine.Loedige The CB mixing machine moves under 1000ppm.
Embodiment 3
In the fluidized-bed on 10cm weir, repeat the method for embodiment 1.This weir has brings up to the residence time in fluidized-bed 5-10 minute effect.
Embodiment 4
At Eirich The pre-composition of preparation embodiment 1 in the high shear mixer.Then PVNO solution is directly added to and cause the agglomerant Eirich of pre-composition In the mixing machine to form wet granular.Then with this particle transport in intermittent type fluidized-bed (being provided with 100 ℃ air), and carry out drying.

Claims (7)

1. one kind has the free flowing powder detergent additives that tap density is at least 600g/l, and this detergent additives mainly is made up of following material:
(a) by the detergent ingredients that is selected from silico-aluminate, Citrate trianion, silicon-dioxide, carbonate, supercarbonate, silicate, vitriol, phosphoric acid salt, water-soluble polymers and composition thereof of moisture-free basis 20%-95% (weight); With
(b) the polymeric dye transfer inhibitor of 5%-50% (weight), it is selected from multipolymer of polyamines N-oxide polymer, N-vinyl pyrrolidone and N-vinyl imidazole and composition thereof.
2. according to the free flowing powder detergent additives of claim 1, this detergent additives mainly is made up of following material:
(a) by the silico-aluminate of moisture-free basis 50%-75% (weight); With
(b) the polymeric dye transfer inhibitor of 10%-30% (weight), it is selected from multipolymer of polyamines N-oxide polymer and N-vinyl pyrrolidone and N-vinyl imidazole and composition thereof.
3. according to the free flowing powder detergent additives of claim 2, this detergent additives mainly is made up of following material: the multipolymer mixture (ii) of polyamines N-oxide compound (i) and N-vinyl pyrrolidone and N-vinyl imidazole, wherein (i) and weight ratio (ii) are 5: 1-1: 5.
4. according to the free flowing powder detergent additives of claim 3, wherein (i) and weight ratio (ii) are 5: 1-1: 1.
5. a production comprises the method for the free flowing powder of hygroscopic polymer powder, and this method may further comprise the steps:
(a) with powdery polymer and other powder mixes, to form the powder pre-composition, described powdery polymer is selected from multipolymer of polyamines N-oxide polymer, N-vinyl pyrrolidone and N-vinyl imidazole and composition thereof, and described other powder is selected from silico-aluminate, Citrate trianion, silicon-dioxide, carbonate, supercarbonate, silicate, vitriol, phosphoric acid salt, water-soluble polymers and composition thereof; With
(b) this powder pre-composition and the aqueous solution of polyamines N-oxide compound are mixed in high shear mixer with the formation free flowing granule,
Wherein finished particle contains the multipolymer by polyamines N-oxide polymer, N-vinyl pyrrolidone and the N-vinyl imidazole of the other powder of moisture-free basis 20-95% (weight) and 5-50% (weight), and composition thereof.
6. according to the method for claim 5, this method may further comprise the steps:
(a) copolymer powder of the N-vinyl pyrrolidone of 5%-25% (weight) and N-vinyl imidazole is mixed with sodium silicoaluminate by moisture-free basis 50%-75% (weight), with form pre-composition and
(b) this powder pre-composition and polyamines N-oxide compound by effective constituent 5%-25% (weight) are mixed in high shear mixer to form free flowing granule.
7. according to the method for claim 6, this method is further comprising the steps of:
(c) mixture of dry pre-composition and binder aqueous solution is to form free flowing powder.
CN95193437A 1994-04-14 1995-04-03 Detergent compositions comprising dye transfer inhibitors, and process for making them Expired - Lifetime CN1077135C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP94302676.5 1994-04-14
EP94302676A EP0677580B1 (en) 1994-04-14 1994-04-14 Detergent compositions comprising dye transfer inhibitors, and process for making them

Publications (2)

Publication Number Publication Date
CN1149885A CN1149885A (en) 1997-05-14
CN1077135C true CN1077135C (en) 2002-01-02

Family

ID=8217650

Family Applications (1)

Application Number Title Priority Date Filing Date
CN95193437A Expired - Lifetime CN1077135C (en) 1994-04-14 1995-04-03 Detergent compositions comprising dye transfer inhibitors, and process for making them

Country Status (10)

Country Link
EP (1) EP0677580B1 (en)
JP (1) JPH09512051A (en)
CN (1) CN1077135C (en)
AT (1) ATE227333T1 (en)
CA (1) CA2187439C (en)
DE (1) DE69431652T2 (en)
DK (1) DK0677580T3 (en)
ES (1) ES2183828T3 (en)
PT (1) PT677580E (en)
WO (1) WO1995028462A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9523571D0 (en) * 1995-11-17 1996-01-17 Unilever Plc Detergent compositions
CA2275147A1 (en) * 1996-12-20 1998-07-02 Robert Gary Welch A process for making a free-flowing particulate dye transfer inhibiting detergent admix
GB9814822D0 (en) * 1998-07-08 1998-09-09 Unilever Plc Dye-transfer-inhibiting compositions and particulate detergent compositions containing them
GB9814819D0 (en) * 1998-07-08 1998-09-09 Unilever Plc Dye-transfer-inhibiting compositions and particulate detergent compositions containing them
EP1201814A1 (en) 2000-10-27 2002-05-02 The Procter & Gamble Company Domestic treatment of fabrics with film-forming materials and blowing agents
PL2627750T3 (en) 2010-10-14 2015-08-31 Unilever Nv Manufacture of coated particulate detergents
ES2614084T3 (en) 2010-10-14 2017-05-29 Unilever N.V. Laundry detergent particles
MX340440B (en) 2010-10-14 2016-07-08 Unilever N V * Laundry detergent particle.
AU2011315791B2 (en) 2010-10-14 2014-03-06 Unilever Plc Laundry detergent particles
AU2011315790B2 (en) 2010-10-14 2014-03-06 Unilever Plc Laundry detergent particles
BR112013008994B1 (en) 2010-10-14 2021-06-15 Unilever Ip Holdings B.V. DETERGENT COATED PARTICLE AND A PLURALITY OF DETERGENT COATED PARTICLES
WO2012117024A1 (en) * 2011-03-01 2012-09-07 Basf Se Polymers inhibiting dye transfer and having improved storage stability and processability for detergents and cleaning agents
CN106049106B (en) * 2016-07-01 2018-06-19 施海峰 A kind of montmorillonite levelling agent and preparation method thereof
EP3802938B1 (en) 2018-05-25 2024-10-30 The Procter & Gamble Company Process for producing nonwoven and apparatus suitable therefor
WO2019222992A1 (en) * 2018-05-25 2019-11-28 The Procter & Gamble Company Nonwoven, and process and apparatus for producing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2814287A1 (en) * 1978-04-03 1979-10-11 Henkel Kgaa Detergent compsn. contg. N-vinyl! imidazole polymer - as discoloration-inhibiting additive
US5133924A (en) * 1988-11-02 1992-07-28 Lever Brothers Company Process for preparing a high bulk density granular detergent composition
EP0579295A1 (en) * 1992-07-15 1994-01-19 The Procter & Gamble Company Detergent compositions inhibiting dye transfer

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE785653A (en) * 1971-07-02 1973-01-02 Procter & Gamble Europ
DE3803630A1 (en) * 1988-02-06 1989-08-17 Henkel Kgaa DETERGENT ADDITIVE
GB9016504D0 (en) * 1990-07-27 1990-09-12 Warwick Int Ltd Granular bleach activator compositions
EP0581751B1 (en) * 1992-07-15 1998-12-09 The Procter & Gamble Company Enzymatic detergent compositions inhibiting dye transfer
DE4235798A1 (en) * 1992-10-23 1994-04-28 Basf Ag Use of vinylpyrrolidone and vinylimidazole copolymers as detergent additive, novel polymers of vinylpyrrolidone and of vinylimidazole and process for their preparation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2814287A1 (en) * 1978-04-03 1979-10-11 Henkel Kgaa Detergent compsn. contg. N-vinyl! imidazole polymer - as discoloration-inhibiting additive
US5133924A (en) * 1988-11-02 1992-07-28 Lever Brothers Company Process for preparing a high bulk density granular detergent composition
EP0579295A1 (en) * 1992-07-15 1994-01-19 The Procter & Gamble Company Detergent compositions inhibiting dye transfer

Also Published As

Publication number Publication date
EP0677580A1 (en) 1995-10-18
JPH09512051A (en) 1997-12-02
ATE227333T1 (en) 2002-11-15
CA2187439A1 (en) 1995-10-26
EP0677580B1 (en) 2002-11-06
ES2183828T3 (en) 2003-04-01
DK0677580T3 (en) 2002-11-25
DE69431652D1 (en) 2002-12-12
CA2187439C (en) 2001-01-16
DE69431652T2 (en) 2003-09-18
CN1149885A (en) 1997-05-14
WO1995028462A1 (en) 1995-10-26
PT677580E (en) 2003-03-31

Similar Documents

Publication Publication Date Title
CN1077135C (en) Detergent compositions comprising dye transfer inhibitors, and process for making them
JP3169616B2 (en) Method for producing low-density detergent composition
JP3305327B2 (en) Method for producing low-density detergent composition by non-tower method
CN1132526A (en) Process for making high density detergent agglomerates
CN1075332A (en) In the sulfonic acid and make the method for granulated detergent
CN1094513C (en) detergent composition
CN1110543C (en) Process for making a low density detergent composition by agglomeration with a hydrated salt
JPH07509267A (en) Process and composition of compact detergent
JP2003530461A (en) Detergent composition with improved calcium sequestering ability
CN1214730A (en) Method for making low-density detergent composition by agglomeration of inorganic double salt
JP5388860B2 (en) Detergent builder granules
CN1101463C (en) Process for producing granular detergent component or compositions
US5849684A (en) Detergent additives comprising dye transfer inhibitors, and process for making them
JP3894953B2 (en) Detergent composition comprising clay agglomerated polymer having a particle size of less than 250 microns
JP3872293B2 (en) High density detergent composition
CN1078246C (en) Process for manufacture of free-flowing detergent granules
CN1211479C (en) Process for making free-flowing particulate dye transfer inhibiting detergent admix
JP2802450B2 (en) High bulk density granular detergent composition
CN1085599A (en) Mix can be in washing lotion the detergent composition of the polyimide biopolymer of hydrolysis
SK51993A3 (en) Application of amorphous aluminosilicate of alkaline metal detergent composition as an trapping agent of calcareous precipitates
CN102666827B (en) Method for producing surfactant-supporting granule cluster
CN1228115A (en) Method of Conditioning Surfactant Slurries to Form Highly Active Surfactant Agglomerates
JP3395997B2 (en) Method for producing enzyme granules for detergents
JP4189208B2 (en) Surfactant-supporting particles
JPS63161096A (en) Bulky granular detergent composition

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
PB01 Publication
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CX01 Expiry of patent term

Expiration termination date: 20150403

Granted publication date: 20020102