EP0571436A1 - Granular additive for washing and cleaning agents. - Google Patents
Granular additive for washing and cleaning agents.Info
- Publication number
- EP0571436A1 EP0571436A1 EP92904218A EP92904218A EP0571436A1 EP 0571436 A1 EP0571436 A1 EP 0571436A1 EP 92904218 A EP92904218 A EP 92904218A EP 92904218 A EP92904218 A EP 92904218A EP 0571436 A1 EP0571436 A1 EP 0571436A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- water
- granules
- spray
- additive
- 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
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
- C11D3/128—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
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
Definitions
- the invention relates to a granular additive for detergents and cleaners and to a process for the preparation of these additives.
- the additives are usually stored separately from granular detergents and cleaning agents and, depending on requirements, are used together with these in washing or cleaning processes. In the sense of an additional builder effect, they improve the cleaning ability of the actual washing and cleaning agent and prevent the formation of hard limescale deposits on the heating elements or on the textile fiber.
- the detergents can be mixed with granular detergents or further processed together with them, whereby they have an advantageous influence on their pouring properties and rinsing behavior or enable trouble-free further processing.
- Known agents of this type often contain salts of polymeric aliphatic carboxylic acids. These include in particular salts of polyacrylic acid and polymethacrylic acid and salts of copolymers of these two acids with maleic acid and / or vinyl esters. It is not difficult to produce storage-stable granules which contain up to about 156% by weight of such polymer salts. Since the salts of the polymeric polycarboxylates are hygroscopic, mixtures with higher proportions of such salts cannot readily be converted into storage-stable and free-flowing granules, especially not if they do not contain any water-binding or water-repellent mixture components.
- German patent application 21 00 500 proposes to use the polymers as free acids or partially neutralized salts with a maximum degree of neutralization of 60% or to convert them from their aqueous solutions into granular products by hot spray drying .
- the polymeric carboxylic acids only develop their full effect as completely neutralized salts.
- the alkaline agent required for neutralization must therefore be added to the acidic granules.
- the invention relates to a granular additive that
- Suitable homopolymers are sodium salts of polymethacrylic acid and preferably polyacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acids). If only homopolymeric polyacrylic acids (in salt form) are used, their relative molecular mass is preferably 1,000 to 80,000 (based on acid) in the interest of good flowability and storage stability.
- Suitable copolymers are those of acrylic acid with methacrylic acid and preferably copolymers of acrylic acid or methacrylic acid with maleic acid.
- Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
- Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred.
- Their relative molecular weight, based on free acids is generally from 5000 to 200,000, preferably from 10,000 to 120000 and in particular 50000 to 100000.
- Mixtures of different homo- and copolymers can also be used with advantage, in particular mixtures of homopolymeric acrylic acid and the copolymers of 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid described above.
- Such mixtures which are characterized by favorable grain properties and high storage stability, can consist, for example, of 10 to 50% by weight of homopolymeric acrylic acid and 90 to 50% by weight of acrylic acid-maleic acid copolymers.
- Highly polymeric polyacrylic acids can also be used in these mixtures, which, when used alone, have a slightly greater tendency to stick or melt than the low molecular weight polyacrylates.
- the content of homopolymeric or copolymeric (meth) acrylates in the additives is preferably 45 to 65% by weight and in particular 50 to 62% by weight.
- the fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. It can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 1 -C 4 -alcohols with 2 to 5 Glycol ether groups. Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water. The zeolite content of the additives is preferably 8 to 30% by weight and in particular 10 to 25% by weight.
- the sodium sulfate is used in anhydrous form, preferably in amounts of 4 to 15% by weight and in particular 7 to 15% by weight.
- zeolite When only small amounts of zeolite are used, for example from 3 to 10% by weight, it is advisable to choose a somewhat higher proportion of sodium sulfate, for example in the range from 8 to 15% by weight.
- Sodium sulfate contents of more than 7% by weight, for example 8 to 15% by weight fundamentally improve the grain properties and the shelf life of the additives. It is very surprising that fractions of 5 to 6% by weight of sodium sulfate are sufficient to contain additives according to the invention with a content of about Stabilize 50 wt .-% of polymeric carboxylates and ensure good flow properties.
- the water content of the additives which is not bound by the zeolite, is preferably not more than 12% by weight, based on the additive, and is in particular in the range from 3 to 11% by weight.
- the additives can have sodium carbonate in anhydrous form in amounts of not more than 20% by weight. In a preferred embodiment, the additives contain 3 to 15% by weight and in particular 4 to 12% by weight of anhydrous sodium carbonate.
- the additives can contain small amounts, for example 0.5 to 3% by weight, based on the additive, of surfactants, such as soap, sulfonates (for example dodecylbenzenesulfonate), organic sulfates (for example fatty alkyl sulfates) or alkypolyglycosides.
- surfactants such as soap, sulfonates (for example dodecylbenzenesulfonate), organic sulfates (for example fatty alkyl sulfates) or alkypolyglycosides.
- the additives can also contain small amounts of further constituents, such as dyes and color pigments, and can be colored uniformly or speckled.
- the proportion of such components is in each case well below 1% by weight.
- the average grain size of the granular additive is usually 0.2 to 1.2 mm, the proportion of the granules below 0.1 mm not more than 10% by weight and above 2 mm not more than 20% by weight (sieve analysis ⁇ se).
- at least 75% by weight, in particular at least 85% by weight, of the granules have a size of 0.2 to 1.6 mm, the proportion of the granules having a grain size between 0.1 and 0.05 mm not more than 4% by weight, in particular not more than 3% by weight and the proportion of the grains between 1.6 and 2.4 mm not more than 20% by weight, preferably not more than 10% by weight and in particular is not more than 6% by weight. Larger proportions of fine grain generally lead to a deterioration in the induction behavior.
- the granules can be produced, for example, by intensive mixing of the dry constituents with participation Liquids, in particular water, are carried out in conventional granulating devices. However, spray drying of an aqueous slurry is preferred.
- the slurry concentration is preferably between 50 and 68% by weight (non-aqueous fraction) and in particular between 55 and 60% by weight, the viscosity of the paste being decisive, which should not exceed 10000 mPa-s and advantageously 2500 to 6000 mPa * s is. (The viscosity is measured in the low-pressure part of the spray tower at temperatures between 60 and 100 ° C. using a truncated cone viscometer). The temperature of the slurry is usually between 50 and 100 ° C.
- the pressure at the spray nozzles is generally 30 to 80 bar, preferably 40 to 70 bar.
- the temperature of the counter-current dry gases in the entrance zone of the spray tower, ie in the so-called ring channel, is advantageously between 200 and 320 ° C, in particular between 220 and 300 ° C. In the area of the tower outlet it should be between 90 and 130 ° C, preferably between 100 and 125 ° C.
- Such comparatively high operating temperatures are advantageous for the production of a perfect product and, despite the high proportion of organic substance in the spray product, are not critical, since the self-ignition temperature is above 330 ° C., usually even above 350 ° C.
- Conventional spray drying systems spray nozzles or spray disks can be used for spray drying, the spray nozzles being able to be arranged in one or more levels.
- the spray material leaving the tower can, if necessary after cooling with flowing air, be immediately further processed or packaged.
- the granules are exceptionally free-flowing and can be washed into washing machines and dishwashers without leaving any residue and retain these advantageous properties even after a long storage period.
- the granules according to the invention usually have a bulk density of 240 to 450 g / 1, usually one of 320 to 400 g / 1. If small amounts, for example 0.5 to 3% by weight, of surfactants, such as soaps, sulfonates, organic sulfates or alkylpolyglycosides, were added to the granules before the spray drying, the bulk density may be 50 to 150 g / l lower than without this addition. In a further and preferred embodiment, granules with a higher bulk density, in particular those of 500 to 900 g / 1, are claimed.
- surfactants such as soaps, sulfonates, organic sulfates or alkylpolyglycosides
- the bulk density can be increased in a manner known per se by compacting the light granules, for which purpose in principle all techniques are suitable which are carried out under pressure and, if appropriate, with the addition of a small amount of liquid, for example by roller compaction, pelleting, extrusion or tableting.
- a small amount of liquid for example by roller compaction, pelleting, extrusion or tableting.
- pressing by means of rollers for example at a pressure between 100 and 200 bar, is preferred. Since the spray-dried granules have a certain plasticity under pressure, a flake-shaped product can be obtained in this way, which can then, if necessary, be comminuted to the desired particle size.
- the compacted products surprisingly retain their good dispersing and dissolving properties.
- the bulk density of such products is in particular between 650 and 800 g / l.
- liquid binders preferably water and / or nonionic, in particular ethoxylated, nonionic surfactants, paste-like anionic surfactants and paraffin oil can be added to the granular additives.
- binder the content of which, based on the compacted granulate, advantageously does not exceed 10% by weight, preferably 2 to 8% by weight and in particular 3 to 6% by weight, improves the plasticizability of the light additive and the density of the compacted additive increases.
- the binders can be mixed with the light additive or sprayed onto the light granulate, for example by spraying the powder stream fed to the roller with water or aqueous surfactant solutions. If water is selected as the binder, water can be omitted if the granules obtained, for example, by spray drying have not been completely dried, so that a residual moisture, for example 6 to 15% by weight of water, is retained in the spray-dried granules. The further processing of such slightly moist spray granules is a preferred method of operation.
- the compacting can also be carried out in a screw press or in a granulating device after the addition of appropriate amounts of liquid. Subsequent post-drying of the compacted additives is generally not necessary and, in particular, is also not preferred.
- the active ingredient content of the non-dried compacts slightly decreases according to the amount of liquid added.
- the compacted granules are also free-flowing and their storage stability under unfavorable conditions, for example in a moist atmosphere, also exceeds the spray-dried products.
- a granular additive of the composition (in% by weight)
- a slurry heated to 77 ° C which contained the aforementioned solids and 47.0 wt .-% water and had a viscosity of 2500 mPa-s (60 ° C; truncated cone viscometer from Brabender, Duisburg, Federal Republic of Germany), was with a Pressure of 40 bar sprayed through nozzles in a drying tower.
- the counter-current dry gas had a temperature of 210 ° C in the ring channel and 120 ° C in the area of the tower outlet.
- the spray product was extremely free-flowing and had a bulk density of 320 g / l.
- the following particle size distribution was determined by sieve analysis (> greater than, ⁇ less than)
- the dust content ( ⁇ 0.05 mm) was less than 0.02% by weight.
- the product proved to be stable in storage and quickly and completely redispersible in cold water.
- the parts with a grain size of more than 1.6 mm and less than 0.1 mm were separated off by sieving.
- Example 1 a free-flowing, storage-stable granulate of the following composition was produced by spray drying: 50.0% by weight Na salt of the acrylic acid-maleic acid copolymer, 20.0% by weight zeolite NaA, spray-dried, 10.0% by weight sodium sulfate (anhydrous), 9.0% by weight sodium carbonate ( anhydrous), 11.0% by weight water.
- the dust content was less than 0.02% by weight.
- the spray product showed an equally good flowability as the product according to Example 1.
- APG stands for an alkyl polyglucoside, derived from linear ones and with an average degree of oligomerization of the glucose residue of 1.4.
- the product made with this addition draws is characterized by an above-average degree of whiteness and a comparatively low bulk density.
- the product according to Example 3 requires a somewhat lower product throughput per unit of time in the drying tower because of its somewhat difficult drying properties. All granules were free-flowing and stable in storage and proved to be completely and quickly redispersible when introduced into cold tap water.
- spray products of the following composition were produced (in% by weight):
- experiment A the same spraying conditions were used as described in example 1, in experiment B the tower outlet temperature of the dry gases was 90 ° C. Both spray products consisted of sticky grains which could already be deformed under slight pressure. The flow behavior was unsatisfactory and when trying to process the products together with other cleaning constituents into stable granules, problems occurred due to sticking to the mixing element and the inner wall of the granulating mixer.
- the granules according to Example 1 • and 2 were fed to a roller compactor.
- the roller pressure was 150 bar.
- the lower-water granules were sprayed with 4% by weight of water before the pressing, while the more water-rich product was compacted according to Example 2.
- the pressed material was continuously in one Hammer basket grinder crushed.
- Granules with a grain size greater than 1.6 mm and less than 0.2 mm were sieved.
- the screened fine and coarse fractions were fed back into the powder stream to be compacted.
- the result was hard-grained, easily pourable, abrasion-resistant splinter granules with the following powder specifications.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4104085 | 1991-02-11 | ||
DE4104085A DE4104085A1 (en) | 1991-02-11 | 1991-02-11 | GRANULAR ADDITIVE FOR DETERGENT AND CLEANING AGENT |
PCT/EP1992/000227 WO1992013937A1 (en) | 1991-02-11 | 1992-02-03 | Granular additive for washing and cleaning agents |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0571436A1 true EP0571436A1 (en) | 1993-12-01 |
EP0571436B1 EP0571436B1 (en) | 1995-06-21 |
Family
ID=6424804
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92904218A Expired - Lifetime EP0571436B1 (en) | 1991-02-11 | 1992-02-03 | Granular additive for washing and cleaning agents |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0571436B1 (en) |
AT (1) | ATE124081T1 (en) |
DE (2) | DE4104085A1 (en) |
ES (1) | ES2073291T3 (en) |
WO (1) | WO1992013937A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4404279A1 (en) * | 1994-02-10 | 1995-08-17 | Henkel Kgaa | Tablet with builder substances |
DE19651072A1 (en) * | 1996-12-09 | 1998-06-10 | Henkel Kgaa | Additive for detergents or cleaning agents |
EP1529834A1 (en) * | 2003-11-10 | 2005-05-11 | The Procter & Gamble Company | Detergent particles |
EP1529833A1 (en) * | 2003-11-10 | 2005-05-11 | The Procter & Gamble Company | Detergent particles |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3604223A1 (en) * | 1985-02-14 | 1986-08-14 | Basf Ag, 67063 Ludwigshafen | Additive for detergents and cleaners |
GB8626082D0 (en) * | 1986-10-31 | 1986-12-03 | Unilever Plc | Detergent powders |
GB8922179D0 (en) * | 1989-10-02 | 1989-11-15 | Rohm & Haas | Polymer-containing granulates |
-
1991
- 1991-02-11 DE DE4104085A patent/DE4104085A1/en not_active Withdrawn
-
1992
- 1992-02-03 WO PCT/EP1992/000227 patent/WO1992013937A1/en active IP Right Grant
- 1992-02-03 ES ES92904218T patent/ES2073291T3/en not_active Expired - Lifetime
- 1992-02-03 EP EP92904218A patent/EP0571436B1/en not_active Expired - Lifetime
- 1992-02-03 DE DE59202625T patent/DE59202625D1/en not_active Expired - Fee Related
- 1992-02-03 AT AT92904218T patent/ATE124081T1/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO9213937A1 * |
Also Published As
Publication number | Publication date |
---|---|
ES2073291T3 (en) | 1995-08-01 |
WO1992013937A1 (en) | 1992-08-20 |
ATE124081T1 (en) | 1995-07-15 |
DE59202625D1 (en) | 1995-07-27 |
EP0571436B1 (en) | 1995-06-21 |
DE4104085A1 (en) | 1992-08-13 |
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