EP0626996A1 - Procede de fabrication de produits de rin age pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds - Google Patents
Procede de fabrication de produits de rin age pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourdsInfo
- Publication number
- EP0626996A1 EP0626996A1 EP93903957A EP93903957A EP0626996A1 EP 0626996 A1 EP0626996 A1 EP 0626996A1 EP 93903957 A EP93903957 A EP 93903957A EP 93903957 A EP93903957 A EP 93903957A EP 0626996 A1 EP0626996 A1 EP 0626996A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- sodium
- meth
- water
- granulation
- 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.)
- Withdrawn
Links
- 239000008187 granular material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 title claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims description 7
- 239000000460 chlorine Substances 0.000 title claims description 7
- 229910052801 chlorine Inorganic materials 0.000 title claims description 7
- 229910019142 PO4 Inorganic materials 0.000 title abstract description 5
- 235000021317 phosphate Nutrition 0.000 title abstract description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 title abstract description 3
- 150000004760 silicates Chemical class 0.000 title description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 47
- 239000007844 bleaching agent Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 17
- 238000005469 granulation Methods 0.000 claims abstract description 14
- 230000003179 granulation Effects 0.000 claims abstract description 14
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000012190 activator Substances 0.000 claims abstract description 10
- 108090000790 Enzymes Proteins 0.000 claims abstract description 9
- 102000004190 Enzymes Human genes 0.000 claims abstract description 9
- 239000000470 constituent Substances 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 20
- 239000003599 detergent Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- 238000004851 dishwashing Methods 0.000 claims description 13
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000012459 cleaning agent Substances 0.000 claims description 7
- 229920000193 polymethacrylate Polymers 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 6
- 239000003205 fragrance Substances 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 150000001253 acrylic acids Chemical class 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 102000004882 Lipase Human genes 0.000 claims description 3
- 108090001060 Lipase Proteins 0.000 claims description 3
- 239000004367 Lipase Substances 0.000 claims description 3
- 108091005804 Peptidases Proteins 0.000 claims description 3
- 239000004365 Protease Substances 0.000 claims description 3
- 235000019421 lipase Nutrition 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002671 adjuvant Substances 0.000 abstract 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- 238000004061 bleaching Methods 0.000 abstract 1
- 239000012263 liquid product Substances 0.000 abstract 1
- 125000005395 methacrylic acid group Chemical class 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 239000002304 perfume Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 11
- 229920002125 Sokalan® Polymers 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
- 229940088598 enzyme Drugs 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229920002257 Plurafac® Polymers 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- -1 sodium perborate mono- Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000010794 food waste Substances 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- 101000740449 Bacillus subtilis (strain 168) Biotin/lipoyl attachment protein Proteins 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000011545 carbonate/bicarbonate buffer Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000021149 fatty food Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- 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
- C11D3/02—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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
Definitions
- the invention relates to a new process for the production of machine washable dishwashing detergents free of low alkali, active chlorine, silicate and phosphate in the form of storage-stable, free-flowing, dust-free granules with high bulk densities - in particular in the range from about 750 to 1,100 g / l.
- powdery poly (meth) acrylate with an active substance content of about 92-95% by weight and / or a granular alkali cleaning additive based on sodium salts of homopolymers or copolyers (meth ) acrylic acids used the subject of German Offenlegungsschrift 39 37469. It consists of:
- low-alkaline active chlorine and phosphate-free machine dishwashers containing calcium-binding framework substances, soda, water glass, solid per compounds, activators and surfactants and, if appropriate, other conventional constituents of such agents are in the form of a storage-stable, free-flowing, dust-free Granules with bulk densities required for practical use above 650 g / l have been developed, which were premixed with at least a portion of the liquid components and, if desired, a portion of the finely divided solid components of the machine dishwashing detergent in a first stage and then combined with the remaining components of the machine dishwashing detergent are.
- They have bulk densities in the range from 750 to 1,000 g / l and are the subject of the older, unpublished German patent applications P 4110510.9 and P 4137470.3.
- the admixture of the sodium carbonate in turn prevents the granules from quickly caking in the pile. This maintains the granulate structure on the way to the swirl channel in the drying zone.
- Dusting with sodium carbonate powder additionally increases the liter weight to 850 to 1,000 g. A further increase in the liter weight is achieved if the granulation is carried out first with the addition of liquid water glass and then water or water alone, if the sodium carbonate introduced in the granulation step is partially hydrated or if the batch size is increased.
- the dishwashing detergents produced by this process contain silicates.
- the object of the invention was, inter alia, the production of silicate-free formulations.
- the granules thus obtained optionally adjusted to a uniform grain distribution in a second granulation stage, it under Movement in a warm air stream dries, fine and coarse fractions are sieved off and then mixed with the bleaching agent and, if appropriate, a bleach activator, a bleach stabilizer, fragrance, enzymes, nonionic surfactants, further builders and / or dyes
- the drying must be carried out in such a way that the bicarbonate decomposition of the sodium bicarbonate to sodium carbonate is as low as possible (or at least as constant as possible). An additional portion of sodium carbonate resulting from the drying would have to be taken into account in the formulation of the granule formulation.
- Low drying temperatures not only counteract sodium bicarbonate decay, but also increase the solubility of the granulated detergent during use. It is therefore advantageous for drying to have a supply air temperature which, on the one hand, should be as low as possible to avoid bicarbonate decomposition and, on the other hand, must be as high as necessary in order to obtain a product with good storage properties.
- a supply air temperature of approximately 80 ° C.
- the granules themselves should not be heated to temperatures above about 60 ° C.
- the disintegration of the sodium bicarbonate is definitely desirable for later use in the cleaning process in the dishwasher, since this increases the alkalinity of the liquor and thus its cleaning performance.
- the in situ formation of sodium carbonate (irritating to the eyes and skin) from sodium bicarbonate (non-irritating) mitigates dangers for the consumer, e.g. in the event of improper use by children.
- Sodium citrate is particularly suitable as a further structural substance. It can already be added in the granulation, but can also be added to the granulate after the drying and subsequent sieving stage, just like the other constituents of dishwashing detergents. These include bleaches, optionally bleach activators, bleach stabilizers, enzymes, dyes and fragrances.
- Setting the pH values to about 9.0 - 10.0 via the alkali carbonate / bicarbonate buffer system is important for preventing limescale deposits on the interior of the machine or on the wash ware in areas with particularly high water hardness or in softening systems that are not used properly Dishwashers.
- the poly (meth) acrylates can be used as powder, but preferably in granulated form.
- the usable polyacrylates include Alcosperse (Alco: AlcosperseQv 102, 104, 106, 404, 406); Acrylsole® from Norsohaas: Acrysole® A IN, LMW 45 N, LMW 10 N, LMW 20 N, SP 02N, Norasole® WL1, WL2, WL3, WL4, Degapas® from Degussa; Good-RiteCüv'K-XP 18 from Goodrich.
- Alcosperse AlcosperseQv 102, 104, 106, 404, 406
- Acrylsole® from Norsohaas: Acrysole® A IN, LMW 45 N, LMW 10 N, LMW 20 N, SP 02N, Norasole® WL1, WL2, WL3, WL4, Degapas® from Degussa; Good-RiteCüv
- Copolymers of polyacrylic acid and maleic acid can also be used, for example SokalaneQy from BASF: SokalanQ / CP 5, CP 7; AcrysoleQ from Norsohaas: Acrysol QR 1014, Alcosperse (5) from Alco: Alcosperse® 175; granular alkaline cleaning additive according to DE 3937469.
- Anhydrous trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate. Trisodium citrate dihydrate can be used as a powder. It then has an average grain size of about 0.2 now. However, higher bulk densities are achieved with crystalline citrate.
- Anhydrous sodium carbonate of any quality is expediently used as the alkali carbonate, e.g. calcined soda or compacted soda.
- Compacted soda is granular calcined sodium carbonate which is commercially available (e.g. V-soda from Matthes & Weber).
- the alkali bicarbonate is preferably sodium bicarbonate.
- the sodium bicarbonate should preferably be used in coarse compact form with a grain size in the main fraction between 0.4 and 1.0 mm.
- active oxygen carriers have been the preferred bleaching agent components of detergents for household dishwashing machines (HGSM). These primarily include sodium perborate mono- and tetrahydrate as well as sodium percarbonate. Compacted sodium perborate monohydrate is preferred because of the increase in bulk density. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are used to activate it at about 60 ° C., the temperatures of the cleaning process in the HGSM.
- Preferred bleach activators are TAED (tetraacetylenediamine), PAG (pentaacetylglucose), DADHT (1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine) and ISA (isatoic anhydride).
- TAED tetraacetylenediamine
- PAG penentaacetylglucose
- DADHT 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine
- ISA isatoic anhydride
- small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates may also be useful.
- Extremely low-foaming compounds are usually used as nonionic surfactants, which serve to better detach fatty food residues and as granulation aids. These preferably include C12-C18 "alkylpolyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
- non-foaming surfactants known as low-foaming, such as, for example, Ci2-Ci8-alkylpolyethylene glycol polybutylene glycol ethers, each with up to to 8 moles of ethylene oxide and butylene oxide units in the molecule, as well as the foaming but ecologically attractive C 1 -C 4 -alkyl polyglucosides and / or - C 1 -C 4 -alkyl polyethylene glycols with 3-8 ethylene oxide units in the molecule with a degree of polymerization of about 1-4, these then together with about 0.2 to 4, preferably 0 , 2 to 2% by weight, based on the finished cleaning agent, of defoaming agents such as silicone oils, mixtures of silicone oil and hydrophobized silica, paraffin oil / Guerbet alcohols and hydrophobized silica.
- defoaming agents such as silicone oils, mixtures of silicone oil and hydrophobized silica, paraffin oil / Guerbe
- C ⁇ -Cio-alkyl polyglucosides with a degree of polymerization of about 1-4 can be used.
- they In order to ensure a uniform distribution of the alkyl polyglucosides, they have to be diluted to about 35% active substance in order to lower their viscosity.
- a bleached quality should be used, otherwise a brown granulate will result.
- protein or starch-containing food residues can be used as other common components of such agents.
- enzymes such as proteases, amylases and lipases can also be used, for example proteases such as BLAP®140 from Henkel; Opitmase® -M-440, Optimase® -M-330, Opticlean® -M-375, Opticleanv!
- Y -M-250 from Solvay Enzymes; Maxacal®.CX 450,000, Maxapem® from Ibis, Savinase®4.0 T 6.0 T 8.0 T from Novo or Experase® T from Ibis and amylases such as Termamyl® 60 T, 90 T from Novo; Amylase-LT® from Solvay Enzymes or Maxamyl® P 5000, CXT 5000 or CXT 2900 from Ibis, lipases such as Lipolase®30 T from NOVO.
- Plurafac® LF 403 alkyl (Ci2-Ci8) -polyethylene glycol ( ⁇ 8 E0) -polypropylene-glycol - ( ⁇ 8 P0) -ether (BASF)
- APG 225 Cs-Cio fatty alcohol polyglucoside with a degree of polymerization of
- Sokalan®CP 5 poly (meth) acrylate (BASF)
- Norasol WL 4 polyacrylate / soda granulate (Norsohaas)
- a trisodium citrate dihydrad quality with a bulk density of approx. 810 g / 1 was used in the preparation.
- the bulk density of the finished product was 920 g / l.
- the bulk density of the finished product was 894 g / 1.
- the granular cleaning additive was partially in the granulation
- Sodium citrate which can be either fine-grained or roughly crystalline, was not mixed in during the preparation, but was already used in the granulation:
- the bulk density after processing was 920 g / 1:
- the non-ionic surfactant Plurafac® was used as the granulating liquid:
- Granular cleaning additive 29.1 (as in Example 1)
- the bulk weight of the finished product was 900 g / 1.
- Sokalan®CP5 granulate from BASF was used in the granulation:
- Sokalan®CP5 granules 17.5% sodium bicarbonate, compressed 60.0% soda, compressed 18.1%
- the bulk density of the finished product was 890 g / 1.
- Example 1 After the addition of water, the wet granules were mixed with 0.5-2% fine-grained soda and then processed further in accordance with Example 1.
- the preparation was also carried out as in Example 1.
- the bulk density of the finished product was 940 g / 1.
- Recipe I was a commercially available, highly alkaline formulation with metasilicate and phosphate.
- the pH of a 1% solution was 12.5.
- Recipe II was a low alkaline formulation according to DE 41 37 470. A 1% solution of this cleaner had a pH of 10.5. Cleaner II contained the weaker alkaline carbonate and disilicate instead of metasilicate.
- Recipe III was a weakly alkaline formulation according to the present invention with a pH of 9.5 (1% by weight aqueous solution). Compared to the prior art, it contained large amounts of sodium bicarbonate.
- Recipe IV was an even weaker alkaline formulation according to the present invention with a pH of 9.2 (1% by weight aqueous solution).
- Table I lists the recipes for the four cleaners, which differ significantly in their alkalinity.
- Table II shows a comparison of the cleaning results of the four formulations. This list shows that, surprisingly, the weakly alkaline cleaner also delivers a well-tolerable dishwashing result. The slight underperformance is largely compensated for by the high ecological value of the formulation.
- Table III shows a comparison of the precipitation formation of the four cleaning agents with different pH values in hard water.
- Dishes (glasses, porcelain, stainless steel cutlery) are washed 10 times in the dishwasher.
- 50 g of mixed soiling starch, protein
- Rinsing is carried out in a 65 ° C program under hard water conditions (16 ° d).
- 20 g of detergent are dosed from the storage container in the main wash cycle per wash cycle.
- the dishes are assessed in the "black box".
- the scale ranges from 0 to 10. 0 means that no deposits were found on the dishes.
- the rubbers up to grade 5 are only visible in the "black box”. Rubbers from grade 6 are also outside, i.e. also visible to the consumer.
- the interior of the machine is assessed according to the same grading scheme as the dishes, so that two values are obtained.
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Procédé de fabrication de produits de rinçage pour lave-vaisselle, exempts de phosphates et renfermant des adjuvants, des agents de blanchiment, de l'eau, éventuellement des agents tensioactifs non ioniques, ainsi que d'autres constituants courants, dans lequel on utilise comme adjuvants, des sels de sodium pulvérulents ou liquides, de monomères ou de copolymères d'acides acrylique et méthacrylique, lesquels sont préalablement mélangés avec du carbonate de sodium et du bicarbonate de sodium, de préférence sous forme compressée, puis sont agglomérés et granulés avec addition de produits liquides. Le granulé obtenu est amené, lors d'un second stade de granulation, à une granulométrie uniforme, séché par agitation dans un courant d'air chaud, tamisé, puis mélangé avec l'agent de blanchiment et, éventuellement avec un activateur de blanchiment, un stabilisant de blanchiment, un parfum, des enzymes, des agents tensioactifs non ioniques et d'autres adjuvants.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19924205071 DE4205071A1 (de) | 1992-02-20 | 1992-02-20 | Verfahren zur herstellung niederalkalischer, aktivchlor-, silikat- und phosphatfreier maschinengeschirrspuelmittel in form von schwergranulaten |
DE4205071 | 1992-02-20 | ||
DE19924210363 DE4210363A1 (de) | 1992-03-30 | 1992-03-30 | Verfahren zur Herstellung niederalkalischer, aktivchlor-, silikat- und phosphatfreier Maschinengeschirrspülmittel in Form von Schwergranulaten |
DE4210363 | 1992-03-30 | ||
PCT/EP1993/000335 WO1993017089A1 (fr) | 1992-02-20 | 1993-02-11 | Procede de fabrication de produits de rinçage pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0626996A1 true EP0626996A1 (fr) | 1994-12-07 |
Family
ID=25912011
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93903957A Withdrawn EP0626996A1 (fr) | 1992-02-20 | 1993-02-11 | Procede de fabrication de produits de rin age pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0626996A1 (fr) |
WO (1) | WO1993017089A1 (fr) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4232170C2 (de) | 1992-09-25 | 1999-09-16 | Henkel Kgaa | Schwachalkalische Geschirreinigungsmittel |
DE4437486A1 (de) * | 1994-10-20 | 1996-04-25 | Henkel Kgaa | Kristalline Schichtsilikate in maschinellen Geschirrspülmitteln |
DE19532304A1 (de) * | 1995-09-01 | 1997-03-06 | Henkel Kgaa | Verfahren zur Herstellung granularer Vorprodukte niederalkalischer Reinigungsmittel |
FR2791581B1 (fr) * | 1999-04-02 | 2001-05-18 | Rhodia Chimie Sa | Composition a base d'un sel mineral substantiellement ou totalement hydrosoluble, formulation la comprenant, et leurs preparations |
BRPI0808513A2 (pt) | 2007-03-09 | 2014-08-19 | Danisco Us Inc Genencor Div | Variantes de alfa-amilase de espécies de bacillus alcalifílico, composições compreendendo variantes de alfa-amilase e métodos de uso |
US9040279B2 (en) | 2008-06-06 | 2015-05-26 | Danisco Us Inc. | Saccharification enzyme composition and method of saccharification thereof |
CA2726803A1 (fr) | 2008-06-06 | 2009-12-10 | Danisco Us Inc. | Alpha amylases variantes de bacillus subtilis et leurs procedes d'utilisation |
EP2698434A1 (fr) | 2008-06-06 | 2014-02-19 | Danisco US Inc. | Utilisations d'une alpha-amylase de Bacillus subtilis |
CA2778471A1 (fr) | 2009-10-23 | 2011-04-28 | Danisco Us Inc. | Procedes destines a reduire le saccharide donnant une couleur bleue |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3937469A1 (de) * | 1989-11-10 | 1991-05-16 | Henkel Kgaa | Granulares, alkalisches, phosphatfreies reinigungsadditiv |
-
1993
- 1993-02-11 EP EP93903957A patent/EP0626996A1/fr not_active Withdrawn
- 1993-02-11 WO PCT/EP1993/000335 patent/WO1993017089A1/fr not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9317089A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1993017089A1 (fr) | 1993-09-02 |
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