EP0628627B1 - Water-soluble, water softening builder - Google Patents
Water-soluble, water softening builder Download PDFInfo
- Publication number
- EP0628627B1 EP0628627B1 EP94108688A EP94108688A EP0628627B1 EP 0628627 B1 EP0628627 B1 EP 0628627B1 EP 94108688 A EP94108688 A EP 94108688A EP 94108688 A EP94108688 A EP 94108688A EP 0628627 B1 EP0628627 B1 EP 0628627B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- water
- polymer
- softening
- softening builder
- 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
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 5
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 239000007884 disintegrant Substances 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 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 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- 229920002988 biodegradable polymer Polymers 0.000 claims description 2
- 239000004621 biodegradable polymer Substances 0.000 claims description 2
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical group OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims 2
- 239000004902 Softening Agent Substances 0.000 abstract description 2
- 229920002125 Sokalan® Polymers 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000005662 Paraffin oil Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229960003512 nicotinic acid Drugs 0.000 description 2
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229960001138 acetylsalicylic acid Drugs 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- -1 alkaline earth metal salts Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 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 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
-
- 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 water-soluble, predominantly organic, water-softening builder.
- DE 36 14 779 discloses a granular, phosphate-free water softener for softening wash liquors and also as an additive to detergents, which consists of 50-60% by weight of finely crystalline zeolite, 3-5% by weight sodium salt of a polyacrylic acid, polymethacrylic acid or acrylic acid-maleic acid Copolymers, 4-15% by weight sodium citrate, 4-12% by weight sodium carbonate and optionally up to 2% by weight sodium carboxymethyl cellulose.
- DE 40 22 005 discloses a mild detergent which, as the only builder, contains a combination of a water-soluble citrate with a polyacrylate or a polymer of acrylic acid and maleic acid.
- DE 36 03 471 discloses a low-phosphorus or phosphorus-free washing and / or cleaning agent which contains a surfactant, an inorganic and / or organic builder and at least one colloidal layered silicate, and additionally at least one water-soluble calcium and / or magnesium salt and polyacrylic acid .
- DE 39 31 871 describes a granular, phosphate-free water softening agent containing 50-70% by weight of finely crystalline zeolite, 2-10% by weight of a layered silicate, 5-15% by weight of the sodium salt of a (co) polymeric carboxylic acid and 1-10% by weight % Sodium sulfate.
- DE 39 43 019 discloses a granular detergent additive containing 20-45% by weight of a layered silicate, 15-50% by weight of a finely crystalline, synthetic zeolite, 0-15% by weight of a sulfate, carbonate of the phosphate, 0-8% by weight the sodium salt of a homopolymeric or copolymeric (meth) acrylic acid, 0-2% by weight of cellulose ether, 0-20% by weight of nonionic surfactants from the class of polyglycol ethers.
- a similar spray-dried composition is disclosed in DE 40 09 618.
- FR-PS 1 599 547 discloses a composition for inhibiting scale formation by alkaline earth metal salts in aqueous systems, comprising a carboxylic acid such as citric acid and a water-soluble organic polymer such as an acrylic acid polymer or copolymer.
- CH-PS 577 937 discloses an agent in tablet form for preventing limescale, containing either citric acid and additions of acetylsalicylic acid and / or boric acid and / or nicotinic acid or nicotinic acid.
- the applicant has set itself the task of providing a water softener in an easily manageable, well metered form.
- a water-soluble, water-softening builder in the form of a tablet, the tablet having a specific composition which, on the one hand, makes the tablet easy to handle, on the other hand, a rapid dissolution of the tablet in the wash liquor is guaranteed.
- the polymers to be used as softeners in accordance with the invention in combination with citrate and / or citric acid are known substances.
- Maleic acid / acrylic acid copolymers and preferably biodegradable polymers, in particular those based on peptides, are suitable for this.
- Such peptide-based polymers are, for example, the Cygnus products from Cygnus Corporation.
- Serine-N-N-diacetic acid derivatives suitable as builders are described in EP 287 885.
- Maleic acid / acrylic acid copolymers suitable as builders are commercially available under various Sokalan brands, for example a maleic acid / acrylic acid copolymer, sodium salt, under the "Sokalan CP 5" brand.
- An essential component of the builder tablets according to the invention is the polyethylene glycol, which should be present in an amount of 0.5-6% by weight, preferably 1-3% by weight.
- Suitable polyethylene glycols are the polyethylene glycols (1000-6000), in particular polyethylene glycol (4000-6000). These polyethylene glycols act as tableting aids. That polyethylene glycol as a tabletting aid was known. However, it was surprisingly found that while there were difficulties in dissolving other tableting aids, the polyethylene glycols mentioned are particularly suitable for the purpose according to the invention.
- a polyethylene glycol with a low degree of ethoxylation for example polyethylene glycol 200, is not suitable as a tabletting agent, but is suitable as a dust-binding agent and as such can also be present in the tablet according to the invention in a small amount, for example in an amount of 0.5-5% by weight.
- the tablet according to the invention should contain a disintegrant.
- An insoluble polyvinylpyrrolidone which can be present in an amount of 1-20% by weight, preferably 7-12% by weight, is suitable as such.
- a polyvinylpyrrolidone suitable for this purpose is commercially available under the "Sokalan HP 50" brand.
- the builder combination (A) it is particularly preferred in the builder combination (A) to use partially neutralized, acidic polymer as component (a) citric acid and / or as component (b) and as a further auxiliary carbonate and / or bicarbonate, for example sodium carbonate, sodium hydrogen carbonate and / or potassium carbonate, which in combination with the aforementioned acidic component serves as a disintegrant.
- the carbonate / bicarbonate can be used in amounts of 5-30% by weight.
- the builders mentioned in combination (A) according to the invention are preferably the only builders in the tablet.
- Zeolites are preferably not used, although the tablet may optionally contain 5-20% by weight of a layered silicate, which makes the builder particularly suitable for hard water with high proportions of magnesium hardness.
- cellulose derivatives such as methylhydroxyethyl cellulose, or paraffin oil can also be used in small quantities.
- a preferred builder tablet according to the present invention contains: 16-40% by weight, preferably 18-35% by weight trisodium citrate, 14-21% by weight, preferably 17-19% by weight citric acid, 20-40% by weight, preferably 30-36% by weight maleic acid / acrylic acid Copolymer, Na salt and / or polymer based on peptides, 2-5% by weight polyethylene glycol (4000-6000) 15-30% by weight carbonate / bicarbonate 1-2% by weight polyvinylpyrrolidone
- the builder tablet according to the invention has particular advantages when used with colorful textiles. It ensures very good color retention and avoids color transfer.
- a builder tablet was pressed from the following components: Maleic acid / acrylic acid copolymer, granules (Sokalan ® CP 45), pH 4 30% Trisodium citrate 19% Citric acid 18% sodium 30% Paraffin oil 0.2% Polyethylene glycol (1500) 2.8% 100.0% ⁇
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
Gegenstand der Erfindung ist ein wasserlöslicher, vorwiegend organischer, wasserenthärtender Builder.The invention relates to a water-soluble, predominantly organic, water-softening builder.
Die DE 36 14 779 offenbart ein granulares, phosphatfreies Wasserenthärtungsmittel zum Enthärten von Waschlaugen als auch als Zusatz zu Waschmitteln, welches aus 50-60 Gew.% feinkristallinem Zeolith, 3-5 Gew.% Natriumsalz eines Polyacrylsäure-, Polymethacrylsäure- oder Acrylsäure-Maleinsäure-Copolymeren, 4-15 Gew.% Natriumcitrat, 4-12 Gew.% Natriumcarbonat und gegebenenfalls bis zu 2 Gew.% Natrium-Carboxymethylcellulose besteht.DE 36 14 779 discloses a granular, phosphate-free water softener for softening wash liquors and also as an additive to detergents, which consists of 50-60% by weight of finely crystalline zeolite, 3-5% by weight sodium salt of a polyacrylic acid, polymethacrylic acid or acrylic acid-maleic acid Copolymers, 4-15% by weight sodium citrate, 4-12% by weight sodium carbonate and optionally up to 2% by weight sodium carboxymethyl cellulose.
In der DE 40 22 005 wird ein Feinwaschmittel offenbart, welches als einzigen Builder eine Kombination aus einem wasserlöslichen Citrat mit einem Polyacrylat oder einem Polymer aus Acrylsäure und Maleinsäure enthält.DE 40 22 005 discloses a mild detergent which, as the only builder, contains a combination of a water-soluble citrate with a polyacrylate or a polymer of acrylic acid and maleic acid.
Die DE 36 03 471 offenbart ein phosphorarmes, bzw. phosphorfreies Wasch- und/oder Reinigungsmittel, welches ein Tensid, einen anorganischen und/oder organischen Builder und mindestens ein kolloidales Schichtsilikat enthält, sowie zusätzlich mindestens ein wasserlösliches Kalzium- und/oder Magnesiumsalz und Polyacrylsäure.DE 36 03 471 discloses a low-phosphorus or phosphorus-free washing and / or cleaning agent which contains a surfactant, an inorganic and / or organic builder and at least one colloidal layered silicate, and additionally at least one water-soluble calcium and / or magnesium salt and polyacrylic acid .
Die DE 39 31 871 beschreibt ein granulares, phosphatfreies Wasserenthärtungsmittel enthaltend 50-70 Gew.% feinkristallinen Zeolith, 2-10 Gew.% eines Schichtsilikates, 5-15 Gew.% des Natriumsalzes einer (Co-)polymeren Carbonsäure und 1-10 Gew.% Natriumsulfat.DE 39 31 871 describes a granular, phosphate-free water softening agent containing 50-70% by weight of finely crystalline zeolite, 2-10% by weight of a layered silicate, 5-15% by weight of the sodium salt of a (co) polymeric carboxylic acid and 1-10% by weight % Sodium sulfate.
Die DE 39 43 019 offenbart ein granulares Waschmitteladditiv enthaltend 20-45 Gew.% eines Schichtsilikates, 15-50 Gew.% eines feinkristallinen, synthetischen Zeoliths, 0-15 Gew.% eines Sulfats, Carbonats der Phosphats, 0-8 Gew.% des Natriumsalzes einer homopolymeren, bzw. copolymeren (Meth-)acrylsäure, 0-2 Gew.% an Celluloseether, 0-20 Gew.% an nichtionischen Tensiden aus der Klasse der Polyglykolether. Eine ähnliche sprühgetrocknete Zusammensetzung wird in der DE 40 09 618 offenbart.DE 39 43 019 discloses a granular detergent additive containing 20-45% by weight of a layered silicate, 15-50% by weight of a finely crystalline, synthetic zeolite, 0-15% by weight of a sulfate, carbonate of the phosphate, 0-8% by weight the sodium salt of a homopolymeric or copolymeric (meth) acrylic acid, 0-2% by weight of cellulose ether, 0-20% by weight of nonionic surfactants from the class of polyglycol ethers. A similar spray-dried composition is disclosed in DE 40 09 618.
Die FR-PS 1 599 547 offenbart eine Zusammensetzung zur Inhibierung der Kesselsteinbildung durch Erdalkalisalze in wässrigen Systemen, enthaltend eine Carbonsäure wie beispielsweise Zitronensäure und ein wasserlösliches organisches Polymer wie beispielsweise ein Acrylsäurepolymer oder -copolymer.FR-PS 1 599 547 discloses a composition for inhibiting scale formation by alkaline earth metal salts in aqueous systems, comprising a carboxylic acid such as citric acid and a water-soluble organic polymer such as an acrylic acid polymer or copolymer.
Die CH-PS 577 937 offenbart ein Mittel in Tablettenform zur Verhinderung von Kalkansatz, enthaltend entweder Zitronensäure und Zusätze von Acetylsalizylsäure und/oder Borsäure und/oder Nikotinsäure oder Nikotinsäure.CH-PS 577 937 discloses an agent in tablet form for preventing limescale, containing either citric acid and additions of acetylsalicylic acid and / or boric acid and / or nicotinic acid or nicotinic acid.
Es ist dem Fachmann bekannt und durch den zitierten Stand der Technik dokumentiert, daß Waschmitteladditive und insbesondere Wasserenthärter bislang in möglichst kleinteiliger, vorzugsweise Pulverform, allenfalls in Granulatform angeboten werden, da die Meinung bestand, daß nur dadurch die erforderliche schnelle Löslichkeit eines Wasserenthärters gewährleistet werden kann.It is known to the person skilled in the art and documented by the cited prior art that detergent additives and in particular water softeners have hitherto been offered in the smallest possible, preferably powder form, at most in the form of granules, since the opinion existed that the required rapid solubility of a water softener can only be guaranteed in this way .
Die Anmelderin hat sich zur Aufgabe gesetzt, einen Wasserenthärter in leicht handhabbarer, gut dosierbarer Form zur Verfügung zu stellen.The applicant has set itself the task of providing a water softener in an easily manageable, well metered form.
Erfindungsgemäß wird dies durch einen wasserlöslichen, wasserenthärtenden Builder in Form einer Tablette erreicht, wobei die Tablette eine bestimmte Zusammensetzung aufweist, die einerseits eine gute Handhabbarkeit der Tablette, andererseits eine schnelle Auflösung der Tablette in der Waschlauge gewährleistet.According to the invention, this is achieved by a water-soluble, water-softening builder in the form of a tablet, the tablet having a specific composition which, on the one hand, makes the tablet easy to handle, on the other hand, a rapid dissolution of the tablet in the wash liquor is guaranteed.
Der erfindungsgemäße wasserlösliche, wasserenthärtende Builder in Form einer Tablette besteht aus
- A) 60-98 Gew.% einer Kombination aus
- a) Citrat und/oder Citronensäure und
- b) einem als Enthärter wirksamen Polymer
- B) 0,5-6 Gew.% Polyethylenglykol
- C) 0-38 Gew.% weiterer Hilfsstoffe.
- A) 60-98% by weight of a combination of
- a) citrate and / or citric acid and
- b) a polymer effective as a softener
- B) 0.5-6% by weight of polyethylene glycol
- C) 0-38% by weight of other auxiliaries.
Die erfindungsgemäß in Kombination mit Citrat und/oder Citronensäure einzusetzenden, als Enthärter wirksamen Polymeren sind bekannte Substanzen. Hierfür eignen sich Maleinsäure/Acrylsäure-Copolymerisate und vorzugsweise biologisch abbaubare Polymere, insbesondere solche auf Peptid-Basis. Solche Polymere auf Peptid-Basis sind beispielsweise die Cygnus-Produkte der Cygnus Corporation. Als Builder geeignete Serin-N-N-Diessigsäurederivate werden in der EP 287 885 beschrieben.The polymers to be used as softeners in accordance with the invention in combination with citrate and / or citric acid are known substances. Maleic acid / acrylic acid copolymers and preferably biodegradable polymers, in particular those based on peptides, are suitable for this. Such peptide-based polymers are, for example, the Cygnus products from Cygnus Corporation. Serine-N-N-diacetic acid derivatives suitable as builders are described in EP 287 885.
Als Builder geeignete Maleinsäure/Acrylsäure-Copolymerisate sind unter verschiedenen Sokalan-Marken im Handel, beispielsweise ein Maleinsäure/Acrylsäure-Copolymerisat, Natriumsalz, unter der Marke "Sokalan CP 5".Maleic acid / acrylic acid copolymers suitable as builders are commercially available under various Sokalan brands, for example a maleic acid / acrylic acid copolymer, sodium salt, under the "Sokalan CP 5" brand.
Ein wesentlicher Bestandteil der erfindungsgemäßen Buildertabletten stellt das Polyethylenglykol dar, welches in einer Menge von 0,5-6 Gew.%, vorzugsweise 1-3 Gew.%, anwesend sein sollte. Als geeignete Polyethylenglykole sind die Polyethylenglykole (1000-6000) zu nennen, insbesondere Polyethylenglykol (4000-6000). Diese Polyethylenglykole wirken als Tablettierungshilfsmittel. Daß Polyethylenglykol als Tablettierungshilfsmittel brauchbar ist, war bekannt. Jedoch ergab sich überraschenderweise, daß, während bei anderen Tablettierungshilfsmitteln Auflösungsschwierigkeiten sich ergaben, die genannten Polyethylenglykole für den erfindungsgemäßen Zweck vorzüglich geeignet sind.An essential component of the builder tablets according to the invention is the polyethylene glycol, which should be present in an amount of 0.5-6% by weight, preferably 1-3% by weight. Suitable polyethylene glycols are the polyethylene glycols (1000-6000), in particular polyethylene glycol (4000-6000). These polyethylene glycols act as tableting aids. That polyethylene glycol as a tabletting aid was known. However, it was surprisingly found that while there were difficulties in dissolving other tableting aids, the polyethylene glycols mentioned are particularly suitable for the purpose according to the invention.
Ein Polyethylenglykol mit niederem Ethoxylierungsgrad, beispielsweise Polyethylenglykol 200, eignet sich nicht als Tablettierungsmittel, wohl aber als Staubbindemittel und kann als solches in der erfindungsgemäßen Tablette ebenfalls in geringer Menge, beispielsweise in einer Menge von 0,5-5 Gew.%, anwesend sein.A polyethylene glycol with a low degree of ethoxylation, for example polyethylene glycol 200, is not suitable as a tabletting agent, but is suitable as a dust-binding agent and as such can also be present in the tablet according to the invention in a small amount, for example in an amount of 0.5-5% by weight.
Die erfindungsgemäße Tablette sollte ein Sprengmittel enthalten. Als solches eignet sich ein unlösliches Polyvinylpyrrolidon, welches in einer Menge von 1-20 Gew.%, vorzugsweise 7-12 Gew.%, vorliegen kann. Ein für diesen Zweck geeignetes Polyvinylpyrrolidon ist unter der Marke "Sokalan HP 50" im Handel.The tablet according to the invention should contain a disintegrant. An insoluble polyvinylpyrrolidone, which can be present in an amount of 1-20% by weight, preferably 7-12% by weight, is suitable as such. A polyvinylpyrrolidone suitable for this purpose is commercially available under the "Sokalan HP 50" brand.
Es wird jedoch besonders bevorzugt in der Builderkombination (A) als Komponente (a) Citronensäure und/oder als Komponente (b) teilneutralisiertes, sauer wirkendes Polymer einzusetzen und als weiteren Hilfsstoff Carbonat und/oder Bicarbonat, beispielsweise Natriumcarbonat, Natriumhydrogencarbonat und/oder Kaliumcarbonat, welches in Kombination mit der vorerwähnten sauren Komponente als Sprengmittel dient. Das Carbonat/Bicarbonat kann in Mengen von 5-30 Gew.% eingesetzt werden.However, it is particularly preferred in the builder combination (A) to use partially neutralized, acidic polymer as component (a) citric acid and / or as component (b) and as a further auxiliary carbonate and / or bicarbonate, for example sodium carbonate, sodium hydrogen carbonate and / or potassium carbonate, which in combination with the aforementioned acidic component serves as a disintegrant. The carbonate / bicarbonate can be used in amounts of 5-30% by weight.
Vorzugsweise stellen die in der erfindungemäßen Kombination (A) genannten Builder die einzigen Builder in der Tablette dar. Zeolithe werden vorzugsweise nicht mitverwendet, obwohl gegebenenfalls die Tablette 5-20 Gew.% eines Schichtsilikates enthalten kann, was den Builder besonders geeignet macht für hartes Wasser mit hohen Anteilen Magnesiumhärte.The builders mentioned in combination (A) according to the invention are preferably the only builders in the tablet. Zeolites are preferably not used, although the tablet may optionally contain 5-20% by weight of a layered silicate, which makes the builder particularly suitable for hard water with high proportions of magnesium hardness.
Als weitere Hilfsmittel zusätzlich zu den bereits genannten können beispielsweise Cellulosederivate, wie Methylhydroxyethylcellulose, oder Paraffinöl in geringen Mengen mitverwendet werden.In addition to those already mentioned, cellulose derivatives such as methylhydroxyethyl cellulose, or paraffin oil can also be used in small quantities.
Eine bevorzugte Builder-Tablette gemäß vorliegender Erfindung enthält:
16-40 Gew.%, vorzugsweise 18-35 Gew.% Trinatriumcitrat, 14-21 Gew.%, vorzugsweise 17-19 Gew.% Citronensäure, 20-40 Gew.%, vorzugsweise 30-36 Gew.% Maleinsäure/Acrylsäure-Copolymerisat, Na-Salz und/oder Polymer auf Peptidbasis, 2-5 Gew.% Polyethylenglykol (4000-6000) 15-30 Gew.% Carbonat/Bicarbonat 1-2 Gew.% PolyvinylpyrrolidonA preferred builder tablet according to the present invention contains:
16-40% by weight, preferably 18-35% by weight trisodium citrate, 14-21% by weight, preferably 17-19% by weight citric acid, 20-40% by weight, preferably 30-36% by weight maleic acid / acrylic acid Copolymer, Na salt and / or polymer based on peptides, 2-5% by weight polyethylene glycol (4000-6000) 15-30% by weight carbonate / bicarbonate 1-2% by weight polyvinylpyrrolidone
Die erfindungsgemäße Buildertablette besitzt besondere Vorteile bei Anwendung mit bunten Textilien. Sie gewährleistet hierbei sehr guteFarberhaltung und vermeidet eine Farbübertragung.The builder tablet according to the invention has particular advantages when used with colorful textiles. It ensures very good color retention and avoids color transfer.
Außerdem wirkt sie einer Vergrauung bei weißen Textilien entgegen, verringert den Wäscheverschleiß und die Knitterbildung der Wäsche, erhält die natürliche Weichheit der Textilien durch deutliche Inkrustationsverminderung und verringert den Gewebeschrumpf insbesonders bei der Heißwäsche (60 - 95°C) von Baumwolltextilien.
Aus folgenden Bestandteilen wurde eine Builder-Tablette gepreßt:
Claims (9)
- Water-soluble, water-softening builder in tablet form consisting of:A) 60% to 98% by weight of a combination ofa) citrate and/or citric acid andb) a polymer which is effective as a softenerat a weight ratio of a:b ranging from 70:30 to 50:50, preferably from 65:35 to 55:45,B) 0.5% to 6% by weight of polyethylene glycolC) 0% to 38% by weight of other auxiliaries.
- Water-softening builder according to Claim 1, characterized in that the polymer is a biodegradable polymer on a peptide basis.
- Water-softening builder according to Claim 1, characterized in that the polymer is a maleic acid-acrylic acid copolymer.
- Water-softening builder according to one of the preceding claims, characterized in that citric acid is used as component (a) and/or a partially neutralized acidic polymer is used as component (b) and carbonate and/or bicarbonate as a disintegrant is used as component (C).
- Water-softening builder according to one of the preceding claims, characterized in that it contains 1% to 3% by weight of polyethylene glycol (1000-6000).
- Water-softening builder according to one of the preceding claims, characterized in that, as an additional auxiliary, it contains 0.5% to 5% by weight of polyethylene glycol (200) as a dust-catching agent.
- Water-softening builder according to one of the preceding claims, characterized in that, as an additional auxiliary, it contains 1% to 20% by weight of an insoluble polyvinyl pyrrolidone as a disintegrant.
- Water-softening builder according to one of the preceding claims, characterized in that, as an additional auxiliary, it contains 5% to 20% by weight of a layer silicate.
- Water-softening builder according to one of the preceding claims, characterized in that it containsa1) 16% to 40% by weight, preferably 18% to 35% by weight, of trisodium citrate,a2) 14% to 21% by weight, preferably 17% to 19% by weight, of citric acid,b) 20% to 40% by weight, preferably 30% to 36% by weight, of maleic acid-acrylic acid copolymer, sodium salt and/or polymer on a peptide basis, 2% to 5% by weight of polyethylene glycol (4000-6000),
15% to 30% by weight of carbonate/bicarbonate, 1% to 2% by weight of polyvinyl pyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SI9430037T SI0628627T1 (en) | 1993-06-07 | 1994-06-07 | Water-soluble, water softening builder |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4318902A DE4318902C2 (en) | 1993-06-07 | 1993-06-07 | Water-soluble, water-softening agent |
| DE4318902 | 1993-06-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0628627A1 EP0628627A1 (en) | 1994-12-14 |
| EP0628627B1 true EP0628627B1 (en) | 1997-03-12 |
Family
ID=6489821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94108688A Expired - Lifetime EP0628627B1 (en) | 1993-06-07 | 1994-06-07 | Water-soluble, water softening builder |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0628627B1 (en) |
| AT (1) | ATE150081T1 (en) |
| DE (2) | DE4318902C2 (en) |
| DK (1) | DK0628627T3 (en) |
| ES (1) | ES2098820T3 (en) |
| GR (1) | GR3023207T3 (en) |
| SI (1) | SI0628627T1 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4404279A1 (en) * | 1994-02-10 | 1995-08-17 | Henkel Kgaa | Tablet with builder substances |
| EP0736595A1 (en) * | 1995-04-03 | 1996-10-09 | The Procter & Gamble Company | Soaker compositions |
| DE19606765A1 (en) * | 1996-02-23 | 1997-08-28 | Henkel Kgaa | Process for the production of dishwasher tablets |
| DE19714657C1 (en) * | 1997-04-09 | 1999-01-07 | Benckiser Nv | Water soluble, water softening builder |
| EP1004661A1 (en) | 1998-11-11 | 2000-05-31 | DALLI-WERKE WÄSCHE- und KÖRPERPFLEGE GmbH & Co. KG | High density granule, method for production thereof, and its use as disintegrant in tablets |
| DE19858888A1 (en) * | 1998-12-19 | 2000-06-21 | Henkel Kgaa | Use of low molecular weight homopolymeric polyacrylates in water softeners and in preventing deposits on heating rods during machine washing of textiles |
| DE19937428A1 (en) * | 1999-08-07 | 2001-02-08 | Henkel Kgaa | Detergent tablets |
| US20030104969A1 (en) | 2000-05-11 | 2003-06-05 | Caswell Debra Sue | Laundry system having unitized dosing |
| DE10123621B4 (en) * | 2001-05-15 | 2006-12-07 | Henkel Kgaa | Process for the preparation of a water softener tablet |
| GB2410496A (en) * | 2004-01-31 | 2005-08-03 | Reckitt Benckiser Nv | Water softening tablets |
| GB0415291D0 (en) * | 2004-07-08 | 2004-08-11 | Reckitt Benckiser Nv | Method of removing laundry ash |
| GB0415316D0 (en) * | 2004-07-08 | 2004-08-11 | Reckitt Benckiser Nv | Method of removing laundry ash |
| DE102007059677A1 (en) * | 2007-12-10 | 2009-06-25 | Henkel Ag & Co. Kgaa | cleaning supplies |
| AU2010291392B2 (en) * | 2009-09-02 | 2013-07-11 | Unilever Plc | Composition and process for treatment of a fabric |
| US8476219B2 (en) | 2009-11-05 | 2013-07-02 | The Procter & Gamble Company | Laundry scent additive |
| CA2682636C (en) | 2009-11-05 | 2010-06-15 | The Procter & Gamble Company | Laundry scent additive |
| DE102010051226A1 (en) | 2010-11-12 | 2012-05-31 | Dental Care Innovation Gmbh | Rinse-off tray with abrasive components |
| WO2014003845A1 (en) * | 2012-06-27 | 2014-01-03 | Amcol International Corporation | Low density builder and detergent particles via high shear agglomeration |
| CN108384666A (en) | 2012-12-20 | 2018-08-10 | 宝洁公司 | laundry scent additive |
| CN103981713B (en) * | 2014-05-21 | 2016-08-17 | 吴江市英力达塑料包装有限公司 | A kind of fabric maintenance softener and preparation method thereof |
| KR102575843B1 (en) | 2017-02-02 | 2023-09-08 | 워어터 피이크, 인코포레이티드 | Tablets containing abrasives for cleaning teeth |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1258068A (en) * | 1968-01-29 | 1971-12-22 | ||
| CH577937A5 (en) * | 1973-07-03 | 1976-07-30 | Lonza Ag | |
| DE3519353A1 (en) * | 1985-05-30 | 1986-12-04 | Henkel KGaA, 4000 Düsseldorf | MELT BLOCK-SHAPED, ALKALINE HYDROXIDE-CONTAINING AGENT FOR THE MACHINE CLEANING OF DISHES AND METHOD FOR THE PRODUCTION THEREOF |
| US5328633A (en) * | 1990-05-04 | 1994-07-12 | The United States Of America As Represented By The Secretary Of The Navy | Extended-release plaque preventing and dissolving compositions |
| DK166548B1 (en) * | 1991-03-15 | 1993-06-07 | Cleantabs As | PHOSPHATE-FREE MACHINE DISHWASH |
-
1993
- 1993-06-07 DE DE4318902A patent/DE4318902C2/en not_active Expired - Fee Related
-
1994
- 1994-06-07 SI SI9430037T patent/SI0628627T1/en unknown
- 1994-06-07 AT AT94108688T patent/ATE150081T1/en active
- 1994-06-07 DE DE59402005T patent/DE59402005D1/en not_active Expired - Lifetime
- 1994-06-07 DK DK94108688.6T patent/DK0628627T3/en active
- 1994-06-07 EP EP94108688A patent/EP0628627B1/en not_active Expired - Lifetime
- 1994-06-07 ES ES94108688T patent/ES2098820T3/en not_active Expired - Lifetime
-
1997
- 1997-04-21 GR GR970400868T patent/GR3023207T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0628627A1 (en) | 1994-12-14 |
| GR3023207T3 (en) | 1997-07-30 |
| DE4318902A1 (en) | 1994-12-08 |
| ES2098820T3 (en) | 1997-05-01 |
| ATE150081T1 (en) | 1997-03-15 |
| SI0628627T1 (en) | 1997-10-31 |
| DE59402005D1 (en) | 1997-04-17 |
| DE4318902C2 (en) | 1996-10-24 |
| DK0628627T3 (en) | 1997-08-25 |
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