EP0374867B1 - Verfahren zur Herstellung eines lagerstabilen, leicht löslichen Bleichaktivator-Granulats - Google Patents

Verfahren zur Herstellung eines lagerstabilen, leicht löslichen Bleichaktivator-Granulats Download PDF

Info

Publication number: EP0374867B1
Authority: EP; European Patent Office
Prior art keywords: activator; water; powder; auxiliary; starch
Prior art date: 1988-12-22
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Expired - Lifetime

Application number

EP89123523A

Other languages

German (de)

English (en)

French (fr)

Other versions

EP0374867A1 (de

Inventor

Jürgen Dr. Cramer

Helmut Kramer

Gerhard Nöltner

Wilfried Schuler

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Clariant Produkte Deutschland GmbH

Original Assignee

Hoechst AG

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1988-12-22

Filing date

1989-12-20

Publication date

1994-11-30

Family has litigation

First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6369820&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0374867(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.

1989-12-20 Application filed by Hoechst AG filed Critical Hoechst AG

1990-06-27 Publication of EP0374867A1 publication Critical patent/EP0374867A1/de

1994-11-30 Application granted granted Critical

1994-11-30 Publication of EP0374867B1 publication Critical patent/EP0374867B1/de

2009-12-20 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

239000012190 activator Substances 0.000 title claims description 43
238000000034 method Methods 0.000 title claims description 17
238000004519 manufacturing process Methods 0.000 title description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
239000000843 powder Substances 0.000 claims description 22
229920002472 Starch Polymers 0.000 claims description 20
239000008107 starch Substances 0.000 claims description 20
235000019698 starch Nutrition 0.000 claims description 20
239000008187 granular material Substances 0.000 claims description 19
239000000203 mixture Substances 0.000 claims description 17
238000002156 mixing Methods 0.000 claims description 8
239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
229920003086 cellulose ether Polymers 0.000 claims description 4
238000002360 preparation method Methods 0.000 claims description 4
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 claims description 2
235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
239000007844 bleaching agent Substances 0.000 description 8
239000011248 coating agent Substances 0.000 description 8
238000005406 washing Methods 0.000 description 8
229920002678 cellulose Polymers 0.000 description 7
239000001913 cellulose Substances 0.000 description 7
238000000576 coating method Methods 0.000 description 7
-1 polyethylene Polymers 0.000 description 7
BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 5
239000003599 detergent Substances 0.000 description 5
150000003839 salts Chemical class 0.000 description 5
229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
239000012752 auxiliary agent Substances 0.000 description 4
235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
239000008112 carboxymethyl-cellulose Substances 0.000 description 4
150000002170 ethers Chemical class 0.000 description 4
239000002245 particle Substances 0.000 description 4
WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
239000007884 disintegrant Substances 0.000 description 3
230000000694 effects Effects 0.000 description 3
230000000977 initiatory effect Effects 0.000 description 3
229960001922 sodium perborate Drugs 0.000 description 3
YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 3
238000004448 titration Methods 0.000 description 3
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
239000003795 chemical substances by application Substances 0.000 description 2
238000001035 drying Methods 0.000 description 2
239000002360 explosive Substances 0.000 description 2
238000001125 extrusion Methods 0.000 description 2
239000006260 foam Substances 0.000 description 2
238000005469 granulation Methods 0.000 description 2
230000003179 granulation Effects 0.000 description 2
239000003112 inhibitor Substances 0.000 description 2
229910052500 inorganic mineral Inorganic materials 0.000 description 2
239000011707 mineral Substances 0.000 description 2
229920001296 polysiloxane Polymers 0.000 description 2
239000000377 silicon dioxide Substances 0.000 description 2
159000000000 sodium salts Chemical class 0.000 description 2
235000019832 sodium triphosphate Nutrition 0.000 description 2
238000003860 storage Methods 0.000 description 2
239000000126 substance Substances 0.000 description 2
239000004094 surface-active agent Substances 0.000 description 2
LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
239000001856 Ethyl cellulose Substances 0.000 description 1
ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
229920001612 Hydroxyethyl starch Polymers 0.000 description 1
229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
239000004698 Polyethylene Substances 0.000 description 1
239000004743 Polypropylene Substances 0.000 description 1
239000004115 Sodium Silicate Substances 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
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 1
238000010521 absorption reaction Methods 0.000 description 1
239000013543 active substance Substances 0.000 description 1
239000000654 additive Substances 0.000 description 1
229910000323 aluminium silicate Inorganic materials 0.000 description 1
150000001408 amides Chemical class 0.000 description 1
150000001412 amines Chemical class 0.000 description 1
239000002518 antifoaming agent Substances 0.000 description 1
239000007864 aqueous solution Substances 0.000 description 1
229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
239000005018 casein Substances 0.000 description 1
BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
235000021240 caseins Nutrition 0.000 description 1
238000006243 chemical reaction Methods 0.000 description 1
230000000052 comparative effect Effects 0.000 description 1
150000001875 compounds Chemical class 0.000 description 1
239000013078 crystal Substances 0.000 description 1
238000002425 crystallisation Methods 0.000 description 1
230000008025 crystallization Effects 0.000 description 1
150000004985 diamines Chemical class 0.000 description 1
239000004205 dimethyl polysiloxane Substances 0.000 description 1
238000004090 dissolution Methods 0.000 description 1
229920001249 ethyl cellulose Polymers 0.000 description 1
235000019325 ethyl cellulose Nutrition 0.000 description 1
239000012530 fluid Substances 0.000 description 1
239000003205 fragrance Substances 0.000 description 1
125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
229940050526 hydroxyethylstarch Drugs 0.000 description 1
239000001863 hydroxypropyl cellulose Substances 0.000 description 1
235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
238000005342 ion exchange Methods 0.000 description 1
239000011777 magnesium Substances 0.000 description 1
229910052749 magnesium Inorganic materials 0.000 description 1
238000002844 melting Methods 0.000 description 1
230000008018 melting Effects 0.000 description 1
229920000609 methyl cellulose Polymers 0.000 description 1
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
239000001923 methylcellulose Substances 0.000 description 1
235000010981 methylcellulose Nutrition 0.000 description 1
239000000049 pigment Substances 0.000 description 1
229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
229920000573 polyethylene Polymers 0.000 description 1
229920001155 polypropylene Polymers 0.000 description 1
239000001253 polyvinylpolypyrrolidone Substances 0.000 description 1
229920000523 polyvinylpolypyrrolidone Polymers 0.000 description 1
235000013809 polyvinylpolypyrrolidone Nutrition 0.000 description 1
239000002994 raw material Substances 0.000 description 1
239000011833 salt mixture Substances 0.000 description 1
238000007873 sieving Methods 0.000 description 1
235000012217 sodium aluminium silicate Nutrition 0.000 description 1
229910000029 sodium carbonate Inorganic materials 0.000 description 1
235000017550 sodium carbonate Nutrition 0.000 description 1
NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
229910052911 sodium silicate Inorganic materials 0.000 description 1
235000019794 sodium silicate Nutrition 0.000 description 1
229910052938 sodium sulfate Inorganic materials 0.000 description 1
235000011152 sodium sulphate Nutrition 0.000 description 1
PWUYHXAEVMUADU-UHFFFAOYSA-M sodium;2-(7-methyloctanoyloxy)benzenesulfonate Chemical compound [Na+].CC(C)CCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O PWUYHXAEVMUADU-UHFFFAOYSA-M 0.000 description 1
239000007787 solid Substances 0.000 description 1
238000001694 spray drying Methods 0.000 description 1
238000005507 spraying Methods 0.000 description 1
239000012463 white pigment 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
- 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
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

Bleach activators already react in the washing powder mixture, favored by the residual moisture present, with the bleaching agent, e.g. Sodium perborate if both components are unprotected.
the bleaching agent e.g. Sodium perborate
one of the two components is coated with a water-soluble agent that dissolves in the wash water during the washing process and releases the active substance.
the bleach activator is preferably coated.
water-soluble agents e.g. surfactants solid at room temperature, as described in EP-A-62523, or starch or cellulose derivatives as described in EP-A-37026.
the activator powder is first premixed completely or partially dry with the auxiliary. In a second stage, this mixture is then moistened with water or with an aqueous solution of the remaining amount of the auxiliary and granulated.
the activator granules are produced by extrusion of a mixture of activator and surfactant.
FR-A-2 109 941 describes a process for the preparation of storage-stable, soluble bleach activator granules by coating the activators with a powdery auxiliary, in which the activator powder is moistened with water and then mixed and granulated with the powdered auxiliary.
Water-soluble, calcined mineral salts, salt mixtures, powdery minerals or water-insoluble, powdery compounds with a large surface area, such as polyethylene or polypropylene, are used as powdery auxiliaries. 50 to 95% by weight of the auxiliary, based on the dry activator powder, are mixed into the moist activator powder.
the present invention thus relates to a process for the preparation of a storage-stable, easily soluble bleach activator granulate by coating the activator with an auxiliary agent, the wettable powdery activator being first moistened with water, then the auxiliary agent being mixed as a powder with the moist activator and this mixture being granulated , characterized in that water-soluble cellulose ethers, water-soluble starch or water-soluble starch ethers are used as powdery auxiliaries.
Suitable bleach activators for the process according to the invention are the known N-acylated amines, diamines, amides and glycolurils, preferably tetraacetylethylenediamine and tetraacetylglycoluril, as well as pentaacetylglucose and isononanoyloxybenzenesulfonate sodium. These activators are produced as a powder. In order to ensure a good dissolution of the activator in the wash liquor, it has proven to be useful to prefer to use those activators which have an average grain diameter of approximately 0.05 to 0.5 mm, in particular 0.07 to 0.2 mm exhibit. The desired average grain diameter can be achieved by sieving with calibrated sieves. However, the method according to the invention is not limited to the processing of particles of the specified grain sizes.
the amount of water which is applied to the activator in the first cut by customary methods, for example by spraying, should be such that a moist, still Granules not prone to caking are formed.
the activator powder is moistened with water in a ratio of 20: 1 to 4: 1, preferably in a ratio of 9: 1 to 5: 1 with water.
a dye or white pigment can be added to the dry activator or the water to color it or to cover the natural color of the raw materials.
a dye or white pigment can be added to the dry activator or the water to color it or to cover the natural color of the raw materials.
generally 0.01 to 0.1 percent by weight, based on the finished product, of dye or pigment is sufficient.
Suitable auxiliaries for this purpose are water-soluble cellulose ethers, water-soluble starch or water-soluble starch ethers.
cellulose ethers are methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose (as sodium salt) and methyl carboxymethyl cellulose (sodium salt).
depolymerized starch can be considered as starch.
Suitable starch ethers are, for example, carboxymethyl starch, hydroxyethyl starch and methyl starch.
Sodium carboxymethyl cellulose has proven to be particularly suitable. All of these products are mixed in dry form with the activator.
the moist activator is mixed with the powdery, dry auxiliary in conventional mixing devices. About 2 to 20% by weight of auxiliaries, based on the dry activator powder, are mixed into the moist activator powder.
powdery disintegrants customary in the tablet industry can also be added, provided that they are used Cellulose and starch ethers do not in themselves have a certain explosive effect.
Usable disintegrants are, for example, partially degraded starch, starch ether, polyvinyl polypyrrolidone, formaldehyde casein and swellable magnesium aluminosilicates. The proportion of such disintegrants can be 0 to 2 percent by weight of the finished granulate.
the mixture thus obtained is then granulated in a suitable granulating device, for example in a granulating drum, in a high-speed mixer or on a granulating plate.
a suitable granulating device for example in a granulating drum, in a high-speed mixer or on a granulating plate.
Devices for press granulation such as extrusion presses or ring roller presses, are also suitable.
the water content of the mixture is then reduced to less than 2, preferably less than 1 percent by weight.
the excess water can be removed by drying with the addition of heat, the temperature of the granules advantageously not exceeding 100 ° C. and below the melting temperature of the bleach activator.
the dried granules should contain less than 2, preferably less than 1 percent by weight of water.
the granulate is intended for later use in detergents or is to be used for washing purposes, in which a certain content of such salts does not interfere, which are normally used in detergents or in washing processes and which can crystallize with the absorption of water of crystallization, the The excess water is also removed by mixing the moist granules with such dehydrating, essentially anhydrous or low-water salts.
dehydrating essentially anhydrous or low-water salts.
such salts are sodium tripolyphosphate, sodium sulfate, sodium carbonate, sodium silicate and low-water sodium aluminosilicates capable of ion exchange and mixtures thereof.
the amount to be used depends on the Water binding capacity of the salts in question and the water content of the moist granules.
the mixing ratio of tripolyphophate to moist granules is 1: 3 to 1: 1.5, in particular 1: 2 to 1: 1.
Mixing can be carried out in conventional mixers or granulating devices, it also being possible to continue to use the mixing devices used for the production of the moist granules and equipped with mixing elements. In this way, simplified, in particular energy-saving, processing is possible since the necessary drying stage can be saved.
the bleach activators obtained in this way, coated with an auxiliary agent, show a significantly better stability during storage in comparison to the activators of an analogous structure obtained by the process of EP-A 37026.
TAED tetraacetylethylene diamine
the resulting moist granules were dried in a fluid bed dryer to a residual moisture of approx. 1%.
the granulate subsequently discharged from the dryer contained approximately 3.5% portions above 1400 ⁇ and approximately 26% below 500 ⁇ .
the gut grain (portions between 500 ⁇ and 1400 ⁇ ) was sieved off and 3% mixed into a standard washing powder mixture containing sodium perborate. After 30 days of storage at 38 ° C and 80% relative humidity, 79% of the initial activity was still detectable by titration.
the powder mixture was made from 11.8 kg TAED and 800 g Carboxymethylcellulose moistened with 1.87 l water in 60 seconds.
the resulting mixture was passed through a perforated plate with 1 mm holes and dried to a residual moisture of 0.2%.
3% of the granules obtained in this way were mixed into a standard washing powder mixture containing perborate and kept in a climatic cabinet at 38 ° C. and 80% relative humidity for 30 days. After that, only 66% of the initial activity was detectable by titrimetry.

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)

EP89123523A 1988-12-22 1989-12-20 Verfahren zur Herstellung eines lagerstabilen, leicht löslichen Bleichaktivator-Granulats Expired - Lifetime EP0374867B1 (de)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE3843195A DE3843195A1 (de)	1988-12-22	1988-12-22	Verfahren zur herstellung eines lagerstabilen, leicht loeslichen bleichaktivator-granulats
DE3843195		1988-12-22

Publications (2)

Publication Number	Publication Date
EP0374867A1 EP0374867A1 (de)	1990-06-27
EP0374867B1 true EP0374867B1 (de)	1994-11-30

Family

ID=6369820

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP89123523A Expired - Lifetime EP0374867B1 (de)	1988-12-22	1989-12-20	Verfahren zur Herstellung eines lagerstabilen, leicht löslichen Bleichaktivator-Granulats

Country Status (6)

Country	Link
US (1)	US5100576A (da)
EP (1)	EP0374867B1 (da)
JP (1)	JP2766915B2 (da)
DE (2)	DE3843195A1 (da)
DK (1)	DK655689A (da)
IE (1)	IE66736B1 (da)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE4040654A1 (de) *	1990-12-19	1992-06-25	Henkel Kgaa	Granulat mit umhuelltem bleichaktivator
AU4777093A (en) *	1992-08-01	1994-03-03	Procter & Gamble Company, The	Peroxyacid bleach precursor compositions
WO1994003568A1 (en) *	1992-08-01	1994-02-17	The Procter & Gamble Company	Low gelling detergent compositions and a process for making such compositions
EP0675978B1 (en) *	1992-12-22	2000-02-02	The Procter & Gamble Company	Coated peroxyacid bleach precursor compositions
EP0693549A1 (en) *	1994-07-19	1996-01-24	The Procter & Gamble Company	Solid bleach activator compositions
DE19515233A1 (de) *	1995-04-28	1996-10-31	Henkel Kgaa	Lagerstabiles, Bleichaktivatoren enthaltendes Granulat und seine Herstellung
GB9519094D0 (en) *	1995-09-19	1995-11-22	Warwick Int Group	Granulated active with controlled release
GB2309976A (en) *	1996-02-08	1997-08-13	Procter & Gamble	Bleach catalyst particles for inclusion in detergents
DE19627427A1 (de) *	1996-07-08	1998-01-15	Henkel Kgaa	Wasch- oder Reinigungsmitteladditiv sowie ein Verfahren zu seiner Herstellung
DE19641708A1 (de) *	1996-10-10	1998-04-16	Clariant Gmbh	Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats
DE19841184A1 (de)	1998-09-09	2000-03-16	Clariant Gmbh	Bleichaktivatorgranulate
DE102005004893B4 (de) *	2005-02-03	2011-02-10	Dow Global Technologies Inc., Midland	Verfahren zur Formgebung von Celluloseethern
GB0710559D0 (en) *	2007-06-02	2007-07-11	Reckitt Benckiser Nv	Composition
EP3053997B2 (en)	2015-02-05	2021-01-13	Dalli-Werke GmbH & Co. KG	Cleaning composition comprising a bleach catalyst and carboxymethylcellulose

Family Cites Families (10)

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Publication number	Priority date	Publication date	Assignee	Title
NL252798A (da) *	1959-06-19	1900-01-01
DE2048331A1 (de) *	1970-10-01	1972-04-06	Henkel & Cie GmbH, 4000 Dusseldorf	Feste, pulverförmige bis kornige Mittel zur Herstellung von kaltwirksamen Bleich flotten, insbesondere von kaltwirksamen blei chenden Waschlaugen, und Verfahren zur Her stellung dieser Mittel
DE3011998C2 (de) *	1980-03-28	1982-06-16	Henkel KGaA, 4000 Düsseldorf	Verfahren zur Herstellung eines lagerstabilen, leichtlöslichen Granulates mit einem Gehalt an Bleichaktivatoren
US4399049A (en) *	1981-04-08	1983-08-16	The Procter & Gamble Company	Detergent additive compositions
FR2504147B1 (fr) *	1981-04-15	1987-11-20	Rhone Poulenc Chim Base	Granules de blanchiment, leur preparation et leur utilisation dans les compositions detergentes et de blanchiment
DE3128336A1 (de) *	1981-07-17	1983-01-27	Henkel KGaA, 4000 Düsseldorf	"verfahren zur herstellung umhuellter koerniger bleichaktivatoren"
EP0075818B2 (de) *	1981-09-28	1990-03-14	BASF Aktiengesellschaft	Körniger Bleichaktivator
JPS58170079A (ja) *	1982-03-31	1983-10-06	Nippon Telegr & Teleph Corp <Ntt>	半導体受光素子
US4678594A (en) *	1985-07-19	1987-07-07	Colgate-Palmolive Company	Method of encapsulating a bleach and activator therefor in a binder
GB8711153D0 (en) *	1987-05-12	1987-06-17	Warwick International Ltd	Bleach activator compositions

1988
- 1988-12-22 DE DE3843195A patent/DE3843195A1/de not_active Withdrawn
1989
- 1989-12-19 JP JP1327467A patent/JP2766915B2/ja not_active Expired - Lifetime
- 1989-12-20 DE DE58908690T patent/DE58908690D1/de not_active Expired - Fee Related
- 1989-12-20 EP EP89123523A patent/EP0374867B1/de not_active Expired - Lifetime
- 1989-12-21 DK DK655689A patent/DK655689A/da not_active Application Discontinuation
- 1989-12-21 IE IE417489A patent/IE66736B1/en not_active IP Right Cessation
- 1989-12-21 US US07/454,163 patent/US5100576A/en not_active Expired - Fee Related

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Publication number	Publication date
JP2766915B2 (ja)	1998-06-18
IE66736B1 (en)	1996-02-07
DE58908690D1 (de)	1995-01-12
JPH02222500A (ja)	1990-09-05
EP0374867A1 (de)	1990-06-27
DE3843195A1 (de)	1990-06-28
DK655689D0 (da)	1989-12-21
DK655689A (da)	1990-06-23
IE894174L (en)	1990-06-22
US5100576A (en)	1992-03-31

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