EP0448581B1 - Flüssiges bis pastöses, bleichmittelhaltiges waschmittel - Google Patents

Flüssiges bis pastöses, bleichmittelhaltiges waschmittel Download PDF

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Publication number
EP0448581B1
EP0448581B1 EP90900135A EP90900135A EP0448581B1 EP 0448581 B1 EP0448581 B1 EP 0448581B1 EP 90900135 A EP90900135 A EP 90900135A EP 90900135 A EP90900135 A EP 90900135A EP 0448581 B1 EP0448581 B1 EP 0448581B1
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
component
salts
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90900135A
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German (de)
English (en)
French (fr)
Other versions
EP0448581A1 (de
Inventor
Uwe Trabitzsch
Günther Amberg
Paul Schulz
Jean-Marie Paillau
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT90900135T priority Critical patent/ATE93890T1/de
Publication of EP0448581A1 publication Critical patent/EP0448581A1/de
Application granted granted Critical
Publication of EP0448581B1 publication Critical patent/EP0448581B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/3947—Liquid 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
    • C11D3/39—Organic or inorganic per-compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D3/3937—Stabilising agents
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a phosphate-free, liquid to pasty detergent, which is primarily intended for use in general laundries due to its special surfactant composition, a strongly alkaline, phosphate-free builder component and a bleach content.
  • Pasty essentially water-free detergents containing bleaching per compounds are known.
  • DE-B-12 79 878 (GB-A-12 05 711) describes a pasty agent whose liquid phase consists of nonionic surfactants and lower alcohols.
  • Sodium tripolyphosphate (TPP) and soda are used as skeleton salts and sodium perborate monohydrate as bleaching agent.
  • TPP Sodium tripolyphosphate
  • soda soda
  • the solids are finely ground and suspension stabilizers in the form of finely divided silica are also added to the agent.
  • DE-A-22 33 771 discloses washing pastes which contain mixtures of nonionic surfactants and polyols as the liquid phase and phosphates, citrate and nitrilotriacetate as the structural salts.
  • Perborate can be used as a per-compound.
  • EP-A-30 096 teaches that the solids, consisting of skeleton salts and persalts, have to be ground to particle sizes below 10 ⁇ m in order to avoid segregation of the pastes during storage.
  • the skeleton salts consist essentially of polyphosphates. Metasilicates and organic builder salts can also be present, but no further details are given.
  • the surfactant component consists exclusively of liquid non-ionic surfactants. Anionic surfactants are not included in the pastes. The means are unsatisfactory for the high requirements in commercial laundries with regard to perfect washing results compared to the most varied stains with the shortest possible wash cycles in the interest of high utilization of the complex washing systems.
  • the present invention enables a substantial improvement here. It had to be taken into account that the detergents foam as little as possible during the washing process and also in the rinse cycle, since a high level of foaming not only leads to malfunctions due to escaping lye, but also delivers poorer washing results, since a high foam cushion dampens the necessary mechanical processing of the laundry. Furthermore, in the interest of minimal wastewater pollution, the aim is to be largely free of phosphates. P-free detergents, however, require a different overall concept compared to P-containing detergents in order to avoid a drop in cleaning power. With powder detergents, this development is already well advanced, while with paste-like detergents, the problems are much greater due to the limited choice with regard to the usable raw materials. In the commercial sector, however, liquid or pasty agents deserve preference because they can be dosed automatically.
  • Suitable constituents of the surfactant component (A1) are alkylbenzenesulfonates with a linear alkyl chain having 10 to 13 carbon atoms, alkanesulfonates with 12 dis 16 carbon atoms, as can be obtained by sulfochlorination or sulfoxidation of n-paraffins and subsequent conversion into the alkali metal salts , and in the alpha position sulfonated fatty acid esters and fatty acid salts derived from saturated C12118 fatty acids and from C1 ⁇ 4 alcohols, preferably methyl alcohol.
  • Preferred sulfonate surfactants are alkylbenzenesulfonates.
  • soaps of saturated or monounsaturated C12 ⁇ 22 fatty acids especially C12 ⁇ 18 fatty acids and fatty acid mixtures, for example coconut oil, tallow oil or rapeseed oil fatty acids.
  • the surfactants of group (A1) are present as alkali salts, preferably as sodium salts. Their proportion, based on the composition, is preferably 1.5 to 3% by weight. Mixtures of alkylbenzenesulfonate and soaps have proven to be particularly suitable, in which case the content of alkylbenzenesulfonate in the compositions is 1 to 2.8% by weight and soaps 0.2 to 1.5% by weight. Surprisingly, it has been shown that the alkylbenzenesulfonates, regardless of their small proportion in the total surfactant component, considerably increase the washing power of the compositions compared to a pure nonionic formulation. On the other hand, the presence of the sulfonate surfactants known to be very foam active does not lead to an undesirable increase in foaming when used.
  • Component (A2) consists of alkoxylated, preferably ethoxylated linear alcohols or alcohols branched in the 2-position methyl (oxo alcohols) having 10 to 18 carbon atoms, those with 18 carbon atoms preferably being predominantly monounsaturated, that is to say predominantly composed of Oleyl alcohol or mixtures thereof.
  • the number of ethylene glycol ether groups (E0) is usually 2 to 10, preferably 3 to 8 and should be matched with respect to the alcohol residue so that the ethoxylates or ethoxylate mixtures have a pour point of at most 10 ° C, preferably below 8 ° C .
  • Alcohol alkoxylates of the general formula R- (PO) x - (EO) y in which PO stands for a propylene glycol ether residue, x for the numbers 1 to 2 and y for the numbers 3 to 10, are also very useful.
  • Particularly suitable nonionics from this class are C10 ⁇ 14 coconut alcohols with 3 - 8 EO, oley alcohol with 5 - 10 EO, or with 1 - 2 PO and 4 - 8 EO, C10 ⁇ 14 oxo alcohols with 3 - 8 EO and C12 ⁇ 15-oxo alcohols with 3 - 7 EO, and their mixtures.
  • the proportion of the surfactant component (A2) is on average 16 to 34% by weight, preferably 18 to 30% by weight.
  • the total amount of surfactants is 20 to 35% by weight, preferably 22 to 33% by weight.
  • Component (B) consists of water-soluble or water-insoluble builder substances which are able to bind or sequester alkaline earth metal ions and possibly also heavy metal ions.
  • Hydrated, finely crystalline, synthetic zeolites of the NaA type are suitable as water-insoluble builder substance.
  • Suitable zeolites have practically no particles larger than 30 ⁇ m and preferably consist of at least 80% of particles smaller than 10 ⁇ m.
  • Their calcium binding capacity which is determined according to the information in DE-A-24 12 837, is in the range from 100 to 200 mg CaO / g.
  • the content of zeolites in the detergents should preferably not exceed 25% by weight and in particular 20% by weight in the interest of sufficient flowability of the paste.
  • Particularly suitable builder substances which are to be assigned to component (B) and are used either alone or in a mixture with the abovementioned zeolites are polyanionic, organic complexing agents, the proportion of which is preferably in total 10 to 20% by weight.
  • Nitrilotriacetic acid (NTA) and polyphosphonic acids in the form of the sodium salts such as ethylenediamine-tetramethylenephosphonic acid (EDTMP), diethylenetriamine-pentamethylenephosphonic acid (DTPMP), aminotrimethylenephosphonic acid (ADTMP) and in particular 1-hydroxyethane-1,1-diphosphonic acid (HED) are suitable.
  • the agent preferably contains 3 to 8% by weight of NTA (NA salt) and 0.5 to 4% by weight of HEDP (Na salt).
  • This component also includes polymeric or copolymeric carboxylic acids in the form of the sodium or potassium salts, the sodium salts being preferred. Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid.
  • Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
  • vinyl ethers such as vinyl methyl ether or vinyl ethyl ether
  • vinyl esters such as vinyl acetate or vinyl propionate
  • acrylamide methacrylamide
  • ethylene, propylene or styrene ethylene, propylene or styrene.
  • the proportion thereof in the interest of sufficient water solubility is not more than 60 mole percent, preferably less than 50 mole percent.
  • Copolymers of acrylic acid or methacrylic acid with maleic acid such as are characterized, for example, in EP 25 551-B1 have proven to be particularly suitable.
  • copolymers which contain 50 to 90% by weight of acrylic acid or methacrylic acid and 50 to 10% by weight of maleic acid. Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred.
  • the content of such (co) polymers in the compositions, based on sodium salts, is up to 10% by weight, preferably 3 to 8% by weight.
  • Component (C) consists of sodium metasilicate, which has a Na2O: SiO2 ratio of 1: 0.8 to 1: 1.5, preferably 1: 0.9 to 1: 1.1.
  • the sodium silicate is used as an anhydrous salt. Its proportion is preferably 20 to 35% by weight.
  • Possible components (D) are persalts or perhydrate salts, such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate.
  • Sodium perborate monohydrate is preferably used.
  • the content of the agents and such per-compounds is 8 to 25% by weight, preferably 10 to 20% by weight.
  • the component (E) comprises known nonionic or anionic polymers with graying-inhibiting action.
  • Cellulose ethers such as sodium carboxymethyl cellulose and mixtures thereof with other cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or mixed ethers such as methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose or ethyl hydroxyethyl cellulose are particularly suitable.
  • Cellulose ethers and (co) polymers can advantageously be used together. Mixtures of carboxymethyl cellulose with methyl cellulose or methyl hydroxyethyl cellulose have proven to be particularly useful.
  • the graying inhibitor content of the agents is up to 3% by weight, preferably 0.5 to 2% by weight.
  • Enzymes, fragrances and customary optical brighteners come into question as cheerful non-surfactant components of component (E) which do not act as builders, in particular optical brighteners with substantivity for cellulose fibers (cotton) from the class of the substituted bis-triazinylstilbene disulfonic acids and sulfonated distyryle , which are usually used in proportions of 0.05 to 0.5% by weight.
  • agents for improving the flowability can also be added to the pastes.
  • hydrotropes such as alkylbenzosulfonates with 1 to 3 carbon atoms in one or two alkyl chains in the form of the sodium salts such as toluene, cumene or xylene sulfonate.
  • Solvents such as lower alcohols and ether alcohols and polyethylene glycols with a molecular weight of 200 to 1000 can also be used. The proportion of polyglycols can be up to 10% by weight. Alcohols can be used in the same amount, but they are less preferred.
  • the water content of the agents should be as low as possible, since free water increases the viscosity of the agents and thus complicates the processing and metering of the agents. Water contents of 2% by weight or less are therefore particularly preferred.
  • the agents are prepared by mixing and homogenizing the solid, finely divided constituents with the liquid nonionic surfactants (component A2), in particular with the liquid surfactant mixture (component A).
  • component A2 liquid nonionic surfactants
  • component A liquid surfactant mixture
  • the solid alkylbenzenesulfonates behave about half of their content as a liquid component and thus favor the incorporation of high solids contents.
  • the mixture is then expediently ground, for example in a colloid mill or on a roller mill, so that the grain size of the suspended solids is between 5 and 80 ⁇ m, preferably 10 to 50 ⁇ m.
  • the proportion of coarse particles (over 80 ⁇ m) should preferably be less than 20, in particular less than 5,% by weight.
  • the agents are generally used in a concentration of 4 to 12 g / l, preferably 5 to 10 g / l, suitably softened, i.e. water softened to a degree of hardness of less than 2 ° dH, in particular less than 1 ° dH, is used to prepare the wash liquor.
  • the agents are characterized by a high washing and bleaching capacity and a low, non-disturbing foam development during use. Surprisingly, it has been found that the agents are extremely stable against loss of oxygen and against segregation even under long-term storage under changing climatic conditions. They are suitable due to their favorable rheological properties Good for use in automatic dosing systems, since they are low-viscosity and easy to convey under the influence of shear effects, but are more viscous in the idle state and are therefore stable in storage.
  • the perborate was used in the form of the monohydrate.
  • the copolymer was composed of acrylic acid and maleic acid (3: 1) and had a molecular weight of approximately 70,000.
  • the cellulose ether consisted of a 2: 1 mixture of sodium carboxymethyl cellulose and methyl hydroxyethyl cellulose (hydroxyethyl content 0.8% by weight).
  • the Na salt of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid was used as the optical brightener .
  • the water came from the moisture content of the raw materials used.
  • Polydiol was a polyethylene glycol with a molecular weight of 400. The contents given in the table mean percentages by weight.
  • the foam development was low in all cases, i.e. the foam level was a maximum of 8 to 10 cm above the liquid level in the main wash cycle and 4 to 6 cm above the liquid level in the first rinse cycle. No foam development was visible in the third rinse cycle.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP90900135A 1988-12-14 1989-12-05 Flüssiges bis pastöses, bleichmittelhaltiges waschmittel Expired - Lifetime EP0448581B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90900135T ATE93890T1 (de) 1988-12-14 1989-12-05 Fluessiges bis pastoeses, bleichmittelhaltiges waschmittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3842007A DE3842007A1 (de) 1988-12-14 1988-12-14 Fluessiges bis pastoeses, bleichmittelhaltiges waschmittel
DE3842007 1988-12-14

Publications (2)

Publication Number Publication Date
EP0448581A1 EP0448581A1 (de) 1991-10-02
EP0448581B1 true EP0448581B1 (de) 1993-09-01

Family

ID=6369101

Family Applications (2)

Application Number Title Priority Date Filing Date
EP89122421A Withdrawn EP0373483A1 (de) 1988-12-14 1989-12-05 Flüssiges bis pastöses, bleichmittelhaltiges Waschmittel
EP90900135A Expired - Lifetime EP0448581B1 (de) 1988-12-14 1989-12-05 Flüssiges bis pastöses, bleichmittelhaltiges waschmittel

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP89122421A Withdrawn EP0373483A1 (de) 1988-12-14 1989-12-05 Flüssiges bis pastöses, bleichmittelhaltiges Waschmittel

Country Status (13)

Country Link
US (1) US5456850A (ko)
EP (2) EP0373483A1 (ko)
JP (1) JPH04502338A (ko)
KR (1) KR970002041B1 (ko)
BR (1) BR8907821A (ko)
DE (2) DE3842007A1 (ko)
DK (1) DK112491A (ko)
ES (1) ES2043353T3 (ko)
FI (1) FI99142C (ko)
IE (1) IE71938B1 (ko)
PT (1) PT92544B (ko)
TR (1) TR24156A (ko)
WO (1) WO1990006986A1 (ko)

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US5663132A (en) * 1995-03-01 1997-09-02 Charvid Limited Liability Company Non-caustic composition comprising peroxygen compound and metasilicate and cleaning methods for using same
US6194367B1 (en) 1995-03-01 2001-02-27 Charvid Limited Liability Co. Non-caustic cleaning composition comprising peroxygen compound and specific silicate and method of making the same in free-flowing, particulate form
US6034048A (en) * 1995-03-01 2000-03-07 Charvid Limited Liability Co. Non-caustic cleaning composition using an alkali salt
DE19535082A1 (de) 1995-09-21 1997-03-27 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
US5869474A (en) * 1997-05-16 1999-02-09 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Low dosage treatment for cocaine craving and withdrawal
US5906215A (en) * 1997-11-20 1999-05-25 Reel Clean Corporation Fishing reel cleaning solution
DE19857687A1 (de) * 1998-12-15 2000-06-21 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Waschmittel
US6225268B1 (en) * 1999-08-23 2001-05-01 Sinon Corporation Liquid detergent composition
DE10004677A1 (de) * 2000-02-03 2001-08-09 Cognis Deutschland Gmbh Tensidmischung mit Fettalkoholalkoxylaten aus pflanzlichen Rohstoffen
JP4407779B2 (ja) 2000-03-27 2010-02-03 信越化学工業株式会社 押出成形用の水硬性組成物用バインダー及び水硬性組成物並びに押出成形品の製造方法
US20030126689A1 (en) * 2001-12-07 2003-07-10 The Procter & Gamble Company Process for providing improved whiteness to fabric and for removing formaldehyde and formaldehyde conjugates from treated fabric
US20060019865A1 (en) * 2004-07-20 2006-01-26 Enrique Hernandez Methods and compositions of multifunctional detergent components
US20060178289A1 (en) * 2004-07-20 2006-08-10 Enrique Hernandez Multifunctional material compositions and methods
ES2438020T3 (es) * 2005-11-10 2014-01-15 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Composiciones y métodos para el tratamiento de adicciones y otros trastornos neuropsiquiátricos
US20070161539A1 (en) * 2006-01-12 2007-07-12 Enrique Hernandez Method of regulating degree of polymerization of an alkali metal silicate in solution using pH
WO2010025452A1 (en) * 2008-08-29 2010-03-04 Micro Pure Solutions, Llc Method for treating hydrogen sulfide-containing fluids
MX359263B (es) 2010-06-16 2018-09-20 Board Of Supervisors Of Louisiana State Univ & Agricultural & Mechanical College Composiciones y métodos para el tratamiento de adicciones, trastornos psiquiátricos , y enfermedades neurodegenerativas.
CN103865666A (zh) * 2014-02-13 2014-06-18 上海方木精细化工有限公司 低泡洗衣液
CN110582278B (zh) 2017-03-10 2023-04-18 伊姆贝拉神经疗法公司 药物组合物及其用途

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US4743394A (en) * 1984-03-23 1988-05-10 Kaufmann Edward J Concentrated non-phosphate detergent paste compositions
DE3424299A1 (de) * 1984-07-02 1986-01-09 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung eines spruehgetrockneten nichtionischen waschhilfsmittels
US4690771A (en) * 1985-08-05 1987-09-01 Colgate-Palmolive Company Phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
JPS6235862A (ja) * 1985-08-09 1987-02-16 Canon Inc 記録装置
DE3545947A1 (de) * 1985-12-23 1987-07-02 Henkel Kgaa Phosphatfreies, granulares waschmittel
NZ221555A (en) * 1986-09-09 1989-08-29 Colgate Palmolive Co Detergent composition containing inorganic bleach and a liquid activator
DE3914504A1 (de) * 1989-05-02 1990-11-08 Henkel Kgaa Pastoeses, phosphatfreies, im wesentlichen wasserfreies waschmittel

Also Published As

Publication number Publication date
ES2043353T3 (es) 1993-12-16
IE893981L (en) 1990-06-14
DK112491D0 (da) 1991-06-12
PT92544A (pt) 1990-06-29
KR910700326A (ko) 1991-03-14
DK112491A (da) 1991-08-05
DE3842007A1 (de) 1990-06-21
US5456850A (en) 1995-10-10
TR24156A (tr) 1991-04-26
FI99142C (fi) 1997-10-10
IE71938B1 (en) 1997-03-12
JPH04502338A (ja) 1992-04-23
PT92544B (pt) 1996-08-30
FI912464A0 (fi) 1991-05-21
DE58905488D1 (de) 1993-10-07
WO1990006986A1 (de) 1990-06-28
FI99142B (fi) 1997-06-30
EP0448581A1 (de) 1991-10-02
BR8907821A (pt) 1991-10-22
EP0373483A1 (de) 1990-06-20
KR970002041B1 (ko) 1997-02-21

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