WO1991014762A1 - Additif d'avivage seche par pulverisation pour agents de lavage - Google Patents

Additif d'avivage seche par pulverisation pour agents de lavage Download PDF

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Publication number
WO1991014762A1
WO1991014762A1 PCT/EP1991/000514 EP9100514W WO9114762A1 WO 1991014762 A1 WO1991014762 A1 WO 1991014762A1 EP 9100514 W EP9100514 W EP 9100514W WO 9114762 A1 WO9114762 A1 WO 9114762A1
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WO
WIPO (PCT)
Prior art keywords
weight
component
water
composition according
spray
Prior art date
Application number
PCT/EP1991/000514
Other languages
German (de)
English (en)
Inventor
Lothar Pioch
Elmar Wilms
Wolfgang Seiter
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to DE59102283T priority Critical patent/DE59102283D1/de
Priority to EP91906393A priority patent/EP0544670B1/fr
Publication of WO1991014762A1 publication Critical patent/WO1991014762A1/fr

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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 present invention relates to the production of a granular detergent additive which, due to its content of layered silicates, enhances, i.e. has fabric softening properties. Because of the high proportion of ingredients with builder properties, it also has detergent properties.
  • Detergent additives of the type mentioned are advantageously added to granular detergents in order to modify and improve their properties.
  • the agents according to the invention consist of easily soluble granules which are very resistant to abrasion and breakage and are therefore very suitable for further processing on detergent and cleaning agent mixtures. They have a pronounced adsorption capacity for liquid to pasty detergent constituents, which can be introduced into detergent granules without problems in this way without impairing their free-flowing properties.
  • EP-A 279 040 discloses laundry builders which contain 50 to 80% by weight of finely crystalline zeolite, 5 to 25% by weight of bentonite and 0.5 to 5% by weight of cellulose ether as binders. In addition, up to 5% by weight of sodium sulfate, up to 1% by weight of alkali and up to 5% by weight of nonionic surfactants can be present. The compositions are said to be produced by spray drying an aqueous slurry. None is said about the Aviva effect of the funds. If present at all, it can only be very small, since in practice (examples) the proportion of bentonite is comparatively low at a maximum of 8% by weight and special layered silicates with a finishing effect are not disclosed.
  • the object of the present invention is to provide means and a suitable method for their production, by means of which a sufficient active ingredient content and thus a good softening effect and favorable grain properties are achieved.
  • the invention relates to a spray-dried, aerating detergent additive containing
  • Suitable sheet silicates which belong to the group of smectites which swell with water are, for example, those of the general formulas 2
  • the layered silicates can contain hydrogen, alkali and alkaline earth ions, in particular Na + and Ca ++ .
  • the amount of water of hydration is usually in the range from 8 to 20% by weight and is dependent on the swelling state or on the type of processing.
  • the particle size is in the range from 0.05 to 25 ⁇ m, usually less than 10 ⁇ m.
  • Layered silicates are preferably used which, for example due to an alkali treatment, are largely free of strongly coloring iron ions and of calcium ions.
  • the layer silicate content of the agents is 12.5 to 20% by weight, preferably 14 to 20% by weight and in particular 15 to 20% by weight.
  • the constituent (B) which is present in proportions of 50 to 65% by weight, preferably 52 to 62% by weight, consists of synthetic sodium aluminosilicate of the zeolite A type containing bound water .
  • Suitable zeolites have no particles larger than 30 ⁇ m and consist of at least 80% of particles smaller than 10 ⁇ m.
  • Your 'calcium binding capacity which is determined according to the information in DE 24 12837, is in the range from 100 to 200 mg CaO / g.
  • the sodium sulfate (C) improves the granulability of the starting mixtures and the dispersing and dissolving behavior of the granules in the wash water. Its content is preferably 3 to 7% by weight.
  • the proportions refer to anhydrous salt. However, this means that some of the moisture contained in the granules can be bound to this salt as water of hydration.
  • the component (-D) consists of a homopolymeric and / or copolymeric carboxylic acid in the form of the sodium salt.
  • Suitable homopolymers are polyacrylic acid and polymethacrylic acid.
  • Suitable copolymers are those of acrylic acid or methacrylic acid with maleic acid.
  • copolymers of acrylic acid or methacrylic acid with maleic acid such as are described, for example, in EP 25551 B1, have proven to be particularly suitable. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred.
  • the molecular weight of the homo- or copolymers is generally 1,000 to 150,000, preferably 1,500 to 100,000.
  • the proportion of polyacid or its salts increases, the resistance of the grains to abrasion increases. With a proportion from 1.5% by weight, sufficient abrasion resistance is achieved in many cases.
  • Mixtures with 2 to 7% by weight of sodium salt of polyacid have optimal abrasion properties.
  • the polymers also do one improved builder effect of the mixtures when used.
  • the water content of the granules includes the water which is bound to the zeolite (18 to 22% by weight, based on zeolite) and is adsorbed by the layered silicate, and also the water of hydration of the salts. It is usually 10 to 25% by weight, in particular 12 to 20% by weight.
  • the agents can contain small amounts of compounds which can be added during the production and processing of the synthetic zeolites in order to increase the stability of the aqueous zeolite dispersions (master batch).
  • additives which can be introduced into the compositions with the zeolite, are described in document DE 25 27 388 cited above.
  • These can be nonionic surfactants containing polyglycol ether groups, for example primary alcohols with 12 to 18 carbon atoms reacted with 2 to 7 moles of ethylene oxide.
  • the proportion of stabilizers introduced into the composition via such zeolite dispersions can be, for example, 0.05 to 2% by weight, depending on the proportion of the zeolite. However, this component is not necessary for the desired properties of the granules.
  • Further optional constituents are dyes or colored pigments, which can be added to the agents in the granulation in proportions of, for example, 0.01 to 1% by weight in order to cover a possible gray or brownish intrinsic color of the layered silicates. After the granules have been mixed into a granular detergent, they give it a visually appealing, color-speckled appearance. In the same way, white Use pigments and optical brighteners if a white granulate and a uniform white mixed product are required.
  • Dyes which are degraded in the subsequent washing process are particularly suitable, so that there is no undesired dyeing of the textiles.
  • Examples include the dyes duasyn acid blue ( R ) and duasyn acid green.
  • the granules can be used to adsorb liquid or pasty detergent constituents and to incorporate them into detergent granules without loss of free-flowing properties.
  • these are fatty acid alkanols (which can bring about an additional softening effect or increase washing power) and, in particular, nonionic surfactants of the polyglycol ether derivative type.
  • nonionic surfactants of the polyglycol ether derivative type.
  • nonionic surfactants it is also possible to adsorb oily additives, such as perfumes or foam-suppressing substances from the class of paraffins, microparaffins, long-chain bisacyl diamines and silicones, and mixtures thereof, onto the grains.
  • oily additives such as perfumes or foam-suppressing substances from the class of paraffins, microparaffins, long-chain bisacyl diamines and silicones, and mixtures thereof, onto the grains.
  • the agents are produced by spray drying an aqueous, paste-like batch (slurry) of the constituents by means of heated gases (combustion gases) in conventional drying towers. Since the combustion air, which is widely used as a dry gas, contains comparatively high proportions of carbon dioxide, it can be particulate if small amounts of sodium hydroxide are added to the slurry before spraying, in order to counteract a pH reduction by a corresponding excess of alkali.
  • the recommended proportions of NaOH are usually between 0.1 and 1% by weight.
  • the aqueous batch contains 50 to 65% by weight of water-free ingredients. Its temperature is advantageously 50 to 90 ° C and its viscosity at this working temperature up to 25000 mPa-s, usually 12000 to 20,000 mPa-s.
  • the atomization pressure is usually 20 to 120 bar, preferably 30 to 80 bar.
  • the drying gas which is generally obtained by burning heating gas or heating oil, is preferably conducted in countercurrent.
  • the inlet temperature measured in the ring channel (ie immediately before entering the lower part of the tower), is 180 to 300 ° C. preferably 220 to 280 ° C.
  • the exhaust gas laden with moisture leaving the tower usually has a temperature of 50 to 110 ° C., preferably 60 to 100 ° C.
  • the granules produced in this way are notable for very good redispersibility in the aqueous wash liquor. With regard to their activating effect, they are largely identical with agents of the same type produced in another way.
  • the average grain size of the agent produced by spray drying is usually 0.2 to 1.2 mm.
  • at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.0 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 2% by weight .-%, in particular less than 1% by weight and the proportion of the grains above 1.5 mm is not more than 15% by weight, in particular not more than 10% by weight.
  • Larger proportions of fine grain favor the formation of dust when mixed with other powder components and should therefore be avoided.
  • Larger proportions of coarse grain cause a lower bulk density and make the product appear visually inconsistent, but are otherwise not disadvantageous.
  • the bulk density of the spray-dried compositions is 500 to 700 g / 1, mostly 550 to 650 g / 1.
  • the agent essentially consists of rounded grains which have a very good flow behavior. This very good flow behavior is still present even when the grains have been impregnated with larger proportions of liquid, semi-liquid or solid nonionic surfactants.
  • the proportion of these adsorbed constituents can be 5 to 30% by weight, preferably 10 to 25% by weight, based on the adsorbate.
  • the starting material was a suspension containing about 50% by weight of water and stabilized with the non-ionic surfactant.
  • the zeolite is calculated to be anhydrous, ie the water content attributable to the zeolite (approx. 20% based on zeolite) is listed under "water”.
  • (D) Copoly eres salt, acrylic acid-maleic acid copolymer, MG 70000, Na salt, product Sokalan ( R ) CP5 from BASF (DE),
  • TA5 means a tallow alcohol reacted with 5 moles of ethylene glycol, used as a dispersion stabilizer for the zeolite dispersion containing 50% by weight.
  • a dianilino-dimorpholino derivative of bis (triazinyl) -stilbene disulfonic acid Na salt) was used as the optical brightener.
  • Example 2 The formulation according to Example 2 was sprayable using stirrers with high torque and a high spray pressure.
  • the recipes according to Examples 1 and 3 could be prepared and spray-dried without special technical effort.
  • the drying gases conducted in countercurrent had an inlet temperature in the ring channel of 263 ° C. (examples 1 and 3) and 267 ° C. (example 2).
  • the temperature in the area of the tower outlet in front of the dust filters was 71 ° C to 72 ° C (Examples 1 and 3) and 76 ° C (Example 2).
  • the atomization pressure was 40 bar in Example 1 and 3 and 49 bar in Example 2.
  • the spray products obtained were free-flowing with an average particle size of 0.35 mm and a dust content (less than 0.05 mm) of less than 0.1% by weight. Grain fractions of over 2 mm were not present.
  • the bulk density was 590 g / 1 in Example 1, 550 g / 1 in Example 2 and 590 g / 1 in Example 3. All spray products were able to use 5 to 30% by weight (based on the end product) of liquid nonionic surfactants in a spray mixing apparatus (Coconut fatty alcohol + 5E0, Ci2-14-oxo alcohol + 7 E0) can be added, the bulk density increasing to 650 to 780 g / l. The flow behavior of the adsorbates thus obtained was unchanged compared to the granules used.
  • the granules were mixed with a granular detergent to give an agent of the following composition (in% by weight):

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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)

Abstract

Un additif granulaire pour agents de lavage ayant des propriétés d'avivage contient (A) 12,5 à 20 % en poids d'un phyllosilicate, (B) 52 à 65 % en poids de zéolite synthétique en fins cristaux (proportion par rapport à la substance anhydre), (C) 2 à 8 % en poids de sulfate de sodium (proportion par rapport à la substance anhydre), (D) 1,5 à 8 % en poids du sel de sodium d'un acide acrylique (méthylique) et (E) 0 à 30 % en poids d'agents tensio-actifs non-ioniques de la classe des éthers de polyglycol. Le reste, c'est-à-dire la différence par rapport à 100 %, est constitué d'eau.
PCT/EP1991/000514 1990-03-26 1991-03-18 Additif d'avivage seche par pulverisation pour agents de lavage WO1991014762A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59102283T DE59102283D1 (de) 1990-03-26 1991-03-18 Sprühgetrocknetes, avivierend wirkendes waschmitteladditiv.
EP91906393A EP0544670B1 (fr) 1990-03-26 1991-03-18 Additif d'avivage seche par pulverisation pour agents de lavage

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4009618.1 1990-03-26
DE4009618A DE4009618A1 (de) 1990-03-26 1990-03-26 Spruehgetrocknetes, avivierend wirkendes waschmitteladditiv

Publications (1)

Publication Number Publication Date
WO1991014762A1 true WO1991014762A1 (fr) 1991-10-03

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ID=6403046

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/000514 WO1991014762A1 (fr) 1990-03-26 1991-03-18 Additif d'avivage seche par pulverisation pour agents de lavage

Country Status (5)

Country Link
EP (1) EP0544670B1 (fr)
AT (1) ATE108823T1 (fr)
DE (2) DE4009618A1 (fr)
ES (1) ES2056643T3 (fr)
WO (1) WO1991014762A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0745662A1 (fr) * 1994-12-15 1996-12-04 Nippon Shokubai Co., Ltd. Adjuvant pour detergent, son procede de fabrication et composition detergente le contenant
WO1997013831A1 (fr) * 1995-10-12 1997-04-17 Süd-Chemie AG Additif de lessive
WO1997013830A1 (fr) * 1995-10-12 1997-04-17 Süd-Chemie AG Additif de lessive
EP0903401A1 (fr) * 1997-09-17 1999-03-24 Ciba SC Holding AG Additif antimicrobien pour détergents
TR199801841A3 (tr) * 1997-09-17 1999-10-21 Ciba Specialty Chemicals Holding Inc. Mikrop-önleyici deterjan katki maddesi.
US6462006B1 (en) * 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2297977A (en) * 1995-02-07 1996-08-21 Procter & Gamble Detergent composition containing Zeolite MAP
DE19756696A1 (de) 1997-12-19 1999-07-01 Clariant Gmbh Schichtsilikathaltige Wasch- und Reinigungsmittelkomponente
GB0102736D0 (en) * 2001-02-05 2001-03-21 Crosfield Joseph & Sons Disintegrants and a process for their manufacture
ES2953916T3 (es) 2016-11-04 2023-11-17 Sa Minera Catalano Aragonesa Partículas coloreadas para detergentes y procedimiento de producción de las mismas

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0184794A2 (fr) * 1984-12-10 1986-06-18 Henkel Kommanditgesellschaft auf Aktien Produit adsorbant granulé
EP0279040A1 (fr) * 1987-01-30 1988-08-24 Degussa Aktiengesellschaft Adjuvant actif pour agents de lavage
EP0419970A2 (fr) * 1989-09-23 1991-04-03 Henkel KGaA Produit granulaire, exempt de phosphate, pour adoucir l'eau
EP0425804A2 (fr) * 1989-11-02 1991-05-08 Henkel KGaA Additif granulaire contenant un agent tensioactif pour détergent et agent de nettoyage avec des propriétés de rinçage améliorées

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0104383D0 (en) * 2001-02-22 2001-04-11 Psimedica Ltd Cancer Treatment

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0184794A2 (fr) * 1984-12-10 1986-06-18 Henkel Kommanditgesellschaft auf Aktien Produit adsorbant granulé
EP0279040A1 (fr) * 1987-01-30 1988-08-24 Degussa Aktiengesellschaft Adjuvant actif pour agents de lavage
EP0419970A2 (fr) * 1989-09-23 1991-04-03 Henkel KGaA Produit granulaire, exempt de phosphate, pour adoucir l'eau
EP0425804A2 (fr) * 1989-11-02 1991-05-08 Henkel KGaA Additif granulaire contenant un agent tensioactif pour détergent et agent de nettoyage avec des propriétés de rinçage améliorées

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0745662A1 (fr) * 1994-12-15 1996-12-04 Nippon Shokubai Co., Ltd. Adjuvant pour detergent, son procede de fabrication et composition detergente le contenant
EP0745662A4 (fr) * 1994-12-15 1999-02-24 Nippon Catalytic Chem Ind Adjuvant pour detergent, son procede de fabrication et composition detergente le contenant
US5962401A (en) * 1994-12-15 1999-10-05 Nippon Shokubai Co., Ltd. Detergent builder process of manufacturing same and detergent composition containing same
CN1093560C (zh) * 1994-12-15 2002-10-30 株式会社日本触媒 洗涤剂助洗剂,其制备方法,和含有该洗涤剂助洗剂的洗涤剂组合物
EP1445304A1 (fr) * 1994-12-15 2004-08-11 Nippon Shokubai Co., Ltd. Adjuvant pour détergent, son procédé de fabrication et composition détergente le contenant
WO1997013831A1 (fr) * 1995-10-12 1997-04-17 Süd-Chemie AG Additif de lessive
WO1997013830A1 (fr) * 1995-10-12 1997-04-17 Süd-Chemie AG Additif de lessive
US6541440B2 (en) 1995-10-12 2003-04-01 Süd-Chemie AG Washing-agent additive
EP0903401A1 (fr) * 1997-09-17 1999-03-24 Ciba SC Holding AG Additif antimicrobien pour détergents
TR199801841A3 (tr) * 1997-09-17 1999-10-21 Ciba Specialty Chemicals Holding Inc. Mikrop-önleyici deterjan katki maddesi.
US6365563B1 (en) 1997-09-17 2002-04-02 Ciba Specialty Chemicals Corporation Agglomerated antimicrobial detergent additive comprising swellable layered silicate and surfactant
US6462006B1 (en) * 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates

Also Published As

Publication number Publication date
ES2056643T3 (es) 1994-10-01
DE4009618A1 (de) 1991-10-02
EP0544670A1 (fr) 1993-06-09
DE59102283D1 (de) 1994-08-25
EP0544670B1 (fr) 1994-07-20
ATE108823T1 (de) 1994-08-15

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