CA2112491A1 - Anti-foam agents - Google Patents
Anti-foam agentsInfo
- Publication number
- CA2112491A1 CA2112491A1 CA002112491A CA2112491A CA2112491A1 CA 2112491 A1 CA2112491 A1 CA 2112491A1 CA 002112491 A CA002112491 A CA 002112491A CA 2112491 A CA2112491 A CA 2112491A CA 2112491 A1 CA2112491 A1 CA 2112491A1
- Authority
- CA
- Canada
- Prior art keywords
- antifoam agents
- antifoam
- agents
- terized
- charac
- 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.)
- Abandoned
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/12—Defoamers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/47—Levelling 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Proposed are anti-foaming agents containing: a) as the carrier oil, dialkyl ethers of the formula R1-O-R2, in which R1 and R2, independently of each other, are straight-chain or branched-chain alkyl groups with 6 to 12 carbon atoms, b) waxy active substances with melting points within the range 80 to 160 ·C and c) stabilizers. Such anti-foaming agents are stable to alkalis and chlorine and are suitable for use in removing foam from cleaning agents for hard surfaces, paints and varnishes, as well as waste water from sewage-treatment plants and from industrial processes such as metalworking and paper manufacture.
Description
Anti-~o~m age~t~
Field of the Invention This inve~tion relates to antifoam agents containing dialkyl ethers, active substances and stabilizers and to their use as additives for cleaning products, in the production of paints and lacquers and for the treatment of wastewater in sewage treatment plants and from industrial processes such as, for example, metalworking or paper-making.
Prior Art 1~
For many industrial processes, the foaming associated with the use of surface-active substances is a serious problem. For example, powder-form or liquid alkaline detergents containing active chlorine or acti~e oxygen lS compounds in addition to surfactants, builders, alkali metal silicates, carbonates and/or hydroxides are used in domestic dishwashing machines and in the industrial washing of beer bottles and milk bottles. To prevent excessive foaming, an antifoam agent is generally added to such detergents.
The water-dilutable binders used in the production of - paints and lacquers, for example water-based lacquers, also show a tendency towards pronounced foaming. In this case, foam can be formed during the actual mixing of the ingredi-ents, i.e. during grinding of the lacquer by stirring in air, with the result that the particular machines used can only be filled and operated with a fraction of the avail-able volume. In this field, too, there is an urgent need , ~ ~ "~ -~ Y J, 1 for defoaming agents and deaerators [Goldschmidt, Inform.
66, 9 (19~g)]-Another field where antifoam agents are used is thetreatment of wastewater in sewage treatment plants. In the activated sludge process, for example, air is introduced into the wastewater to ensure thorough mixing and contac-ting of the soil particles with the microorganisms [ChiuZ
25, 87 (1991)]. The foam formed in this case is often protein foam and is therefore particularly stable. Instead of sedimenting, the solids are undesirably fixed in and to the foam lamellae which makes the treated sludge difficult to separate.
There has been no shortage of attempts in the past to provide corresponding antifoam agents for the complex field of foam regulation.
For example, it is known from DE-Os 14 67 613 and DE-oS 22 42 541 that ketones are suitable as foam inhibitors in soap-containing detergents. In addition, EP 0 3~4 339 A~ describes dispersions containing fatty ketones as active substances and mineral oils or Guerbet alcohols as carrier liquids. However, the defoaming effect of such systems`is inadequate for many applications.
Accordingly, the problem addressed by the present invention was to provide new antifoam agents which would be free from the disadvantages described above.
Description of the Inventio~
The present invention relates to antifoam agents containing a) as carrier oil, dialkyl ethers corresponding to formula (I):
R1-O-R2 (I) in which R1 and R2 independently of one another represent linear or branched C~l2 alkyl radicals, b) wax-like active substances having melting points in the range from 60 to 160 C and c) stabilizers.
It has surprisingly heen found that antifoam agents containing dialkyl ethers as carrier oils have an improved defoaming effect compared with known products and can be universally used. In addition, the antifoam agents accord-ing to the invention are distinguished by high stability to alkalis, active chlorine and active oxygen and are readily biodegradable which satisfies the general requirement for ecologically safe products.
Dialkyl ethers are known compounds which may be obtained by the relevant methods of preparative organic chemistry. In the known WILLIAMSON ether synthesis, dialkyl ethers may be prepared, for example, from fatty alcohols by reaction with alkyl chlorides in the presence of alkali metal hydroxides.
Dialkyl ethers which may be used in accordance with the invention correspond to formula (I) in which R~ and R2 independently of one another represent linear or branched 6-12 alkyl radicals. Antifoam agents having particularly favorable properties are obtained where dialkyl ethers corresponding to formula (I), in which R1 and R~ independ-ently of one another represent C8l0 alkyl radicals, are usedas carrier oils.
Typical examples of such dialkyl ethers are di-n-hexyl ether, di-2-ethylhexyl ether, hexyloctyl ether, di-n-decyl ether, di-n-lauryl ether and, in particular, di-n-octyl ether and the assymetrical compounds derived therefrom.
Suitable defoaming agent~ (component b) are substances of wax-like consistency which have a melting point in the range from 60 to 160-C. Typical examples of sllch substan-ces are:
bl) fatty ketones, b2) wax esters, B3) polyethylene waxes, b4~ paraffin hydrocarhons, b5) fatty acid amides, b6) hydrophobicized silicas, b7) long-chain fatty alcohols and/or b8) long-chain Guerbet alcohols.
15The active substances described above are dispersed in the liquid carrier (the dialkyl ethers) which results in an improved antifoam ef~ect~
Fatty ke~ones ( component bl) are known substances which may be obtained by the relevant methods of prepara-tive organic chemistry. They are produced, for example, - from fatty acid magnesium salts which are pyrolyzed at temperatures above 300-C with elimination of CO2 and water ~DE-OS 25 53 900]. The fatty ketones to be used in accord-ance with the invention correspond to formula (II):
R3-Co-R~ (II) , in which R3 and R4 independently of one another represent linear or branched hydrocarbon radicals containing 11 to 25 carbon atoms and 0 or 1 double bond. Fatty ketones corre-sponding to formula (II), in which R3 and R~ represent Cl622 alkyl radicals, are preferred. Typical examples are fatty ketones obtained by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, arachic acid, gadoleic acid, behenic acid or erucic acid. Stearone (18-pentatriacontanon~) is preferably used.
Wax ~ters (component b2) are the condensation prod-ucts of long-chain fatty acids with long-chain fatty alcohols. Wax esters suitable for use in accordance with the invention correspond to formula (III~:
RsC0-OR6 ~III) in which R5Co is an optionally hydroxy-substituted acyl radical containing 16 to 34 carbon atoms and 0, 1, 2 or 3 double bonds and R6 is an aliphatic hydrocarbon radical containing 16 to 34 car~on atoms and 0, 1, 2 or 3 double bonds. Typical examples are esters of palmitic acid, palmitoleic acid; 9-hydroxystearic acid, ricinoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid, erucic acid, arachidonic acid, clupanodonic acid, lignoceric acid or montanic acid with the correspond-ing alcohols. The acid and alcohol components of the ester may be the same or different in regard to the number of carbon atoms present therein and the number of double bonds. 9-Hydroxystearyl behenate is preferably used.
Polymerization products of ethylene with an average molecular weight of 300 to 3000 and preferably 1000 to 2500 may be used as the polyether waxes (component b3).
Paraffi~ hydrocarbons (component b4) are technical mixtures of substantially linear alkanes containing 20 to 40 carbon atoms.
Fatty acid amides (component bS) suitable for use in accordance with the invention are condensation products of fatty acids containing 12 to 22 carbon atoms and 0 or 1 double bond with polyamines. Typical examples are the amides of lauric acid, myristic acid, palmitic acid, pa]mitoleic acid, stearic acid, oleic acid, elaidic acid, ~, ,.. .L ~ ~
petroselic acid, arachic acid, gadoleic acid, behenic acid or erucic acid with polyamines, for example ethylenedi-amine, ethylenetriamine, diethylenediamine, dipropylene-diamine, triethylenediamine or hexamethylenediamine. The S polyamines may be completely acylated or may still contain free amine functions. Ethylenediamine-bis-stearyl amide is preferably used.
~ ydrophobicized ~ilicas (component b6), which may be used in accordance with the invention, are known reaction ~O products of silicas with silanes, fatty acids or quaternary ammonium compounds. Silicas hydrophobicized with dichloro-dimethyl silane are preferably used [Roempp Chemie Lexikon, Thieme Yerlag, 9th Edition, 1~89, paga 65].
Long-chai~ fatty alcohols (component b7) are primary linear alcohols corresponding to formula tIV):
R70H ~IV) in which R7 is a Cl634 alkyl radical. Typical examples are cetyl alcohol, stearyl alcohol, arachyl alcohol, behenyl alcohol or montan alcohol. Technical mixtures of Cl822 alcohols are preferred.
Long-chain Guerbet alcohols (component b8) are primary branched alcohols which may be obtained by the self-conden-sation of fatty alcohols in the presence of alkalis ~Soap,Cosm., Chem. ~p~c. 53 (1987)]. Self-condensation products of C~622 fatty alcohols may be used for the purposes of the invention, C3236 Guerbet alcohols preferably being used.
The dispersions differ in their viscosity according to their active substance content. With high active substance concentrations, their viscosity ~ay be too high for a particular application. In this case, stabilizers would have to be added to reduce their viscosity. Conversely, dispersions having low active substance contents are disting~ished by unfavorably low viscosities which would ., ,. ~ t/ ~ ~, 1 result in unwanted sedimentation in the dispersion. In this case, it is advisable to add thickening stabilizers to the dispersions.
Suitable stabilizer~ (component c) are substances belonging to any of the following classes:
cl) alkaline earth metal and/or aluminium soaps, c2) hydrophobicized silicas c3) layer silicates;
c4) tackifiers and c5) nonionic surfactants.
The stabilizers cl) to c4) are thickeners while the stabilizers c5) are viscosity-reducing agents.
Alkaline earth metal and/or aluminium ~oap~ (component cl) are the calcium, magnesium, strontium, barium and/or aluminium salts of Cl22z fatty acids, of which typical examples are the optionally basic calcium, magnesium and/or aluminium salts of lauric acid, myristic acid, palmitic acid, stearic acid or behenic acid. Calcium distearate, magnesium distearate and/or aluminium hydroxydistearate are preferably used.
Suitable hydrophobicized ~ilicas (component c2) are reaction products of silicas with silanes, fatty acids or quaternary ammonium compounds. The observations made in b6) apply to the particular choice.
Layer silicates (component c3) are understood in the following to be salts of elements of the 1st to 3rd main groups of the periodic system which have a crystal lattice with Sio4 tetrahedrons linked in one plane ("layer lattice") [Ullmanns Enzyklopadi~ der technischen Chemie, 4th Edition, Vol. 2~, 36s (1984)]. Typical examples are talcum Mg3[(0H)2¦Si~0l0] and kaolinite Al 4 ~ ( OH) 8 I S i 410 ] ' Montmorillonite Al2~(OH) 21 Si~olo] and the r group of bentonites [~en~. 8urf. Det., 25, 1~ tl988)] have proved to be particularly effective stabilizers and are preferably used.
Tackifier~ (component c4) are understood to be coagu-lants and thickeners, such as for example polyacrylates, polyalkyl acrylates, rubber and/or polyisobutylenes having an average molecular weight of 10,000 to 100,000.
Suitable nonio~ic surfactant~ (component c5) are alkyl glycosides, mixed ethers and/or adducts of ethylene oxide with branched alcohols.
Suitable alkyl glycoside~ are compounds corresponding to formula (V): .
R8-O-lG) (V) in which G is the symbol for a glycose unit derived from a Cs or C6 sugar, x is a number of 1 to 10 and R~ is an aliphatic hydrocarbon radical containing 6 to 22 carbon :20 atoms and 0, 1, 2 or 3 double bonds. G is preferably a glucose unit while x is preferably a number of 1.1 to 1.6.
The production of the alkyl glycosides is described, for example, in DE 37 23 826 A1.
~: Suitable mixed ether~ are reaction products of fatty alcohol polyglycol ethers with alkyl chlorides correspond-ing to formula (VI) Rll I
30 R9-(OCH2CH)n-O-Rl (VI) :
in which R~ is an aliphatic hydrocarbon radical containing 6 to 22 carbon atoms and 0, l, 2 or 3 double bonds, Rl is a C14 alkyl radical or a benzyl radical, R1l is hydrogen or a methyl group and n is a number of 1 to 20. A process for .
their production is described, for example, in EP O 322 781 A2.
Adducts of othyle~ oxid~ with branched ~lcoh~ls are understood to be adducts of on average l to 20 and prefer-ably 2 to lO mole of ethylene oxide with C1236 Guerbetalcohols. Also suitable are E0 adducts as technical alcohol mixtures which predominantly, but not exclusively, contain branched components, such as for example oxo-alcohols from ~oelen's oxo synthesis.
The antifoam agents may contain the dialkyl ethers in quantities of 40 to 98% by weight and, more particularly, in quantities of 60 to 95% by weight, based on the antifoam agent. The active substances may be present in quantities of 1 to 50~ ~y weight, preferably l to 20% by weight and, more preferably, 5 to 10~ by weight, based on the antifoam agent.
- The choice of the stabilizers is governed by the active substance concentration and hence by the viscosity of the antifoam agents. Low-viscosity antifoam agents with active substance contents of 1 to 20% by weight may contain the stabiliæers cl) to c4~ in quantities of 0.1 to 10% by weight and preferably in quantities of 1 to S% by weight.
By contrast, for high-viscosity antifoam agents containing the active su~stances in concentrations of 20.1 to 50~ by weight, it is advisable to add stabilizers from group cS) in quantities of 0.1 to 20% by weight and preferably in quantities of 1 to lS% by weight. All the quantities mentioned are based on the antifoam agents.
The antifoam agents according to the invention may be produced purely mechanically by simple stirring of the components at room temperature; no chemical reaction takes place. Equally, a mixture of all the components may be initially heated beyond the melting point of the component melting at the highest temperature and the initially hot clear solution left gradually to cool.
; .. 1 9 ~
Indu~trial application~
The antifoam agents according to the inventi~n show a foam-suppressing or foam-regulating effect, even on par-ticularly stable foams and even at relatively high tempera-tures. They are stable to alkalis, active chlorine and active oxygen and, in addition, are readily biodegradable.
Accordingly, the present invention relates to the use of antifoam agents according to the invention as additives for preparations for cleaning hard surfaces. Examples of such preparations include machine dishwashing detergents, automatic bottle washing detergents, CIP (cleaning in place) detergents and preparations for degreasing metal surfaces in automotive body construction. The antifoam agents may be added to the cleaning preparations in quan-tities of 0.1 to 10% by weight and preferably in quantities of 1 to 5% by weight, based on the detergent/cleaning preparation.
In addition, the antifoam agents according to the invention are also suitable as defoaming and deaerating agents in the production of paints and lacquers and as defoaming agents in the treatment of wastewater from sewage treatment plants and from industrial processes, for example metalworking or papermaking.
- 25 The following Examples are intended to illustrate the in-ention without limiting it in any way.
:
.
Example~
I. Formulations u~ed Table 1 Formulations, quantities in % by weight -Components Formulation A B C D E F G H I J
Carrier oils:
Di-n-octyl ether 80 90 90 90 90 90 94 90 90 Active substances:
Stearone 8 ~ 8 HStB - - 8 - - - - - - -PED 522 - - - 8 - - - ~ - -Wax C - - - - 8 - - - - -Paraffin 68/70 - - - - - 8 - - - -Aerosil R972 - - - - - - ~ - - -StenoI 1822 - ~ - 8 Stabilizers:
Mg-Siel 1 - 2 - 2 2 2 2 2 2 Alugel 30 DF 1 2 - - - - - - - -* Formulations A to I correspond to the invention while formulation J is a comparison formulation.
LeqQnd:
G20 : Guerbet alcohol containing 20 carbon atoms HSt~ : 9-Hydroxystearyl behenate PED 522 : Polyethylene wax (Hoechst) Wax C : Ethylenediamine-bis-Stearyl amide (Hoechst~
Paraffin 68/70 : Paraffin mixture, melting point 68-70-C
AerosilR972 : Dimethyldichlorosilane-hydrophobicized silica ~Degussa) Stenol1822 : Fatty alcohol mixture containing 18 to 22 carbon atoms (Henkel KGaA) G32/36 : Guerbet alcohol mixture containing 32 to 36 carbon atoms Mg-Siel : Magnesium distearate (Barlocher) Alugel~3ODF : Aluminium hydroxydistearate (Barlocher) lS II. ~pplication ExampIe~
ExamPles l to 8:
Description of the test method. 1 Egg (about 50 g) was broken, diluted with 450 g of water (16-d) and whisked for
Field of the Invention This inve~tion relates to antifoam agents containing dialkyl ethers, active substances and stabilizers and to their use as additives for cleaning products, in the production of paints and lacquers and for the treatment of wastewater in sewage treatment plants and from industrial processes such as, for example, metalworking or paper-making.
Prior Art 1~
For many industrial processes, the foaming associated with the use of surface-active substances is a serious problem. For example, powder-form or liquid alkaline detergents containing active chlorine or acti~e oxygen lS compounds in addition to surfactants, builders, alkali metal silicates, carbonates and/or hydroxides are used in domestic dishwashing machines and in the industrial washing of beer bottles and milk bottles. To prevent excessive foaming, an antifoam agent is generally added to such detergents.
The water-dilutable binders used in the production of - paints and lacquers, for example water-based lacquers, also show a tendency towards pronounced foaming. In this case, foam can be formed during the actual mixing of the ingredi-ents, i.e. during grinding of the lacquer by stirring in air, with the result that the particular machines used can only be filled and operated with a fraction of the avail-able volume. In this field, too, there is an urgent need , ~ ~ "~ -~ Y J, 1 for defoaming agents and deaerators [Goldschmidt, Inform.
66, 9 (19~g)]-Another field where antifoam agents are used is thetreatment of wastewater in sewage treatment plants. In the activated sludge process, for example, air is introduced into the wastewater to ensure thorough mixing and contac-ting of the soil particles with the microorganisms [ChiuZ
25, 87 (1991)]. The foam formed in this case is often protein foam and is therefore particularly stable. Instead of sedimenting, the solids are undesirably fixed in and to the foam lamellae which makes the treated sludge difficult to separate.
There has been no shortage of attempts in the past to provide corresponding antifoam agents for the complex field of foam regulation.
For example, it is known from DE-Os 14 67 613 and DE-oS 22 42 541 that ketones are suitable as foam inhibitors in soap-containing detergents. In addition, EP 0 3~4 339 A~ describes dispersions containing fatty ketones as active substances and mineral oils or Guerbet alcohols as carrier liquids. However, the defoaming effect of such systems`is inadequate for many applications.
Accordingly, the problem addressed by the present invention was to provide new antifoam agents which would be free from the disadvantages described above.
Description of the Inventio~
The present invention relates to antifoam agents containing a) as carrier oil, dialkyl ethers corresponding to formula (I):
R1-O-R2 (I) in which R1 and R2 independently of one another represent linear or branched C~l2 alkyl radicals, b) wax-like active substances having melting points in the range from 60 to 160 C and c) stabilizers.
It has surprisingly heen found that antifoam agents containing dialkyl ethers as carrier oils have an improved defoaming effect compared with known products and can be universally used. In addition, the antifoam agents accord-ing to the invention are distinguished by high stability to alkalis, active chlorine and active oxygen and are readily biodegradable which satisfies the general requirement for ecologically safe products.
Dialkyl ethers are known compounds which may be obtained by the relevant methods of preparative organic chemistry. In the known WILLIAMSON ether synthesis, dialkyl ethers may be prepared, for example, from fatty alcohols by reaction with alkyl chlorides in the presence of alkali metal hydroxides.
Dialkyl ethers which may be used in accordance with the invention correspond to formula (I) in which R~ and R2 independently of one another represent linear or branched 6-12 alkyl radicals. Antifoam agents having particularly favorable properties are obtained where dialkyl ethers corresponding to formula (I), in which R1 and R~ independ-ently of one another represent C8l0 alkyl radicals, are usedas carrier oils.
Typical examples of such dialkyl ethers are di-n-hexyl ether, di-2-ethylhexyl ether, hexyloctyl ether, di-n-decyl ether, di-n-lauryl ether and, in particular, di-n-octyl ether and the assymetrical compounds derived therefrom.
Suitable defoaming agent~ (component b) are substances of wax-like consistency which have a melting point in the range from 60 to 160-C. Typical examples of sllch substan-ces are:
bl) fatty ketones, b2) wax esters, B3) polyethylene waxes, b4~ paraffin hydrocarhons, b5) fatty acid amides, b6) hydrophobicized silicas, b7) long-chain fatty alcohols and/or b8) long-chain Guerbet alcohols.
15The active substances described above are dispersed in the liquid carrier (the dialkyl ethers) which results in an improved antifoam ef~ect~
Fatty ke~ones ( component bl) are known substances which may be obtained by the relevant methods of prepara-tive organic chemistry. They are produced, for example, - from fatty acid magnesium salts which are pyrolyzed at temperatures above 300-C with elimination of CO2 and water ~DE-OS 25 53 900]. The fatty ketones to be used in accord-ance with the invention correspond to formula (II):
R3-Co-R~ (II) , in which R3 and R4 independently of one another represent linear or branched hydrocarbon radicals containing 11 to 25 carbon atoms and 0 or 1 double bond. Fatty ketones corre-sponding to formula (II), in which R3 and R~ represent Cl622 alkyl radicals, are preferred. Typical examples are fatty ketones obtained by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, arachic acid, gadoleic acid, behenic acid or erucic acid. Stearone (18-pentatriacontanon~) is preferably used.
Wax ~ters (component b2) are the condensation prod-ucts of long-chain fatty acids with long-chain fatty alcohols. Wax esters suitable for use in accordance with the invention correspond to formula (III~:
RsC0-OR6 ~III) in which R5Co is an optionally hydroxy-substituted acyl radical containing 16 to 34 carbon atoms and 0, 1, 2 or 3 double bonds and R6 is an aliphatic hydrocarbon radical containing 16 to 34 car~on atoms and 0, 1, 2 or 3 double bonds. Typical examples are esters of palmitic acid, palmitoleic acid; 9-hydroxystearic acid, ricinoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid, erucic acid, arachidonic acid, clupanodonic acid, lignoceric acid or montanic acid with the correspond-ing alcohols. The acid and alcohol components of the ester may be the same or different in regard to the number of carbon atoms present therein and the number of double bonds. 9-Hydroxystearyl behenate is preferably used.
Polymerization products of ethylene with an average molecular weight of 300 to 3000 and preferably 1000 to 2500 may be used as the polyether waxes (component b3).
Paraffi~ hydrocarbons (component b4) are technical mixtures of substantially linear alkanes containing 20 to 40 carbon atoms.
Fatty acid amides (component bS) suitable for use in accordance with the invention are condensation products of fatty acids containing 12 to 22 carbon atoms and 0 or 1 double bond with polyamines. Typical examples are the amides of lauric acid, myristic acid, palmitic acid, pa]mitoleic acid, stearic acid, oleic acid, elaidic acid, ~, ,.. .L ~ ~
petroselic acid, arachic acid, gadoleic acid, behenic acid or erucic acid with polyamines, for example ethylenedi-amine, ethylenetriamine, diethylenediamine, dipropylene-diamine, triethylenediamine or hexamethylenediamine. The S polyamines may be completely acylated or may still contain free amine functions. Ethylenediamine-bis-stearyl amide is preferably used.
~ ydrophobicized ~ilicas (component b6), which may be used in accordance with the invention, are known reaction ~O products of silicas with silanes, fatty acids or quaternary ammonium compounds. Silicas hydrophobicized with dichloro-dimethyl silane are preferably used [Roempp Chemie Lexikon, Thieme Yerlag, 9th Edition, 1~89, paga 65].
Long-chai~ fatty alcohols (component b7) are primary linear alcohols corresponding to formula tIV):
R70H ~IV) in which R7 is a Cl634 alkyl radical. Typical examples are cetyl alcohol, stearyl alcohol, arachyl alcohol, behenyl alcohol or montan alcohol. Technical mixtures of Cl822 alcohols are preferred.
Long-chain Guerbet alcohols (component b8) are primary branched alcohols which may be obtained by the self-conden-sation of fatty alcohols in the presence of alkalis ~Soap,Cosm., Chem. ~p~c. 53 (1987)]. Self-condensation products of C~622 fatty alcohols may be used for the purposes of the invention, C3236 Guerbet alcohols preferably being used.
The dispersions differ in their viscosity according to their active substance content. With high active substance concentrations, their viscosity ~ay be too high for a particular application. In this case, stabilizers would have to be added to reduce their viscosity. Conversely, dispersions having low active substance contents are disting~ished by unfavorably low viscosities which would ., ,. ~ t/ ~ ~, 1 result in unwanted sedimentation in the dispersion. In this case, it is advisable to add thickening stabilizers to the dispersions.
Suitable stabilizer~ (component c) are substances belonging to any of the following classes:
cl) alkaline earth metal and/or aluminium soaps, c2) hydrophobicized silicas c3) layer silicates;
c4) tackifiers and c5) nonionic surfactants.
The stabilizers cl) to c4) are thickeners while the stabilizers c5) are viscosity-reducing agents.
Alkaline earth metal and/or aluminium ~oap~ (component cl) are the calcium, magnesium, strontium, barium and/or aluminium salts of Cl22z fatty acids, of which typical examples are the optionally basic calcium, magnesium and/or aluminium salts of lauric acid, myristic acid, palmitic acid, stearic acid or behenic acid. Calcium distearate, magnesium distearate and/or aluminium hydroxydistearate are preferably used.
Suitable hydrophobicized ~ilicas (component c2) are reaction products of silicas with silanes, fatty acids or quaternary ammonium compounds. The observations made in b6) apply to the particular choice.
Layer silicates (component c3) are understood in the following to be salts of elements of the 1st to 3rd main groups of the periodic system which have a crystal lattice with Sio4 tetrahedrons linked in one plane ("layer lattice") [Ullmanns Enzyklopadi~ der technischen Chemie, 4th Edition, Vol. 2~, 36s (1984)]. Typical examples are talcum Mg3[(0H)2¦Si~0l0] and kaolinite Al 4 ~ ( OH) 8 I S i 410 ] ' Montmorillonite Al2~(OH) 21 Si~olo] and the r group of bentonites [~en~. 8urf. Det., 25, 1~ tl988)] have proved to be particularly effective stabilizers and are preferably used.
Tackifier~ (component c4) are understood to be coagu-lants and thickeners, such as for example polyacrylates, polyalkyl acrylates, rubber and/or polyisobutylenes having an average molecular weight of 10,000 to 100,000.
Suitable nonio~ic surfactant~ (component c5) are alkyl glycosides, mixed ethers and/or adducts of ethylene oxide with branched alcohols.
Suitable alkyl glycoside~ are compounds corresponding to formula (V): .
R8-O-lG) (V) in which G is the symbol for a glycose unit derived from a Cs or C6 sugar, x is a number of 1 to 10 and R~ is an aliphatic hydrocarbon radical containing 6 to 22 carbon :20 atoms and 0, 1, 2 or 3 double bonds. G is preferably a glucose unit while x is preferably a number of 1.1 to 1.6.
The production of the alkyl glycosides is described, for example, in DE 37 23 826 A1.
~: Suitable mixed ether~ are reaction products of fatty alcohol polyglycol ethers with alkyl chlorides correspond-ing to formula (VI) Rll I
30 R9-(OCH2CH)n-O-Rl (VI) :
in which R~ is an aliphatic hydrocarbon radical containing 6 to 22 carbon atoms and 0, l, 2 or 3 double bonds, Rl is a C14 alkyl radical or a benzyl radical, R1l is hydrogen or a methyl group and n is a number of 1 to 20. A process for .
their production is described, for example, in EP O 322 781 A2.
Adducts of othyle~ oxid~ with branched ~lcoh~ls are understood to be adducts of on average l to 20 and prefer-ably 2 to lO mole of ethylene oxide with C1236 Guerbetalcohols. Also suitable are E0 adducts as technical alcohol mixtures which predominantly, but not exclusively, contain branched components, such as for example oxo-alcohols from ~oelen's oxo synthesis.
The antifoam agents may contain the dialkyl ethers in quantities of 40 to 98% by weight and, more particularly, in quantities of 60 to 95% by weight, based on the antifoam agent. The active substances may be present in quantities of 1 to 50~ ~y weight, preferably l to 20% by weight and, more preferably, 5 to 10~ by weight, based on the antifoam agent.
- The choice of the stabilizers is governed by the active substance concentration and hence by the viscosity of the antifoam agents. Low-viscosity antifoam agents with active substance contents of 1 to 20% by weight may contain the stabiliæers cl) to c4~ in quantities of 0.1 to 10% by weight and preferably in quantities of 1 to S% by weight.
By contrast, for high-viscosity antifoam agents containing the active su~stances in concentrations of 20.1 to 50~ by weight, it is advisable to add stabilizers from group cS) in quantities of 0.1 to 20% by weight and preferably in quantities of 1 to lS% by weight. All the quantities mentioned are based on the antifoam agents.
The antifoam agents according to the invention may be produced purely mechanically by simple stirring of the components at room temperature; no chemical reaction takes place. Equally, a mixture of all the components may be initially heated beyond the melting point of the component melting at the highest temperature and the initially hot clear solution left gradually to cool.
; .. 1 9 ~
Indu~trial application~
The antifoam agents according to the inventi~n show a foam-suppressing or foam-regulating effect, even on par-ticularly stable foams and even at relatively high tempera-tures. They are stable to alkalis, active chlorine and active oxygen and, in addition, are readily biodegradable.
Accordingly, the present invention relates to the use of antifoam agents according to the invention as additives for preparations for cleaning hard surfaces. Examples of such preparations include machine dishwashing detergents, automatic bottle washing detergents, CIP (cleaning in place) detergents and preparations for degreasing metal surfaces in automotive body construction. The antifoam agents may be added to the cleaning preparations in quan-tities of 0.1 to 10% by weight and preferably in quantities of 1 to 5% by weight, based on the detergent/cleaning preparation.
In addition, the antifoam agents according to the invention are also suitable as defoaming and deaerating agents in the production of paints and lacquers and as defoaming agents in the treatment of wastewater from sewage treatment plants and from industrial processes, for example metalworking or papermaking.
- 25 The following Examples are intended to illustrate the in-ention without limiting it in any way.
:
.
Example~
I. Formulations u~ed Table 1 Formulations, quantities in % by weight -Components Formulation A B C D E F G H I J
Carrier oils:
Di-n-octyl ether 80 90 90 90 90 90 94 90 90 Active substances:
Stearone 8 ~ 8 HStB - - 8 - - - - - - -PED 522 - - - 8 - - - ~ - -Wax C - - - - 8 - - - - -Paraffin 68/70 - - - - - 8 - - - -Aerosil R972 - - - - - - ~ - - -StenoI 1822 - ~ - 8 Stabilizers:
Mg-Siel 1 - 2 - 2 2 2 2 2 2 Alugel 30 DF 1 2 - - - - - - - -* Formulations A to I correspond to the invention while formulation J is a comparison formulation.
LeqQnd:
G20 : Guerbet alcohol containing 20 carbon atoms HSt~ : 9-Hydroxystearyl behenate PED 522 : Polyethylene wax (Hoechst) Wax C : Ethylenediamine-bis-Stearyl amide (Hoechst~
Paraffin 68/70 : Paraffin mixture, melting point 68-70-C
AerosilR972 : Dimethyldichlorosilane-hydrophobicized silica ~Degussa) Stenol1822 : Fatty alcohol mixture containing 18 to 22 carbon atoms (Henkel KGaA) G32/36 : Guerbet alcohol mixture containing 32 to 36 carbon atoms Mg-Siel : Magnesium distearate (Barlocher) Alugel~3ODF : Aluminium hydroxydistearate (Barlocher) lS II. ~pplication ExampIe~
ExamPles l to 8:
Description of the test method. 1 Egg (about 50 g) was broken, diluted with 450 g of water (16-d) and whisked for
2 minutes in an electrical mixer. 100 g of the resulting emulsion was introduced into a 2000 ml capacity double-walled measuring cylinder, made up to a volume of 500 ml with water having a hardness of 16-d and heated to 50-C.
After the test temperature had been reached, quantities of 0.2 ml of the antifoam agents according to formulations A
to H were added to the mixture. Using a laboratory flow inducer, the solution was taken in from the bottom of the measuring cylinder through a glass tube. The liquid was returned through a second tube of which the lower end was arranged level with the top edge of the measuring cylinder.
The liquid was circulated at a rate of 4 l/minut~ and fell back into the measuring cylinder with generation of foam.
The volumes which had formed from foam and liquid were read off after 0.5 to 30 minutes. The results are set out in 3S Table 2.
~ j .' L!~
Table 2: Foam inhibition of fresh egg Ex- Form- Volume o~ liquid + foam phase (ml) after ample ula minutes tion 0 0.5 1 2 3 5 10 20 30
After the test temperature had been reached, quantities of 0.2 ml of the antifoam agents according to formulations A
to H were added to the mixture. Using a laboratory flow inducer, the solution was taken in from the bottom of the measuring cylinder through a glass tube. The liquid was returned through a second tube of which the lower end was arranged level with the top edge of the measuring cylinder.
The liquid was circulated at a rate of 4 l/minut~ and fell back into the measuring cylinder with generation of foam.
The volumes which had formed from foam and liquid were read off after 0.5 to 30 minutes. The results are set out in 3S Table 2.
~ j .' L!~
Table 2: Foam inhibition of fresh egg Ex- Form- Volume o~ liquid + foam phase (ml) after ample ula minutes tion 0 0.5 1 2 3 5 10 20 30
3 C 500 620 640 700 760 860 1100 1160 1260
4 D 500 600 700 780 880 1140 2000 E 500 580 5~0 5~0 600 620 700 1200 2000 1 5 ~
ExamPle 9, Comparison Example 1:
1 Egg (about 50 g) was broken, diluted with 450 g of water having a hardness of 16-d and whisked for 2 minutes in an electrical mixer. 100 g of the resulting emulsion was introduced into a 2000 ml capacity measuring cylinder and made up to a volume of 500 ml with water (16-d) at room temperature. 2000 ppm (based on the suspension) of a test antifoam agent (dodecyl benzenesulfonate Na salt) were added to the mixture. The suspension was foamed to a volume of 2000 ml by means of the same pump circulation system as in Examples 1 to 8. Quantities of 0.5 ml of ! ' antifoam agents I and J were then added and the liquid was circulated at a rate of 4 l/minute. The volumes which had formed from foam and liquid were read off after 0.5 to 30 minutes. The results are set out in Table 3.
Table 3: Foam inhibition of foamed fresh egg -Ex- Form- Volume of liquid + foam phase (mi ) after ample ula- minutes _ tion 0 0. 5 1 2 3 5 lo 20 30 Cl J 2000 640 640 700 760 900 1100 2000
ExamPle 9, Comparison Example 1:
1 Egg (about 50 g) was broken, diluted with 450 g of water having a hardness of 16-d and whisked for 2 minutes in an electrical mixer. 100 g of the resulting emulsion was introduced into a 2000 ml capacity measuring cylinder and made up to a volume of 500 ml with water (16-d) at room temperature. 2000 ppm (based on the suspension) of a test antifoam agent (dodecyl benzenesulfonate Na salt) were added to the mixture. The suspension was foamed to a volume of 2000 ml by means of the same pump circulation system as in Examples 1 to 8. Quantities of 0.5 ml of ! ' antifoam agents I and J were then added and the liquid was circulated at a rate of 4 l/minute. The volumes which had formed from foam and liquid were read off after 0.5 to 30 minutes. The results are set out in Table 3.
Table 3: Foam inhibition of foamed fresh egg -Ex- Form- Volume of liquid + foam phase (mi ) after ample ula- minutes _ tion 0 0. 5 1 2 3 5 lo 20 30 Cl J 2000 640 640 700 760 900 1100 2000
Claims (13)
New claims
1. Antifoam agents containing a) dialkyl ethers corresponding to formula (I):
R1-O-R2 (I) in which R1 and R2 independently of one another represent linear or branched C8-10 alkyl radicals, b) fatty ketones correspond to formula (II):
R3-CO-R4 (II) in which R3 and R4 independently of one another represent linear or branched hydrocarbon radicals containing 11 to 25 carbon atoms and 0 or 1 double bond, and c) stabilizers.
R1-O-R2 (I) in which R1 and R2 independently of one another represent linear or branched C8-10 alkyl radicals, b) fatty ketones correspond to formula (II):
R3-CO-R4 (II) in which R3 and R4 independently of one another represent linear or branched hydrocarbon radicals containing 11 to 25 carbon atoms and 0 or 1 double bond, and c) stabilizers.
2. Antifoam agents as claimed in claim 1, characterized in that the stabilizers are selected fro the group con-sisting of c1) alkaline earth metal and/or aluminum soaps, c2) hydrohpobicized silicas, c3) layer silicates and c4) tackifiers.
3. Antifoam agents as claimed in claims 1 and 2, charac-terized in that the alkaline earth metal and/or aluminum soaps are calcium, magnesium, strontium, barium and/or aluminium salts of C12-22 fatty acids.
4. Antifoam agents as claimed in claims 1 and 2, charac-terized in that the hydrophobicized silicas are reaction products of silicas with silanes, fatty acids or quaternary ammonium compounds.
5. Antifoam agents as claimed in claims 1 and 2, charac-terized in that the layer silicates are bentonites.
6. Antifoam agents as claimed in claims 1 and 2, charac-terized in that the tackifiers are polyacrylates, polyalkyl acrylates, rubber and/or polyisobutylenes.
7. Antifoam agents as claimed in claims 1 to 6, charac-terized in that the dialkyl ethers are present in quan-tities of 40 to 90% by weight, based on the antifoam agent.
8. Antifoam agents as claimed in claims 1 to 7, charac-terized in that the active substances are present in quantities of 1 to 50% by weight, based on the antifoam agent.
9. Antifoam agents as claimed in claims 1 to 8, charac-terized in that the stabilizers are present in quantities of 0.1 to 10% by weight, based on the antifoam agent.
10. The use of the antifoam agents claimed in claims 1 to 9 as additives for preparations for cleaning hard surfaces.
11. The use claimed in claim 10, characterized in that the antifoam agents are added to the cleaning preparations in quantities of 0.1 to 10% by weight, based on the cleaning preparation.
12. The use of the antifoam agents claimed in claims 1 to 9 as defoaming and deaerating agents in the production of paints and lacquers.
13. The use of the antifoam agents claimed in claims 1 to 9 as defoaming agents for the treatment of wastewater in sewage treatment plants.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4121147A DE4121147A1 (en) | 1991-06-26 | 1991-06-26 | ANTI-FOAM AGENTS |
| DEP4121147.2 | 1991-06-26 | ||
| PCT/EP1992/001374 WO1993000144A1 (en) | 1991-06-26 | 1992-06-17 | Anti-foaming agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2112491A1 true CA2112491A1 (en) | 1993-01-07 |
Family
ID=6434810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002112491A Abandoned CA2112491A1 (en) | 1991-06-26 | 1992-06-17 | Anti-foam agents |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0591318A1 (en) |
| JP (1) | JPH06508548A (en) |
| AU (1) | AU2151992A (en) |
| CA (1) | CA2112491A1 (en) |
| DE (1) | DE4121147A1 (en) |
| WO (1) | WO1993000144A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103596655A (en) * | 2011-06-03 | 2014-02-19 | 圣诺普科有限公司 | Defoaming agent |
| CN113512901A (en) * | 2020-04-09 | 2021-10-19 | 江苏四新科技应用研究所股份有限公司 | Preparation method of fatty alcohol emulsion defoaming agent |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4313947A1 (en) * | 1993-04-28 | 1994-11-03 | Henkel Kgaa | Aqueous antifoam dispersions |
| US5874017A (en) * | 1996-08-12 | 1999-02-23 | Geo Specialty Chemicals, Inc. | Use of microcrystalline wax and low foaming emulsifiers as defoamers |
| DE19854531A1 (en) * | 1998-11-26 | 2000-05-31 | Cognis Deutschland Gmbh | Defoamer granules with ether |
| FR2849856B1 (en) * | 2003-01-13 | 2005-03-25 | Cray Valley Sa | MATERIAL OR SATIN COATING COMPOSITIONS |
| JP4618429B2 (en) * | 2005-07-01 | 2011-01-26 | 三菱瓦斯化学株式会社 | Wet paint booth circulating water defoamer |
| DE102006057373B3 (en) * | 2006-12-04 | 2007-10-18 | Byk-Chemie Gmbh | Use of polyamide produced by a diamine and a dicarboxylic acid, in a formulation for defoaming aqueous media |
| DE102009013315A1 (en) * | 2009-03-18 | 2010-09-23 | Sasol Germany Gmbh | Coatings using dialkyl / dialkenyl ethers as water repellents, their use and metals provided with the coating |
| JP5211278B2 (en) * | 2009-10-09 | 2013-06-12 | サンノプコ株式会社 | Antifoam |
| JP2011101849A (en) * | 2009-11-11 | 2011-05-26 | San Nopco Ltd | Antifoaming agent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2902452A (en) * | 1954-10-26 | 1959-09-01 | Socony Vacuum Oil Co Inc | Aqueous glycol inhibited against foaming |
| US3492242A (en) * | 1966-11-30 | 1970-01-27 | Dixie Chem Products Co | Chemical defoaming composition |
| US4631145A (en) * | 1983-02-17 | 1986-12-23 | Amoco Corporation | Defoamer and antifoamer composition and method for defoaming aqueous fluid systems |
| DE3800483A1 (en) * | 1988-01-11 | 1989-07-20 | Henkel Kgaa | CHLORINE STABLE DEFOAMERS FOR CLEANING AGENTS CONTAINING ACTIVE CHLORINE, IN PARTICULAR DISHWASHING AGENTS |
| GB8813018D0 (en) * | 1988-06-02 | 1988-07-06 | Exxon Chemical Patents Inc | Defoamers & their use |
-
1991
- 1991-06-26 DE DE4121147A patent/DE4121147A1/en not_active Withdrawn
-
1992
- 1992-06-17 AU AU21519/92A patent/AU2151992A/en not_active Abandoned
- 1992-06-17 JP JP5501212A patent/JPH06508548A/en active Pending
- 1992-06-17 EP EP92913063A patent/EP0591318A1/en not_active Ceased
- 1992-06-17 CA CA002112491A patent/CA2112491A1/en not_active Abandoned
- 1992-06-17 WO PCT/EP1992/001374 patent/WO1993000144A1/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103596655A (en) * | 2011-06-03 | 2014-02-19 | 圣诺普科有限公司 | Defoaming agent |
| CN103596655B (en) * | 2011-06-03 | 2015-04-22 | 圣诺普科有限公司 | Defoaming agent |
| US9345991B2 (en) | 2011-06-03 | 2016-05-24 | San Nopco Ltd. | Defoaming agent |
| CN113512901A (en) * | 2020-04-09 | 2021-10-19 | 江苏四新科技应用研究所股份有限公司 | Preparation method of fatty alcohol emulsion defoaming agent |
| CN113512901B (en) * | 2020-04-09 | 2023-03-10 | 江苏四新科技应用研究所股份有限公司 | Preparation method of fatty alcohol emulsion defoaming agent |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1993000144A1 (en) | 1993-01-07 |
| AU2151992A (en) | 1993-01-25 |
| DE4121147A1 (en) | 1993-01-07 |
| JPH06508548A (en) | 1994-09-29 |
| EP0591318A1 (en) | 1994-04-13 |
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