CN1177630A - Granular foam-controlling agent - Google Patents
Granular foam-controlling agent Download PDFInfo
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- CN1177630A CN1177630A CN 97118648 CN97118648A CN1177630A CN 1177630 A CN1177630 A CN 1177630A CN 97118648 CN97118648 CN 97118648 CN 97118648 A CN97118648 A CN 97118648A CN 1177630 A CN1177630 A CN 1177630A
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- control agent
- foam control
- alkyl
- granular form
- silicone defoamer
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Abstract
Disclosed are particulate foam control agents and powdered detergents containing these agents. The foam control agents comprise a silicone antifoam and an alkyl saccharide deposited on a solid carrier. These materials are stable on extended storage in the detergent composition.
Description
The present invention relates to contain the foam Control agent in granular form of silicone, particularly those preparations are added to the foam Control agent in granular form that contains silicone in the powder detergent composition.
Containing the foam control agent of silicone defoamer and the foam control agent of particle form is that this specialty is known.Can occur controlling the problem that the bubble ability reduces when the foam control agent that contains silicone exists in powdered detergent for a long time also is that this specialty is known.
The various terms of settlement that overcome storage problem have been proposed.They comprise with silicone defoamer uses various materials.In this specialty, provided such examples of material.EP013028 proposes nonionic surface active agent, if any the ethoxylation aliphatic series C of 4～20 oxyethylenes
12-C
30Alcohols, and amides, thio-alcohol and the glycols of the induced by alkyl hydroxybenzene of ethoxylation, fatty acid, lipid acid, all has 4～20 carbon atoms and 5-15 oxyethylene is arranged at its hydrophobic part.
EP142910 discloses use water miscible or the dispersible organic carrier of water, it is 38-90 ℃ the first organic carrier component that organic carrier contains fusing point, and to be selected from hydrophilic-lipophilic balance be that 9.5-13.5 and fusing point are the second organic carrier component of nonionic surface active agent of 5-36 ℃ ethoxylation.The example of second organic support material comprises tallow alcohol, fatty acid ester, amides and the Polyvinylpyrolidone (PVP) of ethoxylation.
EP206522 discloses and used a kind of like this material, and is impermeable in buttery froth breaking active substance when this material is in the drying regime, but still can destroy when contacting with water.Its example comprises the material that can form the wax shape character of being interrupted coating, and such coating can make water pass through under wet condition.
EP210721 discloses lipid acid or the Fatty Alcohol(C12-C14 and C12-C18) that carbochain that 12-20 carbon atom arranged and fusing point are 45-80 ℃.Its example comprises stearic acid or stearyl alcohol.
Why can solve as for speaking of aforesaid method that a theory of storage stability is in the silicone defoamer, defoamer sealing or in conjunction with in the detergent powder that has reduced around the silicone polymer in the defoamer is distributed to.Such dispersion makes the density loss of silicone polymer in foam control agent; Under extreme case, can exhaust silicone polymer fully.This exhausts and can make the foam control agent inactivation.
Solid support material also is commonly used to prepare the foam control agent solid particulate, and these particles are easy to handle, and can be used as blending behind powder and remaining powder detergent composition.
In prior art, propose to comprise water miscible, water-insoluble and the dispersible material of water, as Sulfates, carbonate, phosphoric acid salt, Tripyrophosphoric acid salt, silica type, silicates, carclazyte class, starch based, Aluminosilicates as the material of carrier.
But if solid support material is helpless to the efficient or the activity of powdered detergent, in fact, they are regarded as additional component, and they constitute the additional dirt that must remove in laundry processes.Therefore, preferably using is the carrier of standard ingredient in detergent powder composition.Particularly preferred carrier is those carriers that produce the alkaline pH value in water.For example, they comprise lime carbonate, tripoly phosphate sodium STPP, silicate, silico-aluminate, Trisodium Citrate, sodium bicarbonate and yellow soda ash.
Observe, the solid support material that can produce the alkaline pH value in water is used in combination in detergent powder composition with silicone defoamer and can makes defoamer lose its efficient when storing.Particularly that's how things stand during based on the silicone polymer of side chain when silicone defoamer.We think that carrier helps the defoamer degraded, and along with period of storage prolongs, this degraded increases.
Be desirable to provide the foam control agent that improves stability in powder detergent composition in the storage process, the material that particularly can produce the alkaline pH value in water is as under the occasion of solid support material.
One aspect of the present invention, the invention provides a kind of foam Control agent in granular form, it contains silicone defoamer, and silicone defoamer can produce when being adsorbed on and contacting with water on the particle of solid carrier of alkaline pH value, it is characterized in that foam Control agent in granular form also contains the alkyl saccharides.
Here the silicone defoamer of Shi Yonging is known material, and is wherein many open in patent specification.It is hydrophobic filler particles that these defoamers contain usually that a kind of liquid organopolysiloxane polymkeric substance and a kind of its surface become.
The liquid organopolysiloxane polymkeric substance that is applicable to silicone defoamer also is known, and open in many patent specifications.So, do not comprise the full-time instruction of all selection schemes, but can in many publications, find, comprise EP0578424.
That liquid organopolysiloxane can be straight chain or side chain, the structure of following general formula can be arranged:
In the formula, R is the monovalence alkyl that 1-8 carbon atom arranged, and R ' is the R base, hydroxyl or following group
In the formula, R
2Be bivalent hydrocarbon radical, hydroxyalkyl cooh or siloxanes or oxygen, Y is R base or hydroxyl, R
3Be C
9-C
35Alkyl, a, b, c and d are 0 or integer, and condition is that at least one is an integer among a and the b, and the summation of a+b+c+d has such numerical value, so that the viscosity of organopolysiloxane polymer is at least 50 millimeters
2/ second (under 25 ℃), preferably at least 500 millimeters
2/ second.
Preferred straight chain organopolysiloxane is the straight chain organopolysiloxane of following formula, wherein R
1Be R or hydroxyl.The organopolysiloxane of preferred non-straight chain is that organopolysiloxane side chain and that said structure is arranged is arranged in siloxane chain, and wherein b is at least 1, R
2Be preferably divalence siloxanes or Sauerstoffatom.Particularly preferred siloxanes R
2Be little three-dimensional siloxanes resin particle, they can have the siloxane polymeric unit of many side chains.
Side chain siloxanes that is fit to and preparation method thereof is known in this specialty, and its example is open in many patent specifications, as GB639673, EP031352, EP217501, EP273448, DE3805661 and GB2257709.
Most preferred liquid organopolysiloxane is the siloxanes of side chain, because they have high control bubble ability in many water phase surfactant mixtures.
The filler particles that is applicable to defoamer of the present invention also is known, and has described in many publications.They are finely divided particulate materials, for example comprise silicon oxide, smog TiO
2, Al
2O
3, zinc oxide, magnesium oxide, aliphatic carboxylate, isocyanic ester and some material such as hexahydroaniline reaction product, alkylamide such as ethylidene or methylene-bis stearylamide:
The surface-area that most preferred filler is measured for the BET method is at least 50 meters
2The silicon oxide particle of/gram.The silicon oxide particle that is fit to can make with the manufacturing technology of any standard, for example the decomposition of the thermolysis of silicon halide, metal silicate such as water glass and precipitation and gel method of formation.So the silicon oxide that is suitable for defoamer comprises the silicon oxide that fumed silica, precipitated silica and gel generate.
The average particle size of filler can be 0.1-20 micron, preferred 0.5-2.5 micron in the present invention.
If filler particles is not hydrophobic in nature, make its surface hydrophobicity can make defoamer enough effective in Aquo System so.Both can before disperseing, filler particles also can after dispersion, make the filler hydrophobization in liquid organopolysiloxane.
In order to make the filler hydrophobization, available processes agent such as reactive silane or siloxane treated filler.The example of treatment agent comprises one or more mixture of dimethyldichlorosilane(DMCS), trimethylchlorosilane, hexamethyldisilazane, hydroxy-end capped and polydimethylsiloxane methyl blocking, silicone resin, lipid acid or its.
The filler of handling with such treatment agent can be purchased by many companies, as the Sipernat that is bought by Degussa company
D10.
If make the surface in situ hydrophobization of filler, promptly after fillers dispersed is in the liquid organopolysiloxane component, so fillers dispersed therein before, in the dispersion process or after disperseing, be added in the liquid organopolysiloxane by treatment agent proper amt, with more than the mixture heating up to 40 ℃, can make filling surface original position hydrophobization then.
The quantity of the treatment agent that uses is for example relevant with the character of treatment agent and filler.This quantity is very clearly or ascertainable for those skilled in the art.Should use the treatment agent of q.s to make filler have the hydrophobicity of discernable at least degree.
Filler particles is added in the organopolysiloxane, and its amount is the 1-25% of defoamer (weight), preferably 1-20% (weight), 2-8% (weight) most preferably.
The alkyl saccharides is known in this specialty.According to general formula Z-O-R
4, they contain by the alkyl chain of ether binding to the sugar, R in the formula
4Be the alkyl chain of 8-20 carbon atom, Z is a sugar.
Sugar can be monose oligose or glycan.Monose is known in this specialty, comprises glucose, seminose, semi-lactosi, fructose.Oligose for example comprises sucrose, maltose, cellobiose, isomaltose and lactose.Glycan for example comprises amylose starch, amylopectin and poly-glucamide.
Preferred alkyl saccharides is by pentose or hexose or its material that constitutes.Most preferred alkyl saccharides is made as the alkyl sucrose of following general formula by sucrose:
In the formula, R
5, R
6, R
7Be identical or different alkyl chains or the hydrogen that 8-20 carbon atom, preferred 8-18 carbon atom are arranged.
Here the alkyl saccharides preferably is made of the glucose unit of following general formula:
In the formula, R
8Be the as above alkyl chain of regulation, preferably have 8-18 carbon atom, more preferably 12-18 carbon atom, most preferably 12-14 or 16-18 carbon atom, n=1,2 or 3.
Commercial alkyl polyglucoside also can comprise various geometrical isomers.The mixture of the alkyl polyglucoside of n=1.1-3 generally can be buied.
Be preferred for the glucose unit that alkyl polyglucoside of the present invention preferably has 2 following general formulas:
In the formula, R
8For afore mentioned rules.
Here carrier is known in this specialty, and wherein many is standard ingredients of detergent powder compositions.Particularly preferred carrier is those carriers that can produce the alkaline pH value in water.They for example comprise lime carbonate, tripoly phosphate sodium STPP, silicate, silico-aluminate, Trisodium Citrate, sodium bicarbonate and yellow soda ash.
Foam control agent of the present invention has the advantage that polymolecularity and good storage stability are arranged in water.
In another aspect of this invention, the invention provides a kind of powdered detergent composition, it contains 100 parts heavy detergent components and the above-mentioned foam Control agent in granular form of q.s, to cause the heavy silicone defoamer of 0.01-20 part is arranged in the detergent composition.
The detergent component that is fit to is that everybody is familiar with in this specialty, and describes in many publications.They contain activated detergent, organic and/or inorganic buider salt and other additives and thinner.
Activated detergent can contain anionic, cationic, non-ionic type or amphoteric organic detergent surfactant or its mixture.The anionic organic detergent surfactant that is fit to comprises the alkali metal soap of higher aliphatic acid; Alkylaryl sulphonate is as Sodium dodecylbenzene sulfonate; Long-chain (fat) alcohol sulfate; Olefin sulphates and sulfonate; Sulfated direactive glyceride, Sulfated ester class, sulfosuccinate, alkane sulfonate, phosphoric acid ester, different thiosulfuric acid alkyl ester, sucrose ester and fluorine-containing tensio-active agent.
The cationic organic detergent surfactant that is fit to comprises alkylamine salt, quaternary ammonium salt, sulfonium salt class and microcosmic salt class.
The non-ionic detergent tensio-active agent that is fit to comprises oxyethane and long-chain (fat) alcohol or (fat) sour condenses, as with the C of 7 moles of epoxy hexanes condensation
14-C
16Alcohol (Dobanol
45-7), the condenses of oxyethane and amine or acid amides; The condensation product of oxyethane and propylene oxide, fatty acid alkyl amide and fatty amine oxide.
The both sexes organic detergent surfactant that is fit to comprises imidazolinium compounds, alkylamino acids and betaines.
The example of inorganic component is phosphoric acid salt, polyphosphoric acid salt, silicates, carbonate, Sulfates, oxygen evolution compound such as Sodium peroxoborate, other SYNTHETIC OPTICAL WHITNER and Aluminosilicates such as zeolite.
The example of organic constituent is an anti-deposition agent, as carboxymethyl cellulose (CMC); Whitening agent; Sequestrant is as ethylenediamine tetraacetic acid (EDTA) (EDTA) and nitrilotriacetic acid(NTA) (NTA); Enzyme and fungistat class.
Other optional components comprise tinting material, dyestuff, spices, tenderizer and carclazyte, and some of them can be to be sealed.
For those skilled in the art, being suitable for the material of making detergent component is that everybody is familiar with, and describes in many textbooks and other publications.
In a third aspect of the present invention, the present invention also provides a kind of method of producing foam Control agent in granular form, this foam control agent contains the silicone defoamer on the solid carrier particle that produces the alkaline pH value when absorption upward contacts with water, it is characterized in that this method comprises that the alkyl saccharides is deposited on step on the carrier earlier than silicone defoamer.
A fourth aspect of the present invention is will be provided in the foam Control agent in granular form alkyl saccharides as the application of stabilization additives, and this foam control agent contains the silicone defoamer that is adsorbed on the solid carrier particle that can produce the alkaline pH value when contacting with water.
The foam control agent that the present invention makes is applicable to any powdery surface surfactant composition that foam height need be controlled, as in the washing machine washing composition and in the dishwasher washing composition.
Foam control agent of the present invention has various influences to cleaning activity in being added to final detergent powder compositions the time.Not observing has on laundering of textile fabrics because the stain that carrier produces.
Provide many embodiment below the present invention is described, unless add explanation in addition, wherein all expressions by weight of umber and percentage ratio.
Embodiment 1-15
1. the preparation of foam control agent
By the yellow soda ash SODASOLV that x part Solvay company is produced
The mixed foam control agent FCA1 to FCA15 that gets of the mixture of L and y part silicone defoamer A and z part component Z.
Silicone defoamer A contains the polydimethylsiloxanepolymer polymer and the 5% hydrophobic silicon oxide of side chain, and it presses the method preparation of EP217501.
Make a kind of like this mixture in order to the below method: with silicone defoamer and the pure mechanically mixing of component Z; Pour mixture into drum tumbler very lentamente then, then yellow soda ash is packed into wherein.Mixture is constantly stirred, until make till the granulate material.Under 80 ℃, granulate material is passed through Aeromatic subsequently
Sponging granulator, 20 minutes time.
The Copolycarbonate (toxilic acid/vinylformic acid) that provides by 40% aqueous solution, trade(brand)name Sokalan are provided component Z
CP5 is called CP5; Be the hydroxypropylcellulose of 20% aqueous solution, trade(brand)name Klucel
The Polyvinylpyrolidone (PVP) of 50% aqueous dispersion, hereinafter referred to as PVP; The secondary alkyl ester of the sulfonic acid that Hoechst company provides, trade(brand)name Hostopus
SAS60 is called SAS60; The polymerization degree that is provided with 50% aqueous dispersions by Henkel company is 1.1-3 and C is arranged
8-C
18The alkyl polyglucoside of alkyl tail end, trade(brand)name Glucopon
600 CS UP are called Glucopon; With the two fat acyloxy ethyl-methyl ammonium sulfate that 70% aqueous dispersions is sold, trade(brand)name HOE S4039; And the alkylamide dimethyl amine trimethyl-glycine that provides with 30% aqueous dispersions, trade(brand)name Empigen BS/F.
The details of foam control agent FCA1 to FCA15 is listed following table 1 in.
Table 1: foam control agent composition F CA Z z x yFCA1----90 10FCA2 CP5 14 76 10FCA3 PVP 10 80 10FCA4 Klucel 8 82 10FCA5 Hoe S4039 16 74 10FCA6 Empigen BS/F 6.5 82.5 11FCA7 SAS60 13 77 10FCA8 Glucopon 7 83 10FCA9 Glucopon 11 79 10FCA10 Glucopon 15 75 10FCA11 Glucopon 11 70 10
CP5 9FCA12 SAS60 10 79 8
CP5 3FCA13 Glucopon 3 84 10
CP5 3FCA14 Glucopon 7 69 10
CP5 14FCA15 Glucopon 9 81 9
Klucel 1
2. the preparation of powder detergent composition
Powder detergent composition is mixed by following component and prepares: 30 parts of zeolite Wessalith
CD.20 parts of yellow soda ash, 7.5 parts of sodium sulfate, 12.5 parts of dodecylbenzene sulfonates, 10 parts by C
14-C
16Nonionic surface active agent and 20 parts of Sodium peroxoborate monohydrates that alcohol and 7 moles of ethylene oxide condensations make.The foam control agent of q.s embodiment 1 to 15 is added in the every batch 100 gram detergent composition, obtains 0.1 gram defoamer, thereby make batch 1 to batches 15.
3. the test that discharges in wash(ing)cycle
The cotton fabric of 3.5 kilograms of cleanings is incorporated with in the conventional front-loading washing machine automatically of see-through look bin gate.Above-mentioned every batch of fabric is washed the wash(ing)cycle of (90 ℃) with the master.There are 4 tolerance to indicate on the door of washing machine, are respectively high by 25,50,75 and 100%, hereinafter be expressed as 1,2,3 or 4,0 expression non-foam and exist, be full of foam in the 5 expression rotary drums, and 6 express liquids are from the opening effusion washing machine at washing machine top.When the rotary drum of washing machine is static, foamy height in record wash(ing)cycle.Numerical value is high more to show that the foam height in the washing machine is high more, so the performance of foam control agent is poor more.
Table 2 is listed 20 minutes foam heights of every batch of wash(ing)cycle.The height of this part is low more to show that the release of defoamer in washings is good more.
Table 2: 05 10 15 20 minutes lot number 102233 lot numbers of result of the test foam height, 222222 lot numbers, 322222 lot numbers, 422222 lot numbers, 502222 lot numbers, 600011 lot numbers, 702222 lot numbers, 802222 lot numbers, 902222 lot numbers, 10 02223 lot numbers, 11 02465 lot numbers, 12 22222 lot numbers, 13 02222 lot numbers, 14 02222 lot numbers 15 00011
Can know from these results and to find out that when using foam control agent of the present invention, the release to defoamer in the initial stage of wash(ing)cycle is beneficial.
The detergent composition identical with lot number 1 to 15 before test also 40 ℃ of 4 weeks of storage down.Test-results is listed table 3 in.
3：40℃ 0 5 10 20 30 40 501 0 6 6 6 6 6 62 6 6 6 6 6 6 63 0 5 6 4 5 5 64 0 2 6 6 6 6 65 0 2 4 6 6 6 66 0 3 3 3 4 4 47 0 2 4 6 6 6 68 0 2 2 2 2 2 39 0 2 2 2 2 2 210 0 2 2 3 3 3 211 0 2 2 2 3 3 312 0 2 6 6 6 6 613 0 2 2 2 3 2 314 0 2 3 3 3 3 315 0 1 2 2 2 2 3。
Can know from test-results and to find out, in FCA, be used as the package stability that tensio-active agent can improve foam control agent by alkyl polyglucoside.
Embodiment 16-26
Sodium bicarbonate is as solid carrier
1. the preparation of foam control agent
By sodium bicarbonate that x part Solvay company is produced with the mixture of y part silicone defoamer A and a kind of component Z of z part is mixed must foam control agent FCA16 to FCA26.
Resemble embodiment 1-15 and prepare mixture, different is to replace yellow soda ash with sodium bicarbonate.
Component z is that the foregoing description 1-15 is described.The details of foam control agent FCA16 to FCA26 is listed following table 4 in.
Table 4:FCA Z z x yFCA16----90 10FCA17 PVP 6 88 6FCA18 Klucel 2 92 6FCA19 Hoe S4039 10 84 6FCA20 Empigen BS/F 4 90 6FCA21 SAS60 7 87 6FCA22 Glucopon 5 90 5FCA23 SAS60 6 88 5
CP5 1FCA24 Glucopon 4.5 89 4.5
CP5 2FCA25 Glucopon 5 89 5
Klucel 1FCA26 Glucopon 4.5 90 4.5
CP5 1
2. the preparation of powder detergent composition
Prepare powder detergent composition by embodiment 1-15, obtain batch with 16 to lot number 26.
3. the test that in wash(ing)cycle, discharges.
Table 5 is listed 20 minutes foam heights of every batch wash(ing)cycle.The release of defoamer is good more in the low more explanation washings of the height of this part.
Table 5: 05 10 15 20 minutes lot number 16 02222 lot numbers of result of the test foam height, 17 02222 lot numbers, 18 02222 lot numbers, 19 02222 lot numbers, 20 00112 lot numbers, 21 02222 lot numbers, 22 01122 lot numbers, 23 02222 lot numbers, 24 02222 lot numbers, 25 02222 lot numbers 26 02222
Can know by these results and to find out that when foam control agent only used alkyl polyglucoside (lot number 22), the release of defoamer improved in the initial period of wash(ing)cycle.
The detergent composition identical with lot number 16 to 26 also stored for 4 weeks down at 40 ℃ before test.Test-results is listed table 6 in.
Table 6: 05 10 20 30 40 50 minutes lot number 16 0466666 lot numbers of result of the test foam height, 17 0466666 lot numbers, 18 0466666 lot numbers, 19 0345353 lot numbers, 20 2234446 lot numbers, 21 0666666 lot numbers, 22 0112233 lot numbers, 23 0666666 lot numbers, 24 0222223 lot numbers, 25 0233333 lot numbers 26 0222333 after 40 ℃ of lower storages
Obviously, in FCA, use alkyl polyglucoside can improve the package stability of foam control agent as tensio-active agent.
Claims (11)
1. one kind contains the foam Control agent in granular form that is adsorbed on the silicone defoamer on the solid carrier particle that can produce the alkaline pH value when contacting with water, it is characterized in that foam Control agent in granular form also contains the alkyl saccharides.
2. according to the foam Control agent in granular form of claim 1, be further characterized in that silicone defoamer contains the organopolysiloxane of following general formula:
In the formula, R is the monovalence alkyl that 1-8 carbon atom arranged, R
1Be R base, hydroxyl or following group
In the formula, R
2Be bivalent hydrocarbon radical, hydroxyalkyl cooh or siloxanes or oxygen, y is R base or hydroxyl, R
3Be C
9-C
35Alkyl, a, c and d are 0 or integer, and b is at least an integer of 1, and the summation of a+b+c+d is such numerical value, so that is at least 50 millimeters in the viscosity of machine polysiloxane polymer under 25 ℃
2/ second.
3. according to the foam Control agent in granular form of claim 2, be further characterized in that at least one R
1Be following group
In the formula, R
2Be divalence siloxanes or Sauerstoffatom.
4. according to claim 1,2 or 3 foam Control agent in granular form, be further characterized in that the alkyl saccharides is the alkyl polyglucoside of following formula:
R in the formula
8For the alkyl of 8-20 carbon atom is arranged, n is 1-3.
5. according to the foam Control agent in granular form of claim 4, be further characterized in that alkyl polyglucoside has following formula:
In the formula, R
8For the alkyl of 8-20 carbon atom is arranged.
6. according to the foam Control agent in granular form of claim 5, be further characterized in that R8 has the alkyl of 8-18 carbon atom.
7. according to each foam Control agent in granular form in the claim 1～6, be further characterized in that carrier is selected from yellow soda ash and sodium bicarbonate.
8. method for preparing foam Control agent in granular form, this foam control agent contains the silicone defoamer that is adsorbed on the solid carrier particle that can produce the alkaline pH value when contacting with water, it is characterized in that this method comprises the alkyl saccharides is deposited on step on the carrier earlier than silicone defoamer.
9. method for preparing foam Control agent in granular form, this foam control agent contains the side chain silicone defoamer that is adsorbed on the solid carrier particle that can produce the alkaline pH value when contacting with water, it is characterized in that this method comprises the alkyl saccharides is deposited on step on the carrier earlier than silicone defoamer.
10. the alkyl saccharides is as the application of stablizer in foam Control agent in granular form, and this foam control agent contains the silicone defoamer that is adsorbed on the solid carrier particle that can produce the alkaline pH value when contacting with water.
11. a powder detergent composition wherein contains in 100 parts heavy detergent components and the requirement of q.s aforesaid right each foam Control agent in granular form, so that the heavy silicone defoamer of 0.01-20 part is arranged in detergent composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97118648 CN1177630A (en) | 1996-09-19 | 1997-09-18 | Granular foam-controlling agent |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9619627.4 | 1996-09-19 | ||
| CN 97118648 CN1177630A (en) | 1996-09-19 | 1997-09-18 | Granular foam-controlling agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1177630A true CN1177630A (en) | 1998-04-01 |
Family
ID=5174876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97118648 Pending CN1177630A (en) | 1996-09-19 | 1997-09-18 | Granular foam-controlling agent |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9023781B2 (en) | 2011-06-29 | 2015-05-05 | Nanjing Sixin Scientific-Technological Application Research Institute Co., Ltd. | Particle defoamer comprising a silicone emulsion and process for preparing same |
| WO2016086349A1 (en) | 2014-12-02 | 2016-06-09 | Dow Global Technologies Llc | Solid adjuvant defoamer |
-
1997
- 1997-09-18 CN CN 97118648 patent/CN1177630A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9023781B2 (en) | 2011-06-29 | 2015-05-05 | Nanjing Sixin Scientific-Technological Application Research Institute Co., Ltd. | Particle defoamer comprising a silicone emulsion and process for preparing same |
| WO2016086349A1 (en) | 2014-12-02 | 2016-06-09 | Dow Global Technologies Llc | Solid adjuvant defoamer |
| CN107206293A (en) * | 2014-12-02 | 2017-09-26 | 陶氏环球技术有限责任公司 | Solid adjuvant defoamer |
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