CN106999804B - Defoaming agent, water-soluble resin composition containing same, and water-soluble resin aqueous solution - Google Patents
Defoaming agent, water-soluble resin composition containing same, and water-soluble resin aqueous solution Download PDFInfo
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- CN106999804B CN106999804B CN201680003785.5A CN201680003785A CN106999804B CN 106999804 B CN106999804 B CN 106999804B CN 201680003785 A CN201680003785 A CN 201680003785A CN 106999804 B CN106999804 B CN 106999804B
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- 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
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
- C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- 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
Abstract
The purpose of the present invention is to provide a defoaming agent that does not reduce transparency even when used for a water-soluble resin and has excellent defoaming properties. The invention is a defoaming agent, characterized in that it comprises a polyether compound having a cloud point of 20 to 60 ℃ in a 1% ion-exchange aqueous solution state and metal oxide fine particles selected from a gas-phase metal oxide and a colloidal metal oxide, wherein the content of the polyether compound is 80 to 99.9% and the content of the metal oxide fine particles is 0.1 to 20%, based on the weight of the polyether compound and the metal oxide fine particles; and a defoaming agent characterized by comprising a polyether compound having a cloud point of 20 to 60 ℃ in a 1% ion-exchange aqueous solution state, metal oxide fine particles and water, wherein the content of the polyether compound is 80 to 99.9%, the content of the metal oxide fine particles is 0.1 to 20%, and the content of the water is 1 to 10% based on the weight of the polyether compound and the metal oxide fine particles.
Description
Technical Field
The present invention relates to a defoaming agent, a water-soluble resin composition containing the same, and a water-soluble resin aqueous solution.
Background
"1 or 2 or more antifoaming agents selected from a fatty acid ester-based compound, an ether-based compound, a metal soap-based compound, or a silicone-based compound" is known (claim 2 of patent document 1, etc.).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 11-277877
Disclosure of Invention
Problems to be solved by the invention
When a conventional defoaming agent is used for a water-soluble resin, there is a problem that the transparency of the water-soluble resin is easily lowered. That is, when a conventional defoaming agent is used for a paste, an adhesive, a film, or the like containing a water-soluble resin, there is a problem that transparency thereof is impaired.
The purpose of the present invention is to provide a defoaming agent that does not reduce transparency even when used for a water-soluble resin and has excellent defoaming properties.
Means for solving the problems
The defoaming agent of the present invention is characterized by comprising a polyether compound (A) having a cloud point of 20 to 60 ℃ in an ion-exchange aqueous solution state in an amount of 1 wt% and metal compound fine particles (B) selected from a gas-phase metal oxide and a colloidal metal oxide, wherein the content of the polyether compound (A) is 80 to 99.9 wt% and the content of the metal oxide fine particles (B) is 0.1 to 20 wt%, based on the weight of the polyether compound (A) and the metal oxide fine particles (B).
The defoaming agent of the present invention is characterized by comprising a polyether compound (A) having a cloud point of 20 to 60 ℃ in a1 wt% ion-exchange aqueous solution state, metal oxide fine particles (B) selected from gas-phase metal oxides and colloidal metal oxides, and water (C), wherein the content of the polyether compound (A) is 80 to 99.9 wt%, the content of the metal oxide fine particles (B) is 0.1 to 20 wt%, and the content of the water (C) is 1 to 10 wt%, based on the weight of the polyether compound (A) and the metal oxide fine particles (B).
The water-soluble resin composition of the present invention is characterized by comprising a water-soluble resin and the defoaming agent.
The water-soluble resin aqueous solution of the present invention is characterized by containing a water-soluble resin, the defoaming agent and water.
ADVANTAGEOUS EFFECTS OF INVENTION
The defoaming agent of the present invention does not lower the transparency even when used for a water-soluble resin, and exhibits excellent defoaming properties.
The water-soluble resin composition of the present invention contains the defoaming agent, and therefore an aqueous solution obtained by dissolving the water-soluble resin composition in water has excellent defoaming properties, and the aqueous solution has excellent transparency.
The water-soluble resin aqueous solution of the present invention contains the defoaming agent, and therefore is excellent in transparency and defoaming property.
Detailed Description
As the polyether compound (a), a compound having a plurality of ether bonds in the molecule and being liquid at 25 ℃ can be used, and a polyoxyalkylene compound can be preferably exemplified.
The cloud point (. degree. C.) of the polyether compound (A) in the form of a1 wt% ion-exchange aqueous solution is preferably 20 to 60, more preferably 22 to 59, particularly preferably 24 to 58, and most preferably 25 to 57. Within this range, the defoaming property becomes further excellent, and the transparency thereof is not lowered even when the composition is used for a water-soluble resin.
The cloud point in the state of a1 wt% ion-exchange aqueous solution is one of physical property values on a hydrophilic scale, and a higher cloud point indicates a higher hydrophilicity, and is a value measured in the following manner.
99g of ion-exchanged water and 1g of the sample were uniformly dissolved (when they were not dissolved, they were cooled until they were dissolved), about 5cc of the sample solution was taken out into a glass test tube, a thermometer was placed in the sample solution, the temperature was raised while stirring to make the sample solution cloudy, then the sample solution was slowly cooled while stirring, and the temperature at which the sample solution became completely transparent was read and used as the cloud point.
The polyether compound (a) includes a polymer having an oxyalkylene group having 2 to 18 carbon atoms as a unit, and preferably includes at least 1 selected from the group consisting of a polyether compound (a1) represented by general formula (1), a polyether compound (a2) represented by general formula (2), a polyether compound (A3) represented by general formula (3), a polyether compound (a4) represented by general formula (4), and a polyether compound (a5) represented by general formula (5).
[ chemical formula 1]
(H-)rR1{-(AO)n-H}s(1)
(H-)qR1{-(AO)n-R2}p(2)
{┖(AO)n-H}r
┏(OA)n-R2
R4{-(OA)n-Rl-(AO)n-R4}m-(OA)n-R5(5)
R1R represents a reactive residue of an active hydrogen compound having 1 to 25 carbon atoms2And R3R is a C1-24 organic group4R is a C1-24 organic group having a valence of 25The compound is characterized in that the compound represents hydroxyl or a 1-valent organic group with 1-24 carbon atoms, AO and OA represent oxyalkylene with 2-18 carbon atoms, a reaction residue of glycidol, a reaction residue of alkyl glycidyl ether with 4-18 carbon atoms or a reaction residue of alkenyl glycidyl ether with 5-18 carbon atoms, n is an integer of 1-100, and when a plurality of n exist in 1 molecule, the n can be the same or different, s is an integer of 1-10, p is an integer of 0-10, q is an integer of 0-9, r is an integer of 0-9, m is an integer of 0-9, p + r is an integer of 1-10, p + q + r is an integer of 1-10, and p + q + r + m is an integer of 2-10.
A reactive residue (R) of an active hydrogen compound having 1 to 25 carbon atoms1) The reactive residue is a reactive residue obtained by removing active hydrogen from an active hydrogen compound having 1 to 25 carbon atoms.
The active hydrogen-containing compound having 1 to 25 carbon atoms includes compounds containing at least 1 hydroxyl group (-OH), imino group (-NH-), amino group (-NH-), and the like2) And/or carboxyl (-COOH) groups including alcohols, amides, amines, carboxylic acids, hydroxycarboxylic acids, and aminocarboxylic acids.
Examples of the alcohol include: monohydric alcohols (methanol, butanol, stearyl alcohol, oleyl alcohol, isostearyl alcohol, etc.) and polyhydric alcohols (ethylene glycol, propylene glycol, glycerol, diglycerol, tetraglycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, dihydroxyacetone, fructose, glucose, mannose, galactose, sucrose, lactose, trehalose, etc.), etc.
As the amide, there may be mentioned: monoamides (formamide, propionamide, stearamide, and the like), and polyamides (malonic diamide, ethylenebisoctoylamide, and the like), and the like.
As amines, mention may be made of: monoamines (dimethylamine, ethylamine, aniline, and stearylamine, etc.) and polyamines (ethylenediamine, diethylenetriamine, and triethylenetetramine, etc.), and the like.
Examples of the carboxylic acid include: monocarboxylic acids (acetic acid, stearic acid, oleic acid, benzoic acid, and the like), and polycarboxylic acids (maleic acid, adipic acid, and the like), and the like.
As hydroxycarboxylic acids, there may be mentioned: glycolic acid, tartaric acid, malic acid, 12-hydroxystearic acid and the like.
As aminocarboxylic acids, there may be mentioned: glycine, 4-aminobutyric acid, 6-aminocaproic acid, 12-aminolauric acid, and the like.
As a C1-24 organic group (R)2、R3) Included are alkyl (R), alkenyl (R '), acyl (-COR), aroyl (-COR '), N-alkylcarbamoyl (-CONHR), N-alkenylcarbamoyl (-CONHR '), alkylcarbonylamino (-NHCOR), alkenylcarbonylamino (-NHCOR '), alkylcarboxyamino (alkylcarbamate, -NHCOOR) and alkenylcarboxyamino (alkenylcarbamate, -NHCOOR ').
Examples of alkyl (R) include: methyl, ethyl, isopropyl, t-butyl, octyl, 2-ethylhexyl, dodecyl, octadecyl, and the like.
As alkenyl groups (R'), there may be mentioned: vinyl, propenyl, hexenyl, isooctenyl, dodecenyl, octadecenyl and the like.
A hydroxyl group or a C1-to C24-valent organic group (R)5) In the above formula, the 1-valent organic group having 1 to 24 carbon atoms includes the same organic groups as described above.
As a C1-24 organic group having a valence of 2 (R)4) Including alkylene (T), alkenylene (T '), 1-oxaalkylene (-OT-), 1-oxaalkenylene (-OT ' -), 1-oxoalkylene (-COT-), 1-oxoalkenylene (-COT ' -), 1-aza-2-oxoalkylene (-NHCOT-) 1-aza-2-oxoalkenylene (-NHCOR ' -), 1-oxo-2-azaalkylene (-CONHT-), 1-oxo-2-azaalkenylene (-CONHT ' -), 1-aza-2-oxo-3-oxaalkylene (-NHCOOT-), and 1-aza-2-oxo-3-oxaalkenylene (-NHCOOT ' -).
Examples of the alkylene group (T) include: methylene, ethylene, isobutylene, 1, 10-decylene, 1, 2-decylene, 1, 12-dodecylene, 1, 2-octadecylene, and the like.
As alkenylene (T'), there may be mentioned: vinylidene, isobutylene, 1, 10-decylenene, 1-octylvinylene, 1-octyleneethylene, 1, 12-dodecenylene, 1-octadecenylethylene, and the like.
Among oxyalkylene groups having 2 to 18 carbon atoms, reaction residues of glycidol, reaction residues of alkyl glycidyl ethers having 4 to 18 carbon atoms or reaction residues (AO, OA) of alkenyl glycidyl ethers having 5 to 18 carbon atoms, as oxyalkylene groups having 2 to 18 carbon atoms, there can be mentioned: oxyethylene, oxypropylene, oxybutylene, oxy-1, 2-decylene, oxy-1, 12-dodecylene, oxy-1, 2-octadecylene and the like.
In addition, (AO, OA), examples of the alkyl glycidyl ether having 4 to 18 carbon atoms include: methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, octadecyl glycidyl ether, and the like.
In addition, (AO, OA), as the alkenyl glycidyl ether having 5 to 18 carbon atoms, there can be mentioned: vinyl glycidyl ether, butenyl glycidyl ether, 2-ethylhexenyl glycidyl ether, dodecenyl glycidyl ether, octadecenyl glycidyl ether, and the like.
n is an integer of 1 to 100, preferably an integer of 10 to 90, and more preferably an integer of 15 to 80.
Examples of the polyether compound (a1) represented by the general formula (1) include: polyoxyethylene polyoxypropylene monobutyl ether, ethylene oxide-propylene oxide block adduct of dodecanol, propylene oxide-ethylene oxide block adduct of tetradecanol, ethylene oxide-propylene oxide block adduct of 2-ethylhexanol, propylene oxide-ethylene oxide block adduct of trimethylolpropane, polyoxyethylene glycol polyoxypropylene glycol (block addition), ethylene oxide-propylene oxide block adduct of glycerin, propylene oxide-ethylene oxide block adduct of glycerin, ethylene oxide-propylene oxide block adduct of monododecylamine, and ethylene oxide-propylene oxide block adduct of pentaerythritol, and the like.
Examples of the polyether compound (a2) represented by the general formula (2) include: dioleate of polyoxyethylene glycol polyoxypropylene glycol (block addition), monostearate of ethylene oxide-propylene oxide block adduct of glycerin, and monomethyl ether of ethylene oxide-propylene oxide block adduct of maleic acid.
Examples of the polyether compound (a3) represented by the general formula (3) include: ethylene oxide adducts of ethylene bis stearamide, and esters of trimellitic acid with polyoxyethylene polyoxypropylene monobutyl ether and 2-ethylhexanol, and the like.
Examples of the polyether compound (a4) represented by the general formula (4) include: monooleate of ethylene oxide adduct of castor oil and ethylene oxide adduct of glycerol bis (12-hydroxystearate), and the like.
Examples of the polyether compound (a5) represented by the general formula (5) include: polyoxyethylene monolaurate, a reactant of polyoxyethylene glycol and hexamethylene diisocyanate, and the like.
Among these, the polyether compound (a1) represented by the general formula (1) and the polyether compound (a2) represented by the general formula (2) are preferable from the viewpoint of defoaming property and the like.
As the metal oxide fine particles (B) selected from the group consisting of a fumed metal oxide and a colloidal metal oxide, hydrophilic fumed metal oxide, hydrophobic fumed metal oxide, hydrophilic colloidal metal oxide and hydrophobic colloidal metal oxide are included, and hydrophilic fumed silica, hydrophobic fumed alumina, hydrophobic fumed titanium, hydrophilic colloidal silica, hydrophobic colloidal silica and the like can be used. Among these, from the viewpoint of defoaming property and cost, a fumed metal oxide is preferable, a hydrophobic fumed metal oxide is more preferable, and hydrophobic fumed silica is particularly preferable.
The metal oxide fine particles (B) can be easily obtained from the market. As trade names of hydrophobic fumed silica, there can be mentioned: the AEROSIL series (R972, R974, RX200, RX300, RY200, R202 and R805, etc., available from Japan AEROSIL corporation, "AEROSIL" is a registered trademark of Evonik Degussa GmbH, the same applies hereinafter); REOLOSIL series (MT-10, DM-20S, etc., available from Deshan, Inc.; "REOLOSIL" is a registered trademark of this company, the same applies hereinafter); the HDK series (HDKH15 and HDKH18, et al, ASAHI KASEI WACKER SILICONE CO., LTD, "HDK" is a registered trademark of Wacker ChemieAG. the same applies hereinafter); and CAB-O-SIL series (TS-720, TS-622, TS-382, etc., Cabot Carbon Corporation, "CAB-O-SIL" is a registered trademark of Cabot Carbon Corporation. the same applies hereinafter), etc.
As trade names of the hydrophilic fumed silica, there can be mentioned: AEROSIL series (50, 130, 200, 300, R812, etc.); REOLOSIL series (QS-10, QS-30, QS-40, S-102, etc., Deshan, Kyoho, Ltd.); HDK series (HDKN20, HDKS13 and the like, ASAHI KASEI WACKER SILICONE CO., LTD) CAB-O-SIL series (EH-5, S-5 and the like, Cabot Carbon Co., Ltd.), and the like.
As trade names of the hydrophobic vapor phase alumina, there can be mentioned: the AEROXIDE series (AluC805, Japan AEROSIL Co., Ltd., "AEROXIDE" is a registered trademark of Evonik Degussa GmbH. the same applies hereinafter).
Trade names of hydrophobic vapor phase titanium include: the AEROXIDE series (T805 and NKT90, etc.).
Trade names of hydrophilic colloidal silica include: snowtex series (S, NS, manufactured by Nissan chemical industries, Ltd. "Snowtex" is a registered trademark of the company), Adelite series (AT-20A, manufactured by ADEKA, Ltd. "Adelite (ァデライト)" is a registered trademark of the company), and the like.
Trade names of hydrophobic colloidal silica include: CAB-O-SIL TGC191, and the like.
The metal oxide fine particles (B) preferably have a methanol wettability (M value) of 35 to 65, more preferably 36 to 63, particularly preferably 38 to 62, and most preferably 40 to 60. In the range, the defoaming property becomes further favorable.
The M value is an index indicating the degree of hydrophobization, and is a value measured as follows, indicating the volume% of a uniform dispersion liquid having the smallest methanol concentration among several water/methanol mixed solutions having different concentrations. The higher the value, the higher the hydrophobicity can be said to be.
< method for measuring methanol wettability (M value) >
A water/methanol mixed solution in which the methanol concentration was changed at 5 vol% intervals was prepared, and 5ml was added to a test tube having a volume of 10 ml. Then, 0.2g of the measurement sample was added, the test tube was covered, the test tube was turned upside down 20 times, and the test tube was left standing for 1 to 2 minutes, and then aggregates were observed, and in a dispersion liquid in which all the measurement samples were wet and uniformly dispersed without aggregates, the concentration (volume%) of methanol in the dispersion liquid having the smallest methanol concentration was set as the M value { the unit (volume%) in which the M value is not described is a common practice. }.
The content (% by weight) of the polyether compound (A) is preferably 80 to 99.9, more preferably 85 to 99.8, particularly preferably 88 to 99.7, and most preferably 90 to 99.5 based on the weight of the polyether compound (A) and the metal oxide fine particles (B). When the amount is within the above range, the defoaming property and handling property are further improved.
The content (% by weight) of the metal oxide fine particles (B) is preferably 0.1 to 20, more preferably 0.2 to 15, particularly preferably 0.3 to 12, and most preferably 0.5 to 10 based on the weight of the polyether compound (A) and the metal oxide fine particles (B). When the amount is within the above range, the defoaming property and handling property are further improved.
The defoaming agent of the present invention is composed of the polyether (a) and the metal oxide fine particles (B), that is, contains no other component, but the defoaming agent of the present invention may further contain water (C). The antifoaming agent of the present invention has the effect of reducing the risk of ignition and improving the safety in handling by containing water. In addition, the low-temperature fluidity of the defoaming agent is improved. As the water, distilled water, ion-exchanged water, tap water, industrial water, well water, spring water, river water, and the like can be used. Of these, tap water, industrial water, ion-exchanged water, and distilled water are preferable, and ion-exchanged water and distilled water are more preferable.
When water (C) is contained, the content (wt%) of water (C) is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6 based on the weight of the polyether compound (A) and the metal oxide fine particles (B).
The defoaming agent of the present invention exhibits excellent defoaming properties for an aqueous solution of a water-soluble resin (particularly, polyvinyl alcohol), and is effective for aqueous foaming liquids other than an aqueous solution of a water-soluble resin { for example, drainage, papermaking process white water, aqueous coating materials, etc. }, without lowering the transparency.
When the defoaming agent of the present invention is added to a water-soluble resin, the addition may be performed at any timing, and it is preferable to mix the water-soluble resin uniformly after the addition. In addition, when the defoaming agent is added, the defoaming agent may be diluted with an appropriate diluting solvent (for example, methanol or water) (the diluting solvent is preferably distilled off during or after mixing).
The defoaming agent of the present invention may be added to the aqueous solution of a water-soluble resin at any timing, and the defoaming agent may be diluted with an appropriate diluting solvent (for example, methanol or water) at the time of addition.
The water-soluble resin composition of the present invention contains a water-soluble resin and the above-mentioned defoaming agent, and as the water-soluble resin, there are alkyd resin, acrylic resin, styrene maleic acid copolymer, cellulose derivatives (methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and the like), polyvinylpyrrolidone, polyvinyl alcohol, starch derivatives (oxidized starch, cationized starch, and the like), polyacrylamide, polyethylene glycol, and polysaccharides (xanthan gum, guar gum, and the like). Among these, polyvinyl alcohol is preferred.
The content of the defoaming agent may be appropriately determined depending on the foaming state, and the content of the defoaming agent contained in the water-soluble resin composition is about 0.01 to 1% by weight based on the weight of the water-soluble resin.
The water-soluble resin aqueous solution of the present invention contains a water-soluble resin, the defoaming agent and water, and the same substances as described above can be used as the water-soluble resin and water.
The content of the defoaming agent may be appropriately determined depending on the foaming state, and the content of the defoaming agent in the aqueous solution of the water-soluble resin is about 0.01 to 1% by weight based on the weight of the water-soluble resin.
The water content may be determined as appropriate depending on the application, and the water content in the aqueous solution of the water-soluble resin is about 300 to 10000% by weight based on the weight of the water-soluble resin.
Examples
Hereinafter, "part" means part by weight and "%" means wt.%; the term "cloud point" means a cloud point% in the state of a1 wt% ion exchange aqueous solution.
As the polyether compound (a), the following polyether compounds (a1) to (a5) were used.
Polyether compound (a 1): propylene oxide (40 moles) ethylene oxide (15 moles) block adduct of glycerol, cloud point 31 deg.C
Polyether compound (a 2): ethylene oxide (8 moles) propylene oxide (7 moles) block adduct of 2-ethylhexanol, cloud point 20 deg.C
Polyether compound (a 3): dioleate of an ethylene oxide (13 moles) propylene oxide (30 moles) block copolymer, cloud point 25 deg.C
Polyether compound (a 4): ethylene oxide (45 mol) propylene oxide (35 mol) block adduct of butanol, cloud point 57 deg.C
Polyether compound (a 5): ethylene oxide (22 moles) propylene oxide (19 moles) block adduct of lauryl alcohol, cloud point 28 deg.C
As the metal oxide fine particles (B), fumed silicas (B1) to (B4) obtained by aescil corporation, japan were used.
Fumed silica (b 1): AEROSIL R974, M value 40
Fumed silica (b 2): AEROSIL R972, M value 45
Fumed silica (b 3): AEROSIL R805, M value 50
Fumed silica (b 4): AEROSIL RX300, M value 60
< example 1 >
In a vessel capable of stirring, 990 parts of polyether compound (a1) and 10 parts of fumed silica (b1) were mixed with stirring for 30 minutes to obtain defoaming agent (1) of the present invention.
< example 2 >
In a vessel capable of stirring, 995 parts of the polyether compound (a2) and 5 parts of fumed silica (b2) were mixed with stirring for 30 minutes, thereby obtaining the defoaming agent (2) of the present invention.
< example 3 >
In a vessel capable of stirring, 900 parts of the polyether compound (a3) and 100 parts of fumed silica (b3) were mixed with stirring for 30 minutes, thereby obtaining the defoaming agent (3) of the present invention.
< example 4 >
In a vessel capable of stirring, 970 parts of polyether compound (a4), 30 parts of fumed silica (b1) and 60 parts of water (c1) { ion-exchanged water } were mixed with stirring for 30 minutes, thereby obtaining defoaming agent (4) of the present invention.
< example 5 >
In a vessel capable of stirring, 950 parts of the polyether compound (a5), 50 parts of fumed silica (b4), and 30 parts of water (c1) were mixed with stirring for 30 minutes, thereby obtaining the defoaming agent (5) of the present invention.
< example 6 >
In a vessel capable of stirring, 500 parts of the polyether compound (a2), 470 parts of the polyether compound (a5), 30 parts of fumed silica (b1) and 60 parts of water (c1) were stirred and mixed for 30 minutes, thereby obtaining the defoaming agent (6) of the present invention.
< example 7 >
In a vessel capable of stirring, 300 parts of the polyether compound (a1), 697 parts of the polyether compound (a5), 3 parts of fumed silica (b2), and 100 parts of water (c1) were stirred and mixed for 30 minutes, thereby obtaining the defoaming agent (7) of the present invention.
< example 8 >
In a vessel capable of stirring, 300 parts of the polyether compound (a3), 600 parts of the polyether compound (a5), 100 parts of fumed silica (b3), and 30 parts of water (c1) were stirred and mixed for 30 minutes, thereby obtaining the defoaming agent (8) of the present invention.
< example 9 >
In a vessel capable of stirring, 300 parts of the polyether compound (a4), 695 parts of the polyether compound (a5), 5 parts of fumed silica (b4), and 30 parts of water (c1) were stirred and mixed for 30 minutes, thereby obtaining the defoaming agent (9) of the present invention.
< comparative example 1 >
A metal soap defoaming agent "Nopco DF 122-NS" (DF-5 used in examples of patent document 1) was used as a comparative defoaming agent (H1).
Defoaming properties and transparency were evaluated using the defoaming agents (1) to (9) and (H1) in the following manner, and the evaluation results are shown in tables 1 and 2.
< evaluation of defoaming Property >
1. Preparation of Water-soluble resin composition for testing
100 parts of polyvinyl alcohol [ Kuraray Poval PVA-217 (polymerization degree 1,700, saponification degree 88 mol%), Kokulepi K.K. ] and 0.5 part of each evaluation sample (defoaming agent) were mixed uniformly to obtain a water-soluble resin composition for testing.
2. Preparation of defoaming test solution
40 parts of the water-soluble resin composition for testing and 960 parts of ion-exchanged water (about 25 ℃ C.) were heated to 90 ℃ while stirring and mixing, and after stirring and mixing at 90 ℃ for 30 minutes to uniformly dissolve the water-soluble resin composition for testing, the mixture was cooled to about 25 ℃ C., and an amount of ion-exchanged water equivalent to the water evaporated by heating was added to adjust the concentration of polyvinyl alcohol to 4%, thereby obtaining a defoaming test solution.
A defoaming test solution (blank) was prepared in the same manner as described above, except that the water-soluble resin composition for a test was changed to polyvinyl alcohol (defoaming agent was not uniformly mixed).
3. Defoaming Property test
A glass 500ml measuring cylinder (hereinafter, referred to as a foam tube) was immersed in a water bath adjusted to 80 ℃ in an upright state to a scale of 95ml of the foam tube, 100ml of a defoaming test solution adjusted to 80 ℃ was added to the foam tube, a diffusing stone (diffuser stone) was inserted into the bottom of the foam tube, and nitrogen gas was blown at 300 ml/min to foam the defoaming test solution, and the changed volumes of foam and the foaming solution were read 15 seconds, 1 minute, and 2 minutes after the start of the test. A small value means high defoaming property, and is preferable.
[ Table 1]
In the table, "-" indicates that more than 500ml was measured using the measuring cylinder and could not be measured.
The defoaming agent of the present invention exhibits excellent defoaming properties as compared with comparative defoaming agents.
< evaluation of transparency >
After the test, the defoaming test solution used in the defoaming test was left to stand under a seal at 25 ℃ for 24 hours to be defoamed, and the haze value (% not by weight but by percentage of scattered light to total light transmitted light) of the transparency test solution was measured using a haze meter (WATER ANALYZER 2000N, japan electro-color industries, ltd.) as a transparency test solution, and the haze value was used as an index of transparency. The lower the haze value, the more excellent the transparency.
[ Table 2]
When the defoaming agent of the present invention is used, the transparency is not adversely affected as in the case of not mixing the defoaming agent. The antifoaming agent (H1) used in patent document 1 has a significant adverse effect on transparency.
Industrial applicability
The defoaming agent of the present invention is suitably used in a process using a water-soluble resin in the fields of chemical industry, petroleum industry, textile industry, pulp industry, and the like, in which a water-soluble resin is used.
Claims (12)
1. An antifoaming agent characterized by comprising a polyether compound (A) having a cloud point of 20 to 60 ℃ in a1 wt% ion-exchange aqueous solution state and metal oxide fine particles (B) selected from the group consisting of a gas-phase metal oxide and a colloidal metal oxide,
the content of the polyether compound (A) is 80 to 99.9% by weight and the content of the metal oxide fine particles (B) is 0.1 to 20% by weight based on the weight of the polyether compound (A) and the metal oxide fine particles (B).
2. The antifoaming agent according to claim 1, wherein the metal oxide fine particles (B) have a methanol wettability (M value) of 35 to 65.
3. The antifoaming agent according to claim 1, wherein the metal oxide fine particles (B) are fumed silica.
4. The defoaming agent according to claim 1, wherein the polyether compound (A) is at least 1 selected from the group consisting of a polyether compound (A1) represented by the general formula (1), a polyether compound (A2) represented by the general formula (2), a polyether compound (A3) represented by the general formula (3), a polyether compound (A4) represented by the general formula (A4), and a polyether compound (A5) represented by the general formula (5),
(H-)rR1{-(AO)n-H}s(1)
R1represents an active hydrogen compound having 1 to 25 carbon atomsReaction residue of (a) R2And R3R is a C1-24 organic group4R is a C1-24 organic group having a valence of 25The compound is characterized in that the compound represents hydroxyl or a 1-valent organic group with 1-24 carbon atoms, AO and OA represent oxyalkylene with 2-18 carbon atoms, a reaction residue of glycidol, a reaction residue of alkyl glycidyl ether with 4-18 carbon atoms or a reaction residue of alkenyl glycidyl ether with 5-18 carbon atoms, n is an integer of 1-100, and when a plurality of n exist in 1 molecule, the n can be the same or different, s is an integer of 1-10, p is an integer of 0-10, q is an integer of 0-9, r is an integer of 0-9, m is an integer of 0-9, p + r is an integer of 1-10, p + q + r is an integer of 1-10, and p + q + r + m is an integer of 2-10.
5. An antifoaming agent characterized by comprising a polyether compound (A) having a cloud point of 20 to 60 ℃ in the state of a1 wt% ion-exchange aqueous solution, metal oxide fine particles (B) selected from the group consisting of gas-phase metal oxides and colloidal metal oxides, and water (C),
the content of the polyether compound (A) is 80 to 99.9 wt%, the content of the metal oxide fine particles (B) is 0.1 to 20 wt%, and the content of the water (C) is 1 to 10 wt%, based on the weight of the polyether compound (A) and the metal oxide fine particles (B).
6. The defoaming agent according to claim 5, wherein the metal oxide fine particles (B) have a methanol wettability (M value) of 35 to 65.
7. The antifoaming agent according to claim 5, wherein the metal oxide fine particles (B) are fumed silica.
8. The defoaming agent according to claim 5, wherein the polyether compound (A) is at least 1 selected from the group consisting of a polyether compound (A1) represented by the general formula (1), a polyether compound (A2) represented by the general formula (2), a polyether compound (A3) represented by the general formula (3), a polyether compound (A4) represented by the general formula (A4), and a polyether compound (A5) represented by the general formula (5),
(H-)rR1{-(AO)n-H}s(1)
R1r represents a reactive residue of an active hydrogen compound having 1 to 25 carbon atoms2And R3R is a C1-24 organic group4R is a C1-24 organic group having a valence of 25The compound is characterized in that the compound represents hydroxyl or a 1-valent organic group with 1-24 carbon atoms, AO and OA represent oxyalkylene with 2-18 carbon atoms, a reaction residue of glycidol, a reaction residue of alkyl glycidyl ether with 4-18 carbon atoms or a reaction residue of alkenyl glycidyl ether with 5-18 carbon atoms, n is an integer of 1-100, and when a plurality of n exist in 1 molecule, the n can be the same or different, s is an integer of 1-10, p is an integer of 0-10, q is an integer of 0-9, r is an integer of 0-9, m is an integer of 0-9, p + r is an integer of 1-10, p + q + r is an integer of 1-10, and p + q + r + m is an integer of 2-10.
9. A water-soluble resin composition comprising a water-soluble resin and the defoaming agent according to any one of claims 1 to 8.
10. The water-soluble resin composition according to claim 9, wherein the water-soluble resin is polyvinyl alcohol.
11. An aqueous solution of a water-soluble resin, comprising a water-soluble resin, the defoaming agent according to any one of claims 1 to 8, and water.
12. The aqueous water-soluble resin solution according to claim 11, wherein the water-soluble resin is polyvinyl alcohol.
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| JP2015072453 | 2015-03-31 | ||
| JP2015-072453 | 2015-03-31 | ||
| PCT/JP2016/056446 WO2016158177A1 (en) | 2015-03-31 | 2016-03-02 | Anti-foaming agent, water-soluble resin composition containing said agent, and water-soluble resin containing said agent |
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| JP7278622B2 (en) * | 2018-11-01 | 2023-05-22 | サンノプコ株式会社 | Oil-in-water emulsion antifoaming agent, resin aqueous dispersion and water-soluble resin aqueous solution containing the same |
| CN113501951A (en) * | 2021-06-09 | 2021-10-15 | 内蒙古科学技术研究院 | Polyether defoaming agent and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1652997A (en) * | 2002-06-12 | 2005-08-10 | 日本板硝子株式会社 | Porous metal oxide material in flake form, method for producing the same and cosmetic, coating material, resin composition, ink composition and paper comprising the same |
| CN101632908A (en) * | 2009-08-19 | 2010-01-27 | 南京四新科技应用研究所有限公司 | Method for preparing defoaming agent composition |
| CN101884852A (en) * | 2010-06-30 | 2010-11-17 | 南京四新科技应用研究所有限公司 | Method for improving properties of polyether defoaming agent |
| CN102190892A (en) * | 2010-02-01 | 2011-09-21 | 日东电工株式会社 | Silicone resin composition |
| CN102344595A (en) * | 2010-07-27 | 2012-02-08 | 住友化学株式会社 | Radiation screening polyolefine resin film |
| CN102548631A (en) * | 2009-10-09 | 2012-07-04 | 圣诺普科有限公司 | Defoaming agent |
| CN102869423A (en) * | 2010-04-28 | 2013-01-09 | 瓦克化学股份公司 | Antifoam compositions |
| WO2014073312A1 (en) * | 2012-11-08 | 2014-05-15 | 富士フイルム株式会社 | Aqueous composition and hard coat layer |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0368401A (en) * | 1989-08-09 | 1991-03-25 | Mitsubishi Petrochem Co Ltd | Defoaming agent |
| JP3610505B2 (en) * | 1995-10-25 | 2005-01-12 | サンノプコ株式会社 | Antifoam composition |
| JP3799428B2 (en) * | 1998-03-05 | 2006-07-19 | サンノプコ株式会社 | Water-soluble antifoam composition |
| JP4096044B2 (en) * | 2003-04-04 | 2008-06-04 | サンノプコ株式会社 | Emulsion type antifoaming agent |
| JP2007231176A (en) * | 2006-03-01 | 2007-09-13 | Dai Ichi Kogyo Seiyaku Co Ltd | Low-foaming nonionic surfactant |
| JP5433829B2 (en) * | 2009-02-09 | 2014-03-05 | サンノプコ株式会社 | Antifoaming agent and resin containing the same |
| JP2011101849A (en) * | 2009-11-11 | 2011-05-26 | San Nopco Ltd | Antifoaming agent |
| WO2013122619A1 (en) * | 2012-02-16 | 2013-08-22 | Dow Corning Corporation | Granulated foam control agent for the rinse cycle using siloxane wax |
| JP6155441B2 (en) * | 2013-07-01 | 2017-07-05 | サンノプコ株式会社 | Oil-in-water silicone emulsion |
| JP6361006B2 (en) * | 2014-03-13 | 2018-07-25 | サンノプコ株式会社 | Antifoam |
-
2016
- 2016-03-02 JP JP2017509431A patent/JP6700517B2/en active Active
- 2016-03-02 CN CN201680003785.5A patent/CN106999804B/en active Active
- 2016-03-02 WO PCT/JP2016/056446 patent/WO2016158177A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1652997A (en) * | 2002-06-12 | 2005-08-10 | 日本板硝子株式会社 | Porous metal oxide material in flake form, method for producing the same and cosmetic, coating material, resin composition, ink composition and paper comprising the same |
| CN101632908A (en) * | 2009-08-19 | 2010-01-27 | 南京四新科技应用研究所有限公司 | Method for preparing defoaming agent composition |
| CN102548631A (en) * | 2009-10-09 | 2012-07-04 | 圣诺普科有限公司 | Defoaming agent |
| CN102190892A (en) * | 2010-02-01 | 2011-09-21 | 日东电工株式会社 | Silicone resin composition |
| CN102869423A (en) * | 2010-04-28 | 2013-01-09 | 瓦克化学股份公司 | Antifoam compositions |
| CN101884852A (en) * | 2010-06-30 | 2010-11-17 | 南京四新科技应用研究所有限公司 | Method for improving properties of polyether defoaming agent |
| CN102344595A (en) * | 2010-07-27 | 2012-02-08 | 住友化学株式会社 | Radiation screening polyolefine resin film |
| WO2014073312A1 (en) * | 2012-11-08 | 2014-05-15 | 富士フイルム株式会社 | Aqueous composition and hard coat layer |
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| WO2016158177A1 (en) | 2016-10-06 |
| CN106999804A (en) | 2017-08-01 |
| JPWO2016158177A1 (en) | 2018-01-25 |
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