Classifications

• • 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
  • B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
  • C10M155/02—Monomer containing silicon
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  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
• • 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
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
  • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
  • C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M173/00—Lubricating compositions containing more than 10% water
  • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/006—Additives being defined by their surface area
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/10—Compounds containing silicon
  • C10M2201/105—Silica
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
  • C10M2229/04—Siloxanes with specific structure
  • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
  • C10M2229/04—Siloxanes with specific structure
  • C10M2229/047—Siloxanes with specific structure containing alkylene oxide groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/18—Anti-foaming property
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/20—Metal working
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/01—Emulsions, colloids, or micelles
  • C10N2050/011—Oil-in-water

Definitions

• the present invention relates to a silicone-based defoaming agent composition.
• Defoaming agents are used to suppress the generation of foam in industrial processes such as the process of processing or processing liquids.
• silicone-based defoamers are generally used because they are chemically stable and have little effect on the object to which they are applied.
• Patent Document 1 describes a silicone defoaming composition containing a polyorganosiloxane having a specific general formula and a viscosity at 25 ° C. of 20 cs to 100,000 cs, a silane, and a fine powdery filler.
• Patent Document 2 is characterized by containing a first component made of a silicone-based defoaming agent and a second component made of a crosslinked polyorganosiloxane polymer having a polyoxyalkylene group. Defoaming agent compositions are described.
• the conventional defoaming agent composition has a slow defoaming speed, and the initial defoaming performance may be insufficient.
• the defoaming performance may deteriorate when used repeatedly or when used for a relatively long time. Therefore, it has been desired to develop a defoaming agent composition which has a high defoaming speed, does not deteriorate the defoaming performance even after repeated use, and has excellent defoaming durability.
• the second component specifically described in Patent Document 2 is used, the dilution stability of the defoaming agent composition is not sufficient, and further improvement is required.
• the present invention has been made to solve the above-mentioned problems of the prior art, and not only has excellent defoaming speed, but also defoaming performance does not deteriorate even when repeatedly used or used for a long time, and further. , It is an object of the present invention to provide a silicone defoaming agent composition having excellent dilution stability.
• the object of the present invention is Partial structure (I): -R 1- (R 2 2 SiO) d -R 1- (In the formula, R 1 is an alkylene group having 2 to 20 carbon atoms bonded to a silicon atom on the polysiloxane chain, R 2 is a monovalent hydrocarbon group, and d is a number in the range of 200 to 1000. ), And partial structure (II):-( CeH 2e ) -O- (EO) x- (PO) y- (BO) z -R 3 (During the ceremony, EO is an ethyleneoxy unit represented by C 2 H 4 O.
• PO is a propyleneoxy unit represented by C 3 H 6 O.
• BO is a butyleneoxy unit represented by C 4 H 8 O.
• the single bond at the left end is bonded to a silicon atom on the polysiloxane chain
• R 3 is a hydrogen atom, an alkyl group, an aryl group or an acyl group
• e is a number in the range of 2 to 10
• x + y + z is 40 to 100.
• X is a number in the range of 15 to 50
• y is a number in the range of 15 to 50
• z is a number in the range of 0 to 50). It is achieved by a silicone defoaming agent composition containing a crosslinked polyorganosiloxane polymer having a polyoxyalkylene group.
• d is preferably a number in the range of 250 to 900.
• x is a number in the range of 20 to 40
• y is a number in the range of 20 to 40
• z is preferably 0.
• the crosslinked polyorganosiloxane polymer having a polyoxyalkylene group has the following structural formula: (In the formula, a is a number in the range of 10 to 200, b + c is a number in the range of 2 to 50, b and c are numbers of 1 or more, respectively, EO and PO are the same groups as described above, and R Is a hydrogen atom, an alkyl group, an aryl group or an acyl group, and d, x and y are the same numbers as those defined in the partial structures (I) and (II). It is preferably represented by.
• the silicone-based defoaming agent composition of the present invention is (A) Intrinsically hydrophobic organopolysiloxane having a viscosity at 25 ° C. of 10-100,000 mPa ⁇ s: 20-80 parts by mass, (B) Hydrophobic organopolysiloxane or cyclic organopolysiloxane containing silanol groups at least at both ends: 20 to 80 parts by mass, (C) Silane or a condensate of silane: 1 to 10 parts by mass, and (D) Fine powder silica having a specific surface area of 50 m 2 / g or more: 2 to 10 parts by mass, the total of (A) and (B) It is preferable to further contain an oil compound for a silicone-based defoaming agent, which is 100 parts by mass.
• the component (B) is (B1) Hydrophobic organopolysiloxane containing silanol groups at both ends at 1000 to 10,000,000 mPa ⁇ s, and (B2) containing silanol groups at both ends at 1 to 1,000 mPa ⁇ s. It preferably contains a hydrophobic organopolysiloxane or a cyclic siloxane.
• the molar ratio of the component (B) to the total amount of the component (A) and the component (B) is preferably 0.7 or more.
• the molar ratio of the component (B1) to the total amount of the component (A) and the component (B1) is preferably 0.2 or more.
• the silicone-based defoaming oil compound is preferably emulsified with the crosslinked polyorganosiloxane polymer having the polyoxyalkylene group.
• the silicone-based defoaming oil compound preferably has a viscosity at 25 ° C. of 10,000 to 1,000,000 mPa ⁇ s.
• the particle size of the emulsion of the silicone defoaming agent composition of the present invention is preferably 0.1 to 10 ⁇ m.
• the silicone defoaming agent composition of the present invention is preferably used for metal processing oils.
• the silicone defoaming agent composition of the present invention since the defoaming speed is excellent, not only the initial defoaming performance is excellent, but also the defoaming performance is greatly deteriorated even when used repeatedly or for a long time. It is possible to provide an antifoaming agent composition that does not occur.
• the silicone defoaming agent composition of the present invention is Partial structure (I): -R 1- (R 2 2 SiO) d -R 1- (In the formula, R 1 is an alkylene group having 2 to 20 carbon atoms bonded to a silicon atom on the polysiloxane chain, R 2 is a monovalent hydrocarbon group, and d is a number in the range of 200 to 1000. ), And partial structure (II):-( CeH 2e ) -O- (EO) x- (PO) y- (BO) z -R 3 (During the ceremony, EO is an ethyleneoxy unit represented by C 2 H 4 O. PO is a propyleneoxy unit represented by C 3 H 6 O.
• BO is a butyleneoxy unit represented by C 4 H 8 O.
• the single bond at the left end is bonded to a silicon atom on the polysiloxane chain
• R 3 is a hydrogen atom, an alkyl group, an aryl group or an acyl group
• e is a number in the range of 2 to 10
• x + y + z is 40 to 100.
• X is a number in the range of 15 to 50
• y is a number in the range of 15 to 50
• z is a number in the range of 0 to 50).
• R 1 is an alkylene group having 2 to 20 carbon atoms bonded to a silicon atom on a polysiloxane chain.
• the alkylene group having 2 to 20 carbon atoms may be a linear group or a branched chain, and a methylmethylene group, an ethylene group, a methylethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group and an octylene group may be used.
• R 2 is a monovalent hydrocarbon group.
• R2 is preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 15 carbon atoms, and these may be the same or different.
• Specific examples of the monovalent hydrocarbon group of R2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
• Dodecyl group tridecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups, cyclohexyl group and other cycloalkyl groups, vinyl group, allyl group and other alkenyl groups, phenyl group, trill group and other aryl groups and styryl groups.
• An aralkyl group such as ⁇ -methylstyryl group, or a chloromethyl group in which a part or all of the hydrogen atom bonded to the carbon atom of these groups is substituted with a halogen atom, a cyano group, an amino group, or a hydroxyl group, 3-chloro.
• a propyl group a 3,3,3-trifluoropropyl group, a cyanoethyl group, a 3-aminopropyl group, an N- ( ⁇ -aminoethyl) - ⁇ -aminopropyl group and the like.
• d is a number in the range of 200 to 1000, preferably a number in the range of 250 to 900, and more preferably a number in the range of 270 to 800.
• the polyorganosiloxane weight having a polyoxyalkylene group is selected by selecting the above range for d and combining it with the chain length of a specific range of (EO) and (PO) in the partial structure (II) described later.
• the defoaming performance and dilution stability of the emulsified defoaming agent are greatly improved by the combined crosslinked product.
• the partial structure (II) is one of the characteristic structures of the present invention, and is a polyoxyalkylene group bonded to a silicon atom via an alkylene group having a carbon atom number e, and has a constant number of ethyleneoxy units and a constant number. It always contains a number of propyleneoxy units and may optionally further contain butyleneoxy units. More specifically, in the partial structure (II), EO is an ethyleneoxy unit represented by C 2 H 4 O, and an ethylene oxy unit represented by CH 2 CH 2 O is preferable. PO is a propyleneoxy unit represented by C 3 H 6 O, and may be either CH 2 CH (CH 3 ) O or CH 2 CH 2 CH 2 O. preferable.
• BO is a butylene oxy unit represented by C 4 H 8 O, and may have any linear / branched butylene structure like the propylene oxy unit.
• R 3 is a hydrogen atom, an alkyl group, an aryl group or an acyl group.
• the alkyl group may be an unsubstituted or substituted alkyl group having 1 to 18 carbon atoms, particularly 1 to 15, and may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and the like.
• Examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group.
• the aryl group may be an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a tolyl group.
• the acyl group may be an acyl group having 2 to 12 carbon atoms, and examples thereof include an acetyl group, a propionyl group and a benzoyl group.
• e is a number in the range of 2 to 10, preferably a number in the range of 3 to 8.
• the alkylene group having the number of carbon atoms e represented by Ce H 2e preferably the alkylene group having the number of carbon atoms 3 to 8, may have a partially branched structure or a linear structure.
• x + y + z is a number in the range of 40 to 100
• x is a number in the range of 15 to 50
• y is a number in the range of 15 to 50
• z is a number in the range of 0 to 50.
• x is a number in the range 20-45
• y is a number in the range 20-45
• z is a number in the range 0-25
• x is a number in the range 20-40.
• Y is a number in the range of 20 to 40
• z is 0.
• the above range is selected for x, y and x + y (z may be 0), and combined with the polysiloxane structure having a chain length in the specific range in the above-mentioned partial structure (I).
• the defoaming performance and the dilution stability of the defoaming agent emulsified by the crosslinked polyorganosiloxane polymer having a polyoxyalkylene group are greatly improved.
• the crosslinked polyorganosiloxane polymer having a polyoxyalkylene group containing the partial structure (I) and the partial structure (II) has the following structural formula: It is preferably represented by.
• A is a partial structure (I): ⁇ R 1 ⁇ (R 2 2 SiO) d ⁇ R 1 ⁇ , and R 4 to R 7 and R 9 to R 12 are independently and monovalent hydrocarbons. It is a hydrogen group, and R 8 and R 13 have a partial structure (II):-(C e H 2e ) -O- (EO) x- (PO) y- (BO) z -R 3 . Further, the preferable range of the variables a to c representing the number of repetitions is as follows.
• a 1 ⁇ a ⁇ 1000, preferably 1 ⁇ a ⁇ 500, most preferably 1 ⁇ a ⁇ 250 b: 0 ⁇ b ⁇ 30, preferably 0 ⁇ b ⁇ 20, most preferably 0 ⁇ b ⁇ 15 c: 1 ⁇ c ⁇ 20, preferably 1 ⁇ c ⁇ 15, most preferably 0 ⁇ c ⁇ 10
• the monovalent hydrocarbon groups of R 4 to R 7 and R 9 to R 12 are preferably unsubstituted or substituted monovalent hydrocarbon groups having 1 to 18 carbon atoms, particularly 1 to 15 carbon atoms, and these are the same. It may or may not be different.
• Specific examples of the monovalent hydrocarbon group of R2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
• Dodecyl group tridecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups, cyclohexyl group and other cycloalkyl groups, vinyl group, allyl group and other alkenyl groups, phenyl group, trill group and other aryl groups and styryl groups.
• An aralkyl group such as ⁇ -methylstyryl group, or a chloromethyl group in which a part or all of the hydrogen atom bonded to the carbon atom of these groups is substituted with a halogen atom, a cyano group, an amino group, or a hydroxyl group, 3-chloro.
• a propyl group a 3,3,3-trifluoropropyl group, a cyanoethyl group, a 3-aminopropyl group, an N- ( ⁇ -aminoethyl) - ⁇ -aminopropyl group and the like. It is preferably an alkyl group, and particularly preferably a methyl group.
• the crosslinked polyorganosiloxane polymer having a polyoxyalkylene group containing the partial structure (I) and the partial structure (II) has the following structural formula: (In the formula, a is a number in the range of 10 to 200, b + c is a number in the range of 2 to 50, b and c are numbers of 1 or more, respectively, EO and PO are the same groups as described above, and R Is a hydrogen atom, an alkyl group, an aryl group or an acyl group, and d, x and y are the same numbers as those defined in the partial structures (I) and (II)). It is preferably represented by.
• R is a group similar to R 3 in the partial structure (II), and is a hydrogen atom, an alkyl group, an aryl group or an acyl group.
• the alkyl group may be an unsubstituted or substituted alkyl group having 1 to 18 carbon atoms, particularly 1 to 15, and may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and the like.
• Examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group.
• the aryl group may be an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a tolyl group.
• the acyl group may be an acyl group having 2 to 12 carbon atoms, and examples thereof include an acetyl group, a propionyl group and a benzoyl group.
• the crosslinked polyorganosiloxane polymer having a polyoxyalkylene group contained in the silicone defoaming agent composition of the present invention is obtained by the following reaction.
• the crosslinked polyorganosiloxane polymer having a polyoxyalkylene group is (i) a polyorganosiloxane having two or more Si—H groups in the middle chain of one molecule and a vinyl group or alkenyl at both ends.
• the polyorganosiloxane sealed with a group is hydrosilylated in isopropyl alcohol or toluene with a platinum catalyst to obtain a crosslinked siloxane, and the product obtained in steps (ii) and (i) is also a platinum catalyst.
• the components (a) and (b) are reacted, and the Si—H groups and vinyl thereof are reacted. It has the characteristics that a three-dimensional crosslinked structure is formed by an addition reaction with a group or an alkenyl group and that it has fluidity.
• the three-dimensional crosslinked structure represents a structure in which two or more molecules of polyorganosiloxane are bonded via two or more branched structures.
• the method for obtaining a specific siloxane crosslinked product having the above characteristics is not limited, and a method for obtaining a crosslinked product of a polyorganosiloxane polymer and adding a polyoxyalkylene group to the crosslinked product, and a polyoxyalkylene group. It is also possible to obtain a linear polyorganosiloxane to which the above is added and to crosslink the polyorganosiloxane.
• the crosslinked polyorganosiloxane polymer having a polyoxyalkylene group contained in the silicone defoaming agent composition of the present invention preferably has a viscosity at 25 ° C. of 100 to 100,000 mPa ⁇ s.
• the silicone defoaming agent composition of the present invention is (A) Intrinsically hydrophobic organopolysiloxane having a viscosity at 25 ° C. of 10-100,000 mPa ⁇ s: 20-80 parts by mass, (B) Hydrophobic organopolysiloxane or cyclic organopolysiloxane containing silanol groups at least at both ends: 20 to 80 parts by mass, (C) Silane or a condensate of silane: 1 to 10 parts by mass, and (D) Fine powder silica having a specific surface area of 50 m 2 / g or more: 2 to 10 parts by mass, the total of (A) and (B) It is preferable to further contain an oil compound for a silicone-based defoaming agent, which is 100 parts by mass.
• organopolysiloxane having a viscosity at 25 ° C. of 10 to 100,000 mPa ⁇ s The organopolysiloxane of the component (A) is essentially hydrophobic.
• essentially hydrophobic means that even if some functional groups contain hydrophilic groups, the organopolysiloxane as a whole exhibits hydrophobicity.
• the essentially hydrophobic organopolysiloxane (A) may be linear or branched, but the one represented by the following average composition formula (I) is preferable.
• R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 15 carbon atoms, which may be the same or different.
• the monovalent hydrocarbon group of R 1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
• Dodecyl group tridecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups, cyclohexyl group and other cycloalkyl groups, vinyl group, allyl group and other alkenyl groups, phenyl group, trill group and other aryl groups and styryl groups.
• An aralkyl group such as ⁇ -methylstyryl group, or a chloromethyl group in which a part or all of the hydrogen atom bonded to the carbon atom of these groups is substituted with a halogen atom, a cyano group, an amino group, or a hydroxyl group, 3-chloro.
• Examples thereof include a propyl group, a 3,3,3-trifluoropropyl group, a cyanoethyl group, a 3-aminopropyl group, an N- ( ⁇ -aminoethyl) - ⁇ -aminopropyl group, etc. From the aspect, it is preferable that 80 mol% or more, particularly 90 mol% or more of the total R 1 is a methyl group.
• G is a positive number of 1.9 ⁇ g ⁇ 2.2, preferably 1.95 ⁇ g ⁇ 2.15.
• the end of the organopolysiloxane may be sealed with the triorganosilyl group represented by R1 3 Si- or the diorganohydroxysilyl group represented by ( HO) R12 Si- . good.
• the viscosity of an essentially hydrophobic organopolysiloxane at 25 ° C. measured by a rotational viscometer is 10 to 100,000 mPa ⁇ s, and is 100 to 100 in terms of defoaming speed and sustainability of defoaming performance. It may be 000 mPa ⁇ s, preferably 2,500 to 50,000 mPa ⁇ s, more preferably 3,000 to 45,000 mPa ⁇ s, and most preferably 4,000 to 40,000 mPa ⁇ s. Is.
• the defoaming performance may be deteriorated, and if it exceeds the upper limit, the viscosity of the silicone-based defoaming agent oil compound may increase and the workability may be deteriorated.
• the component (A) is usually produced by ring-opening polymerization of cyclic low-molecular-weight siloxane such as octamethylcyclotetrasiloxane using a catalyst, but after polymerization, it contains cyclic low-molecular-weight siloxane as a raw material. It is preferable to use the distillate of this under heating and reduced pressure while aerating an inert gas during reaction generation.
• an essentially hydrophobic organopolysiloxane having a viscosity at 25 ° C. of 10 to 100,000 mPa ⁇ s may be used alone, or a mixture of two or more thereof may be used.
• the organopolysiloxane of the component (B) is hydrophobic or cyclic, containing silanol groups at least at both ends.
• the hydrophobicity means that, like the component (A), even if some functional groups contain a hydrophilic group, the organopolysiloxane as a whole exhibits hydrophobicity.
• the hydrophobic organopolysiloxane (B) containing a silanol group at least at both ends may be linear or branched, but the one represented by the following average composition formula (II) is preferable.
• R 2 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 15 carbon atoms, which may be the same or different.
• the monovalent hydrocarbon group of R2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
• Dodecyl group tridecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups, cyclohexyl group and other cycloalkyl groups, vinyl group, allyl group and other alkenyl groups, phenyl group, trill group and other aryl groups and styryl groups.
• An aralkyl group such as ⁇ -methylstyryl group, or a chloromethyl group in which a part or all of the hydrogen atom bonded to the carbon atom of these groups is substituted with a halogen atom, a cyano group, an amino group, or a hydroxyl group, 3-chloro.
• Examples thereof include a propyl group, a 3,3,3-trifluoropropyl group, a cyanoethyl group, a 3-aminopropyl group, an N- ( ⁇ -aminoethyl) - ⁇ -aminopropyl group and the like.
• R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 15 carbon atoms, which may be the same or different.
• the average value of p + q is preferably 1.9 to 2.2, q is a value sufficient to provide silanol groups at both ends, and at least one OH group is present at each end.
• the structure of the cyclic siloxane is not particularly limited, and examples thereof include those represented by the following average composition formula (III).
• R4 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 15 carbon atoms, particularly 1 to 10 carbon atoms, which may be the same or different.
• the monovalent hydrocarbon group of R4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
• Aralkyl groups such as, or chloromethyl group, 3-chloropropyl group, 3,3 in which a part or all of the hydrogen atom bonded to the carbon atom of these groups is substituted with a halogen atom, a cyano group, an amino group, or a hydroxyl group.
• R is preferably an integer of 3 to 20, more preferably an integer of 3 to 10.
• the component (B) is (B1) Hydrophobic organopolysiloxane containing silanol groups at both ends at 1,000 to 10,000,000 mPa ⁇ s, and (B2) Silanol groups at both ends at 1 to 1,000 mPa ⁇ s. It is preferable to contain hydrophobic organopolysiloxane or cyclic siloxane.
• the viscosity of a hydrophobic organopolysiloxane containing silanol groups at both ends at 25 ° C. as measured by a rotational viscometer is preferably 2,000 to 1,000,000 mPa ⁇ s, more preferably 5. It is 000 to 100,000 mPa ⁇ s.
• the viscosity of the hydrophobic organopolysiloxane containing silanol groups at both ends at 25 ° C. measured by a rotational viscometer is preferably 5 to 500 mPa ⁇ s, more preferably 10 to 100 mPa ⁇ s. Is.
• the component (B) can be used in an amount of 20 to 80 parts by mass with respect to 20 to 80 parts by mass of the component (A), and the total of the component (A) and the component (B) is 100 parts by mass.
• the component (B) can be used in an amount of 30 to 70 parts by mass with respect to 30 to 70 parts by mass of the component (A), and the total of the component (A) and the component (B) is 100 parts by mass.
• the molar ratio of the component (B) to the total amount of the component (A) and the component (B) is preferably 0.7 or more, more preferably 0.75 or more, and more preferably 0.8 or more. Most preferred.
• the molar ratio of the component (B1) to the total amount of the component (A) and the component (B1) is preferably 0.2 or more, more preferably 0.25 or more, and preferably 0.3 or more. Most preferred.
• silane or condensate of silane The structure of the silane of the component (C) or a condensate of silane is not particularly limited, and examples thereof include those represented by the following average composition formula (IV).
• R5 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 15 carbon atoms, particularly 1 to 10 carbon atoms, which may be the same or different.
• the monovalent hydrocarbon group of R5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
• Aralkyl groups such as, or chloromethyl group, 3-chloropropyl group, 3,3 in which a part or all of the hydrogen atom bonded to the carbon atom of these groups is substituted with a halogen atom, a cyano group, an amino group, or a hydroxyl group.
• Y is an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms, particularly 1 to 10 carbon atoms, for example, an alkylene group.
• Z is an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms, particularly 1 to 10 carbon atoms, for example, an alkylene group.
• the mean value of s is 1 or less, thus meaning that it is a single body of R5 SiX 3 or SiX 4 or a mixture thereof.
• Silane as a component (C) is a compound well known to those skilled in the art, and examples thereof include the following compounds.
• silane of the component (C) may be a partially hydrolyzed condensate thereof.
• the above-mentioned silane or a condensate of silane may be used alone, or two or more kinds may be mixed and used.
• the component (C) can be used in an amount of 1 to 10 parts by mass, preferably 2 to 5 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
• hydrophilic silica such as fumed silica or precipitated silica is desirable, and these can be used alone or in combination of two or more.
• the specific surface area (BET method) of the fine powdered silica is 50 m 2 / g or more, preferably 100 to 700 m 2 / g, and more preferably 150 to 500 m 2 / g. By setting the specific surface area to 50 m 2 / g or more, preferable defoaming performance can be obtained.
• AEROSIL® 300 hydrophilic fumed silica having a BET specific surface area of 300 m 2 / g
• AEROSIL® 200 hydrophilic fumed silica with a BET specific surface area of 200 m 2 / g
• NIPSIL® L-250 170 m 2 / g
• the ratio of the component (D) is 2 to 10 parts by mass, preferably in the range of 3 to 5 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). If it is less than 2 parts by mass, sufficient defoaming performance cannot be obtained, and if it exceeds 10 parts by mass, the viscosity of the obtained oil compound for silicone-based defoaming agent increases and workability deteriorates.
• Oil compound for silicone defoaming agent Oil compound for silicone defoamers (1) Step of kneading all or part of the components of the silicone-based defoaming oil compound, (2) A step of heat-treating the kneaded product obtained in the step (1) at 50 to 300 ° C. (3) A step of adding an alkali catalyst or an acid catalyst to the kneaded product obtained in the step (2) and kneading the kneaded product. (4) If the kneaded product obtained in the steps (3) is present, the remaining components of the oil compound for a silicone-based defoaming agent are added and kneaded, and the kneaded product obtained in the steps (5) and (4). It can be produced by a method including a step of neutralizing the catalyst in the obtained kneaded product.
• the alkali catalyst or acid catalyst used in step (3) in the method for producing an oil compound for a silicone-based defoaming agent is not particularly limited.
• the alkali catalyst a known alkali catalyst used for the equilibrium reaction of polysiloxane, an oxide of an alkali metal or an alkaline earth metal, a hydroxide, an alkoxide or a silanolate can be used, preferably potassium silanolate and silanolate. It is potassium hydroxide.
• the acid catalyst include organic acids such as acetic acid, butyric acid, maleic acid and citric acid, and inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid.
• an alkaline catalyst is preferable to an acid catalyst.
• the amount of the alkaline catalyst or acid catalyst used is 0.001 to 5 parts by mass, preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the component (A). It is by mass, more preferably 0.05 to 3 parts by mass. If it is less than 0.001 part by mass, a sufficient catalytic effect cannot be obtained, and if the amount exceeds 5 parts by mass, the effect of the catalyst is not significantly improved, which is disadvantageous in terms of cost.
• a neutralizing agent used in step (5) in the method for producing an oil compound for a silicone-based defoaming agent as a neutralizing agent for an alkaline catalyst, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid or a carboxylic acid in a solid state at room temperature.
• An acid can be used, preferably a carboxylic acid that is solid at room temperature.
• carboxylic acid solid at room temperature examples include monocarboxylic acids such as benzoic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, and terephthalic acid, citric acid, and isoquen.
• monocarboxylic acids such as benzoic acid
• dicarboxylic acids such as oxalic acid, malonic acid
• succinic acid glutaric acid, adipic acid, phthalic acid, isophthalic acid, and terephthalic acid, citric acid, and isoquen.
• Tricarboxylic acids such as acids, oxalosuccinic acids and aconitic acids are used.
• succinic acid which has a small acid dissociation constant, is strong as an acid, and is easily available, is preferable.
• an oxide of an alkali metal or an alkaline earth metal, a hydroxide, an alkoxide or silanolate can be used, and potassium silanolate and potassium hydroxide are preferable.
• the amount of the neutralizing agent used may be any amount that can neutralize the alkaline catalyst or the acid catalyst.
• the temperature of the components (A) to (C) or the components (A) to (D) is preferably 100 ° C. or lower, more preferably 80 ° C. or lower. Knead with. It is not necessary to heat from the outside, and it can be kneaded at room temperature (for example, 10 to 30 ° C.), and the temperature raised by the heat generated in the system due to the frictional resistance generated during kneading is adjusted to 100 ° C. or lower, especially 80 ° C. or lower. It is preferable to do so.
• the processing time of this step (1) largely depends on the kneading device and scale and cannot be unconditionally specified, but is usually 0.1 to 3 hours, particularly preferably about 0.5 to 2 hours.
• the kneaded product obtained in the step (1) is kneaded at 50 to 300 ° C., preferably 70 to 200 ° C., preferably while kneading. Heat treat. By setting the heat treatment temperature within the above range, excellent defoaming performance can be obtained.
• the processing time of this step (2) largely depends on the kneading device and the scale and cannot be unconditionally specified, but is usually 0.1 to 4 hours, particularly preferably about 0.5 to 2 hours.
• the step (3) in the method for producing an oil compound for a silicone-based defoaming agent is carried out by adding an alkali catalyst or an acid catalyst to the kneaded product obtained in the step (2) and kneading the mixture in the oil compound system. Is made alkaline or acidic. (3)
• the step can be carried out at 10 to 300 ° C, preferably 20 to 200 ° C.
• the processing time of this step (3) also depends largely on the kneading device and scale and cannot be unconditionally specified, but it is usually preferably about 0.05 to 3 hours, particularly preferably about 0.1 to 2 hours.
• Step (4) in the method for producing an oil compound for a silicone-based defoaming agent, if present in the kneaded product obtained in the step (3), is the remaining component of the oil compound for a silicone-based defoaming agent, for example, (. B)
• This is a step of adding and kneading a part of the component and the component (D), and is a step for immobilizing the reactive group of each component on the surface of fine powder silica.
• the step can be carried out at 50 to 300 ° C, preferably 70 to 200 ° C.
• the processing time of the step also depends largely on the kneading device and the scale and cannot be unconditionally specified, but it is usually about 0.05 to 6 hours, particularly preferably about 0.1 to 4 hours.
• the step (5) in the method for producing an oil compound for a silicone-based defoaming agent is a step of neutralizing the catalyst in the kneaded product obtained in the step (4), and is a step of 10 to 300 ° C., preferably 20 to 200 ° C. Can be done at ° C.
• the processing time of this step (3) also depends largely on the kneading device and scale and cannot be unconditionally specified, but is usually 0.1 to 4 hours, particularly preferably about 0.5 to 3 hours.
• the kneading machine used for kneading includes, for example, a planetary mixer, a kneader, a pressure kneader, a twin-screw kneader, an intensive mixer, and an ajihomo mixer.
• a disper and a planetary dispar examples thereof include a disper and a planetary dispar, but the present invention is not particularly limited.
• These kneaders can be used in any of the steps (1) to (5).
• the viscosity of the finally obtained oil compound for silicone defoaming agent at 25 ° C. measured by a rotational viscometer is 10,000 to 1,000,000 mPa ⁇ s, preferably 20,000 to 100,000 mPa. -S, more preferably 30,000 to 50,000 mPa ⁇ s.
• an oil compound for a silicone-based defoaming agent is emulsified by a crosslinked polyorganosiloxane polymer having a polyoxyalkylene group containing partial structures (I) and (II). It is preferable to have.
• the viscosity of the defoaming agent may be appropriately designed according to the emulsification conditions, the viscosity and the like.
• the crosslinked polyorganosiloxane polymer having a polyoxyalkylene group containing the partial structures (I) and (II) may be used alone or as a mixture of two or more, but the content thereof. Is preferably 5 to 95% by mass, more preferably 10 to 70% by mass, based on the total amount of the silicone defoaming agent composition. If the content is too large, the defoaming performance as a defoaming agent composition may be inferior. In addition, when blending, it can be an effective amount, but it is preferable to blend 20% by mass or more.
• EO is an ethyleneoxy unit represented by C 2 H 4 O, preferably an ethylene oxy unit represented by CH 2 CH 2 O.
• PO is represented by C 3 H 6 O.
• Polyoxyalkylene polymer exemplified in, sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxyethyleneoxypropylene alkyl ether, polyoxy.
• Nonionic surfactants such as ethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene bean oil, and polyoxyethylene hydrogenated bean oil may be used.
• the polyoxyalkylene polymer is blended to enhance the dispersibility of the silicone-based defoaming agent oil compound, and may be used alone or as a mixture of two or more kinds, but the content thereof is It is preferably 0 to 95% by mass, more preferably 0 to 70% by mass, based on the total amount of the silicone defoaming agent composition. If the content is too large, the defoaming performance as a defoaming agent composition may be inferior. In addition, when blending, it can be an effective amount, but it is preferable to blend 20% by mass or more.
• the nonionic surfactant is blended in order to enhance the dispersibility of the silicone-based defoaming oil compound, and may be used alone or as a mixture of two or more kinds.
• the content is preferably 0 to 95% by mass, more preferably 0 to 70% by mass, based on the entire silicone defoaming agent composition. If the content is too large, the defoaming performance as a defoaming agent may be inferior.
• it can be an effective amount, but it is preferable to blend 20% by mass or more.
• the content of the silicone defoaming agent oil compound is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and further preferably 20 to 20 to 70% by mass of the entire silicone defoaming agent composition. It is 60% by mass. If the content of the oil compound for silicone-based defoaming agent is too small, the defoaming performance as a defoaming agent composition may be inferior, and if it is too large, the purpose is to improve the dispersibility of the oil compound for silicone-based defoaming agent. You may not be satisfied.
• each component such as an oil compound for a silicone-based defoaming agent, a crosslinked product of a polyorganosiloxane polymer having a polyoxyalkylene group, a polyoxyalkylene polymer, and a nonionic surfactant is emulsified. It is necessary to add water necessary for the addition, and the amount thereof is the balance with respect to the total content ratio of each component, preferably 50 to 2,000 parts by mass with respect to the total 100 parts by mass of each component, more preferably. Is added so as to be 80 to 400 parts by mass.
• the silicone defoaming agent composition is prepared by mixing a predetermined amount of each component other than water and heating as necessary by a known method, for example, a mixer / disperser such as a homomixer, a homogenizer, or a colloid mill. It can be prepared by stirring and emulsifying, but in particular, after uniformly mixing and dispersing a predetermined amount of each component other than water, a part of water is added, and after stirring and emulsifying, the rest is further. A method of adding water, stirring and mixing uniformly is preferable.
• preservative / bactericidal agent may be optionally added to the silicone defoaming agent composition for the purpose of antiseptic.
• the preservative / bactericidal agent include sodium hypochlorite, sorbic acid, potassium sorbate, salicylic acid, sodium salicylate, benzoic acid, sodium benzoate, parabens, isothiazoline compounds and the like.
• the addition amount is preferably 0 to 0.5% by mass, particularly 0.005 to 0.5% by mass, based on the entire silicone defoaming agent composition.
• thickener may be optionally added to the silicone defoaming agent composition for the purpose of thickening.
• this thickener include polyacrylic acid, sodium polyacrylate, acrylic acid / methacrylic acid copolymer, sodium carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, xanthan gum, guar gum and the like.
• the addition amount is preferably 0 to 1.0% by mass, particularly preferably 0.01 to 0.5% by mass, based on the entire silicone defoaming agent composition.
• the particle size of the emulsion of the silicone defoaming agent composition is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 8 ⁇ m, and most preferably 0.7 to 6 ⁇ m.
• the particle size of the emulsion is the median diameter (particle size corresponding to 50% of the cumulative distribution, based on the number), and can be measured by a laser diffraction type particle size distribution measuring device.
• the silicone defoaming agent composition of the present invention comprises metal processing oils such as cutting oils, grinding oils, plastic processing oils, heat treatment oils and discharge processing oils; engine oils such as gasoline engine oils, diesel engine oils and gas engine oils; automatic It is preferably used in automobile gear oils such as transmission oils and manual transmission oils; industrial gear oils; turbine oils; bearing oils; and rust preventive oils.
• metal processing oils such as cutting oils, grinding oils, plastic processing oils, heat treatment oils and discharge processing oils
• engine oils such as gasoline engine oils, diesel engine oils and gas engine oils
• automatic It is preferably used in automobile gear oils such as transmission oils and manual transmission oils; industrial gear oils; turbine oils; bearing oils; and rust preventive oils.
• the self-emulsifying compound was dispersed in water and measured with a laser diffraction type particle size distribution measuring device (LS-230 manufactured by Beckman Coulter), and the median diameter (particle size corresponding to 50% of the cumulative distribution, 50% particle size) was measured. was taken as the average particle size.
• the silicone-based defoaming agent oil compound # 1 was produced by the following method. That is, a trimethylsilyl group-terminated closed polydimethylsiloxane (viscosity at 25 ° C., 1,000 mPa ⁇ s) 59.10 was placed in a 1 L capacity three-necked flask equipped with a stirrer, a thermometer, a reflux cooling tube, and a nitrogen gas input.
• silica (Aerosil 200” specific surface area 200 m 2 / g, manufactured by Evonik Industries, Inc.) was added, heated at 110 ° C. for 30 minutes, and uniformly dispersed using a homomixer. A mixture of 0.02 parts by mass of 501 W of polyether-modified silicone and 0.13 parts by mass of ion-exchanged water is added, and after stirring, 5.15 parts by mass of silanol group-terminated closed polydimethylsiloxane (viscosity at 25 ° C. 40 mPa ⁇ s) is added. It was added and the temperature was raised to 190 ° C.
• Example 1 45 parts by mass of a crosslinked polyorganosiloxane polymer having a polyoxyalkylene group and 25 parts by mass of an EOPOEO copolymer (Adecapluronic (registered trademark) L-31) produced in Production Examples 1 to 3 and Comparative Production Examples 1 and 2. After mixing, 30 parts by mass of the above-mentioned silicone-based defoaming agent oil compound # 1 was added, and a self-emulsifying defoaming agent composition was obtained using a homomixer. The diluted appearance of the obtained defoaming agent composition was a slightly bluish emulsion.
• Examples 2 and 3 and Comparative Examples 1 and 2 A defoaming agent composition was prepared in the same procedure as in Example 1 except that the crosslinked polyorganosiloxane polymer having a polyoxyalkylene group was changed as shown in Table 3. The diluted appearance of the obtained defoaming agent composition was a slightly bluish emulsion.
• a mixture of 0.1 part by mass of 501 W of polyether-modified silicone and 0.13 part by mass of ion-exchanged water is added, and after stirring, 5.15 parts by mass of silanol group-terminated closed polydimethylsiloxane (viscosity at 25 ° C. 40 mPa ⁇ s) is added. It was added and the temperature was raised to 190 ° C. 1.25 parts by mass of a potassium dimethyl silanolate catalyst was added, and the mixture was reacted at 190 ° C. for 1 hour.
• Example 4 follows the same procedure as in Example 1 except that the above-mentioned oil compound # 2 for silicone-based defoaming agent is used instead of the oil compound # 1 for silicone-based defoaming agent.
• the antifoaming agent compositions of 6 to 6 were prepared, and the evaluation results are shown in Table 4.
• Table 4 Examples 4 to 6
• the defoaming sustainability is further excellent, and in the present invention, the defoaming according to the present invention is made. It is expected that better defoaming property can be realized by using the agent oil compound in combination with the crosslinked product of a polyorganosiloxane polymer having a polyoxyalkylene group having an optimized structure.

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