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
• • 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
  • 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
• • 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
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
• • 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
  • C10N2040/25—Internal-combustion engines

Definitions

• the present invention relates to an antifoaming agent, a lubricating oil composition containing the antifoaming agent, and a machine using the lubricating oil composition.
• the problem to be solved by the present invention is to provide a defoaming agent that exhibits excellent defoaming properties even in a high-temperature environment.
• Another problem to be solved by the present invention is to provide a lubricating oil composition that is capable of exhibiting excellent lubricating performance even in a high-temperature environment.
• a polymer having as at least one polymerization component a polymerizable monomer having a specific silicone functional group and two or more polymerizable unsaturated groups is an antifoaming agent that exhibits excellent antifoaming properties even in high temperature environments, and thus completed the present invention.
• A-3 a polymerizable monomer
• Each R 13 independently represents a hydrogen atom or a methyl group
• R 51 is independently an alkyl group having 1 to 6 carbon atoms
• L 15 is a divalent organic group which may have an ether bond
• a is a repeating unit and is an integer of 0 to 3.
• A-4 a polymer having as at least a polymerization component a polymerizable monomer (A′′) which is a compound represented by the following general formula (A-4):
• Each R 13 is independently a hydrogen atom or a methyl group
• Each R 52 is independently an alkyl group having 1 to 6 carbon atoms
• Each L 16 is independently a divalent organic group which may have an ether bond.
• Each R 13 independently represents a hydrogen atom or a methyl group
• R 53 is independently an alkyl group having 1 to 6 carbon atoms
• Each R 54 is independently an alkyl group having 1 to 6 carbon atoms
• Each L 17 independently represents a divalent organic group which may have an ether bond
• each t is a repeating unit, each independently an integer from 1 to 100
• u is a repeating unit and is an integer from 1 to 10.
• Each R 13 independently represents a hydrogen atom or a methyl group;
• Each R 55 is independently an alkyl group having 1 to 6 carbon atoms;
• Each L 18 independently represents a divalent organic group which may have an ether bond;
• v is a repeating unit, each independently an integer from 1 to 100.
• r is an integer of 2 or more
• L31 is an organic group which may have an ether bond having a valence of r.
• the defoaming agent according to [1] which contains a polymerizable monomer (D) in which the number of polymerizable unsaturated groups in the polymerizable monomer (A) is one.
• the lubricating oil composition according to [18] which is used to lubricate a driving part of a machine equipped with an internal combustion engine or an electric motor.
• the lubricating oil composition according to [18] which is used in a vehicle equipped with an internal combustion engine or an electric motor to lubricate a driving part of the vehicle.
• the present invention provides a defoaming agent that exhibits excellent defoaming properties even in a high-temperature environment.
• the present invention can provide a lubricating oil composition that exhibits excellent lubricating performance even in a high-temperature environment.
• (meth)acrylate refers to either or both of an acrylate and a methacrylate.
• the defoaming agent of the present invention contains a polymer having at least a polymerizable monomer (A) as a polymerization component, which is a polymerizable monomer (a1) having a polysiloxane structure represented by -[OSi(R) 2 ] x - (each R is independently an alkyl group having 1 to 6 carbon atoms; x is the number of repetitions) and having two or more polymerizable unsaturated groups, and/or a polymerizable monomer (a2) having a functional group represented by -Si[OSi(R) 3 ] n [R'] 3-n (n is an integer of 1 to 3; each R is independently an alkyl group having 1 to 6 carbon atoms; each R' is independently an alkyl group having 1 to 6 carbon atoms) and having two or more polymerizable unsaturated groups.
• the term "polymerization component” as used herein means a component that constitutes a polymerizable monomer
• the term "polymerizable monomer” refers to a compound having a polymerizable unsaturated group
• examples of the polymerizable unsaturated group contained in the polymerizable monomer (A) include a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinyl ether group, an allyl group, a styryl group, a (meth)acryloylamino group, and a maleimide group.
• a polymer having as at least a polymerization component the polymerizable monomer (A) contained in the defoaming agent of the present invention may be referred to as the "polymer of the present invention".
• the polymer of the present invention Each component constituting the polymer of the present invention will be described below.
• the polysiloxane structure represented by --[OSi(R) 2 ] x -- contained in the polymerizable monomer (A) is preferably a polydimethylsiloxane structure.
• the functional group represented by -Si[OSi(R) 3 ] n [R'] 3-n contained in the polymerizable monomer (A) is preferably a functional group represented by -Si[OSi(R) 3 ] 3 , and more preferably -Si[OSi(CH 3 ) 3 ] 3 .
• the polymerizable monomer (A) is preferably a compound represented by the following general formula (A-1) and/or a compound represented by the following general formula (A-2).
• R 11 is each independently an alkyl group having 1 to 6 carbon atoms
• R 12 is independently an alkyl group having 1 to 6 carbon atoms
• Each R 13 independently represents a hydrogen atom or a methyl group
• R 14 is an alkyl group having 1 to 12 carbon atoms
• R 15 each independently represents an alkyl group having 1 to 6 carbon atoms or a group represented by -OSi(R 16 ) 3 (each R 16 independently represents an alkyl group having 1 to 6 carbon atoms)
• x indicates the number of repetitions
• y is an integer of 1 or more
• z1 and z2 each independently represent an integer of 1 or more
• z3 is an integer of 2 or more
• L 11 is an organic group having a valence of z1+1 which may have an ether bond
• L 12 is an organic group having a valence of z2+1 which may have an ether bond
• L 13 is an organic group having a valence of z
• P is a polymerizable group represented by general formula (P-1), a polymerizable group represented by general formula (P-2), or a polymerizable group represented by general formula (P-3).
• R 13 is a hydrogen atom or a methyl group.
• R 17 is a hydrogen atom or an organic group. * is a bond bonded to L11 or L14 .
• the polymerizable monomer (A) is more preferably a compound represented by the general formula (A-1) and/or a compound represented by the general formula (A-2), in which P is a polymerizable group represented by the general formula (P-1), and is represented by the following general formula:
• the alkyl group having 1 to 6 carbon atoms for R 11 , R 12 , R 15 and R 16 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
• the alkyl group having 1 to 12 carbon atoms for R 14 is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
• the organic group for R 17 may be, for example, an alkyl group having 1 to 18 carbon atoms.
• the alkylene group having 1 to 18 carbon atoms for R 17 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, an isopropyl group, a 2-methylpropyl group, a 2-methylhexyl group, and a tetramethylethyl group.
• the number of repetitions of x may be, for example, an integer of 1 or more.
• the number average of x is, for example, in the range of 1 to 150, preferably in the range of 1 to 75, more preferably in the range of 1 to 50, and further preferably in the range of 1 to 20.
• the number average value of x can be confirmed by measuring the number average molecular weight of the polymerizable monomer (A) by the method described in the Examples.
• z1 is an integer of 1 or more, preferably an integer in the range of 1 to 4, more preferably an integer of 1 or 2, and even more preferably 1.
• the divalent organic group is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.
• Examples of the alkylene group having 1 to 50 carbon atoms for L 11 include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decylene group, an n-dodecylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group.
• the alkylene group having 1 to 50 carbon atoms for L 11 is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group.
• the alkyleneoxy group having 1 to 50 carbon atoms for L 11 is, for example, a group in which one or more —CH 2 — within the alkylene group is substituted with —O—.
• the alkyleneoxy group having 1 to 50 carbon atoms for L11 is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and even more preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a propyleneoxyethylene group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group, or an octyleneoxy group.
• divalent organic group of L11 is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms
• the divalent organic group of L 11 is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms
• a carbon atom of these groups may further be substituted with a substituent such as a hydroxyl group.
• the trivalent or higher valent organic group is, for example, an organic group in which a hydrogen atom bonded to a carbon atom of the above-described divalent organic group is replaced with a bond so as to have a corresponding valence.
• z2 is an integer of 1 or more, preferably an integer in the range of 1 to 4, more preferably an integer of 1 or 2, and even more preferably 1.
• the z2+1 valent organic group of L 12 is the same as the z1+1 valent organic group of L 11 .
• y is an integer of 1 or more, preferably an integer in the range of 1 to 4, more preferably an integer in the range of 1 to 3, and even more preferably 1 or 2.
• z3 is an integer of 2 or more, preferably an integer in the range of 2 to 6, more preferably an integer of 2 or 3, and even more preferably 2.
• the z3+y valent organic group of L 13 can be the same as the organic group of the z1+1 valent organic group of L 11 having a valence corresponding to L 13.
• L 13 is a trivalent organic group
• the trivalent organic group of L 13 may be the same as the trivalent organic group of L 11 .
• the divalent organic group of L 14 is the same as the divalent organic group of L 11 .
• the defoaming agent of the present invention may be in an embodiment that contains not only the above-mentioned polymerizable monomer (A), but also the polymerizable monomer (A'), polymerizable monomer (A"), polymerizable monomer (A'"), and polymer having polymerizable monomer (A"") as at least one polymerization component, as shown below. These embodiments are described below.
• the polymerizable monomer (A') is a compound represented by the following general formula (A-3) that has a cyclic siloxane structure and 3 to 6 (meth)acrylate groups branched therefrom.
• Each R 13 independently represents a hydrogen atom or a methyl group;
• R 51 is independently an alkyl group having 1 to 6 carbon atoms;
• L 15 is a divalent organic group which may have an ether bond;
• a is a repeating unit and is an integer of 0 to 3.
• R 51 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
• a is preferably 1 or 2, more preferably 1.
• adjacent Si and O are bonded to form a cyclic siloxane compound having three (meth)acrylate groups.
• the -Si-O- in the cyclic siloxane structure also increases, and when a is 2, the compound has five (meth)acrylate groups, and when a is 3, the compound has six (meth)acrylate groups.
• the divalent organic group of L 15 is the same as L 11 described above, and is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.
• Specific examples of the compound represented by the general formula (A-3) include the compounds represented by the following formulas (A-3-1), (A-3-2), (A-3-3), (A-3-4), (A-3-5), and (A-3-6).
• the polymerizable monomer (A'') is a linear siloxane compound having (meth)acrylate groups at both ends, represented by the following general formula (A-4):
• Each R 13 independently represents a hydrogen atom or a methyl group;
• Each R 52 is independently an alkyl group having 1 to 6 carbon atoms;
• Each L 16 is independently a divalent organic group which may have an ether bond.
• R 52 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
• L 16 in general formula (A-4) is the same as L 15 in general formula (A-3), and is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.
• Specific examples of the compound represented by the general formula (A-4) include the compounds represented by the following formulas (A-4-1) and (A-4-2).
• the polymerizable monomer (A''') is a compound having one or more (meth)acrylate groups and a branched siloxane structure, represented by the following general formula (A-5):
• Each R 13 independently represents a hydrogen atom or a methyl group
• R 53 is independently an alkyl group having 1 to 6 carbon atoms
• Each R 54 is independently an alkyl group having 1 to 6 carbon atoms
• Each L 17 independently represents a divalent organic group which may have an ether bond
• each t is a repeating unit, each independently an integer from 1 to 100
• u is a repeating unit and is an integer from 1 to 10.
• R 53 and R 54 are preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
• the number average of t is, for example, in the range of 0 to 150, preferably in the range of 0 to 75, more preferably in the range of 0 to 50, and even more preferably in the range of 0 to 20.
• u is preferably 1 to 4, more preferably 1 to 2.
• L 17 in general formula (A-5) is the same as L 15 in general formula (A-3), and is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.
• Specific examples of the compound represented by the general formula (A-5) include the compounds represented by the formulae (A7), (A8), and (A9) described in Synthesis Example 7 below, and the compounds represented by the following formulae (A7'), (A8'), and (A9') (wherein t1, t2, and t3 are each independently an integer from 0 to 7).
• the polymerizable monomer (A''') is a compound represented by the following general formula (A-6):
• Each R 13 independently represents a hydrogen atom or a methyl group;
• Each R 55 is independently an alkyl group having 1 to 6 carbon atoms;
• Each L 18 independently represents a divalent organic group which may have an ether bond;
• v is a repeating unit, each independently an integer from 1 to 100.
• R 55 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
• the number average of v is, for example, in the range of 1 to 150, preferably in the range of 1 to 75, more preferably in the range of 1 to 50, and even more preferably in the range of 1 to 20.
• L 18 in general formula (A-6) is the same as L 15 in general formula (A-3), and is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.
• Specific examples of the compound represented by the general formula (A-6) include the compounds represented by formula (A10) in Synthesis Example 8 below and the compounds represented by the following formula (A10').
• the polymerizable monomer (A) can be produced by a known method.
• the polymerizable monomer (A) can be produced by reacting a compound having a linking group represented by -[OSi(R) 2 ] x - and/or a functional group represented by -Si[OSi(R) 3 ] n [R'] 3-n and two or more hydroxyl groups, with a compound having an isocyanate group and a polymerizable unsaturated group.
• the polymerizable monomer (A) can also be produced by, for example, reacting a compound having a linking group represented by -[OSi(R) 2 ] x - and/or a functional group represented by -Si[OSi(R) 3 ] n [R'] 3-n and a polymerizable unsaturated group with an alcohol having a mercapto group to produce a precursor, and then reacting the precursor with a compound having an isocyanate group and two or more polymerizable unsaturated groups.
• the polymerizable monomer (A'), polymerizable monomer (A"), polymerizable monomer (A'"), and polymerizable monomer (A"”) can also be produced in the same manner as the polymerizable monomer (A).
• the lower limit of the content of the polymerizable monomer (A) is, for example, 3 mass% or more, 5 mass% or more, 10 mass% or more, 20 mass% or more, 25 mass% or more, or 30 mass% or more, based on the total amount of the polymerization components of the polymer.
• the upper limit of the content of the polymerizable monomer (A) is, for example, 90 mass % or less, 80 mass % or less, 75 mass % or less, 70 mass % or less, or 60 mass % or less based on the total amount of polymerization components of the polymer.
• the combination of the upper and lower limits of the content of the polymerizable monomer (A) may be, for example, in the range of 3 mass % to 90 mass % of the total amount of the polymerization components of the polymer, preferably in the range of 5 mass % to 75 mass %, and more preferably in the range of 30 mass % to 70 mass % of the total amount of the polymerization components of the polymer.
• the content ratio of the polymerizable monomer (A) can be adjusted by the raw material charge ratio of the polymerizable monomer (A) when producing the polymer of the present invention.
• the polymerizable monomer (A'), polymerizable monomer (A"), polymerizable monomer (A"'), and polymerizable monomer (A"" are also in the same ratio as the polymerizable monomer (A).
• the polymerization component of the polymer of the present invention preferably has one or more groups selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain, and a group containing a polyester chain, and further contains a polymerizable monomer (B) having one polymerizable unsaturated group.
• a polymerizable monomer (B) having one polymerizable unsaturated group.
• the alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (B) may be any one of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a n-butyl group, a t-butyl group, a n-hexyl group, a cyclohexyl group, a n-octyl group, and a hexadecyl group.
• the alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (B) is preferably an alkyl group having 1 to 6 carbon atoms.
• aromatic groups having 6 to 18 carbon atoms contained in the polymerizable monomer (B) include phenyl groups, naphthyl groups, anthracen-1-yl groups, and phenanthren-1-yl groups.
• the group containing a (poly)oxyalkylene chain contained in the polymerizable monomer (B) is a monovalent group containing a repeating oxyalkylene portion or a divalent linking group containing a repeating oxyalkylene portion.
• the group containing a polyester chain in the polymerizable monomer (B) is a monovalent group containing a repeating ester bond portion or a divalent linking group containing a repeating ester bond portion.
• the alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (B) may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group.
• the aromatic group having 6 to 18 carbon atoms contained in the polymerizable monomer (B) may further have a substituent, and examples of the substituent include a hydroxyl group and an alkyl group.
• Examples of the polymerizable monomer (B) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and ethyl (meth)acrylate.
• (meth)acrylic acid alkyl esters having 1 to 18 carbon atoms such as dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and the like; and (meth)acrylic acid bridged cyclic alkyl esters having 1 to 18 carbon atoms, such as dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate
• Examples of polymerizable monomer (B) having a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include benzyl (meth)acrylate, phenoxymethyl (meth)acrylate, and 2-phenoxyethyl (meth)acrylate.
• Examples of the polymerizable monomer (B) having an alkyl group with 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a vinyl ether group include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; cycloalkyl vinyl ethers, etc.
• polymerizable monomers (B) having an aromatic group with 6 to 18 carbon atoms examples include styrene, ⁇ -methylstyrene, p-methylstyrene, and p-methoxystyrene.
• Examples of the polymerizable monomer (B) having an alkyl group with 1 to 18 carbon atoms and a polymerizable unsaturated group being a (meth)acryloylamino group include N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, and acroylmorpholine.
• Examples of the polymerizable monomer (B) having an alkyl group with 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a maleimide group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.
• Examples of the polymerizable monomer (B) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol.propylene glycol) mono(meth)acrylate, polyethylene glycol.polypropylene glycol mono(meth)acrylate, poly(ethylene glycol.tetramethylene glycol) mono(meth)acrylate, polyethylene glycol.polytetramethylene glycol ethylene glycol mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, polypropylene glycol-polytetramethylene glycol mono(meth)acrylate, polypropylene glycol-polyte
• poly(ethylene glycol-propylene glycol) means a random copolymer of ethylene glycol and propylene glycol
• polyethylene glycol-polypropylene glycol means a block copolymer of ethylene glycol and propylene glycol
• the polymerizable monomer (B) is preferably at least one selected from the group consisting of a compound represented by the following general formula (B-1), a compound represented by the following general formula (B-2), a compound represented by the following general formula (B-3), a compound represented by the following general formula (B-4), a compound represented by the following general formula (B-5), a compound represented by the following general formula (B-6), a compound represented by the following general formula (B-7), a compound represented by the following general formula (B-8), a compound represented by the following general formula (B-9), and a compound represented by the following general formula (B-10).
• B-1 a compound represented by the following general formula (B-1), a compound represented by the following general formula (B-2), a compound represented by the following general formula (B-3), a compound represented by the following general formula (B-4), a compound represented by the following general formula (B-5), a compound represented by the following general formula (B-6), a compound represented by the following general formula (B-7), a compound represented by
• R21 is a hydrogen atom or a methyl group
• R 22 is an alkyl group having 1 to 18 carbon atoms
• R 23 is a hydrogen atom or a methyl group
• R 24 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms
• R 25 is a hydrogen atom or a methyl group
• R 26 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having an ether bond having 1 to 18 carbon atoms
• R 27 is a hydrogen atom or a methyl group
• R 28 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having an ether bond having 1 to 18 carbon atoms
• R 29 is a hydrogen atom or a methyl group
• R 30 is independently an alkyl group having 1 to 18 carbon atoms
• R 23 is a hydrogen atom or a methyl group
• R 24 is a hydrogen atom or
• the m's in the parentheses may be the same or different.
• the q p's in the parentheses may be the same or different.
• the q p's in the parentheses may be the same or different.
• the m's in the parentheses may be the same or different.
• the q p's in the parentheses may be the same or different.
• the q p's in the parentheses may be the same or different.
• the alkyl group having 1 to 18 carbon atoms represented by R 22 , R 24 , R 26 and R 28 may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group.
• the alkyl group having 1 to 18 carbon atoms and an ether bond represented by R 26 and R 28 may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group.
• the alkyl group having 1 to 6 carbon atoms represented by R 30 may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group.
• the alkoxy group having 1 to 6 carbon atoms represented by R 30 may further have a substituent, and examples of the substituent include a hydroxyl group and an aryl group.
• the divalent organic groups of L 19 to L 22 in the formulae (B-1) to (B-4) may be the same as those in the case where L 11 is a divalent organic group.
• m represents the number of repetitions, and may be, for example, an integer of 1 or more.
• the number average of m is, for example, in the range of 1 to 100, preferably in the range of 2 to 30, and more preferably in the range of 3 to 15.
• the number average value of m can be confirmed by measuring the number average molecular weight of the polymerizable monomer (B) by the method described in the Examples.
• q indicates the number of repetitions, and may be, for example, an integer of 1 or more.
• the numerical average of q is, for example, in the range of 1 to 100, preferably in the range of 2 to 30, and more preferably in the range of 3 to 15.
• r1 and r4 to r6 are preferably 2 or 3, and more preferably 2.
• Each of r2 and r3 is preferably 1 or 2, more preferably 1.
• the polymerizable monomer (B) preferably includes compounds represented by the above formulas (B-2), (B-7) and (B-8).
• the polymerizable monomer (B) preferably contains one or more compounds selected from the group consisting of compounds represented by the formulas (B-2), (B-3), (B-4), (B-5), (B-6), (B-7), (B-8), (B-9), and (B-10).
• the polymerizable monomer (B) contains one or more selected from the group consisting of the compounds represented by the formulas (B-2), (B-3), (B-4), (B-5), (B-6), (B-7), (B-8), (B-9), and (B-10)
• the total amount of the compounds represented by the formulas (B-2), (B-3), and (B-4) and the compounds represented by the formulas (B-7), (B-8), (B-9), and (B-10 relative to the total amount of the polymerizable monomer (B) is, for example, 1 mass% or more, preferably 5 mass% or more, and more preferably 7 mass% or more.
• the polymerizable monomer (B) which is a polymerization component may be one type alone, or may be two or more types of polymerizable monomers (B) which are different in structure from each other.
• the polymerizable monomer (B) can be produced by a known method, and a commercially available product may be used.
• the content of the polymerizable monomer (B) is, for example, in the range of 0.1 to 900 parts by mass relative to 100 parts by mass of the polymerizable monomer (A), preferably in the range of 1 to 500 parts by mass relative to 100 parts by mass of the polymerizable monomer (A), more preferably in the range of 5 to 300 parts by mass relative to 100 parts by mass of the polymerizable monomer (A). Further preferably, it is in the range of 10 to 200 parts by mass relative to 100 parts by mass of the polymerizable monomer (A).
• the content of the polymerizable monomer (B) is the same for 100 parts by mass of the polymerizable monomer (A'), the polymerizable monomer (A'', the polymerizable monomer (A'"), and the polymerizable monomer (A"").
• the content of the polymerizable monomer (B) can be adjusted by the raw material charge ratio of the polymerizable monomer (B) when producing the polymer of the present invention.
• the proportion of the polymerizable monomer (B) in the polymerization components is, for example, in the range of 5 to 90% by mass, preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and particularly preferably 30 to 60% by mass, based on the total amount of the polymerization components of the polymer.
• the polymerization components of the polymer of the present invention preferably include, as optional components, polymerizable monomer (A), polymerizable monomer (A'), polymerizable monomer (A"), polymerizable monomer (A'"), and polymerizable monomer (C) having two or more polymerizable unsaturated groups other than polymerizable monomer (A""').
• the polymerizable monomer (C) is not particularly limited as long as it is a polymerizable monomer having two or more polymerizable unsaturated groups and does not fall under the polymerizable monomers (A) and (B) described above, but is preferably a compound represented by the following general formula (C-1).
• R 36 is a hydrogen atom or a methyl group.
• r is an integer of 2 or more,
• L31 is an organic group which may have an ether bond having a valence of r.
• r may be an integer of 2 or more, for example, an integer in the range of 2 to 12, preferably an integer in the range of 2 to 8, more preferably an integer in the range of 2 to 6, and even more preferably an integer in the range of 2 to 4.
• the r-valent organic group of L 31 is an organic group having a valence corresponding to the numerical value of r. For example, when r is 2, it is a divalent organic group, and when r is 6, it is a hexavalent organic group.
• Examples of the alkylene group having 1 to 50 carbon atoms for L 31 include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decylene group, an n-dodecylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group.
• the alkylene group having 1 to 50 carbon atoms for L 31 is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group.
• the alkyleneoxy group having 1 to 50 carbon atoms for L 31 is, for example, a group in which one or more —CH 2 — within the alkylene group is substituted with —O—.
• the alkyleneoxy group having 1 to 50 carbon atoms for L 31 is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and even more preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group, or an octyleneoxy group.
• the divalent organic group of L 31 is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms
• a carbon atom of these groups may further be substituted with a substituent such as a hydroxyl group.
• polymerizable monomer (C) examples include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxy-3-methacrylpropyl acrylate, 2-hydroxy-1,3-dimethacryloxypropane, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethoxylated bisphenol A,
• the acrylates include Nol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate,
• the polymerizable monomer (C) that is the polymerization component may be one type alone, or may be two or more types of polymerizable monomers (C) that are different in structure from each other.
• the polymerizable monomer (C) can be produced by a known method, and a commercially available product may be used.
• the content of the polymerizable monomer (C) is, for example, in the range of 1 to 300 parts by mass relative to 100 parts by mass of the polymerizable monomer (A), preferably in the range of 5 to 250 parts by mass relative to 100 parts by mass of the polymerizable monomer (A), more preferably in the range of 10 to 200 parts by mass relative to 100 parts by mass of the polymerizable monomer (A), and further preferably in the range of 10 to 150 parts by mass relative to 100 parts by mass of the polymerizable monomer (A).
• the content of the polymerizable monomer (C) can be adjusted by the raw material charge ratio of the polymerizable monomer (C) when producing the polymer of the present invention.
• the content of the polymerizable monomer (C) is, for example, 5 to 70% by mass, preferably 6 to 65% by mass, more preferably 7 to 60% by mass, particularly preferably 8 to 55% by mass, and most preferably 10 to 50% by mass, based on the total amount of the polymerized components of the polymer.
• the polymerization components of the polymer of the present invention may contain a polymerizable monomer (D) in which the number of polymerizable unsaturated groups in the polymerizable monomer (A) is reduced to one.
• the polymerizable monomer (D) is preferably a compound represented by the following general formula (D-1):
• R 41 is independently an alkyl group having 1 to 6 carbon atoms or a group represented by -OSi(R 44 ) 3 (each R 44 is independently an alkyl group having 1 to 3 carbon atoms);
• Each R 42 is independently an alkyl group having 1 to 6 carbon atoms;
• R 43 is an alkyl group having 1 to 12 carbon atoms;
• R 45 is a hydrogen atom or a methyl group;
• L 41 is a divalent organic group which may have an ether bond; s indicates the number of repetitions.
• the divalent organic group of L 41 is preferably a single bond, an alkylene group having 1 to 50 carbon atoms, or an alkyleneoxy group having 1 to 50 carbon atoms.
• Examples of the alkylene group having 1 to 50 carbon atoms for L 41 include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decylene group, an n-dodecylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group.
• the alkylene group having 1 to 50 carbon atoms for L 41 is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group.
• the alkyleneoxy group having 1 to 50 carbon atoms for L 41 is, for example, a group in which one —CH 2 — in the alkylene group is replaced with —O—.
• the alkyleneoxy group having 1 to 50 carbon atoms for L 41 is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and even more preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group, or an octyleneoxy group.
• the divalent organic group of L 41 is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms
• the number of repetitions of s may be, for example, an integer of 1 or more.
• the number average of s is, for example, in the range of 1 to 150, preferably in the range of 1 to 100, more preferably in the range of 1 to 50, and further preferably in the range of 1 to 25.
• the number average value of s can be confirmed by measuring the number average molecular weight of the polymerizable monomer (D) by the method described in the Examples.
• the alkyl group having 1 to 6 carbon atoms for R 41 and R 42 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
• the alkyl group having 1 to 12 carbon atoms for R 43 is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
• the polymerizable monomer (D) can be produced by a known method, and a commercially available product may be used. Specific examples of the polymerizable monomer (D) include ⁇ -(3-methacryloyloxy)propylpolydimethylsiloxane, 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane, and the like.
• the polymerizable monomer (D) which is a polymerization component may be one type alone or two or more types.
• the content ratio of the polymerizable monomer (D) is, for example, in the range of 10 to 500 parts by mass relative to 100 parts by mass of the polymerizable monomer (A), preferably in the range of 30 to 400 parts by mass relative to 100 parts by mass of the polymerizable monomer (A), and more preferably in the range of 50 to 300 parts by mass relative to 100 parts by mass of the polymerizable monomer (A).
• the content of the polymerizable monomer (D) can be adjusted by the raw material charge ratio of the polymerizable monomer (D) when producing the polymer of the present invention.
• the polymer of the present invention may be, for example, a polymer having the polymerizable monomer (A), the optional polymerizable monomer (B), and the optional polymerizable monomer (C) as polymerization components, and may contain other polymerizable monomers as polymerization components other than the polymerizable monomer (A), the optional polymerizable monomer (B), and the optional polymerizable monomer (C) within a range that does not impair the effects of the present invention.
• examples of such other polymerizable monomers as polymerization components include the above-mentioned polymerizable monomer (D).
• the polymer of the present invention is preferably a polymer whose polymerization components are substantially composed of the polymerizable monomer (A) and the optional polymerizable monomer (B) and/or the optional polymerizable monomer (C), and more preferably a copolymer whose polymerization components are composed only of the polymerizable monomer (A), the optional polymerizable monomer (B) and/or the optional polymerizable monomer (C).
• substantially consisting of refers to a case where the total content of the polymerizable monomer (A), the optional polymerizable monomer (B) and the optional polymerizable monomer (C) in the polymerization components of the polymer of the present invention is 80 mass% or more, 90 mass% or more, 95 mass% or more, or 99 mass% or more.
• the polymerization method for the polymer of the present invention is not particularly limited.
• the polymer of the present invention may be, for example, a random polymer of the polymerizable monomer (A), the optional polymerizable monomer (B), and the optional polymerizable monomer (C).
• the polymer of the present invention may be, for example, a block polymer having one or more polymer blocks of the polymerizable monomer (A), the optional polymerizable monomer (B), and the optional polymerizable monomer (C).
• the polymer of the present invention preferably does not contain fluorine atoms in order to reduce the environmental impact.
• the number average molecular weight (Mn) of the polymer of the present invention is preferably in the range of 1,000 to 50,000, more preferably in the range of 1,000 to 30,000, and further preferably in the range of 1,500 to 10,000.
• the weight average molecular weight (Mw) of the polymer of the present invention is preferably in the range of 1,000 to 300,000, more preferably in the range of 1,500 to 200,000, further preferably in the range of 2,000 to 100,000, and particularly preferably in the range of 3,000 to 50,000.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are values calculated in terms of polystyrene based on gel permeation chromatography (GPC) measurements.
• the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer of the present invention are measured by the method described in the Examples.
• the defoaming agent of the present invention may contain a defoaming agent other than the polymer of the present invention.
• the defoaming agent of the present invention may also be the polymer of the present invention.
• the method for producing the polymer of the present invention is not particularly limited, and the polymer can be produced by a known method.
• the polymer of the present invention can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, etc. based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, etc.
• a radical polymerization method the polymer of the present invention can be produced by charging a polymerizable monomer mixture in an organic solvent and adding a general-purpose radical polymerization initiator.
• initiators various types of initiators can be used, and examples thereof include peroxides such as t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, and diacyl peroxide, azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, and phenylazotriphenylmethane, and metal chelate compounds such as Mn(acac) 3 .
• peroxides such as t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, and diacyl peroxide
• azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, and phenylazotriphenylmethane
• metal chelate compounds such as Mn(acac) 3 .
• additives such as chain transfer agents, for example, lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, and octyl thioglycolic acid, and thiol compounds having a coupling group, for example, ⁇ -mercaptopropyltrimethoxysilane, may be used.
• chain transfer agents for example, lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, and octyl thioglycolic acid
• thiol compounds having a coupling group for example, ⁇ -mercaptopropyltrimethoxysilane
• organic solvent examples include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol, and tert-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate; monocarboxylic acid esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; dimethylformamide, dimethyl sulfoxide, N-methyl
• the solvent include polar solvents such as pyrrol
• the polymer of the present invention can also be produced by living polymerization, such as living radical polymerization or living anionic polymerization.
• living radical polymerization a dormant species, whose active polymerization terminal is protected by an atom or atomic group, reversibly generates radicals and reacts with a monomer, and the propagation reaction proceeds. Even if the first monomer is consumed, the propagation terminal does not lose its activity, and reacts with the second monomer that is added sequentially to obtain a block polymer.
• living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), and radical polymerization using organotellurium (TERP).
• ATRP atom transfer radical polymerization
• RAFT reversible addition-fragmentation radical polymerization
• NMP nitroxide-mediated radical polymerization
• TERP radical polymerization using organotellurium
• polymerization initiators that can be used in ATRP include 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, ⁇ , ⁇ '-dichloroxylene, ⁇ , ⁇ '-dibromoxylene, hexakis( ⁇ -bromomethyl)benzene, and alkyl esters having 1 to 6 carbon atoms of 2-halogenated carboxylic acids (e.g., 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.).
• 2-halogenated carboxylic acids e.g., 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.
• alkyl ester having 1 to 6 carbon atoms of a 2-halogenated carboxylic acid having 1 to 6 carbon atoms include, for example, methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate.
• Transition metal compounds that can be used in ATRP are represented by M n+ X n .
• the transition metal Mn + of the transition metal compound represented by Mn + Xn can be selected from the group consisting of Cu + , Cu2 + , Fe2 + , Fe3 + , Ru2 + , Ru3 + , Cr2 + , Cr3 + , Mo0 , Mo + , Mo2 + , Mo3 + , W2 + , W3 + , Rh3 + , Rh4 + , Co + , Co2 + , Re2 + , Re3 + , Ni0 , Ni + , Mn3+ , Mn4 + , V2 + , V3 + , Zn + , Zn2 + , Au+, Au2 + , Ag + , and Ag2 + .
• X in the transition metal compound represented by M n+ X n can be selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (SO 4 ) 1/2 , (PO 4 ) 1/3 , (HPO 4 ) 1/2 , (H 2 PO 4 ), triflate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 11 , CN, and R 12 COO, where R 11 represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R 12 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted 1 to 5 times with a halogen (preferably 1 to 3 times with fluorine or chlorine).
• Examples of ligand compounds capable of forming coordinate bonds with the transition metals of the above transition metal compounds include compounds having a ligand containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms, or sulfur atoms that can be coordinated with the transition metal via a ⁇ bond, compounds having a ligand containing two or more carbon atoms that can be coordinated with the transition metal via a ⁇ bond, and compounds having a ligand that can be coordinated with the transition metal via a ⁇ bond or ⁇ bond.
• transition metal complexes are not particularly limited, but preferred ones are complexes of transition metals of Groups 7, 8, 9, 10 and 11, and more preferred ones are complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel.
• ligands such as 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives
• polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris(2-aminoethyl)amine when the central metal is copper.
• divalent ruthenium complexes examples include dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzeneruthenium, dichlorop-cymeneruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, and carbonylchlorohydridotris(triphenylphosphine)ruthenium.
• divalent iron complexes examples include bistriphenylphosphine complexes and triazacyclononane complexes.
• solvents used in living radical polymerization include ester-based solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether-based solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen-based solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene and xylene; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol-based solvents such as methanol, ethanol, and isopropanol; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.
• ester-based solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate
• ether-based solvents
• the polymerization temperature during the living radical polymerization is preferably in the range of room temperature to 120°C.
• metals resulting from the transition metal compounds used in the polymerization may remain in the resulting polymer. Metals remaining in the resulting polymer may be removed using activated alumina or the like after the polymerization is completed.
• the antifoam agent of the present invention can be suitably used as an antifoam agent for lubricating oil compositions, and the lubricating oil compositions of the present invention contain the antifoam agent of the present invention.
• the defoaming agent of the present invention is a polymer having a crosslinked structure by using a polymerizable monomer (A) having two or more polymerizable unsaturated groups as a polymerization component, and can suppress the spread of the molecules of the defoaming agent even in a high-temperature environment and maintain a low solubility in the lubricating base oil.
• the defoaming agent of the present invention can exhibit high defoaming performance even in a high-temperature environment.
• a high shear force is applied to a driving part of the machine.
• the crosslinked structure of the defoaming agent of the present invention suppresses the depolymerization, and therefore the deterioration of the defoaming performance can be suppressed.
• the defoaming agent of the present invention has high defoaming performance and can be used without restrictions in lubricating oil compositions for drive system devices such as shock absorbers, transmissions, and power steering in automobiles.
• the content of the antifoaming agent of the present invention in the lubricating oil composition of the present invention is not particularly limited, and is, for example, in the range of 1 to 1,000 ppm by mass of the total amount of the lubricating oil composition, preferably in the range of 5 to 700 ppm by mass, and more preferably in the range of 10 to 400 ppm by mass.
• the lubricating base oil of the lubricating oil composition of the present invention may be any known oil, and may be a mineral oil, a synthetic oil, or a mixture of a mineral oil and a synthetic oil.
• mineral oils examples include mineral oils obtained by subjecting lubricating oil fractions obtained by vacuum distillation of atmospheric residual oil obtained by atmospheric distillation of crude oil to one or more of the following treatments: solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, etc.
• mineral oils include paraffinic mineral oils and naphthenic mineral oils.
• Other examples include mineral oils produced by isomerizing mineral oil waxes and waxes produced by the Fischer-Tropsch process or the like (GTL waxes).
• Synthetic oils include polyolefins such as polybutene, ⁇ -olefin homopolymers and copolymers (e.g., ethylene- ⁇ -olefin copolymers), various esters such as polyol esters, dibasic acid esters, and phosphate esters, various ethers such as polyphenyl ether, polyglycols, alkylbenzenes, and alkylnaphthalenes.
• polyolefins such as polybutene, ⁇ -olefin homopolymers and copolymers (e.g., ethylene- ⁇ -olefin copolymers)
• various esters such as polyol esters, dibasic acid esters, and phosphate esters
• various ethers such as polyphenyl ether, polyglycols, alkylbenzenes, and alkylnaphthalenes.
• the lubricating base oil may be used alone or in combination of two or more types.
• the kinematic viscosity at 100° C. of the lubricating base oil is preferably in the range of 1 to 20 mm 2 /s, more preferably in the range of 2 to 15 mm 2 /s, and even more preferably in the range of 2 to 10 mm 2 /s.
• the kinetic viscosity at 100° C. of the lubricating base oil is within the above range, evaporation loss is small and power loss due to viscous resistance is not so large, so that the fuel economy improvement effect is easily obtained.
• the lubricating base oil preferably has a paraffin content (sometimes referred to as % Cp) by ndM ring analysis of 70% or more, more preferably 75% or more, and even more preferably 80% or more.
• the lubricating base oil has good oxidation stability and the like when the paraffin content is within the above range.
• the content of the lubricating base oil in the lubricating oil composition is, for example, in the range of 65 to 95 mass% of the total amount of the lubricating oil composition, preferably in the range of 70 to 95 mass%, and more preferably in the range of 70 to 90 mass%.
• the lubricating oil composition of the present invention only needs to contain the antifoam agent of the present invention and a lubricating base oil, and may further contain other additives.
• Other additives may be added, such as ashless detergents, ashless friction modifiers, anti-wear agents, extreme pressure agents, viscosity index improvers, metal deactivators, pour point depressants, rust inhibitors, etc. These additives may be used alone or in combination of two or more.
• each of the other additives can be appropriately adjusted within a range that does not impair the effects of the present invention, and is usually 0.001 to 25 mass %, preferably 0.005 to 20 mass %, and more preferably 0.01 to 15 mass %, based on the total amount of the lubricating oil composition.
• the total content of the other additives is preferably 25 mass % or less, more preferably 20 mass % or less, and even more preferably 15 mass % or less, based on the total amount of the lubricating oil composition.
• ashless detergents examples include alkenyl succinimides such as alkenyl succinic acid monoimides and alkenyl succinic acid bisimides, and boron-modified alkenyl succinimides.
• ashless friction modifiers include fatty amines, fatty acid esters, fatty acid amides, fatty acids, fatty alcohols, and fatty ethers, each of which has at least one alkyl or alkenyl group having 6 to 30 carbon atoms in the molecule.
• anti-wear agents or extreme pressure agents include sulfur-containing compounds such as zinc dithiophosphate; phosphorus-containing compounds such as phosphites, phosphates, phosphonates, and their amine salts or metal salts; and sulfur- and phosphorus-containing anti-wear agents such as thiophosphites, thiophosphates, thiophosphonates, and their amine salts or metal salts.
• viscosity index improvers examples include polymethacrylate, disperse polymethacrylate, olefin copolymers (e.g., ethylene-propylene copolymers, etc.), disperse olefin copolymers, and styrene copolymers (e.g., styrene-diene copolymers, styrene-isoprene copolymers, etc.).
• olefin copolymers e.g., ethylene-propylene copolymers, etc.
• styrene copolymers e.g., styrene-diene copolymers, styrene-isoprene copolymers, etc.
• metal deactivators examples include benzotriazole compounds, tolyltriazole compounds, imidazole compounds, pyrimidine compounds, etc.
• pour point depressants examples include ethylene-vinyl acetate copolymers, condensates of chlorinated paraffin and naphthalene, condensates of chlorinated paraffin and phenol, polymethacrylates, polyalkylstyrenes, etc.
• rust inhibitors include petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenyl succinic acid esters, polyhydric alcohol esters, etc.
• the lubricating oil composition of the present invention is suitable for use in lubricating the driving parts of machines equipped with an internal combustion engine or an electric motor.
• the drive unit generally includes a motor, an inverter, and a gearbox, and the drive unit can be lubricated by filling the gearbox with the lubricating oil composition of the present invention.
• the lubricating oil composition of the present invention is stored in an oil pan in the internal combustion engine, which is the drive unit, and is supplied into the cylinder via an oil pump to lubricate the starting unit.
• the lubrication of the drive unit is not limited to these forms, and the drive unit can be lubricated by filling or supplying the lubricating oil composition of the present invention to the parts where metals come into contact with each other.
• Machines in which the lubricating oil composition of the present invention can be used include, without limitation, automobiles (gasoline-powered vehicles, electric vehicles), robots (industrial robots, entertainment robots), aircraft (airplanes, helicopters), ships, and various home appliances, as long as they are equipped with an internal combustion engine or an electric motor.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are values calculated in terms of polystyrene based on gel permeation chromatography (GPC) measurements.
• GPC gel permeation chromatography
• the GPC measurement conditions are as follows:
• n in the chemical formula represents an arbitrary repeating unit.
• the molecular weight of the obtained defoamer (1) was measured by GPC, and the weight average molecular weight (Mw) was 13,300.
• the molecular weight of the obtained defoamer (2) was measured by GPC, and the weight average molecular weight (Mw) was 36,700.
• the molecular weight of the obtained defoamer (3) was measured by GPC, and the weight average molecular weight (Mw) was 18,800.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 52 parts by mass of n-butyl acetate as a solvent, and the temperature was raised to 85° C. with stirring under a nitrogen stream.
• the molecular weight of the obtained defoamer (4) was measured by GPC, and the weight average molecular weight (Mw) was 5,400.
• the molecular weight of the obtained defoamer (5) was measured by GPC, and the weight average molecular weight (Mw) was 26,000.
• the molecular weight of the obtained defoamer (6) was measured by GPC, and the weight average molecular weight (Mw) was 10,000.
• the molecular weight of the obtained defoamer (7) was measured by GPC, and the average weight average molecular weight (Mw) was 44,000.
• the molecular weight of the obtained defoamer (8) was measured by GPC, and the weight average molecular weight (Mw) was 20,000.
• two types of dropping liquids namely, 30 parts by mass of 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane dissolved in 50 parts by mass of n-butyl acetate, 20 parts by mass of methoxypolyethylene glycol methacrylate (the number of repeating ethylene oxide chains is approximately 9), and a polymerization initiator solution in which 3 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was dissolved in 15 parts by mass of n-butyl acetate, were each set in a separate dropping device.
• the monomer solution and the polymerization initiator solution were simultaneously dropped over 2 hours while keeping the temperature inside the flask at 85° C. After the dropwise addition was completed, the mixture was stirred at 85° C. for 4 hours, then heated to 110° C. and further stirred for 1 hour to obtain a solution of defoamer (1′).
• the molecular weight of the obtained defoamer (1') was measured by GPC, and the weight average molecular weight (Mw) was 40,000.
• Synthesis Comparative Example 2 Synthesis of Defoamer (2')
• a solution of defoaming agent (2') was obtained in the same manner as in Synthesis Comparative Example 1, except that 30 parts by mass of a compound (number average molecular weight 5,000) represented by the following general formula (A2') was used instead of 3-methacryloyloxypropyltris(trimethylsiloxy)silane.
• the molecular weight of the obtained defoamer (2') was measured by GPC, and the weight average molecular weight (Mw) was 25,000.
• the molecular weight of the obtained defoamer (3') was measured by GPC, and the weight average molecular weight (Mw) was 27,000.
• a lubricating oil composition was prepared by adding the amount of an antifoaming agent shown in Table 1 diluted with kerosene shown in Table 1 to 100 parts by mass of a base lubricating oil containing a lubricating base oil (paraffinic mineral oil) as the main component and small amounts of various additives (viscosity index improver, phosphite compound, thiadiazole compound, calcium-based detergent, metal deactivator, ashless dispersant, antioxidant, etc.). In Comparative Example 5, no antifoaming agent was added.
• the resulting lubricating oil composition was subjected to the following foaming test, and the results are shown in Table 1.
• the foaming test was carried out in accordance with the homogenizer method disclosed in JP-A-2008-120880.
• the lubricating oil composition was stirred under the following conditions using a homogenizer ("T.K. Robomix” manufactured by Primix Corporation) equipped with a generator shaft ("Mini Mixer” manufactured by Primix Corporation), and the foam volume (mL) was determined by subtracting the oil surface reading (mL) before stirring from the foam surface reading (mL) 3 seconds after stirring was stopped. The smaller the foam volume, the better the defoaming ability.
• Revolution speed 16,000 rpm
• Oil temperature 80°C or 120°C Oil amount: 80ml
• Container 200 ml graduated cylinder (inner diameter ⁇ 36 mm) Mixing time: 1 minute

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• 2024
  • 2024-10-31 WO PCT/JP2024/038817 patent/WO2025105187A1/ja active Pending
  • 2024-10-31 JP JP2025507113A patent/JP7697608B1/ja active Active
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