Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09D201/10—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

• a known method for imparting oil repellency to the surface of an article, such as a textile product, is to treat the article with an oil repellent composition containing a fluoropolymer.
• an oil repellent composition containing a non-fluoropolymer that can impart sufficient oil repellency to the surface of an article and does not pose environmental impact concerns.
• An oil repellent comprising a coating composition containing a copolymer having units based on a compound represented by the following formula 1 and units based on a compound represented by the following formula 2: X 1 -A 1 -B 1 formula 1
• X 1 is a monovalent group having a polymerizable carbon-carbon double bond or a hydrolyzable silyl group
• a 1 is a divalent organic group
• B 1 is a monovalent organic group having at least one trialkylsilyl group.
• R 5 , R 6 and R 7 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, n is an integer of 0 to 3, and A1 * is a bond to A1 .
• [12] A method for producing an article, comprising treating the article with the oil repellent according to any one of [1] to [10].
• [13] The article according to [11] or [12], which contains fibers.
• [1A] A copolymer having units based on a compound represented by the following formula 1A and units based on a compound represented by the following formula 2A: X 1 -A 1 -B 1 formula 1A In the formula 1A, X 1 is a monovalent polymerizable reactive group, A 1 is a divalent organic group, and B 1 is a monovalent organic group having at least one trialkylsilyl group.
• X2 is a monovalent polymerizable reactive group
• A2 is a divalent hydrocarbon group
• B2 is a divalent organic group having at least one heteroatom (excluding divalent organic groups including an —O— group and an oxyalkylene group)
• R2 is a monovalent hydrocarbon group
• the atom in B2 that bonds to R2 is an atom other than a silicon atom.
• [2A] The copolymer according to [1A], wherein X1 and X2 each independently represent a (meth)acryloyloxy group or a hydrolyzable silyl group, B1 has 10 or less silicon atoms, B2 represents a urethane bond, a urea bond, or an amide bond, and R2 represents a linear or branched alkyl group having 1 to 12 carbon atoms.
• [3A] The copolymer according to [1A] or [2A], wherein B 1 is a monovalent organic group represented by the above formula 31 or a monovalent organic group represented by the below-described formula 41.
• [4A] The copolymer according to any one of [1A] to [3A], wherein a hydrogen atom is bonded to the heteroatom.
• [5A] A coating composition comprising the copolymer according to any one of [1A] to [4A].
• [6A] An oil repellent comprising the coating composition according to [5A].
• One embodiment of the present invention provides an oil repellent comprising a coating composition containing a copolymer that can provide articles with superior oil repellency, articles treated with the oil repellent, and a method for producing the articles.
• a "unit based on a compound” is an atomic group having a structure formed by polymerization of one molecule of a compound, which is a monomer.
• the unit may be an atomic group formed directly by polymerization of a monomer, or may be an atomic group obtained by chemically converting a part of an atomic group formed by polymerization of another monomer having a partially different structure.
• (Meth)acrylate is a general term for acrylate and methacrylate.
• (meth)acryloyl(oxy) group is a general term for acryloyl(oxy) group and methacryloyl(oxy) group
• (meth)acrylic acid is a general term for acrylic acid and methacrylic acid.
• the number average molecular weight (hereinafter also referred to as "Mn”) and weight average molecular weight (hereinafter also referred to as "Mw”) of the copolymer are molecular weights in terms of polymethyl methacrylate obtained by measurement by gel permeation chromatography (hereinafter also referred to as "GPC") using a calibration curve prepared using standard polymethyl methacrylate samples.
• the solid content concentration is calculated by (solid content mass/sample mass) ⁇ 100, where the mass of the sample before heating is the sample mass and the mass of the sample after drying for 4 hours in a convection dryer at 120° C. is the solid content mass.
• the symbol "to" indicating a numerical range means that the numerical values before and after it are included as the upper and lower limits.
• the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
• the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.
• a hydrocarbon group means a group consisting solely of carbon and hydrogen.
• the copolymer of this embodiment (hereinafter also referred to as "copolymer A”) has units (hereinafter also referred to as “units m1") based on a compound represented by formula 1 (hereinafter also referred to as “compound m1”) described below, and units (hereinafter also referred to as “units m2") based on a compound represented by formula 2 (hereinafter also referred to as “compound m2”) described below.
• the copolymer may also have units (hereinafter also referred to as "units m3") based on a compound other than units m1 and m2 (hereinafter also referred to as "compound m3"). Note that a unit that corresponds to both unit m1 and unit m2 is treated as unit m1.
• the unit m1 is a unit based on the compound m1 represented by the following formula 1.
• X 1 -A 1 -B 1 formula 1 In the above formula 1, X 1 is a monovalent polymerizable reactive group, A 1 is a divalent hydrocarbon group, and B 1 is a monovalent organic group having at least one trialkylsilyl group.
• Polymerizable reactive group examples include a group having a polymerizable carbon-carbon double bond and a hydrolyzable silyl group, with a group having a polymerizable carbon-carbon double bond being preferred.
• Examples of the group having a polymerizable carbon-carbon double bond include a vinyl group, a fumarate group, a maleimide group, a styryl derivative group represented by the following formula 5, and a monovalent group represented by the following formula 6, with the monovalent group represented by the following formula 6 being preferred.
• one of R 101 to R 105 is a bond to A 1 , and the others are each independently a hydrogen atom, a halogen atom, or an optionally halogenated alkyl group having 1 to 4 carbon atoms.
• R 11 is a single bond, an oxygen atom, or a divalent group represented by NR 12
• R 13 is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms
• * A1 is a bond to A 1.
• R 12 is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms.
• R 11 is preferably an oxygen atom.
• formula 6 represents a (meth)acryloyloxy group.
• R 12 is preferably a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
• R 13 is preferably a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.
• the monovalent group represented by the above formula 6 is preferably a (meth)acryloyloxy group.
• hydrolyzable silyl group examples include monovalent groups represented by the following formula 7: * A1 -Si(R 14 ) 3-a X aFormula 7
• a is an integer of 2 or 3.
• X represents a hydroxy group, a halogen atom, or a hydrolyzable group. Multiple Xs may be the same or different.
• R14 represents a monovalent organic group having 1 to 20 carbon atoms, and is an organic group other than the hydrolyzable group in X.
• * A1 is a bond to A1 .
• R14 is preferably at least one group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an ⁇ -chloroalkyl group, and a triorganosiloxy group, and is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, an ⁇ -chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group, or a triphenylsiloxy group.
• Examples of the hydrolyzable group for X include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group, and an alkenyloxy group.
• An alkoxy group is preferred because it is mildly hydrolyzable and easy to handle.
• the alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, siloxane bonds are easily formed quickly.
• hydrolyzable silyl group represented by formula 7 above examples include trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, methyldiisopropoxysilyl, ( ⁇ -chloromethyl)dimethoxysilyl, and ( ⁇ -chloromethyl)diethoxysilyl.
• trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, and diethoxymethylsilyl are preferred, with dimethoxymethylsilyl being more preferred.
• the divalent organic group of A1 is preferably a divalent hydrocarbon group.
• divalent hydrocarbon groups include linear or branched alkylene groups, cycloalkylene groups, alkylene groups or cycloalkylene groups having a combination of cyclic, linear, or branched chains, groups in which at least one carbon-carbon single bond of the alkylene group is substituted with a carbon-carbon double bond or a carbon-carbon triple bond (e.g., alkenylene groups, alkynylene groups), groups in which at least one carbon-carbon single bond of the cycloalkylene group is substituted with a carbon-carbon double bond, and arylene groups.
• Carbon in the hydrocarbon group may be substituted with a heteroatom.
• Hydrogen in the hydrocarbon group may be substituted with a heteroatom or a monovalent group having a heteroatom.
• heteroatoms include nitrogen, oxygen, sulfur, boron, and phosphorus atoms, with nitrogen and oxygen atoms being preferred.
• A1 does not have a silicon atom.
• the divalent organic group for A 1 is preferably a linear or branched alkylene group or a cycloalkylene group, more preferably a linear or branched alkylene group, and even more preferably a linear alkylene group.
• the divalent organic group preferably has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and even more preferably 2 to 10 carbon atoms.
• the divalent organic group for A1 is preferably a linear alkylene group having 1 to 8 carbon atoms, such as a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, or octylene group, or a branched alkylene group in which at least one hydrogen atom of the linear alkylene group is substituted with an alkyl group having 1 to 3 carbon atoms, such as a methyl group, ethyl group, or propyl group, and more preferably the linear alkylene group.
• a linear alkylene group having 1 to 8 carbon atoms such as a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, or octylene group
• a branched alkylene group in which at least one hydrogen atom of the linear alkylene group is substituted with an alkyl group having 1 to 3 carbon atom
• the number of trialkylsilyl groups in B1 is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 3, particularly preferably 2 or 3, and most preferably 3.
• the effect of imparting oil repellency to the treated article is more excellent.
• the multiple trialkylsilyl groups may be the same or different.
• alkyl group in the trialkylsilyl group examples include linear or branched alkyl groups having 1 to 6 carbon atoms, with t-butyl, isopropyl, ethyl, and methyl being preferred, and ethyl and methyl being more preferred.
• the three alkyl groups in the trialkylsilyl group may be the same or different.
• B1 preferably has a siloxane bond.
• the number of Si—O bonds in B1 is preferably 1 to 80, more preferably 1 to 20, and even more preferably 1 to 10. When the number of Si—O bonds is within the above range, the effect of imparting oil repellency to the treated article is more excellent.
• the number of silicon atoms in B1 is preferably 10 or less, more preferably 1 to 8, even more preferably 1 to 6, particularly preferably 2 to 5, and most preferably 3 to 4. When it is equal to or less than the upper limit of the above range, the effect of imparting oil repellency to the article to be treated is more excellent.
• B1 is preferably a monovalent organic group represented by the following formula 3 or a monovalent organic group represented by the following formula 4, and more preferably a monovalent organic group represented by the following formula 3.
• A1 * is a bond to A1 .
• R3 and R4 each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.
• b represents an integer of 0 to 3, preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.
• R3 and R4 are preferably a t-butyl group, an isopropyl group, an ethyl group, or a methyl group, more preferably an ethyl group or a methyl group, and even more preferably a methyl group.
• R3 and R4 may be the same or different.
• R 5 , R 6 and R 7 each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 3.
• R 5 , R 6 and R 7 are preferably a t-butyl group, an isopropyl group, an ethyl group or a methyl group, more preferably an ethyl group or a methyl group, and even more preferably a methyl group.
• Multiple R 5 , R 6 and R 7 may be the same or different.
• the monovalent organic group represented by the above formula 3 is preferably a monovalent organic group represented by the following formula 31:
• A1 * is a bond to A1 .
• B1 is preferably a monovalent organic group represented by the above formula 31.
• Examples of compound m1 include 3-(1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxanyl)propyl(meth)acrylate, 3-((meth)acryloyloxy)propyltris(trimethylsiloxy)silane, and 3-((meth)acryloyloxy)propylbis(trimethylsiloxy)methylsilane, of which 3-((meth)acryloyloxy)propyltris(trimethylsiloxy)silane and 3-((meth)acryloyloxy)propylbis(trimethylsiloxy)methylsilane are preferred, and 3-((meth)acryloyloxy)propyltris(trimethylsiloxy)silane is more preferred.
• the compound m1 may be used alone or in combination of two or more kinds.
• the unit m2 is a unit based on a compound represented by the following formula 2.
• X 2 -A 2 -B 2 -R 2Formula 2 In the above formula 2, X2 is a monovalent polymerizable reactive group, A2 is a divalent hydrocarbon group, B2 is a divalent organic group having at least one heteroatom and is a group containing any of the structures described below, and R2 is a monovalent hydrocarbon group.
• the divalent hydrocarbon group of A2 and the monovalent hydrocarbon group of R2 are first identified, and the remainder are identified as the monovalent polymerizable reactive group of X2 and the divalent organic group having at least one heteroatom of B2 .
• X2 is considered to be a vinyl group, and the methylene group is included in A2 .
• X2 is a styryl derivative group in which R101 to R105 other than the bond to A1 in the above formula 5 are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms
• the styryl group is regarded as X2
• the benzene ring portion in the styryl derivative group is not included in A2 .
• Polymerizable reactive group X 2
• the polymerizable reactive group for X2 include a group having a polymerizable carbon-carbon double bond and a hydrolyzable silyl group, with a group having a polymerizable carbon-carbon double bond being preferred.
• the group having a polymerizable carbon-carbon double bond and the hydrolyzable silyl group include the same groups as those explained for X1 , and preferred embodiments are also the same as for X1 .
• X1 is a group having a polymerizable carbon-carbon double bond
• X2 is also preferably a group having a polymerizable carbon-carbon double bond.
• the groups having a polymerizable carbon-carbon double bond of X1 and X2 may be the same or different, and are preferably the same.
• X 1 is a hydrolyzable silyl group
• X 2 is also preferably a hydrolyzable silyl group.
• the hydrolyzable silyl groups of X 1 and X 2 may be the same or different, and are preferably the same.
• divalent hydrocarbon group of A2 examples include the same groups as the divalent hydrocarbon groups explained for A1 , and preferred embodiments are also the same as those for A1 .
• B1 in unit m1 and B2 in unit m2 are close to each other.
• the ratio of the number of carbon atoms in the linear portion of A2 to the number of carbon atoms in the linear portion of A1 is preferably 0.25 to 4, more preferably 0.3 to 2, and even more preferably 0.5 to 1.5. When this ratio is within this range, the effect of imparting oil repellency to the treated article is more excellent.
• B 2 (Divalent organic group having at least one heteroatom: B 2 )
• heteroatoms contained in B2 include nitrogen, oxygen, sulfur, boron, phosphorus, and silicon atoms, with nitrogen and oxygen atoms being preferred.
• the number of heteroatoms contained in B2 is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, and particularly preferably 1 to 4. When the number of heteroatoms is within the above range, the effect of imparting oil repellency to the treated article is more excellent.
• the atom in B2 bonding to R2 is not a silicon atom.
• R22 is a linear or branched alkyl group having 1 to 6 carbon atoms.
• B2 preferably has a carbon atom, and the number of carbon atoms contained in B2 is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 1 to 3.
• a hydrogen atom is bonded to the heteroatom.
• the number of hydrogen atoms bonded to the heteroatom in B2 is preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 or 2.
• the effect of imparting oil repellency to the treated article is more excellent.
• the heteroatom bonded to a hydrogen atom may be located in the main chain or in the side chain of B2 .
• the main chain refers to the atomic group with the minimum number of atoms connecting A2 and R2 .
• Examples of B2 in which the heteroatom is located in the main chain include groups containing at least one bond selected from a urethane bond, an amide bond, a urea bond, and a thiocarbamate bond, or groups consisting only of the above bonds.
• Examples of B2 in which the heteroatom is located in the side chain include groups containing a group in which at least one hydrogen atom of a methylene group is substituted with a heteroatom bonded to a hydrogen atom.
• heteroatom bonded to a hydrogen atom examples include -NH2 , -NHR23 , -SH, and -OH, with -OH being preferred.
• R23 is a linear or branched alkyl group having 1 to 6 carbon atoms.
• B2 may have a heteroatom to which a hydrogen atom is bonded in the main chain of B2 , in the side chain, or in both the main chain and the side chain.
• B2 is a group containing any of the following structures: B2 preferably contains 1 to 5 of the following structures, and more preferably 1 to 3 of them. When it contains a plurality of the following structures, the following structures may be the same or different. The following structures may be combined to form a cyclic structure. Of the following structures, B2 is preferably a structure having —(C ⁇ O)—. However, a carbon atom or a hydrogen atom is bonded to the end of the dotted line.
• B2 is more preferably a group containing any of the following structures: B2 more preferably contains 1 to 5 of the following structures, and even more preferably 1 to 3 of them. When it contains a plurality of the following structures, the following structures may be the same or different. The following structures may be combined to form a cyclic structure. Examples of the cyclic structure include an isocyanuric ring. Of the following structures, B2 is preferably a structure having —(C ⁇ O)—. However, a carbon atom or a hydrogen atom is bonded to the end of the dotted line.
• the monovalent hydrocarbon group preferably has 1 or more carbon atoms, more preferably 2 or more carbon atoms, and even more preferably 4 or more carbon atoms.
• the monovalent hydrocarbon group preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, even more preferably 1 to 12 carbon atoms, particularly preferably 2 to 12 carbon atoms, and most preferably 4 to 8 carbon atoms.
• the number of carbon atoms is within the above range, the effect of imparting oil repellency to the article to be treated is more excellent.
• the polymerizable reactive group possessed by compound m3 is preferably a hydrolyzable silyl group.
• X1 , X2 , and the hydrolyzable silyl groups possessed by compound m3 may be the same or different, and are preferably the same.
• vinyl carboxylate esters examples include vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl octylate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotonate, and vinyl cinnamate.
• carboxylic acid allyl ester examples include allyl acetate and diallyl adipate.
• the content of units m2 relative to all units constituting copolymer A is preferably 1 to 90 mol%, more preferably 3 to 85 mol%, even more preferably 5 to 80 mol%, particularly preferably 15 to 75 mol%, and most preferably 31 to 49 mol%.
• the content of units m2 relative to all units constituting copolymer A is preferably 4 to 90 mass%, more preferably 6 to 87 mass%, even more preferably 8 to 83 mass%, and particularly preferably 10 to 80 mass%. When the content is equal to or greater than the lower limit of the above range, the effect of imparting oil repellency to the treated article is more excellent.
• the content of fluorine atoms relative to the total mass of copolymer A is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 1% by mass or less, particularly preferably 0.1% by mass or less, and most preferably contains no fluorine atoms.
• copolymer A is preferably a non-fluorine copolymer.
• the content of fluorine atoms relative to the total mass of copolymer A can be measured by combustion ion chromatography or the like.
• each unit can be calculated from the reaction ratio of compounds m1 to m3 by 1H -NMR, gas chromatography, and high-performance liquid chromatography. For example, it can be calculated by adding 1,4-bis(trifluoromethyl)benzene as a standard substance, measuring 1H NMR in deuterated chloroform, and comparing the integral ratio.
• the Mn of Copolymer A is preferably 1,000 to 1,000,000, more preferably 10,000 to 1,000,000, and even more preferably 10,000 to 800,000.
• the Mn of Copolymer A is equal to or greater than the lower limit above, the effect of imparting oil repellency to the treated article is superior.
• the Mn of Copolymer A is equal to or less than the upper limit above, the dispersibility in various solvents is superior.
• the Mw of Copolymer A is preferably 1,000 to 1,000,000, more preferably 10,000 to 1,000,000, and even more preferably 10,000 to 800,000.
• the Mw of Copolymer A is equal to or greater than the lower limit above, the effect of imparting oil repellency to the treated article is superior.
• the Mw of Copolymer A is equal to or less than the upper limit above, the dispersibility in various solvents is superior.
• Copolymer A can be produced by polymerizing compound m1, compound m2, and, if necessary, compound m3.
• the amounts of compounds m1 to m3 charged may be appropriately determined so as to satisfy the composition of copolymer A described above.
• initiator In the polymerization of copolymer A, it is preferable to use an initiator.
• the initiator is not particularly limited and can be appropriately selected depending on the type of polymerizable reactive group of compounds m1 to m3.
• examples of initiators include organic peroxides, inorganic peroxides, azo compounds, etc., which are used in radical polymerization; organic acids, inorganic acids, Lewis acids, and thermal cationic polymerization initiators or photocationic polymerization initiators, which generate these in the polymerization system, which are used in cationic polymerization; and photoanionic polymerization initiators, which generate organic metals and organic bases in the polymerization system, which are used in anionic polymerization.
• the organic peroxide is not particularly limited, and examples thereof include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, t-butyl- ⁇ -cumyl peroxide, etc. These may be used alone or in combination of two or more.
• the inorganic peroxide is not particularly limited, and examples thereof include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, percarbonate, etc. These may be used alone or in combination of two or more.
• the azo compound is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, and 2,2'-azobis(2-amidinopropane) dihydrochloride. These may be used alone or in combination of two or more.
• the organic acid is not particularly limited, and examples thereof include methanesulfonic acid.
• the inorganic acid is not particularly limited, and examples thereof include hydrochloric acid, nitric acid, sulfuric acid, tetrafluoroboric acid, fluoroantimonic acid, and hexafluorophosphoric acid.
• the Lewis acid is not particularly limited, and examples thereof include trichloroaluminum, ethylaluminum dichloride, and ethylaluminum sesquichloride.
• the thermal cationic polymerization initiator is not particularly limited, and examples thereof include benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate.
• the photocationic polymerization initiator is not particularly limited, and examples thereof include commercially available products such as WPI-113, WPI-116, and WPI-170 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• the organic metal is not particularly limited, and examples thereof include n-butyllithium, sec-butyllithium, t-butyllithium, diethylzinc, and triethylaluminum.
• the photoanionic polymerization initiator is not particularly limited, and examples thereof include commercially available products such as WPBG-266, WPBG-300, and WPGB-345 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
• the amount of the polymerization initiator added is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total of the compounds m1 to m3.
• the polymerization temperature is preferably 20 to 150° C., more preferably 40 to 90° C.
• the polymerization time varies depending on the reaction temperature, but is, for example, 1 to 144 hours, preferably 3 to 86 hours.
• the polymerization is preferably carried out in an inert atmosphere such as nitrogen.
• a molecular weight modifier may be used when polymerizing compounds m1 to m3.
• the molecular weight modifier include aromatic compounds, mercapto alcohols, mercapto carboxylic acids, and alkyl mercaptans, and more preferably mercapto carboxylic acids or alkyl mercaptans.
• the molecular weight modifier examples include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, and ⁇ -methylstyrene dimer (CH 2 ⁇ C(Ph)CH 2 C(CH 3 ) 2 Ph, where Ph is a phenyl group).
• the amount of the molecular weight modifier added is preferably 0 to 5 parts by mass, more preferably 0 to 2 parts by mass, per 100 parts by mass of the total of the compounds m1 to m3.
• Chain transfer agent When polymerizing compounds m1 to m3, a chain transfer agent that enables living radical polymerization may be used to further control the molecular weight.
• Preferred examples of the chain transfer agent are reversible addition-fragmentation chain transfer agents, such as cyanomethyl dodecyl trithiocarbonate, 2-cyano-2-propyl benzodithioate, 2-(dodecylthiocarbonothioylthio)-2-methylpropanoic acid, and cyanomethyl methyl(phenyl)carbamodithioate.
• the addition of such a chain transfer agent is preferred because it can suppress gelation and precipitation of copolymer A.
• the amount of the chain transfer agent added is preferably 0 to 2 parts by mass, more preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total of the compounds m1 to m3.
• R2 is a hydrocarbon group derived from compound Z2 and bonded to the isocyanate group of compound Z2.
• compounds having a hydroxy group include, but are not limited to, ethanol, 1-butanol, 1-hexanol, 1-dodecanol, isopropanol, cyclohexanol, etc. These may be used alone or in combination of two or more.
• compounds having an acid anhydride group are not particularly limited, and include, for example, acetic anhydride, propionic anhydride, butyric anhydride, and decanoic anhydride. These may be used alone or in combination of two or more.
• the liquid medium may be a non-aqueous medium, an aqueous medium, or a mixed medium of a non-aqueous medium and a water-soluble organic solvent.
• the coating composition is preferably a polymer solution containing Copolymer A and the non-aqueous medium or the mixed medium, and may contain an emulsifier.
• the amount of the emulsifier in the polymer solution is typically 0.3 parts by mass or less per 100 parts by mass of Copolymer A.
• the coating composition is preferably a polymer dispersion containing copolymer A, an aqueous medium, and an emulsifier.
• Hydrocarbon organic solvents are not particularly limited, and examples include pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. These may be used alone or in combination of two or more.
• the alcohol-based organic solvent is not particularly limited, and examples include ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol. These may be used alone or in combination of two or more.
• ester-based organic solvents include methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, ⁇ -butyrolactone, 3-methyl-3-methoxybutyl acetate, and glycerin triacetate. These may be used alone or in combination of two or more.
• the amide-based organic solvent is not particularly limited, and examples include dimethylacetamide, 3-methoxy-dimethylpropanamide, 3-butoxydimethylpropanamide, and methylpyrrolidone. These may be used alone or in combination of two or more.
• aprotic polar solvents examples include N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (hereinafter referred to as "THF"), acetonitrile, and acetone.
• the water-soluble organic solvent is preferably an ether alcohol, and more preferably dipropylene glycol, tripropylene glycol, and dipropylene glycol monomethyl ether, because these improve the compatibility between Copolymer A and the aqueous medium and facilitate the formation of a uniform film on the surface of the article.
• the aqueous medium contains a water-soluble organic solvent
• the content of the water-soluble organic solvent is preferably 1 to 80 parts by mass, more preferably 10 to 60 parts by mass, per 100 parts by mass of water.
• the mixed medium is a mixed medium capable of dissolving copolymer A and made by combining a non-aqueous medium with a water-soluble organic solvent that is optionally miscible with the non-aqueous medium.
• a water-soluble organic solvent constituting the mixed medium
• the water-soluble organic solvents mentioned above for the aqueous medium can be used, and aprotic polar solvents are preferred, with THF, acetone and N,N-dimethylformamide being more preferred.
• Emulsifiers are surfactants that have both hydrophilic and hydrophobic moieties.
• examples of the emulsifier include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers.
• the emulsifier is preferably a non-fluorine-based emulsifier that does not contain fluorine atoms.
• nonionic emulsifiers include surfactants s 1 to s 6 described in paragraphs [0067] to [0095] of JP-A No. 2009-215370.
• the surfactant s1 is a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, a polyoxyalkylene monoalkapolyenyl ether, or a polyoxyalkylene monopolyfluoroalkyl ether.
• a polyoxyethylene alkyl ether is preferred.
• the surfactant s2 is a compound having one or more carbon-carbon triple bonds and one or more hydroxy groups in the molecule, and is preferably an acetylene glycol ethylene oxide adduct.
• Surfactant s3 is a compound in which a polyoxyethylene chain is linked to a polyoxyalkylene chain in which two or more oxyalkylene units each having three or more carbon atoms are linked in succession, and both ends are terminated with hydroxy groups.
• an ethylene oxide propylene oxide polymer is preferred.
• the nonionic emulsifiers may be used alone or in combination of two or more.
• surfactant s7 is a cationic emulsifier in the substituted ammonium salt form.
• an ammonium salt in which one or more hydrogen atoms bonded to the nitrogen atom are substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene chain terminated in a hydroxy group is preferred, and a compound s71 represented by the following formula s71 is more preferred. [(R 21 ) 4 N + ] ⁇ X - Formula s 71 .
• R 21 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a polyoxyalkylene chain having a hydroxy group at the end.
• the four R 21 may be the same or different, but all four R 21 are not hydrogen atoms at the same time.
• X ⁇ is a counter ion.
• X ⁇ is preferably a chloride ion, an ethyl sulfate ion, or an acetate ion.
• Examples of compound s71 include monostearyltrimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono(stearyl)monomethyldi(polyethylene glycol)ammonium chloride, monofluorohexyltrimethylammonium chloride, di(tallow alkyl)dimethylammonium chloride, and dimethylmonococonutamine acetate.
• the cationic emulsifiers may be used alone or in combination of two or more.
• the other components may be added to the solution or dispersion obtained by the method for producing copolymer A of the present invention, or may be added to a liquid obtained by further diluting the solution or dispersion.
• examples of other components that may be added to the dispersion obtained by the method for producing copolymer A of the present invention include resins other than copolymer A, sizing agents, crosslinking agents, catalysts, organic fillers, inorganic fillers, supporting agents, preservatives, flocculants, buffers, bactericides, biocides, sequestering agents, hydrophobizing agents, surfactants, antifoaming agents, and volatile organic solvents.
• Examples of other components that can be added to a liquid obtained by further diluting the above-mentioned solution or dispersion in order to treat an article include, for example, paper strength agents (various starches, resins, etc.), sizing agents, penetrating agents, antifoaming agents, chelating agents, dyes, pigments, binders, acids, alkalis, alginates, and aluminum sulfate as coagulants for internal addition, which will be described later, and coagulants, retention agents, sizing agents, paper strength agents, pigments, dyes, and pH adjusters as coagulants for internal addition. Two or more of the other components may be used.
• methylol-based crosslinking agents include condensates or precondensates of urea or melamine with formaldehyde, methylol-dihydroxyethylene-urea and its derivatives, methylol-ethylene-urea, methylol-propylene-urea, methylol-triazone, dicyandiamide-formaldehyde condensates, methylol-carbamate, methylol-(meth)acrylamide, and polymers of these.
• Carbodiimide-based crosslinking agents are polymers that contain carbodiimide groups in their molecules and are crosslinking agents that exhibit excellent reactivity with carboxyl groups, amino groups, and active hydrogen groups on the surface of articles.
• Oxazoline-based crosslinking agents are polymers that contain oxazoline groups in their molecules and are crosslinking agents that exhibit excellent reactivity with carboxyl groups on the surface of articles.
• catalysts include, for example, inorganic amine salts and organic amine salts.
• inorganic amine salts include ammonium chloride.
• organic amine salts include amino alcohol hydrochloride and semicarbazide hydrochloride.
• amino alcohol hydrochloride include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanolamine hydrochloride, and 2-amino-2-methylpropanol hydrochloride.
• the content of the liquid medium can be appropriately selected depending on the desired solid content concentration of the coating composition.
• the solid content concentration of the coating composition immediately after production is preferably 5 to 80 mass %, more preferably 10 to 50 mass %, and even more preferably 10 to 40 mass %.
• the solid content of the coating composition is preferably 0.1 to 80 mass %, more preferably 0.1 to 50 mass %, and even more preferably 0.1 to 30 mass %.
• the content of copolymer A relative to the total mass of the coating composition is preferably from 0.1 to 80 mass %, more preferably from 0.1 to 50 mass %, and even more preferably from 0.1 to 30 mass %.
• the oil repellent comprising the coating composition of the present embodiment exhibits excellent oil repellency because it contains a specific polymer that includes a unit having a trialkylsilyl group that is thought to exhibit oil repellency, and a unit having a specific polar group that is thought to be able to prevent swelling and dissolution of the polymer.
• Examples 1 to 6 are working examples, and Examples 7 to 9 are comparative examples.
• composition ratio of the (co)polymer (the ratio of each unit to all units constituting the (co)polymer) was calculated by adding 1,4-bis(trifluoromethyl)benzene as a standard substance, measuring H NMR in deuterated chloroform, and comparing the integral ratios.
• the measurement device used was a gel permeation chromatograph analyzer HLC-8320GPC (product name of Tosoh Corporation).
• the column used was a TSKgel Supermultipore HZ-M (product name of Tosoh Corporation), and the solvent used was tetrahydrofuran.
• a calibration curve was prepared using polymethyl methacrylate as a standard substance.
• the glass substrate was then dried for 10 minutes on a hot plate set at 80°C to obtain a glass substrate treated with the oil repellent, which was used as a measurement sample.
• 2 ⁇ L of n-hexadecane was added to the surface of the measurement sample, and the contact angle of n-hexadecane after 5 seconds was measured using a contact angle measurement device (Kyowa Interface Science Co., Ltd., DM-500). Measurements were performed at five different locations on the surface, and the average value was calculated. The ⁇ /2 method was used to calculate the contact angle.
• Examples 1 to 9 The raw materials used in Examples 1 to 9 are as follows: Compounds m1-1 (manufactured by Tokyo Chemical Industry Co., Ltd.) and m1-2 shown below were used as compound m1.
• Compound m1-1 is a compound in which, in the above formula 1, X 1 is a methacryloyloxy group, A 1 is a trimethylene group, and B 1 is a group represented by the above formula 3.
• Compound m1-2 is a compound in which, in the above formula 1, X 1 is a methacryloyloxy group, A 1 is a trimethylene group, and B 1 is a group represented by the above formula 4 (a compound in the above formula 4 where n is 2 on average).
• a 300 mL four-neck flask was charged with 5.00 g of hydroxytrimethylsilane and 100 mL of THF. After cooling to 0°C, n-butyllithium (33 mL of a 1.6 M hexane solution) was added and stirred for 30 minutes. After warming to room temperature, 25 mL of a THF solution containing 8.28 g of hexamethylcyclotrisiloxane was added and stirred for 16 hours. Subsequently, 12.24 g of 3-(chlorodimethylsilyl)propyl methacrylate was added and stirred for 3 hours.
• the compound represented by compound m2-1 is a compound in which, in the above formula 2, X 2 is a methacryloyloxy group, A 2 is an ethylene group, B 2 is a urethane bond, and R 2 is an n-hexyl group.
• the compound represented by compound m2-2 is a compound in which, in the above formula 2, X 2 is a methacryloyloxy group, A 2 is an ethylene group, B 2 is —NHC( ⁇ O)OC 2 H 4 NHC( ⁇ O)—, and R 2 is an n-pentadecyl group.
• the compound represented by compound m2-3 is a compound in which, in the above formula 2, X 2 is a methacryloyloxy group, A 2 is an ethylene group, B 2 is —NHC( ⁇ O)NHCH 2 C( ⁇ O)NH—, and R 2 is an n-butyl group.
• Compound m2-4 is a compound in which, in the above formula 2, X 2 is a methacryloyloxy group, A 2 is a methylene group, B 2 is —CH(—OH)CH 2 OC( ⁇ O)NH—, and R 2 is an n-stearyl group.
• reaction solution was separated into saturated aqueous sodium bicarbonate, 2 M aqueous hydrochloric acid, and saturated saline, and the resulting organic layer was dried over sodium sulfate and concentrated.
• Liquid medium methyl ethyl ketone (MEK) or 1-methoxy-2-propanol (PGME).
• Polymerization initiator 2,2'-azobis(2-methylbutyronitrile).
• Example 1 A 200 mL glass reactor was charged with 3.8 g of compound m1-1, 6.2 g of compound m2-1, and 40 g of methyl ethyl ketone, and the mixture was stirred to homogenize. 0.04 g of 2,2'-azobis(2-methylbutyronitrile) was added as a polymerization initiator, and the mixture was sealed with nitrogen. The temperature was raised to 70°C, and polymerization was carried out for 24 hours. The resulting crude liquid was reprecipitated with hexane, and the solids were filtered and dried to obtain 7.3 g of copolymer A1. The Mw of copolymer A1 was 125,000.
• Copolymer A2 (Example 2), Copolymer A3 (Example 3), Copolymer A4 (Example 4), Copolymer A5 (Example 5), Copolymer A6 (Example 6), Comparative Polymer B1 (Example 7), Comparative Polymer B2 (Example 8), and Comparative Copolymer B3 (Example 9) were obtained in the same manner as in Example 1, except that the types and amounts of raw materials were changed as shown in Table 1.
• the hexadecane contact angle was 30° or less, demonstrating poor oil repellency. The reason for this is thought to be that Example 7 contains only units m1, Example 8 contains only units m2, and Example 9 contains units m1 and m3 but does not contain units m2.
• the contact angle with hexadecane was 62° or more, and it was found that the oil repellency was superior.

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