Oil repellent agent, article, and method for producing article

Abstract

The present invention relates to an oil repellent agent comprising a coating composition that includes a copolymer having a unit which is based on a compound represented by formula 1 and a unit which is based on a compound represented by formula 2. In formula 1, X1 is a hydrolyzable silyl group or a monovalent group having a polymerizable carbon-carbon double bond, A1 is a divalent organic group, and B1 is monovalent organic group having at least one trialkylsilyl group.　Formula 1: X1-A1-B1 Formula 2: X2-A2-B2-R2

Description

Oil repellent, article, and method for manufacturing article

[0001] The present invention relates to an oil repellent, an article, and a method for manufacturing an article. This application claims priority from Japanese Patent Application No. 2024-054168, filed on March 28, 2024, the contents of which are incorporated herein by reference.

[0002] As a method for imparting oil repellency to the surface of an article such as a textile product, for example, a method of treating the article with an oil repellent composition containing a fluoropolymer is known. However, in recent years, the fluoropolymer used in the above method has tended to raise concerns about its environmental impact. Therefore, it is considered that there is a demand for an oil repellent composition containing a non-fluoropolymer that can impart sufficient oil repellency to the surface of an article and is not concerned about its environmental impact.

[0003] As an oil repellent composition containing a non-fluorinated polymer, for example, Patent Document 1 discloses a liquid repellent containing a silicone-containing polymer, which is a polymer having as polymerization components at least a polymerizable monomer having a siloxane bond and a trialkylsilyl group having 1 to 6 carbon atoms, and a polymer monomer having a functional group.

[0004] Japanese Patent Application Laid-Open No. 2023-169574

[0005] However, the oil repellency of articles treated with the liquid repellent described in the examples of Patent Document 1 is insufficient. An object of one embodiment of the present invention is to provide an oil repellent comprising a coating composition containing a copolymer that can provide articles with better oil repellency, an article treated with the oil repellent, and a method for producing the article.

[0006] The present invention has the following aspects: [1] 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 In the 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.２ -A ２ -B ２ -R ２ Formula 2 In the formula 2, X ２ is a monovalent polymerizable reactive group, and A ２ is a divalent hydrocarbon group, B ２ is a divalent organic group having at least one heteroatom and including any one of the following structures, and R ２ is a monovalent hydrocarbon group. However, a carbon atom or a hydrogen atom is bonded to the end of the dotted line. [2] The B １ The oil repellent according to [1], wherein the silicon number of B is 10 or less. １ is a monovalent organic group represented by the following formula 3 or a monovalent organic group represented by the following formula 4. Ａ１ -Si(OSi(R ３ ) ３ ) ３－ｂ R ４ ｂ ...Formula 3 In Formula 3, R ３ and R ４ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, and b is an integer of 0 to 3; Ａ１ * is A １ It is a combination with. Ａ１ -Si(R ５ ) ２ (OSi(R ６ ) ２ ) ｎ OSi(R ７ ) ３ ...Formula 4 In Formula 4, R ５ , R ６ and R ７ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 3; Ａ１ * is A １ It is a combination of.

[0007] [4] The B １ is a monovalent organic group represented by the following formula 31: [1] The oil repellent according to any one of [1] to [3].

[0008] [5] B in the formula 2２ is a group having the following structure: However, a carbon atom or a hydrogen atom is bonded to the end of the dotted line. [6] The X １ and the X ２ are each independently a (meth)acryloyloxy group or a hydrolyzable silyl group, ２ is a urethane bond, a urea bond, or an amide bond, and ２ The oil repellent according to any one of [1] to [5], wherein R is a saturated hydrocarbon group having 1 to 12 carbon atoms. [7] ２ is a linear or branched alkyl group having 2 to 12 carbon atoms. [8] The oil repellent according to any of [1] to [7], wherein the total content of units based on the compound represented by formula 1 and units based on the compound represented by formula 2 relative to all units constituting the copolymer is 70 mass% or more. [9] The oil repellent according to any of [1] to [8], wherein the mass ratio of units based on the compound represented by formula 2 to units based on the compound represented by formula 1 is 0.1 to 4.

[10] The oil repellent according to any of [1] to [9], which is for use with fibers.

[11] An article treated with the oil repellent according to any of [1] to

[10] .

[12] A method for producing an article, comprising treating the article with the oil repellent according to any of [1] to

[10] .

[13] The article according to

[11] or

[12] , comprising fibers. [1A] A copolymer having units based on a compound represented by formula 1A below and units based on a compound represented by formula 2A below: １ -A １ -B １ Formula 1A In the above formula 1A, X １ is a monovalent polymerizable reactive group, and A １ is a divalent organic group, B １ is a monovalent organic group having at least one trialkylsilyl group. ２ -A ２ -B ２ -R ２ Formula 2A In the formula 2A, X ２ is a monovalent polymerizable reactive group, and A ２ is a divalent hydrocarbon group, B ２is a divalent organic group having at least one heteroatom (excluding divalent organic groups including an —O— group and an oxyalkylene group), and R ２ is a monovalent hydrocarbon group, and R ２ B combines with ２ The atom in the X is an atom other than a silicon atom. １ and the X ２ are each independently a (meth)acryloyloxy group or a hydrolyzable silyl group, １ The silicon number of B is 10 or less, ２ is a urethane bond, a urea bond, or an amide bond, and ２ is a linear or branched alkyl group having 1 to 12 carbon atoms. １ is a monovalent organic group represented by the above formula 31 or a monovalent organic group represented by the below-mentioned 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].

[0009] According to one embodiment of the present invention, there can be provided an oil repellent comprising a coating composition containing a copolymer that can provide an article with better oil repellency, an article treated with the oil repellent, and a method for producing the article.

[0010] The meanings and definitions of terms used in this disclosure are as follows. A "unit based on a compound" is an atomic group having a structure formed by polymerization of one molecule of a monomeric compound. 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 portion of an atomic group formed by polymerization of another monomer with a partially different structure. "(Meth)acrylate" is a general term for acrylate and methacrylate. Similarly, "(meth)acryloyl(oxy) group" is a general term for acryloyl(oxy) group and methacryloyl(oxy) group, and (meth)acrylic acid is a general term for acrylic acid and methacrylic acid. The same applies to (meth)acrylamide and other compounds. 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 polymethyl methacrylate-equivalent molecular weights obtained by gel permeation chromatography (hereinafter also referred to as "GPC") using a calibration curve prepared using a standard polymethyl methacrylate sample. The solid content concentration is calculated by (solid content mass / sample mass) x 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. In the numerical ranges described in this specification in stages, the upper or lower limit of a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of a certain numerical range may be replaced with a value shown in the Examples. A hydrocarbon group refers to a group consisting only of carbon and hydrogen.

[0011] <Copolymer> 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.

[0012] <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, and A １ is a divalent hydrocarbon group, B １ is a monovalent organic group having at least one trialkylsilyl group.

[0013] (Polymerizable reactive group: X １ ) X １ Examples of the polymerizable reactive group include a group having a polymerizable carbon-carbon double bond and a hydrolyzable silyl group, with the 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.

[0014] In the above formula 5, R １０１ ~R １０５ One of them is 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.

[0015] * Ａ１ -R １１ C(=O)CR １３ =CH ２ Formula 6 In the above formula 6, R １１is a single bond, an oxygen atom, or NR １２ is a divalent group represented by R １３ is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, and * Ａ１ is A １ It is a bond with R. １２ is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms.

[0016] R １１ is preferably an oxygen atom. １１ is an oxygen atom, and R １３ When R is a hydrogen atom or a methyl group, formula 6 represents a (meth)acryloyloxy group. 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. 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. As the monovalent group represented by the above formula 6, a (meth)acryloyloxy group is preferred.

[0017] Examples of the hydrolyzable silyl group include monovalent groups represented by the following formula 7: Ａ１ -Si(R １４ ) ３－ａ X ａ Formula 7 In the above formula 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. R １４ represents a monovalent organic group having 1 to 20 carbon atoms other than the hydrolyzable group in X. Ａ１ is A １ It is a combination of.

[0018] R １４ Examples of the hydrolyzable group in the "organic group other than a hydrolyzable group" of R are the same as the hydrolyzable group of X described below. １４is preferably at least one group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an α-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 α-chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group, or a triphenylsiloxy group.

[0019] Examples of the hydrolyzable group of 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, a siloxane bond is easily formed quickly.

[0020] Examples of the hydrolyzable silyl group represented by the above formula 7 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a methyldiisopropoxysilyl group, an (α-chloromethyl)dimethoxysilyl group, and an (α-chloromethyl)diethoxysilyl group. Among these, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group are preferred, and a dimethoxymethylsilyl group is more preferred.

[0021] (Divalent organic group: A １ ) A １The divalent organic group is preferably a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include a straight-chain or branched-chain alkylene group, a cycloalkylene group, an alkylene group or a cycloalkylene group having a combination of cyclic, straight-chain, and branched chains, a group 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., an alkenylene group, an alkynylene group), a group in which at least one carbon-carbon single bond of the cycloalkylene group is substituted with a carbon-carbon double bond, an arylene group, and the like. A carbon in the hydrocarbon group may be substituted with a heteroatom. A hydrogen in the hydrocarbon group may be substituted with a heteroatom or a monovalent group having a heteroatom. Examples of the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, a boron atom, and a phosphorus atom, with a nitrogen atom or an oxygen atom being preferred. A １ does not have a silicon atom. １ The divalent organic group 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.

[0022] 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.

[0023] A １ The divalent organic group is preferably a linear alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, or an 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, an ethyl group, or a propyl group, and more preferably the linear alkylene group.

[0024] (Monovalent organic group having at least one trialkylsilyl group: B １ ) B １ The number of trialkylsilyl groups in the hydroxyl group 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. When the number of trialkylsilyl groups is within the above range, the effect of imparting oil repellency to the treated article is more excellent.１ When has two or more trialkylsilyl groups, the multiple trialkylsilyl groups may be the same or different.

[0025] Examples of the alkyl group of the trialkylsilyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, and t-butyl, isopropyl, ethyl, and methyl groups are preferred, with ethyl and methyl being more preferred. The three alkyl groups of the trialkylsilyl group may be the same or different.

[0026] B １ Preferably, B has a siloxane bond. １ The number of Si—O bonds in the copolymer 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. １ The number of silicon atoms 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.

[0027] A １ B combines with １ The atom in B is preferably a silicon atom. １ 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 １ It is a combination of.

[0028] * Ａ１ -Si(OSi(R ３ ) ３ ) ３－ｂ R ４ ｂ ...Formula 3 * Ａ１ -Si(R ５ ) ２ (OSi(R ６ ) ２ ) ｎ OSi(R ７ ) ３ ...Formula 4

[0029] In formula 3, R３ and R ４ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms. b is an integer of 0 to 3, preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0030] R ３ and R ４ As R, a t-butyl group, an isopropyl group, an ethyl group, or a methyl group is preferable, an ethyl group or a methyl group is more preferable, and a methyl group is even more preferable. ３ and R ４ may be the same or different.

[0031] In formula 4, R ５ , R ６ and R ７ are each independently a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 3.

[0032] R ５ , R ６ and R ７ As the R, a t-butyl group, an isopropyl group, an ethyl group, or a methyl group is preferable, an ethyl group or a methyl group is more preferable, and a methyl group is even more preferable. ５ , R ６ and R ７ may be the same or different.

[0033] 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 １ It is a combination of.

[0034]

[0035] The monovalent organic group represented by the above formula 4 is preferably a monovalent organic group represented by the following formula 41. In formula 41, n is an integer of 0 to 3, Ａ１ * is A １ It is a combination of.

[0036]

[0037] B １ As the group, a monovalent organic group represented by the above formula 31 is preferred.

[0038] 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. One type of compound m1 may be used alone, or two or more types may be used in combination.

[0039] <Unit m2> The unit m2 is a unit based on a compound represented by the following formula 2: X ２ -A ２ -B ２ -R ２ Formula 2 In the above formula 2, X ２ is a monovalent polymerizable reactive group, and A ２ is a divalent hydrocarbon group, B ２ is a divalent organic group having at least one heteroatom and including any of the structures described below, and R ２ is a monovalent hydrocarbon group. When identifying the compound m2 represented by formula 2, ２ a divalent hydrocarbon group of the formula R ２ First, identify the monovalent hydrocarbon group, and then identify the rest as X ２ a monovalent polymerizable reactive group represented by the formula: ２ That is, X is identified as a divalent organic group having at least one heteroatom. ２ Even if it can be read as an allyl group, X ２ is a vinyl group, and a methylene group is A ２ However, X ２ In the above formula 5, A １ R other than the bond with １０１ ~R １０５ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, the styryl group is ２The benzene ring portion of the styryl derivative group is A ２ is not included.

[0040] (Polymerizable reactive group: X ２ ) X ２ Examples of the polymerizable reactive group include a group having a polymerizable carbon-carbon double bond and a hydrolyzable silyl group, and the group having a polymerizable carbon-carbon double bond is preferred. Examples of the group having a polymerizable carbon-carbon double bond and the hydrolyzable silyl group include X １ The same groups as those described in the above are exemplified, and preferred embodiments are also X １ It is the same as X １ is a group having a polymerizable carbon-carbon double bond, X ２ A group having a polymerizable carbon-carbon double bond is also preferred. １ and X ２ The groups having a polymerizable carbon-carbon double bond in X may be the same or different, and are preferably the same. １ is a hydrolyzable silyl group, X ２ X is also preferably a hydrolyzable silyl group. １ and X ２ The hydrolyzable silyl groups may be the same or different, and are preferably the same.

[0041] (Divalent hydrocarbon group: A ２ ) A ２ As the divalent hydrocarbon group, A １ The divalent hydrocarbon groups described in the above are exemplified, and preferred embodiments are also those described in the above. １ In this embodiment, B in unit m1 is the same as １ and B in units m2 ２ are preferably close to each other. １ and B in units m2 ２ From the perspective of bringing A closer together, １ A relative to the number of carbon atoms in the linear portion ２ The ratio of the number of carbon atoms in the linear portion of the alkyl group is preferably 0.25 to 4, more preferably 0.3 to 2, and even more preferably 0.5 to 1.5. When the ratio is within the above range, the effect of imparting oil repellency to the article to be treated is more excellent.

[0042] (Divalent organic group having at least one heteroatom: B ２ ) B ２ Examples of heteroatoms contained in B include nitrogen, oxygen, sulfur, boron, phosphorus, and silicon atoms, and nitrogen and oxygen atoms are preferred. ２ The number of heteroatoms contained in R 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 article to be treated is more excellent. ２ B combines with ２ The atom in is not a silicon atom. ２ B combines with ２ The structure in the ２２ -, -O-, and -C(=O)- are preferred, and -NH- or -C(=O)- is more preferred. ２２ is a straight or branched chain alkyl group having 1 to 6 carbon atoms.

[0043] B ２ preferably has a carbon atom, and B ２ has preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, further preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

[0044] The heteroatom preferably has a hydrogen atom bonded thereto. ２ The number of hydrogen atoms bonded to the heteroatom in the hydroxyl group is preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 or 2. When the number of hydrogen atoms bonded to the heteroatom is within the above range, the effect of imparting oil repellency to the article to be treated is more excellent.

[0045] The heteroatom to which the hydrogen atom is bonded is B ２ The main chain may be located in the main chain or in the side chain of A. ２ and R ２ The B group is an atomic group having the minimum number of atoms connecting the heteroatoms. ２ Examples of the B in which the hetero atom is located in the side chain include a group containing at least one bond selected from a urethane bond, an amide bond, a urea bond, and a thiocarbamate bond, or a group consisting of only the above bonds.２ Examples of the heteroatom having a hydrogen atom bonded thereto include a group containing a methylene group in which at least one hydrogen atom has been substituted with a heteroatom having a hydrogen atom bonded thereto. ２ , -NHR ２３ , —SH, and —OH are examples, and —OH is preferred. ２３ is a straight or branched chain alkyl group having 1 to 6 carbon atoms. ２ The heteroatom to which the hydrogen atom is bonded is represented by B. ２ The alkyl group may be present in the main chain, in the side chain, or in both the main chain and the side chain.

[0046] B ２ is a group containing any of the following structures: ２ Preferably, the compound contains 1 to 5 of the following structures, more preferably 1 to 3 of them. When the compound 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. B ２ Among the following structures, a structure having —(C═O)— is preferred. However, a carbon atom or a hydrogen atom is bonded to the end of the dotted line.

[0047] B ２ is more preferably a group containing any of the following structures: ２ More preferably, the compound contains 1 to 5 of the following structures, and even more preferably 1 to 3 of them. When the compound 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. B ２ Among the following structures, a structure having —(C═O)— is preferred. However, a carbon atom or a hydrogen atom is bonded to the end of the dotted line.

[0048] B ２ is more preferably a urethane bond, a urea bond, or an amide bond, and particularly preferably a urethane bond. ２ When B is a urethane bond, the effect of imparting oil repellency to the treated article is more excellent. ２is a urethane bond, the direction of the urethane bond is not particularly limited, but the nitrogen atom of the urethane bond may be ２ and the oxygen atom is A ２ It is preferable to combine with B. ２ is an amide bond, the orientation of the amide bond is not particularly limited, but the nitrogen atom of the amide bond is ２ and the carbon atom is bonded to R ２ It is preferred to combine with

[0049] (Monovalent hydrocarbon group: R ２ ) R ２ Examples of the monovalent hydrocarbon group include saturated hydrocarbon groups such as linear or branched alkyl groups, cycloalkyl groups, alkyl groups or cycloalkyl groups that combine cyclic, linear, or branched chains, groups in which at least one carbon-carbon single bond of the saturated hydrocarbon group is substituted with a carbon-carbon double bond or a carbon-carbon triple bond (e.g., alkenyl groups, alkynyl groups), and aryl groups. Among these, linear or branched alkyl groups and cycloalkyl groups are preferred, linear or branched alkyl groups are more preferred, and linear alkyl groups are even more preferred. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 22, more preferably 1 to 18, even more preferably 2 to 12, particularly preferably 2 to 12, and most preferably 4 to 8. When the number of carbon atoms is within the above range, the effect of imparting oil repellency to the treated article is more excellent.

[0050] The number of carbon atoms in the monovalent hydrocarbon group is preferably 1 or more, more preferably 2 or more, and more preferably 4 or more. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1 to 22, more preferably 1 to 18, still more preferably 1 to 12, particularly preferably 2 to 12, and most preferably 4 to 8. When 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.

[0051] R ２As the alkyl group, a linear alkyl group having 1 to 122 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-cetyl, n-stearyl, or n-behenyl is preferred, a linear alkyl group having 1 to 22 carbon atoms is more preferred, and a linear alkyl group having 2 to 12 carbon atoms is particularly preferred. When the carbon number is within the above range, the effect of imparting oil repellency to the treated article is more excellent. Alternatively, the alkyl group may be a branched hydrocarbon group in which at least one hydrogen atom of the linear alkyl group is substituted with a hydrocarbon group having 1 to 10 carbon atoms such as a methyl, ethyl, or phenyl group. A branched-chain alkyl group having 1 to 22 carbon atoms in which at least one hydrogen atom of the linear alkyl group has been substituted with an alkyl group having 1 to 10 carbon atoms, such as a methyl group or an ethyl group, is preferred, and the substituted branched-chain alkyl group having 2 to 12 carbon atoms is more preferred. When 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.

[0052] Examples of compound m2 include the following compounds. The area surrounded by the dotted line is B ２ where R represents a hydrogen atom or a methyl group. The compound m2 may be used alone or in combination of two or more.

[0053] <Unit m3> The unit m3 is a unit based on the compound m3. The unit m3 is a unit other than the unit m1 and the unit m2. The compound m3 preferably has a polymerizable reactive group. Examples of the polymerizable reactive group include a group having a polymerizable carbon-carbon double bond and a hydrolyzable silyl group, and a group having a polymerizable carbon-carbon double bond is preferred. Examples of the group having a polymerizable carbon-carbon double bond and the hydrolyzable silyl group include X １ The same groups as those described in the above are exemplified, and preferred embodiments are also X １ is the same as

[0054] X １ and X ２ is a group having a polymerizable carbon-carbon double bond, the polymerizable reactive group of compound m3 is also preferably a group having a polymerizable carbon-carbon double bond.１ , X ２ and the group having a polymerizable carbon-carbon double bond that compound m3 has may be the same or different, and are preferably the same.

[0055] X １ and X ２ When X is a hydrolyzable silyl group, the polymerizable reactive group of compound m3 is also preferably a hydrolyzable silyl group. １ , X ２ and the hydrolyzable silyl groups possessed by compound m3 may be the same or different, and are preferably the same.

[0056] Examples of the compound m3 having a group having a polymerizable carbon-carbon double bond as a polymerizable reactive group include, but are not limited to, vinyl carboxylic acid esters, allyl carboxylic acid esters, vinyl ethers, allyl ethers, vinyl halides, olefins, (meth)acrylates, (meth)acrylic acid, (meth)acrylamide, and halogenated olefins.

[0057] Examples of vinyl carboxylic acid esters 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. Examples of allyl carboxylic acid esters include allyl acetate and diallyl adipate.

[0058] Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, chloromethyl vinyl ether, 2-chloroethyl vinyl ether, chloropropyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol monovinyl ether, and diethylene glycol monovinyl ether. Examples of allyl ethers include allyl ethyl ether, diallyl ether, 1,3-diallyloxy-2-propanol, allyloxy polyethylene glycol mono(meth)acrylate, and allyloxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate. Examples of olefins include ethylene and propylene.

[0059] Examples of (meth)acrylates include alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, aromatic (meth)acrylates, and aliphatic cyclic (meth)acrylates. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyoxyethylene glycol mono(meth)acrylate, polyoxypropylene glycol mono(meth)acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth)acrylate. Examples of aromatic (meth)acrylates include phenyl (meth)acrylate, benzyl (meth)acrylate, and pentafluorophenyl (meth)acrylate. Examples of aliphatic cyclic (meth)acrylates include cyclohexyl (meth)acrylate and isobornyl (meth)acrylate. Examples of (meth)acrylates other than those mentioned above include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-diisopropylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, glycidyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol ethyl ether (meth)acrylate, and 2-acetoxyethyl (meth)acrylate.

[0060] Examples of (meth)acrylamides include alkyl(meth)acrylamides, hydroxyalkyl(meth)acrylamides, and (meth)acrylamides in which the nitrogen atom forms a heterocyclic structure. Examples of alkyl(meth)acrylamides include N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropylacrylamide, N,N-diisopropylacrylamide, N-(n-butyl)(meth)acrylamide, N-(t-butyl)(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N-lauryl(meth)acrylamide, N-stearyl(meth)acrylamide, N-behenyl(meth)acrylamide, and N,N-dimethylaminoethyl(meth)acrylamide. Examples of hydroxyalkyl(meth)acrylamides include N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, and N-(4-hydroxybutyl)(meth)acrylamide. Examples of (meth)acrylamides in which the nitrogen atom forms a heterocyclic structure include N-(meth)acryloylmorpholine and N-(meth)acryloylpiperidine.

[0061] Examples of halogenated olefins include vinyl chloride and vinylidene chloride.

[0062] Compound m3 may have a group capable of reacting with a crosslinking agent, which will be described later. Examples of the group capable of reacting with a crosslinking agent include an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, a primary amino group, an alkoxymethylamide group, a silanol group, a primary amide group, an epoxy group, a hydroxy group, an oxazoline group, a carboxyl group, and a sulfonic acid group.

[0063] Examples of compound m3 having a group having a hydrolyzable silyl group as the polymerizable reactive group include compounds in which the polymerizable reactive group of compound m3 having a group having a polymerizable carbon-carbon double bond as the polymerizable reactive group is substituted with a hydrolyzable silyl group. Compound m3 may be used singly or in combination of two or more types.

[0064] (Copolymer Composition) The content of units m1 relative to all units constituting copolymer A is preferably 1 to 80 mol%, more preferably 3 to 70 mol%, even more preferably 10 to 65 mol%, particularly preferably 20 to 65 mol%, and most preferably 51 to 60 mol%. The content of units m1 relative to all units constituting copolymer A is preferably 10 to 95 mass%, more preferably 20 to 92 mass%, even more preferably 30 to 88 mass%, particularly preferably 40 to 85 mass%, and most preferably 55 to 70 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 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% by mass, more preferably 6 to 87% by mass, even more preferably 8 to 83% by mass, and particularly preferably 10 to 80% by 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 article to be treated is more excellent. The total content of units m1 and units m2 relative to all units constituting copolymer A is preferably 0.1 to 100 mol%, more preferably 1 to 100 mol%, even more preferably 10 to 100 mol%, particularly preferably 30 to 100 mol%, and most preferably 60 to 100 mol%. The total content of units m1 and units m2 relative to all units constituting copolymer A is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by 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 article to be treated is more excellent. When copolymer A contains unit m3, the content of unit m3 relative to all units constituting copolymer A is preferably 0.01 to 98 mol%, more preferably 0.01 to 90 mol%, even more preferably 0.1 to 50 mol%, particularly preferably 0.1 to 30 mol%, and most preferably 0.1 to 20 mol%. When copolymer A contains unit m3, the content of unit m3 relative to all units constituting copolymer A is preferably 0.1 to 90 mass%, more preferably 0.5 to 50 mass%, even more preferably 1 to 30 mass%, and particularly preferably 2 to 20 mass%.

[0065] The molar ratio of units m2 to units m1 is preferably 0.1 to 9.0, more preferably 0.1 to 5.0, even more preferably 0.2 to 3.0, and particularly preferably 0.5 to 2.5. The mass ratio of units m2 to units m1 is preferably 0.05 to 10, more preferably 0.07 to 7, even more preferably 0.1 to 4, and particularly preferably 0.3 to 2.7. Within the above ranges, the effect of imparting oil repellency to the treated article is more excellent. When copolymer A contains units m3, the molar ratio of units m3 to units m1 is preferably 0.0001 to 1,000, more preferably 0.0001 to 500, even more preferably 0.001 to 500, particularly preferably 0.1 to 400, and most preferably 0.19 to 300. When copolymer A contains units m3, the mass ratio of units m3 to units m1 is preferably 0.005 to 2, more preferably 0.01 to 1.5. When copolymer A contains units m3, the molar ratio of units m3 to units m2 is preferably 0.0001 to 1000, more preferably 0.0001 to 500, even more preferably 0.001 to 500, particularly preferably 0.15 to 400, and most preferably 0.29 to 300. When copolymer A contains units m3, the mass ratio of units m3 to units m2 is preferably 0.01 to 20, more preferably 0.03 to 15.

[0066] The units m1 to m3 may form a random copolymer or a block copolymer. The unit m1 contained in the copolymer A may be of only one type or may be of two or more types. The unit m2 contained in the copolymer A may be of only one type or may be of two or more types. The unit m3 contained in the copolymer A may be of only one type or may be of two or more types.

[0067] The content of fluorine atoms relative to the total mass of copolymer A is preferably 20 mass% or less, more preferably 10 mass% or less, even more preferably 1 mass% or less, particularly preferably 0.1 mass% or less, and most preferably contains no fluorine atoms. In other words, 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.

[0068] The content of each unit is: １ It can be calculated from the reaction rates of compounds m1 to m3 measured by H-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 H NMR in deuterated chloroform, and comparing the integral ratios.

[0069] 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. When the Mn of copolymer A is equal to or greater than the lower limit, the effect of imparting oil repellency to the article to be treated is more excellent. When the Mn of copolymer A is equal to or less than the upper limit, the dispersibility in various solvents is more excellent.

[0070] 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. When the Mw of copolymer A is equal to or greater than the above lower limit, the effect of imparting oil repellency to the article to be treated is more excellent. When the Mw of copolymer A is equal to or less than the above upper limit, the dispersibility in various solvents is more excellent.

[0071] <Method for Producing Copolymer A> 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 set so as to satisfy the composition of copolymer A described above.

[0072] (Initiator) It is preferable to use an initiator when polymerizing copolymer A. There are no particular restrictions on the initiator, and it can be appropriately selected depending on the type of polymerizable reactive group in compounds m1 to m3. Examples of initiators include organic peroxides, inorganic peroxides, azo compounds, etc. used in radical polymerization; organic acids, inorganic acids, Lewis acids, and thermal cationic polymerization initiators or photocationic polymerization initiators that generate these in the polymerization system that are used in cationic polymerization; and photoanionic polymerization initiators that generate organometallics and organic bases in the polymerization system that are used in anionic polymerization. These may be used alone or in combination of two or more. There are no particular restrictions on the organic peroxide, and examples include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, t-butyl-α-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, and percarbonate. 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. In addition, commercially available products such as V-59 and V-65 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) can also be used as an azo polymerization initiator. The organic acid is not particularly limited and examples thereof include methanesulfonic acid, etc. The inorganic acid is not particularly limited and examples thereof include hydrochloric acid, nitric acid, sulfuric acid, tetrafluoroboric acid, fluoroantimonic acid, hexafluorophosphoric acid, etc. The Lewis acid is not particularly limited and examples thereof include trichloroaluminum, ethylaluminum dichloride, ethylaluminum sesquichloride, etc.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.).

[0073] The amount of polymerization initiator added is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total of compounds m1 to m3. The polymerization temperature is preferably 20 to 150°C, and more preferably 40 to 90°C. The polymerization time varies depending on the reaction temperature, but is, for example, 1 to 144 hours, and preferably 3 to 86 hours. The polymerization is preferably carried out in an inert atmosphere such as nitrogen.

[0074] (Molecular Weight Regulator) When polymerizing the compounds m1 to m3, a molecular weight regulator may be used. Examples of the molecular weight regulator include aromatic compounds, mercapto alcohols, mercaptocarboxylic acids, and alkyl mercaptans, and more preferred are mercaptocarboxylic acids and alkyl mercaptans. Examples of the molecular weight regulator include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, α-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, and more preferably 0 to 2 parts by mass, per 100 parts by mass of the total of compounds m1 to m3.

[0075] (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. Examples of the chain transfer agent are preferably 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. In particular, when a monomer having two or more polymerizable groups in one molecule is used for polymerization, the addition of such a chain transfer agent is preferred because it can suppress gelation and precipitation of copolymer A. The amount of 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 compounds m1 to m3 combined.

[0076] (Catalyst) A catalyst may be used to obtain copolymer A. The catalyst is not particularly limited, and examples thereof include tin compounds such as dibutyltin dilaurate (dibutyltin dilaurate (DBTDL)); basic catalysts such as 1,4-diazabicyclo[2.2.2]octane (DABCO); and the like. These may be used alone or in combination of two or more. The amount of catalyst 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 compounds m1 to m3.

[0077] Examples of the polymerization method include solution polymerization, emulsion polymerization, and bulk polymerization. Among these, solution polymerization and emulsion polymerization are preferred, with solution polymerization being particularly preferred. Solution polymerization is advantageous in that it polymerizes compounds m1 to m3 without using an emulsifier, making it easy to control the composition and preventing impurities from entering.

[0078] The medium used in the solution polymerization method is preferably an organic solvent. The organic solvent is not particularly limited, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, and ester organic solvents. These may be used alone or in combination of two or more.

[0079] The hydrocarbon organic solvent is not particularly limited, and examples thereof include pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. These may be used alone or in combination of two or more.

[0080] The alcohol-based organic solvent is not particularly limited, and examples thereof include ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, etc. These may be used alone or in combination of two or more.

[0081] The ketone-based organic solvent is not particularly limited, and examples thereof include methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone, cyclohexanone, etc. These may be used alone or in combination of two or more.

[0082] The ether-based organic solvent is not particularly limited, and examples thereof include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dibutyl ether, diethylene glycol methyl ethyl ether, etc. These may be used alone or in combination of two or more.

[0083] The ester-based organic solvent is not particularly limited, and examples thereof 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, γ-butyrolactone, 3-methyl-3-methoxybutyl acetate, glycerin triacetate, etc. These may be used alone or in combination of two or more.

[0084] In the case of emulsion polymerization, for example, compounds m1 to m3 are polymerized in an emulsion containing compounds m1 to m3, an aqueous medium, an emulsifier, and a polymerization initiator. Examples of the aqueous medium include water or a mixed medium of water and a water-soluble organic solvent. The water-soluble organic solvent is an organic solvent that is miscible with water in any ratio. The water-soluble organic solvent is preferably at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols, and aprotic polar solvents. When 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.

[0085] The emulsifier is a surfactant having both a hydrophilic moiety and a hydrophobic moiety. 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 have a fluorine atom. The emulsifier can be the same as the emulsifier described below. As the emulsifier, from the viewpoint of excellent dispersion stability of the coating composition, it is preferable to use a nonionic emulsifier alone, a nonionic emulsifier in combination with a cationic emulsifier or an amphoteric emulsifier, or an anionic emulsifier alone, and more preferably a nonionic emulsifier in combination with a cationic emulsifier.

[0086] (Polymerization 1) When the polymerizable reactive groups of compounds m1 to m3 are groups having a polymerizable carbon-carbon double bond, compounds m1 to m3 are polymerized in the presence of an initiator used in the above-mentioned radical polymerization or an initiator used in anionic polymerization to obtain copolymer A having units m1 to m3. In particular, it is preferable to use an initiator used in radical polymerization, and an azo compound is more preferable.

[0087] (Polymerization 2) When the polymerizable reactive groups of compounds m1 to m3 are hydrolyzable silyl groups, copolymer A having units m1 to m3 can be obtained by polymerizing compounds m1 to m3 in the presence of an initiator used in the above-mentioned cationic polymerization or an initiator used in anionic polymerization. It is particularly preferable to use an initiator used in cationic polymerization. The initiators used in cationic polymerization, such as organic acids, inorganic acids, and Lewis acids, function as catalysts for the hydrolysis reaction. The initiator is not limited to organic acids, inorganic acids, and Lewis acids, and any initiator that catalyzes hydrolysis may be used. For example, an inorganic base or an organic base may also be used. For example, in the case of a hydrolyzable silyl group represented by the above formula 7, the hydrolyzable group is hydrolyzed and converted into a hydroxy group, and the hydroxy group undergoes dehydration condensation to form a siloxane bond, thereby progressing the polymerization.

[0088] Polymerization 2 may be carried out by a sol-gel method (Method 1), or by a method in which a solution containing compounds m1 to m3 is coated on an article and then polymerization is caused to proceed by moisture in the air (Method 2).

[0089] In the case of Method 1, it is preferable to add the compounds m1 to m3 and, if necessary, the initiator to the aqueous medium, and then stir the mixture to polymerize it. If necessary, the reaction solution may be heated.

[0090] In the case of Method 2, a solution in which compounds m1 to m3 are dissolved in the organic solvent or the aqueous medium is coated on an article by a known method such as application, impregnation, immersion, spraying, brushing, padding, size press, or roller, and then the organic solvent or the aqueous medium is dried. Drying may be performed at room temperature or with heating, and heating is preferred. The drying atmosphere is preferably an atmosphere containing water vapor.

[0091] (Formation of Unit m2 After Polymerization) The unit m2 in the copolymer may be formed after polymerization. For example, a compound Z1, which is a precursor compound of compound m2 and has a reactive group (Z1 group), may be used instead of compound m2, and compound m1, compound Z1, and, if necessary, compound m3 may be polymerized to obtain a precursor copolymer A'. Compound Z2, which has a reactive group (Z2 group) and a hydrocarbon group capable of reacting with the reactive group (Z1 group) in unit Z1 of precursor copolymer A', may then be reacted with the reactive group (Z1 group) in unit Z1 to form unit m2.

[0092] The reactive group (Z1 group) is not particularly limited, and examples thereof include a hydroxy group, an amino group, an isocyanate group, a mercapto group, an acid anhydride group, and an acyl chloride group. Such a compound Z1 includes, in the above formula 2, ２ is a single bond, and R ２ is a hydrogen atom, ２ At least one hydrogen atom in the divalent hydrocarbon group (R ２ and the like. Examples of such compounds include compounds in which the above Z1 group is substituted with a hydrogen atom of the formula (including a hydrogen atom of the formula).

[0093] Examples of the reactive group (Z2) include reactive groups that can react with the reactive group (Z1), such as an isocyanate group, a hydroxy group, an amino group, an acid anhydride group, and an acyl chloride group.

[0094] For example, when the reactive group (Z1) of the compound Z1 (unit Z1) is a hydroxy group and the reactive group of the compound Z2 is an isocyanate group, the hydroxy group of the unit Z1 reacts with the isocyanate group of the compound Z2 to form B ２ In this case, a urethane bond is formed. ２ is a hydrocarbon group derived from compound Z2 that is bonded to the isocyanate group of compound Z2.

[0095] Compound Z2 is not particularly limited, and examples thereof include compounds having an isocyanate group, compounds having a hydroxy group, compounds having an amino group, compounds having an acid anhydride group, and compounds having an acyl chloride group. These may be used alone or in combination of two or more. Compound Z2 is preferably a compound in which at least one hydrogen atom in a hydrocarbon compound is substituted with a reactive group Z2.

[0096] Specific examples of the compound having an isocyanate group are not particularly limited and include, for example, 1-adamantyl isocyanate, cyclohexyl isocyanate, tertiary butyl isocyanate, isopropyl isocyanate, ethyl isocyanate, butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, etc. These may be used alone or in combination of two or more.

[0097] Specific examples of the compound having a hydroxy group are not particularly limited and include, for example, ethanol, 1-butanol, 1-hexanol, 1-dodecanol, isopropanol, cyclohexanol, etc. These may be used alone or in combination of two or more.

[0098] Specific examples of the compound having an amino group are not particularly limited, and include, for example, propylamine, butylamine, hexylamine, dodecylamine, isopropylamine, cyclohexylamine, etc. These may be used alone or in combination of two or more.

[0099] Specific examples of the compound having an acid anhydride group are not particularly limited, and include, for example, acetic anhydride, propionic anhydride, butyric anhydride, decanoic anhydride, etc. These may be used alone or in combination of two or more.

[0100] Specific examples of the compound having an acyl chloride group are not particularly limited and include, for example, acetyl chloride, propionyl chloride, butyric acid chloride, decanoic acid chloride, etc. These may be used alone or in combination of two or more.

[0101] The combination of the reactive group Z1 of compound Z1 and the reactive group Z2 of compound Z2 is not particularly limited, but for example, the following combinations are preferred. Combination 1: The Z1 group is a hydroxy group, and the Z2 group is an isocyanate group. Combination 2: The Z1 group is an isocyanate group, and the Z2 group is a hydroxy group. Combination 3: The Z1 group is an acid anhydride group or an acyl chloride group, and the Z2 group is an amino group. Combination 4: The Z1 group is an amino group, and the Z2 group is an acid anhydride group or an acyl chloride group. Combination 5: The Z1 group is an amino group, and the Z2 group is an isocyanate group. Combination 6: The Z1 group is an isocyanate group, and the Z2 group is an amino group. In the case of combinations 1 and 2, B ２ is a urethane bond, and in the case of combinations 3 and 4, B ２ is an amide bond, and in the case of combinations 5 and 6, B ２ Among these, combinations 1 and 2 are particularly preferred.

[0102] <Coating Composition> The coating composition of the present embodiment contains copolymer A. The coating composition may contain a liquid medium. The coating composition may contain other components as necessary. The coating composition may be the solution or dispersion obtained by the method for producing copolymer A, or may be a liquid obtained by further diluting the solution or dispersion.

[0103] Examples of the liquid medium include a non-aqueous medium, an aqueous medium, or a mixed medium of a non-aqueous medium and a water-soluble organic solvent. When the liquid medium is a non-aqueous medium or a mixed medium, the coating composition is preferably a polymer solution containing copolymer A and a non-aqueous medium or a mixed medium, and may contain an emulsifier. The emulsifier in the polymer solution is typically 0.3 parts by mass or less per 100 parts by mass of copolymer A. When the liquid medium is an aqueous medium, the coating composition is preferably a polymer dispersion containing copolymer A, an aqueous medium, and an emulsifier.

[0104] (Non-aqueous medium) The non-aqueous medium is a liquid medium that does not contain an aqueous medium, and is typically an organic solvent other than a water-soluble organic solvent. The non-aqueous medium is not particularly limited as long as it can dissolve Copolymer A, and examples thereof include hydrocarbon organic solvents, ketone organic solvents, alcohol organic solvents, ester organic solvents, amide organic solvents, and ether organic solvents.

[0105] The hydrocarbon organic solvent is not particularly limited, and examples thereof include pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. These may be used alone or in combination of two or more.

[0106] The ketone-based organic solvent is not particularly limited, and examples thereof include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These may be used alone or in combination of two or more.

[0107] The alcohol-based organic solvent is not particularly limited, and examples thereof include ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, etc. These may be used alone or in combination of two or more.

[0108] Examples of 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, γ-butyrolactone, 3-methyl-3-methoxybutyl acetate, glycerin triacetate, etc. These may be used alone or in combination of two or more.

[0109] The amide organic solvent is not particularly limited, and examples thereof include dimethylacetamide, 3-methoxy-dimethylpropanamide, 3-butoxydimethylpropanamide, and methylpyrrolidone. These may be used alone or in combination of two or more.

[0110] The ether-based organic solvent is not particularly limited, and examples thereof include diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dibutyl ether, and diethylene glycol methyl ethyl ether. These may be used alone or in combination of two or more. Two or more types may be used as the non-aqueous medium.

[0111] (Aqueous Medium) Examples of aqueous media include water and a mixture of water and a water-soluble organic solvent. The water-soluble organic solvent is an organic solvent that can be mixed with water in any ratio. The water-soluble organic solvent is preferably at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols, and aprotic polar solvents. Examples of alcohols include t-butanol and propylene glycol. Examples of ether alcohols include 3-methoxymethylbutanol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol. Examples of aprotic polar solvents include N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (hereinafter referred to as "THF"), acetonitrile, and acetone. When the liquid medium is an aqueous medium, 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 of Copolymer A with the aqueous medium and facilitate the formation of a uniform film on the surface of the article. When 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.

[0112] (Mixed Medium) The mixed medium is a mixed medium that can dissolve Copolymer A and is a combination of a non-aqueous medium and a water-soluble organic solvent that is optionally miscible with the non-aqueous medium. As the water-soluble organic solvent constituting the mixed medium, the water-soluble organic solvents listed above for the aqueous medium can be used, and aprotic polar solvents are preferred, with THF, acetone, and N,N-dimethylformamide being more preferred.

[0113] (Emulsifier) ​​The emulsifier is a surfactant having both a hydrophilic moiety and a hydrophobic moiety. 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 have a fluorine atom. As the emulsifier, from the viewpoint of excellent dispersion stability of the coating composition, the use of a nonionic emulsifier alone, a combination of a nonionic emulsifier with a cationic emulsifier or an amphoteric emulsifier, or the use of an anionic emulsifier alone is preferred, and the combination of a nonionic emulsifier with a cationic emulsifier is more preferred. The ratio of the nonionic emulsifier to the cationic emulsifier (nonionic emulsifier / cationic emulsifier) ​​is preferably 100 / 0 to 40 / 60 (mass ratio), and more preferably 97 / 3 to 40 / 60 (mass ratio). In a specific combination of a nonionic emulsifier and a cationic emulsifier, the total amount of emulsifier per 100 parts by mass of copolymer A can be 5 parts by mass or less, thereby reducing the adverse effect of the emulsifier on the oil repellency of waterproof and oil-resistant paper and the like using the coating composition.

[0114] Examples of nonionic emulsifiers include surfactants described in paragraphs

[0067] to

[0095] of JP-A-2009-215370. １ ~s ６ Surfactants include: １ is a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, a polyoxyalkylene monoalkapolyenyl ether, or a polyoxyalkylene monopolyfluoroalkyl ether. １ As the surfactant, polyoxyethylene alkyl ether is preferred. ２ is a compound having one or more carbon-carbon triple bonds and one or more hydroxy groups in the molecule. ２ As the surfactant, acetylene glycol ethylene oxide adduct is preferred. ３ 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 of the chain are hydroxyl groups. ３As the nonionic emulsifier, ethylene oxide propylene oxide polymer is preferred. One type of nonionic emulsifier may be used alone, or two or more types may be used in combination.

[0115] Examples of the cationic emulsifier include surfactants described in paragraphs

[0096] to

[0100] of JP-A-2009-215370. ７ Surfactants include: ７ is a cationic emulsifier in the substituted ammonium salt form. ７ As the ammonium salt, 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 with a hydroxy group is preferred, and the ammonium salt represented by the following formula s ７１ Compounds represented by ７１ [(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 terminal hydroxy group. ２１ may be the same or different, but four R ２１ is not a hydrogen atom at the same time. － is a counter ion. － The compound s is preferably a chloride ion, an ethyl sulfate ion, or an acetate ion. ７１ Examples of cationic emulsifiers include monostearyl trimethyl ammonium chloride, monostearyl dimethyl monoethyl ammonium ethyl sulfate, mono(stearyl) monomethyl di(polyethylene glycol) ammonium chloride, monofluorohexyl trimethyl ammonium chloride, di(tallow alkyl) dimethyl ammonium chloride, and dimethyl monococonut amine acetate. One type of cationic emulsifier may be used alone, or two or more types may be used in combination.

[0116] Examples of amphoteric emulsifiers include surfactants described in paragraphs

[0101] to

[0102] of JP-A-2009-215370. ８ These surfactants may be used alone or in combination of two or more. ８ is alanine, imidazolinium betaine, amidobetaine or acetic acid betaine.

[0117] (Other Components) Other components may be added to the solution or dispersion obtained by the method for producing copolymer A of the present invention, or to a liquid obtained by further diluting the solution or dispersion. Examples of other components 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 added to a liquid obtained by further diluting the above solution or dispersion to treat articles 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, which are used as coagulants for external additives described below, and coagulants, retention agents, sizing agents, paper strength agents, pigments, dyes, and pH adjusters, which are used as coagulants for internal additives described below. Two or more of these other components may be used. Other types of components that are the same as or have the same effect as those added to the solution or dispersion obtained by the method for producing copolymer A may be added to a liquid obtained by diluting the solution or dispersion for further treating an article. Examples of other components are not limited to these.

[0118] When the coating composition contains a crosslinking agent, adhesion to the article is likely to be improved. Preferred crosslinking agents include polyfunctional acrylic crosslinking agents, isocyanate crosslinking agents, methylol crosslinking agents, carbodiimide crosslinking agents, crosslinking systems using an enethiol reaction with the addition of a polyfunctional thiol, and oxazoline crosslinking agents. Examples of isocyanate crosslinking agents include aromatic block-type isocyanate crosslinking agents, aliphatic block-type isocyanate crosslinking agents, aromatic unblock-type isocyanate crosslinking agents, and aliphatic unblock-type isocyanate crosslinking agents. The isocyanate crosslinking agent is preferably a water-dispersible type emulsified with a surfactant, or a self-water-dispersible type having a hydrophilic group.

[0119] Examples of the methylol-based crosslinking agent include condensates or precondensates of urea or melamine with formaldehyde, methylol-dihydroxyethylene-urea and derivatives thereof, methylol-ethylene-urea, methylol-propylene-urea, methylol-triazone, dicyandiamide-formaldehyde condensates, methylol-carbamate, methylol-(meth)acrylamide, and polymers thereof.

[0120] Carbodiimide-based crosslinking agents are polymers having carbodiimide groups in their molecules, and are crosslinking agents that exhibit excellent reactivity with carboxy groups, amino groups, and active hydrogen groups on the surface of articles, etc. Oxazoline-based crosslinking agents are polymers having oxazoline groups in their molecules, and are crosslinking agents that exhibit excellent reactivity with carboxy groups on the surface of articles, etc.

[0121] Other crosslinking agents include, for example, divinyl sulfone, polyamide and its cationic derivatives, polyamine and its cationic derivatives, epoxy derivatives such as diglycidyl glycerol, halide derivatives such as (epoxy-2,3-propyl)trimethylammonium chloride and N-methyl-N-(epoxy-2,3-propyl)morpholinium chloride, pyridinium salts of chloromethyl ether of ethylene glycol, polyamine-polyamide-epichlorohydrin resins, polyvinyl alcohol or its derivatives, polyacrylamide or its derivatives, and glyoxal resin-based wrinkle inhibitors.

[0122] When the coating composition contains a methylol-based crosslinking agent or a glyoxal resin-based wrinkle-preventing agent, it is preferable to contain a catalyst as an additive. Preferred catalysts include, for example, inorganic amine salts and organic amine salts. Examples of inorganic amine salts include ammonium chloride. Examples of organic amine salts include amino alcohol hydrochlorides and semicarbazide hydrochloride. Examples of amino alcohol hydrochlorides include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanolamine hydrochloride, and 2-amino-2-methylpropanol hydrochloride.

[0123] (Proportion of Each Component) When the coating composition contains a liquid medium, 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%. When the coating composition is used to coat an article, the solid content concentration 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 0.1 to 80 mass%, more preferably 0.1 to 50 mass%, and even more preferably 0.1 to 30 mass%.

[0124] The content of fluorine atoms relative to the total mass of the coating composition is preferably 20 mass% or less, more preferably 10 mass% or less, even more preferably 1 mass% or less, particularly preferably 0.1 mass% or less, and most preferably contains no fluorine atoms. The content of fluorine atoms relative to the total mass of the coating composition can be measured by combustion ion chromatography or the like.

[0125] <Oil Repellents> Coating compositions are widely used in coating applications. The coating composition is preferably used as an oil repellent. Oil repellents can also be used as agents having oil repellency, such as oil-resistant agents, water- and oil-repellents, water- and oil-resistant agents, and stain-resistant agents. When used as an oil repellent, the oil repellent comprising the coating composition can be applied to an article to be treated. For example, when the coating composition contains a liquid medium, the oil repellent can be applied to an article by a known method such as application, impregnation, immersion, spraying, brushing, padding, size press, or roller, followed by drying. The amount of solids in the oil repellent applied to the article to be treated is not particularly limited. For example, in the case of a fiber fabric, the amount is preferably 0.1 to 5 g, more preferably 0.1 to 3 g, and even more preferably 0.1 to 1 g per 100 g of fiber fabric. The content of copolymer A in the oil repellent to be attached to the article to be treated is not particularly limited. For example, in the case of a fiber fabric, the content is preferably 0.01 to 5 g, more preferably 0.02 to 3 g, and even more preferably 0.03 to 1 g per 100 g of fiber fabric. Drying may be performed at room temperature or with heating, with heating being preferred. If heated, the heating temperature is preferably 90 to 200°C. Furthermore, if the oil repellent contains a crosslinking agent, it is preferably cured by heating to a temperature equal to or higher than the crosslinking temperature of the crosslinking agent, if necessary. The oil repellent of this embodiment is suitable for imparting oil repellency to fibers, glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, porous resins, porous fiber bodies, and the like. From the viewpoint of oil repellency, the oil repellent is preferably used for fibers.

[0126] <Article> The article of this embodiment is an article treated with an oil repellent comprising a coating composition. Examples of articles that can be treated with an oil repellent comprising a coating composition include fibers, glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, porous resins, and porous fibrous bodies. Among these, fibers are preferred. The fiber may be a fiber fabric (e.g., woven fiber fabric, knitted fiber fabric, nonwoven fabric, or raised fabric), or a textile product comprising a fiber fabric (e.g., skiwear, rainwear, coat, blouson, windbreaker, down jacket, sportswear, workwear, uniform, protective clothing, backpack, bag, or tent). The type of fiber is not particularly limited, and examples include natural fibers such as cotton, wool, silk, or cellulose; chemical fibers such as polyester, polyamide, acrylic, aramid, rayon, or lyocell; and fibers obtained by using a combination of these fibers. Examples of fibers in nonwoven fabrics include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass, and rayon. The thickness of the fiber fabric is not particularly limited, but is 10 μm to 5 cm. Porous resins are used, for example, as filters. Examples of porous resin materials include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene. Examples of porous fibrous materials include glass fiber, cellulose nanofiber, carbon fiber, and cellulose acetate fiber.

[0127] The article to be treated preferably comprises a fiber (including a fiber fabric and a textile product comprising a fiber fabric), and more preferably consists of a fiber.

[0128] When the article of this embodiment is a glass substrate, the upper limit of the n-hexadecane contact angle on the treated surface, measured by the method described in the Examples below, is not particularly limited, but is generally 180° or less. The lower limit of the n-hexadecane contact angle is preferably more than 30°, more preferably 45° or more, even more preferably 55° or more, particularly preferably 60° or more, and most preferably 65° or more.

[0129] <Method for manufacturing an article> The article of this embodiment is manufactured by treating, with the oil repellent of this embodiment, fibers, glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, porous resins, porous fibrous bodies, etc. Details of the article to be treated are as described above.

[0130] <Mechanism of Action> It is presumed that 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.

[0131] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. Examples 1 to 6 are working examples, and Examples 7 to 9 are comparative examples.

[0132] <Content of Each Unit> The 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 1H NMR in deuterated chloroform, and comparing the integral ratios.

[0133] <Mw, Mn> A gel permeation chromatograph analyzer HLC-8320GPC (product name of Tosoh Corporation) was used as the measuring device. A TSKgel Supermultipore HZ-M (product name of Tosoh Corporation) column was used, and tetrahydrofuran was used as the solvent. A calibration curve was prepared using polymethyl methacrylate as a standard substance.

[0134] <Oil Repellency Evaluation: Hexadecane Contact Angle> The copolymers or polymers obtained in Examples 1 to 9 described below were diluted with methyl ethyl ketone to a solids concentration of 2% by mass to obtain a coating composition, which was used as an oil repellent. A glass substrate (AGC, 50 mm x 50 mm x 0.7 mm) was ultrasonically cleaned in ethanol for 30 seconds and then ultraviolet / ozone cleaned for 5 minutes (apparatus: PL7-200, Sen Engineering Co., Ltd.) and spin-coated (2000 rpm, 30 seconds) using a spinner (Mikasa Co., Ltd., IH-DX2). 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 μL 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 contact angle was calculated using the θ / 2 method.

[0135] <Raw Materials, etc.> The raw materials used in Examples 1 to 9 are as follows. Compound m1 used was compound m1-1 (manufactured by Tokyo Chemical Industry Co., Ltd.) and m1-2 shown below. Compound m1-1 is a compound represented by the formula 1 above, where X １ is a methacryloyloxy group, and A １ is a trimethylene group, and B １ is a group represented by the above formula 3. Compound m1-2 is a compound represented by the above formula 1, １ is a methacryloyloxy group, and A １ is a trimethylene group, and B １ is a group represented by the above formula 4 (a compound in which n in the above formula 4 is 2 on average).

[0136]

[0137]

[0138] (Synthesis of Compound m1-2) Compound m1-2 was synthesized according to the reaction route shown below.

[0139]

[0140] 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. After completion of the reaction, water was added, and the mixture was extracted with ethyl acetate, washed sequentially with water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain a crude product as a colorless liquid. This was purified by silica gel column chromatography (hexane / ethyl acetate = 99 / 1), yielding 14.8 g of compound m1-2 as a colorless, transparent oil. NMR analysis of the resulting compound m1-2 revealed that n in the above formula (4) was 2 on average. The molecular weight was measured by GPC (polymethyl methacrylate equivalent molecular weight) and found to be Mn 625 and Mw 691. １ H NMR (400 MHz, CDCl ３ )δ 6.10 (d, J=0.7Hz, 1H), 5.54 (t, J=1.5Hz, 1H), 4.10 (t, J=6.9Hz, 2H), 1 .95 (s, 3H), 1.77-1.64 (m, 2H), 0.61-0.54 (m, 2H), 0.12-0.02 (m, 27H).

[0141] Compound m2-1, compound m2-2, compound m2-3, and compound m2-4 shown below were used as compound m2. The compound represented by compound m2-1 is a compound represented by formula 2 above, where X ２ is a methacryloyloxy group, and A ２ is an ethylene group, and B ２ is a urethane bond, and R ２ The compound represented by compound m2-2 is a compound in which, in the above formula 2, X ２ is a methacryloyloxy group, and A ２ is an ethylene group, and B ２ -NHC(=O)OC ２ H ４ NHC(=O)-, and R ２The compound represented by compound m2-3 is a compound in which, in the above formula 2, X ２ is a methacryloyloxy group, and A ２ is an ethylene group, and B ２ -NHC(=O)NHCH ２ C(=O)NH-, and R ２ Compound m2-4 is a compound in which, in the above formula 2, X ２ is a methacryloyloxy group, and A ２ is a methylene group, and B ２ -CH(-OH)CH ２ OC(=O)NH-, and R ２ is an n-stearyl group.

[0142] (Synthesis of Compound m2-1) 25.31 g of 2-hydroxyethyl methacrylate, 20 mL of ethyl acetate, and 0.03 mL of dibutyltin dilaurate were placed in a 200 mL three-neck flask, cooled to 0°C, and 22.0 g of hexyl isocyanate was added dropwise over 10 minutes, followed by stirring at room temperature for 1 hour. After completion of the reaction, the mixture was purified by silica gel column chromatography (hexane / ethyl acetate), yielding 44.51 g of Compound m2-1 as a white solid. １ H NMR (400 MHz, CDCl ３ )δ 6.15-6.12 (m, 1H), 5.60-5.57 (m, 1H), 5.01 (s, br, 1H), 4.32 (s, 4H), 3.17 (dt, J=6.7, 6.7Hz, 2H), 1.95 (s, 3H), 1.56-1.42 (m, 2H), 1.40-1.24 (m, 6H), 0.88 (t, J = 6.8Hz, 3H).

[0143] ​(Synthesis of Compound m2-2) 12.01 g of palmitoylethanolamide, 20 mL of tetrahydrofuran, and 0.03 mL of dibutyltin dilaurate were placed in a 200 mL three-neck flask and cooled to 0° C., and 8.08 g of 2-isocyanatoethyl methacrylate was added dropwise over 10 minutes, followed by stirring for 1 hour at 40° C. After completion of the reaction, the solvent was removed using an evaporator, and the mixture was purified by silica gel column chromatography (hexane / ethyl acetate=1:2), yielding 14.37 g of compound m2-2 as a white solid. １ H NMR (400 MHz, CDCl ３ )δ 6.63-6.33 (s, 1H), 6.12 (s, 1H), 5.59 (s, 1H), 5.30-5.20 (s, 1H), 4.24 (t, 2H), 4.1 5 (t, 2H), 3.48 (q, 4H), 2.52 (t, 2H), 1.93 (s, 3H), 1.63-1.25 (m, 26H), 0.88 (t, 3H).

[0144] (Synthesis of Compound m2-3) A 200 mL three-neck flask was charged with 10.05 g of 2-amino-N-butylacetamide, 25 mL of dimethylformamide, and 0.04 mL of dibutyltin dilaurate, and the flask was cooled to 0° C. 13.1 g of 2-isocyanatoethyl methacrylate was added dropwise over 10 minutes, followed by stirring at room temperature for 1 hour. After completion of the reaction, the reaction solution was poured into 500 mL of ethyl acetate, and the precipitated solid was filtered and dried to obtain 19.62 g of Compound m2-3 as a white solid. １ H NMR (400MHz, DMSO-D ６ )δ 7.73 (s, 1H), 6.32 (s, 1H), 6.20 (s, 1H), 6.07 (s, 1H), 5.69 (s, 1H), 4.06 (t, 2H), 3. 59 (d, 2H), 3.29 (q, 2H), 2.58 (t, 2H), 1.89 (s, 3H), 1.65-1.31 (m, 4H), 0.88 (t, 3H).

[0145] (Synthesis of Compound m2-4) 10.03 g of (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate and 30 mL of dichloromethane were placed in a 200 mL three-neck flask, and 15.92 g of stearylamine was added and stirred for 3 hours at 40° C. After completion of the reaction, the solvent was removed using an evaporator, and the mixture was purified by silica gel column chromatography (hexane / ethyl acetate=1:1), yielding 11.54 g of Compound m2-4 as a white solid. １ H NMR (400 MHz, CDCl ３ ) δ 6.15 (s, 1H), 5.61 (s, 1H), 5.03 (s, 1H), 4.34-4.08 (m, 5H), 3.18 (br, 3H), 1.96 (s, 3H), 1.50 (d, 2H), 1.27 (m, 32H), 0.88 (t, 3H).

[0146] As compound m3, methacrylic acid (compound m3-1) and the following compound m3-2 were used.

[0147] (Synthesis of Compound m3-2) 11.63 g of 2-hydroxyethyl methacrylate (HEMA), 100 mL of dichloromethane, and 9.80 g of triethylamine were added to a 300 mL two-necked recovery flask and heated under N ２ The mixture was stirred under atmospheric pressure. The solution was cooled to 0°C, and 12.01 g of heptanoyl chloride was added dropwise over 30 minutes. After the addition was complete, the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the 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. The resulting mixture was purified by silica gel chromatography (hexane / ethyl acetate = 10:1), yielding 17.87 g of compound m3-2 as a colorless, transparent liquid. １ H NMR (400 MHz, CDCl ３ )δ 6.13 (s, 1H), 5.60-5.58 (m, 1H), 4.37-4.32 (m, 4H), 2.33 (t, J=7.5Hz, 2H), 1 .95 (t, J=1.2Hz, 3H), 1.66-1.59 (m, 2H), 1.29 (s, 6H), 0.88 (t, J=6.9Hz, 3H).

[0148] ​Liquid medium: methyl ethyl ketone (MEK) or 1-methoxy-2-propanol (PGME) Polymerization initiator: 2,2'-azobis(2-methylbutyronitrile).

[0149] 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. An oil repellent consisting of a coating composition was obtained using copolymer A1 according to the procedure described above, and the contact angle with hexadecane was measured. The amounts of each raw material charged in the production of copolymer A1 are shown in Table 1 (the same applies to Examples 2 to 9 below). The content of each unit, the molar ratio of unit m2 to unit m1, Mw, and the contact angle with hexadecane are shown in Table 2 (the same applies to Examples 2 to 9 below).

[0150] (Examples 2 to 9) 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.

[0151]

[0152]

[0153] In the copolymers A1 to A6 of Examples 1 to 6, which contain units m1 and m2, the contact angle with hexadecane, an index of oil repellency, was 55° or more, demonstrating excellent oil repellency. On the other hand, in Examples 7, 8, and 9, the contact angle with hexadecane was 30° or less, demonstrating poor oil repellency. This is thought to be due to the fact 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. When unit m2-1 was used as unit m2, the hexadecane contact angle was 62° or more, demonstrating even better oil repellency.

Claims

1. 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 In the 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. ２ -A ２ -B ２ -R ２ Formula 2 In the formula 2, X ２ is a monovalent polymerizable reactive group, and A ２ is a divalent hydrocarbon group, B ２ is a divalent organic group having at least one heteroatom and including any one of the following structures, and R ２ is a monovalent hydrocarbon group. However, a carbon atom or a hydrogen atom is bonded to the end of the dotted line.

2. B above １ The oil repellent according to claim 1, wherein the silicon number of 3. B above １ The oil repellent according to claim 1, wherein is a monovalent organic group represented by the following formula 3 or a monovalent organic group represented by the following formula 4: Ａ１ -Si(OSi(R ３ ) ３ ) ３－ｂ R ４ ｂ ...Formula 3 In Formula 3, R ３ and R ４ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, and b is an integer of 0 to 3; Ａ１ * is A １ It is a combination with. Ａ１ -Si(R ５ ) ２ (OSi(R ６ ) ２ ) ｎ OSi(R ７ ) ３ ...Formula 4 In Formula 4, R ５ , R ６ and R ７ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 3; Ａ１ * is A １ It is a combination of.

4. B above １ The oil repellent according to claim 1 , wherein: is a monovalent organic group represented by the following formula 31:

5. B in the above formula 2 ２ The oil repellent according to claim 1, wherein is a group having the following structure: However, a carbon atom or a hydrogen atom is bonded to the end of the dotted line.

6. The above X １ and the X ２ are each independently a (meth)acryloyloxy group or a hydrolyzable silyl group, ２ is a urethane bond, a urea bond, or an amide bond, and ２ The oil repellent according to claim 1, wherein is a saturated hydrocarbon group having 1 to 12 carbon atoms.

7. The above R ２ The oil repellent according to claim 6, wherein is a linear or branched alkyl group having 2 to 12 carbon atoms.

8. An oil repellent according to claim 1, wherein the total content of units based on the compound represented by formula 1 and units based on the compound represented by formula 2 relative to all units constituting the copolymer is 70 mass% or more.

9. The oil repellent according to claim 1, wherein the mass ratio of units based on the compound represented by formula 2 to units based on the compound represented by formula 1 is 0.1 to 4.

10. The oil repellent according to claim 1, which is for use on textiles.

11. An article treated with the oil repellent according to any one of claims 1 to 10.

12. A method for producing an article, which comprises treating the article with the oil repellent according to any one of claims 1 to 10.

13. An article comprising fibers treated with an oil repellent according to any one of claims 1 to 10.

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