compound

Abstract

To provide a new compound that has liquid-repellent properties. [Solution] A compound obtained by modifying at least one base compound selected from the group consisting of polycarboxylic acids, polyols, polyamines, aromatic compounds, nitrogen-containing cyclic compounds, isocyanate derivatives, and derivatives thereof with an aliphatic hydrocarbon group having 4 to 40 carbon atoms, which has at least one alkylsilyl group and may also have substituents.

Description

[Technical Field]

[0001] This disclosure relates to compounds. [Background technology]

[0002] In recent years, development has been progressing on fluorine-free repellents that can impart liquid repellency (water repellency and / or oil repellency) to various substrates.

[0003] Non-patent document 1 discloses the synthesis of amine compounds from imine compounds using an asymmetric hydrogenation catalyst. The disclosed amine compounds include those in which a hydrocarbon group having a trimethylsilyl group is directly bonded to a carbon atom of pyrrolidine, but no compounds that can be used as water-repellent or oil-repellent agents are disclosed. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] JACS, 1994, 116, 8952. / Christopher A. Willoughby and Stephen L. Buchwald [Overview of the project] [Problems that the invention aims to solve]

[0005] This disclosure aims to provide novel compounds that exhibit liquid-repellent properties. [Means for solving the problem]

[0006] This disclosure includes the following aspects: [Section 1] A compound obtained by modifying at least one parent compound selected from the group consisting of polycarboxylic acids, polyols, polyamines, aromatic compounds, nitrogen-containing cyclic compounds, isocyanate derivatives, and derivatives thereof with an aliphatic hydrocarbon group having 4 to 40 carbon atoms, which has at least one alkylsilyl group and may also have substituents. [Section 2] The alkylsilyl group is defined by the following formula: -Si(R 1 )3 [In the formula, R 1 Each is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may have a hydrogen atom or a substituent, and at least one R 1 This is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may have substituents. The compound described in item 1, which is a group represented by the group. [Section 3] The aforementioned R 1 The compound according to item 3, wherein is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, which may have substituents. [Section 4] The following formula: -XR n [In the formula, X is a directly bonded or 1+n valence group, R is an aliphatic hydrocarbon group having 4 to 40 carbon atoms, independently having at least one alkylsilyl group in each instance and possibly having substituents. n is between 1 and 3 (inclusive). The compound described in item 3, having a Z group represented by . [Section 5] X is composed of one or more elements selected from the group consisting of direct bonds, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each instance). 1 and, X is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents. 2 and, The compound according to item 4, which is a 1+n-valent group composed of one or more selected from the group consisting of [Item 6] X is -X 1 -, -X 2 -X 1 -, -X 1 -X 2 -X 1 - or -X 2 -X 1 -X 2 -X 1 - [wherein X 1 is, independently at each occurrence, a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-, -C(=O)-O-, -C(=O)-NR’-, -SO2-, -SO2NR’-, -C(OR’)R’-, or -C(OR’)(-)2 (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.) is a group represented by X 2 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.) is a group represented by [Item 7] The base material compound is a polycarboxylic acid, The polycarboxylic acid is at least one selected from the group consisting of dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and carboxyl group-containing compound polymers. The compound according to any one of claims 4 to 6, wherein one or more hydroxyl groups of the polycarboxylic acid are substituted with the Z group. [Section 8] The aforementioned polycarboxylic acid Citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aldaric acid; Tricarbaryl acid, t-aconitic acid, trimellitic acid; The compound according to item 7, which is at least one selected from the group consisting of pyromellitic acid and derivatives thereof. [Section 9] The following formula, including the aforementioned Z group: CH2=C(-Q)-C(=O)-Z [In the formula, Q is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom. A compound according to any one of claims 4 to 6, which is a polymer containing repeating units derived from a compound represented by . [Section 10] The aforementioned base material compound is a polyol. The polyol is at least one selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, sugar alcohols, hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, and hydroxy group-containing compound polymers. The compound according to any one of claims 4 to 6, wherein one or more hydroxyl groups of the polyol are substituted with the Z group. [Section 11] The polyol is glucose, fructose, galactose, or xylose; Sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; Sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; Starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomaltodextrin, gellan gum, tamarind seed gum; Kojic acid, quinic acid, chlorogenic acid, gluconic acid, aldonic acid, uronic acid; Glucosamine; Ascorbic acid, inositol; Catechins, quercetin, anthocyanins; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; The compound according to claim 10, which is at least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer and derivatives thereof. [Section 12] The aforementioned matrix compound is a polyamine, The polyamine is composed of a 1-3 valent amino group and a chain-like saturated aliphatic hydrocarbon group or aromatic hydrocarbon group which may be cleaved by oxygen and / or sulfur atoms, and the molar ratio of carbon atoms to nitrogen atoms (C / N ratio) is 8 or less. The compound according to any one of claims 4 to 6, wherein one or more hydrogen atoms bonded to the nitrogen atom of the polyamine are substituted by the Z group. [Section 13] The aforementioned base material compound is an aromatic compound or a nitrogen-containing cyclic compound. The following formula: A(-Z) m [In the formula, A is an m-valent group obtained by removing m hydrogen atoms from an aromatic compound having 7 or more carbon atoms, which may have substituents, or a nitrogen-containing cyclic compound having 5 or more carbon atoms. m is an integer between 1 and 6 (inclusive). A compound represented by any one of items 4 to 6. [Section 14] The aforementioned base compound is an isocyanate derivative, The compound according to any one of claims 4 to 6, wherein the isocyanate derivative is a polyurethane obtained by reacting an isocyanate group-containing compound with an isocyanate-reactive compound. [Section 15] The compound according to item 15, wherein the isocyanate group-containing compound is triisocyanate. [Section 16] A compound described in any one of items 1 to 15, wherein the water contact angle of the compound is 95° or greater. [Section 17] A liquid-repellent composition comprising a compound described in any one of items 1 to 16. [Section 18] The liquid-repellent composition described in item 17, which is an aqueous dispersion. [Section 19] A liquid-repellent composition according to item 17 or 18, used as a water-repellent, oil-repellent, or water- and oil-repellent agent. [Section 20] A liquid-repellent composition according to any one of items 17 to 19, used as a surface treatment agent, anti-fogging agent, rust inhibitor, or antifreeze agent. [Effects of the Invention]

[0007] According to this disclosure, it is possible to provide novel compounds that have liquid-repellent properties. [Modes for carrying out the invention]

[0008] <Definition of Terms> As used herein, "n-valent group" means a group having n bonds, that is, a group that forms n bonds. Furthermore, "n-valent organic group" means an n-valent group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A hydrocarbon group derivative means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the terminal or molecular chain of a hydrocarbon group.

[0009] As used herein, "hydrocarbon group" means a group containing carbon and hydrogen, obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but include C 1-40 Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

[0010] In this specification, unless otherwise stated, whether or not the phrases "independently in each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition shall apply independently to each occurrence.

[0011] The chemical structures described herein should be understood to exclude any chemical structures that would be considered chemically impossible or extremely unstable by those skilled in the art.

[0012] <Compound> The compounds in this disclosure are The compound may be a compound obtained by modifying at least one base compound selected from the group consisting of polycarboxylic acids, polyols, polyamines, aromatic compounds, nitrogen-containing cyclic compounds, isocyanate derivatives, and derivatives thereof with an aliphatic hydrocarbon group having 4 to 40 carbon atoms, which may have at least one alkylsilyl group and a substituent.

[0013] The above-mentioned derivatives are, for example, compounds in which a carboxyl group, a hydroxyl group, or an amino group, or the active hydrogen contained in these groups, is substituted with another atom or substituent. Examples of such derivatives include halides (e.g., chlorides) and acid anhydrides.

[0014] The compounds of this disclosure can adhere to a substrate and impart water-repellent and oil-repellent properties to the substrate. More specifically, the compounds of this disclosure can impart liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to a substrate. The compounds of this disclosure can effectively impart oil resistance (oil repellency) and / or water resistance (water repellency) to a substrate, and for example, can effectively impart both oil resistance and water resistance.

[0015] [Characteristics of the compound, etc.] The water contact angle of the compound may be 35° or higher, 40° or higher, 45° or higher, 50° or higher, 55° or higher, 65° or higher, 75° or higher, 80° or higher, 85° or higher, 90° or higher, 95° or higher, or 100° or higher. The water contact angle of the compound may be 160° or lower, 140° or lower, 130° or lower, 120° or lower, 110° or lower, or 100° or lower. By having a water contact angle of the compound above the lower limit, good water-repellent and oil-repellent properties (especially water-repellent) can be imparted to the substrate. The water contact angle is the static contact angle of the compound with respect to the spin-coated film, as shown in the examples, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop.

[0016] The HD (n-hexadecane) contact angle of the compound may be 10° or more, 15° or more, 25° or more, 35° or more, 40° or more, 45° or more, 55° or more, or 65° or more, preferably 30° or more. The HD contact angle of the compound may be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the compound above the lower limit, good liquid repellency (especially oil repellency) can be imparted to the substrate. The HD contact angle is the static contact angle of the compound with respect to the spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after dropping.

[0017] [Material compound] The following describes polycarboxylic acids, polyols, polyamines, aromatic compounds, nitrogen-containing cyclic compounds, and isocyanate derivatives that can be used as the base compounds of the compounds of this disclosure.

[0018] 〇 Polycarboxylic acid A polycarboxylic acid is a compound having two or more carboxylic acids in its molecule. Polycarboxylic acids may be low molecular weight (e.g., weight-average molecular weight less than 1000, 500 or less) and / or high molecular weight. The weight-average molecular weight of a polycarboxylic acid may be 30 or more, 50 or more, 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 30000 or more, 30000 or more, 30000 or more, or 500000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 300000 or less, 10000 or less, 5000 or less, 30000 or less, 2000 or less, 1000 or less, or 500 or less.

[0019] The number of carboxyl groups in a polycarboxylic acid may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may also be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0020] The polycarboxylic acid may be at least one selected from the group consisting of dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, carboxyl group-containing compound polymers, and salts thereof.

[0021] Dicarboxylic acids are compounds having two carboxyl groups, and examples include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldaric acid, and salts thereof.

[0022] Tricarboxylic acids are compounds having three carboxyl groups, and examples include citric acid, tricarbaryl acid, t-aconitic acid, trimetic acid, and their salts.

[0023] Tetracarboxylic acids are compounds having four carboxyl groups, such as pyromellitic acid and its salts.

[0024] Carboxyl group-containing compound polymers are compounds having five or more carboxyl groups, and examples include alginic acid, tragacanth gum, gum arabic, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyglutamic acid, hyaluronic acid, heparin, xanthan gum, gellan gum, carboxymethylcellulose alginate, galacturonic acid, mannuronic acid, and salts thereof.

[0025] Preferred polycarboxylic acids include polyacrylic acid, polymethacrylic acid, and citric acid.

[0026] 〇 Polyol A polyol is a compound having two or more hydroxyl groups in its molecule. Polyols may be low molecular weight (e.g., weight-average molecular weight less than 1000, 500 or less) and / or high molecular weight. The weight-average molecular weight of a polyol may be 30 or more, 50 or more, 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 30000 or more, 30000 or more, or 500000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 30000 or less, 2000 or less, 1000 or less, or 500 or less.

[0027] The number of hydroxyl groups in a polyol may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may also be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0028] Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxy group-containing polymer compounds, polyether polyols, polymer polyols, polyester polyols, and other polyols.

[0029] Examples of monosaccharides include glucose, fructose, galactose, and xylose.

[0030] Examples of oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, and sucralose.

[0031] Examples of sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, and lactitol.

[0032] Examples of polysaccharides include starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomaltodextrin, gellan gum, tamarind seed gum, and sterols.

[0033] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, and gluconic acid.

[0034] Examples of amino acids include glucosamine.

[0035] Examples of vitamins include ascorbic acid and inositol.

[0036] Examples of flavonols include catechins, quercetin, and anthocyanins.

[0037] Examples of hydroxy hydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, monoglycerin, trimethylolpropane, and trimethylolethane. Hydroxy hydrocarbons are hydrocarbons having a hydroxyl group and may be aromatic or aliphatic, but are preferably aliphatic. When referring to hydroxy hydrocarbons, it may also mean hydroxy hydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxy hydrocarbons).

[0038] Examples of hydroxyl group-containing compound polymers include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer.

[0039] Examples of polyether polyols include compounds obtained by addition polymerization of alkylene oxide to an initiator. Examples of initiators include compounds having two or more hydroxyl groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol, and sucrose. Examples of alkylene oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by addition polymerization of alkylene oxide to the above initiators are also called polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Examples of polyether polyols include polyoxypropylenetriol obtained by addition polymerization of propylene oxide to glycerin, and polyoxypropylene polyglyceryl ether obtained by addition polymerization of propylene oxide to polyglycerin.

[0040] Examples of polymer polyols include compounds obtained by polymerizing a polyether polyol with an ethylenically unsaturated monomer in a polyether polyol. Examples of such ethylenically unsaturated monomers include acrylonitrile and styrene.

[0041] Examples of polyester polyols include compounds obtained by dehydration condensation of a compound having two or more carboxyl groups and a compound having two or more hydroxyl groups. Examples of compounds having two or more carboxyl groups include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and their acid anhydrides. Examples of compounds having two or more hydroxyl groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0042] The polyols are preferably starch, cellulose, pullulan, sorbitol, sterol, monoglycerin, polyglycerin, and polyvinyl alcohol, with sorbitol, monoglycerin, polyglycerin, and polyvinyl alcohol being particularly preferred.

[0043] 〇 Polyamines A polyamine is a compound having one or more amino groups in its molecule. Polyamines may be low molecular weight (e.g., weight-average molecular weight less than 1000, 500 or less) and / or high molecular weight. The weight-average molecular weight of a polyamine may be 30 or more, 50 or more, 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 30000 or more, 30000 or more, 30000 or more, or 500000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 300000 or less, 10000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 30000 or less, 2000 or less, 1000 or less, or 500 or less.

[0044] A polyamine has one or more amino groups. The amino group is a 1- to 3-valent amino group, and is one or more groups selected from the group consisting of -NH2, -NH-, and -N(-)2. Note that a polyamine is an amine compound that may contain multiple amino groups, and may also contain only one amino group. The number of amino groups in a polyamine is preferably two or more, for example, two or more, three or more, four or more, five or more, or six or more, preferably two or more, and may also be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0045] Polyamines may have hydrocarbon groups (aliphatic hydrocarbon groups or aromatic hydrocarbon groups). Hydrocarbon groups may be cyclic, branched, or linear. Hydrocarbon groups may be saturated or unsaturated (e.g., saturated). Here, hydrocarbon groups may be cleaved by oxygen atoms and / or sulfur atoms, or they may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. Hydrocarbon groups may be hydrocarbon groups cleaved by oxygen atoms and / or sulfur atoms (e.g., linear saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups having 1-2 hydrocarbon aromatic rings), or they may be general hydrocarbon groups (e.g., linear saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups having 1-2 hydrocarbon aromatic rings). When hydrocarbon groups are cleaved by oxygen atoms and / or sulfur atoms, they have an ether, thioether, polyether, or polythioether structure. The number of hydrocarbon groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and may also be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0046] The polyamine may consist of a 1-3 valent amino group and a chain-like saturated aliphatic hydrocarbon group or aromatic hydrocarbon group, which may be cleaved by an oxygen atom and / or a sulfur atom.

[0047] The molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the polyamine may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, and may also be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, preferably 6 or less or 4 or less.

[0048] Examples of polyamines include alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylentriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl) ether, bis[2-(2-aminoethoxy)ethyl] ether, and bis[2-(3-aminoprothoxy)ethyl] Polyalkylene polyamines such as ethers, spermine, and spermidine; oxygen or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine, and polyoxyethylenediamine; monocyclic aromatic polyamines such as o-, m-, or p-phenylenediamine, o-, m-, or p-xylylenediamine, diaminotoluene, and 2,3-, 2,4-, or 2,5-tolylenediamine;Diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, bisaminoditrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α, α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, Polycyclic aromatic polyamines such as diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, and 4,4'-bis(aminophenyl)amine; oxygen or sulfur-containing polycyclic aromatic polyamines such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfide;Examples of hydroxyl group-containing polyamines include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine.

[0049] In one embodiment, examples of polyamines include ethylenediamine, propylenediamine, butylenediamine, trimethylhexamethylenediamine, 1,2-diaminopropane, diethylenetriamine, triethylenetetramine, propylenediamine, hexamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, 2,4-(or m-, o-)tolylenediamine, m-aminobenzylamine, benzidine, bis(3,4-diaminophenyl)sulfone, diaminonaphthalene, 2,4-diamino-1,3,5-triazine, piperazine, N-aminoethylpiperazinecycline, spellin, polyethyleneimine, polypropyleneamine, polyvinylamine, polyallylamine, polyetheramine, poly-L-lysine, poly-L-ornithine, Polyment® (aminoethylated acrylic polymer), and derivatives thereof.

[0050] The polyamines are preferably ethylenediamine, hexamethylenediamine, p-phenylenediamine, polyethyleneimine, and Polyment® (aminoethylated acrylic polymer), with ethylenediamine, hexamethylenediamine, and p-phenylenediamine being particularly preferred.

[0051] 〇Aromatic compounds Examples of aromatic compounds include benzene, biphenyl, naphthalene, anthracene, phenanthrene, tetracene, pentacene, pyrene, and coronene. The number of ring-constituting atoms in the aromatic compounds is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12.

[0052] 〇 Nitrogen-containing cyclic compounds Examples of nitrogen-containing cyclic compounds include pyrrole, pyridine, pyrazine, pyrimidine, pyridazine, diazine, oxazine, thiaidine, triazine, tetrazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzodriazole, benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, oxadiazole, imidazopyridine, pyrrolopyridine, thiadiazolopyridine, azepine, diazepine, thiazepine, dibenzazepine, tripenzazepine, etc. The total number of carbon and nitrogen atoms in the ring structure of the nitrogen-containing cyclic compound is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12.

[0053] 〇Isocyanate derivatives Isocyanate derivatives are compounds that are reaction products of an isocyanate group-containing compound and an isocyanate-reactive compound. Isocyanate derivatives have a moiety derived from the isocyanate-reactive compound and a moiety derived from the isocyanate group-containing compound. Unlike isocyanate-based curing agents, isocyanate derivatives typically do not contain an isocyanate group.

[0054] -Isocyanate group-containing compound Isocyanate group-containing compounds have an isocyanate group. Examples of isocyanate group-containing compounds include higher functional isocyanates, such as isocyanates, diisocyanates, triisocyanates, and polymeric isocyanates. They may be aliphatic (including alicyclic) and cyclic (including aromatic).

[0055] Examples of isocyanate group-containing compounds include the following:

[0056] Examples of diisocyanates include 4,4'-methylenediphenyl diisocyanate (MDI), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, o-, m-, and p-xylylene diisocyanate, 4,4'-diisocyanatodiphenyl ether, 3,3'-dichloro-4,4'-diisocyanatodiphenylmethane, 4,4'-diphenyl diisocyanate, 4,4'-diisocyanatodibenzyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl, 2,2'-dichloro-5,5'-dimethoxy-4,4'-diisocyanatodiphenyl, 1,3-diisocyanatobenzene, and 1,2-naphthylenediphenyl. Examples include alicyclic diisocyanates such as socianates, 4-chloro-1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, and 1,8-dinitro-2,7-naphthylene diisocyanate, and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate; aliphatic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, and 1,2-ethylene diisocyanate; and cyclic diisocyanates such as isophorone diisocyanate (IPDI) and dicyclohexylmethane-4,4'-diisocyanate.

[0057] Examples of triisocyanates include aliphatic triisocyanates such as 1,3,6-hexamethylene triisocyanate, and aromatic triisocyanates such as tri-(4-isocyanatophenyl)-methane.

[0058] An example of a polymer isocyanate is polymethylene polyphenyl isocyanate (PAPI).

[0059] - Isocyanate-reactive compounds Isocyanate-reactive compounds are compounds containing isocyanate-reactive groups, and examples include monofunctional, difunctional, and polyfunctional alcohols, thiols, and amines. Examples of isocyanate-reactive compounds include linear or branched long-chain alkanols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, 2-ethylhexanol, glycidol, (iso)stearyl alcohol, and behenyl alcohol; and alkyl alcohols having C6-C40 alkyl chains; and poly(oxyalkylene) group-containing alcohols such as methyl or ethyl ether of polyethylene glycol, ethylene oxide and / or propylene oxide, and hydroxy-terminated methyl or ethyl ether of polysiloxane (e.g., polydimethylsiloxane) group-containing alcohols. Further examples include diols, triols, and polyols such as 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, 4,4'-isopropylidenediphenol (bisphenol A), glycerol, pentaerythritol, and dipentaerythritol, as well as polycaprolactone diols, fatty acid dimerols, and poly(oxy)alkylenediols having oxyalkylene groups with 2 to 4 carbon atoms, such as -OCH2CH2-, -O(CH2)4-, -OCH2CH2CH2-, -OCH(CH3)CH2-, and -OCH(CH3)CH(CH3)- (the oxyalkylene units in the above poly(oxyalkylene) may be the same as in the case of polypropylene glycol or present as a mixture), as well as ester diols such as glycerol monostearate and polysiloxane-containing diols (e.g., polydimethylsiloxane-containing diols).Examples of isocyanate-reactive compounds include amino-containing compounds such as octadecylamine, di(octadecyl)amine, and 1,6-hexamethylenediamine; amino-terminated polyethylene oxide or propylene oxide or copolymers thereof; amino-terminated methyl or ethyl ethers of polyethylene oxide or polypropylene oxide or copolymers thereof; and amino-terminated polysiloxanes, such as polydimethylsiloxane.

[0060] In isocyanate derivatives, it is preferable that the isocyanate-reactive compound has the above-mentioned Z group in addition to the isocyanate-reactive group.

[0061] The isocyanate derivative may be a polymer obtained by the continuous reaction of an isocyanate and an isocyanate-reactive compound.

[0062] [Aliphatic hydrocarbon group] The aliphatic hydrocarbon group, which may have at least one alkylsilyl group and substituents, is preferably a saturated aliphatic hydrocarbon group. The hydrocarbon group may be cyclic, linear, or branched, and is preferably linear. It may also have unsaturated bonds. If it has unsaturated bonds, it is preferably two, most preferably one.

[0063] The number of carbon atoms in the aliphatic hydrocarbon group may be 4 or more, 6 or more, 8 or more, 9 or more, 11 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 6 or more, 8 or more, 9 or more, or 11 or more. The number of carbon atoms in the aliphatic hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 18 or less, 15 or less, 13 or less, 11 or less, or 9 or less, preferably 30 or less, 20 or less, or 11 or less.

[0064] Aliphatic hydrocarbon groups may have substituents, but are preferably unsubstituted. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms in each occurrence). Substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In substituted aliphatic hydrocarbon groups, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In substituted aliphatic hydrocarbon groups, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0065] The alkyl group bonded to the Si of the alkylsilyl group may be an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and may be branched or linear, more preferably linear.

[0066] The number of carbon atoms in the alkyl group bonded to the Si of the alkylsilyl group may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, preferably 1, and may also be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less, preferably 9 or less, 8 or less, or 7 or less.

[0067] The aliphatic hydrocarbon group having at least one alkylsilyl group and which may have substituents, as referred to here, may correspond to R as described below.

[0068] An alkylsilyl group refers to a group in which one or more alkyl groups are bonded to a trivalent silyl group. The alkylsilyl group may be at least one alkylsilyl group selected from monoalkylylsilyl groups, dialkylsilyl groups, and trialkylsilyl groups. Dialkylsilyl groups and trialkylsilyl groups are preferred, and trialkylsilyl groups are most preferred.

[0069] The silyl group of the alkylsilyl group may have a hydrogen atom, a hydroxyl group, an aromatic ring (for example, a benzene ring), etc., bonded to it.

[0070] The compound may have 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 7 or more, 10 or more, 15 or more, 20 or more, 25 or more, 50 or more, 75 or more, 100 or more, 300 or more, or 500 or more alkylsilyl groups per molecule, preferably 10 or more alkylsilyl groups. The compound may have 1000 or less, 500 or less, 300 or less, 100 or less, 75 or less, 50 or less, 25 or less, 20 or less, 15 or less, 10 or less, 7 or less, 5 or less, 4 or less, 3 or less, or 2 or less alkylsilyl groups per molecule.

[0071] The amount of alkylsilyl groups may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more in the compound, preferably 5% by weight or more. The amount of alkylsilyl groups may be 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, or 25% by weight or less in the compound, preferably 70% by weight or less.

[0072] [Z] As previously shown, the compound of this disclosure has the following formula: -XR n [In the formula, X is a directly bonded or 1+n valence group, R is an aliphatic hydrocarbon group having 4 to 40 carbon atoms, independently having at least one alkylsilyl group in each instance and possibly having substituents. n is between 1 and 3 (inclusive). It has a Z group represented by [the symbol].

[0073] -X X is a direct bond or a 1+n valence group. n may be 1 or greater, 2 or greater, or 3 or greater. n may be 3 or less, 2 or less, or 1 or less, for example, 1, 2, or 3.

[0074] The molecular weight of X may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. The molecular weight of X may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more.

[0075] X is X 1 and X 2 It is preferable that the group consists of one or more 1+n valencies selected from the group comprising the following: X 1 This is a group composed of one or more elements selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each instance). X 2 is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents, and n is an integer between 1 and 3.

[0076] Below, X 1 and X 2 I will explain this.

[0077] ○ X 1 X 1 It is a non-hydrocarbon linker.

[0078] X 1 X is a directly bonded or divalent or more group. 1 The valence of X may be 2-4, 2-3, or 2. 1 It is preferable that the bonding is not solely direct.

[0079] X 1 The molecular weight may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0080] X 1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR’-, -C(OR’)R’-, and -C(OR’)(-)2, (wherein, R’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms).

[0081] X 1 Examples of a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, <00​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ X 2 The number of carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more. 2 The number of carbon atoms may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0085] X 2 X may be a cyclic, branched, or linear hydrocarbon group. 2 This may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, for example, an aliphatic hydrocarbon group (e.g., a saturated aliphatic hydrocarbon group).

[0086] X 2 Specific examples include: -(CH2) p -(p is between 1 and 40, for example, between 1 and 10) A linear hydrocarbon group having 1 to 40 carbon atoms, for example, 1 to 10 unsaturated bonds, A hydrocarbon group having 1 to 40 carbon atoms, for example, a branched structure with 1 to 10 carbon atoms. -(CH2) q -(Ar) s -(CH2) r Examples include -(q and r are each independently 0 to 40, for example 1 to 10, -Ar- is benzene or naphthalene, and the Ar group may have any substituent, s is an integer from 1 to 3), etc.

[0087] X 2The hydrocarbon group in the formula may have substituents, but is preferably unsubstituted. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms in each occurrence). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a hydrocarbon group having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In a hydrocarbon group having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0088] Example of X Let's explain the example of X. In the following, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms (e.g., 1 to 2 or 1) in each instance.

[0089] A preferred example of X is -X 1 -, -X 2 -X 1 -, -X 1 -X 2 -X 1 -, or -X 2 -X 1 -X 2 -X 1 - are listed.

[0090] X is -X 1 -, -X 2 -X 1 -, -X 1 -X 2 -X 1 -, -X2 -X 1 -X 2 -X 1 - [wherein, X 1 is, independently at each occurrence, a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2 (wherein, R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms (e.g., 1 to 20, 1 to 12, 1 to 8, or 1 to 4).) and X 2 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.) is preferably a group represented by this. Thereby, good liquid repellency can be imparted to the substrate.

[0091] X may have an amide group, a urea group or a urethane group. Examples of such X include -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR' -C(=O)-NR' and the like.

[0092] <C Examples of X include, when X is divalent, -X 1-, -X 1 -C(=O)-, -C(=O)-X 1 -, -X 1 -C(=O)-X 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 -X 1 -C(=O)-, -X 1 -X 2 -C(=O)-X 1 -, -X 1 -X 2 -X 1 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​2 (-X 1 -X 2 -X 1 -C(=O)-X 1 -)2, -X 2 (-X 1 -X 2 -X 1 -X 2 -) 2nd place is an example.

[0094] An example of X is when X has four valencies, -X 1 -X 2 (-X 1 -)3, -X 2 (-X 1 -)3, -X 2 (-X 1 -C(=O)-)3, -X 2 (-C(=O)-X 1 -)3, -X 2 (-X 1 -C(=O)-X 1 -)3, -X 2 (-X 1 -X 2 -)3, -X 2 (-X 1 -X 2 -X 1 -)3, -X 2 (-X 1 -X 2 -X 1 -C(=O)-)3, -X 2 (-X 1 -X 2 -C(=O)-X 1 -)3, -X 2 (-X 1 -X 2 -X 1 -C(=O)-X 1 -)3, -X 2 (-X 1 -X 2 -X 1 -X 2 -) 3rd place is one example.

[0095] Specific examples of X include, when X is divalent, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, and -OX. 2-S(=O)2-NR'-、-OX 2 -NR'-、-OX 2 -NR'-S(=O)2-、-OX 2 -NR'-C(=O)-、-OX 2 -NR'-C(=O)-O-、-OX 2 -NR'-C(=O)-NR'-、-OX 2 -NR'-X 2 -、-OX 2 -O-、-OX 2 -OC(=O)-、-OX 2 -OC(=O)-NR'-、-OX 2 -C(=O)-O-、-OX 2 -C(=O)-NR'-、-OX 2 -OX 2 -、-OX 2 -、-NR'-、-NR'-C(=O)-、-NR'-C(=O)-O-、-NR'-C(=O)-NR'-、-NR'-X 2 -S(=O)2-NR'-、-NR'-X 2 -NR'-、-NR'-X 2 -NR'-S(=O)2-、-NR'-X 2 -NR'-C(=O)-、-NR'-X 2 -NR'-C(=O)-O-、-NR'-X 2 -NR'-C(=O)-NR'-、-NR'-X 2 -NR'-X 2 -、-NR'-X 2 -O-、-NR'-X 2 -OC(=O)-、-NR'-X 2 -OC(=O)-NR'-、-NR'-X 2 -OX 2 -、-NR'-X 2 -C(=O)-O-、-NR'-X 2 -C(=O)-NR'-、-NR'-X 2 -、-C(=O)-、-C(=O)-O-、-C(=O)-NR'-、-C(=O)-S-、-SO2-、-SO2NR'-、-C(OR')(R')(-) 、 etc. can be mentioned.

[0096] As a specific example of X, if X is a third value, -X 2 (-O-)2-、-X 2 (-OC(=O)-)2-、-X 2 (-OC(=O)-O-)2-、-X 2 (-OC(=O)-NR'-)2-、-X 2 (-OX 2 -S(=O)2-NR'-)2-、-X 2 (-OX 2 -NR'-)2-、-X 2 (-OX 2 -NR'-S(=O)2-)2-、-X 2 (-OX 2 -NR'-C(=O)-)2-、-X 2 (-OX 2 -NR'-C(=O)-O-)2-、-X 2 (-OX 2 -NR'-C(=O)-NR'-)2-,-X 2 (-OX 2 -NR'-X 2 -)2-、-X 2 (-OX 2 -O-)2-、-X 2 (-OX 2 -OC(=O)-)2-、-X 2 (-OX 2 -OC(=O)-NR'-)2-、-X 2 (-OX 2 -C(=O)-O-)2-、-X 2 (-OX 2 -C(=O)-NR'-)2-,-X 2 (-OX 2 -OX 2 -)2-、-X 2 (-OX 2 -)2-、-X 2 (-NR'-)2-、-X 2 (-NR'-C(=O)-)2-、-X 2 (-NR'-C(=O)-O-)2-、-X 2 (-NR'-C(=O)-NR'-)2-、-X 2 (-NR'-X 2 -S(=O)2-NR'-)2-、-X 2 (-NR'-X2 -NR'-)2-, -X 2 (-NR'-X 2 -NR'-S(=O)2-)2-、-X 2 (-NR'-X 2 -NR'-C(=O)-)2-, -X 2 (-NR'-X 2 -NR'-C(=O)-O-)2-, -X 2 (-NR'-X 2 -NR'-C(=O)-NR'-)2-, -X 2 (-NR'-X 2 -NR'-X 2 -)2-, -X 2 (-NR'-X 2 -O-)2-, -X 2 (-NR'-X 2 -OC(=O)-)2-, -X 2 (-NR'-X 2 -OC(=O)-NR'-)2-, -X 2 (-NR'-X 2 -OX 2 -)2-, -X 2 (-NR'-X 2 -C(=O)-O-)2-, -X 2 (-NR'-X 2 -C(=O)-NR'-)2-, -X 2 (-NR'-X 2 -)2-, -X 2 (-C(=O)-)²-, -X 2 (-C(=O)-O-)2-, -X 2 (-C(=O)-NR'-)2-, -X 2 (-C(=O)-S-)2-, -X 2 (-SO2-)2-, -X 2 (-SO2NR'-)2-, -X 2 (-C(OR')(R')(-))2-, -C(OR')(-) 2、 These are some examples.

[0097] A concrete example of X is when X is tetravalent, -X 2 (-O-)3-, -X 2 (-OC(=O)-)3-, -X 2 (-OC(=O)-O-)3-, -X2 (-O-C(=O)-NR‘-)3-、-X 2 (-O-X 2 -S(=O)2-NR‘-)3-、-X 2 (-O-X 2 -NR‘-)3-、-X 2 (-O-X 2 -NR‘-S(=O)2-)3-、-X 2 (-O-X 2 -NR‘-C(=O)-)3-、-X 2 (-O-X 2 -NR‘-C(=O)-O-)3-、-X 2 (-O-X 2 -NR‘-C(=O)-NR‘-)3-、-X 2 (-O-X 2 -NR‘-X 2 -)3-、-X 2 (-O-X 2 -O-)3-、-X 2 (-O-X 2 -O-C(=O)-)3-、-X 2 (-O-X 2 -O-C(=O)-NR‘-)3-、-X 2 (-O-X 2 -C(=O)-O-)3-、-X 2 (-O-X 2 -C(=O)-NR‘-)3-、-X 2 (-O-X 2 -O-X 2 -)3-、-X 2 (-O-X 2 -)3-、-X 2 (-NR‘-)3-、-X 2 (-NR‘-C(=O)-)3-、-X 2 (-NR‘-C(=O)-O-)3-、-X 2 (-NR‘-C(=O)-NR‘-)3-、-X 2 (-NR‘-X 2 -S(=O)2-NR‘-)3-、-X 2 (-NR‘-X 2 -NR‘-)3-、-X 2 (-NR‘-X 2 -NR‘-S(=O)2-)3-、-X 2 (-NR‘-X2 -NR'-C(=O)-)3-, -X 2 (-NR'-X 2 -NR'-C(=O)-O-)3-, -X 2 (-NR'-X 2 -NR'-C(=O)-NR'-)3-, -X 2 (-NR'-X 2 -NR'-X 2 -)3-, -X 2 (-NR'-X 2 -O-)3-, -X 2 (-NR'-X 2 -OC(=O)-)3-, -X 2 (-NR'-X 2 -OC(=O)-NR'-)3-, -X 2 (-NR'-X 2 -OX 2 -)3-, -X 2 (-NR'-X 2 -C(=O)-O-)3-, -X 2 (-NR'-X 2 -C(=O)-NR'-)3-, -X 2 (-NR'-X 2 -)3-, -X 2 (-C(=O)-)3-, -X 2 (-C(=O)-O-)3-, -X 2 (-C(=O)-NR'-)3-, -X 2 (-C(=O)-S-)3-, -X 2 (-SO2-)3-, -X 2 (-SO2NR'-)3-, -X 2 Examples include (-C(OR')(R')(-))3-, etc.

[0098] -R R is an aliphatic hydrocarbon group having 4 to 40 carbon atoms, which independently has at least one alkylsilyl group in each instance and may have substituents.

[0099] 〇Aliphatic hydrocarbon group The aliphatic hydrocarbon group in R may be a monovalent aliphatic hydrocarbon group having 4 to 40 carbon atoms. The aliphatic hydrocarbon group may be branched or linear, and is more preferably linear.

[0100] The number of carbon atoms in the aliphatic hydrocarbon group in R may be 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 6 or more, 10 or more, 12 or more, or 16 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0101] In one embodiment, the aliphatic hydrocarbon group of R has 6 to 40 carbon atoms. At least one alkylsilyl group is bonded to the aliphatic hydrocarbon group in R. The aliphatic hydrocarbon group in R may have one or more, two or more, three or more, four or more, five or more, six or more, eight or more, ten or more, twelve or more, fourteen or more, sixteen or twenty or more alkylsilyl groups bonded to it, or it may have 30 or fewer, 28 or fewer, 26 or fewer, 24 or fewer, 22 or fewer, 20 or fewer, 18 or fewer, 16 or fewer, 14 or fewer, 10 or fewer, 8 or fewer, 6 or fewer, 5 or fewer, 4 or fewer, 3 or fewer, 2 or fewer, or 1 or fewer alkylsilyl groups bonded to it.

[0102] Aliphatic hydrocarbon groups may have substituents, but are preferably unsubstituted. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms in each occurrence). Substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In substituted aliphatic hydrocarbon groups, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In substituted aliphatic hydrocarbon groups, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0103] ○ Alkylsilyl group The aliphatic hydrocarbon group in R has at least one alkylsilyl group. The alkylsilyl group is defined by the following formula: -Si(R 1 )3 [In the formula, R 1 Each of these is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may contain a hydrogen atom or a substituent. It is a base represented by .

[0104] The aliphatic hydrocarbon group in R has at least one alkylsilyl group. The number of alkylsilyl groups in the aliphatic hydrocarbon group in R can be one or more, two or more, or three. The above may be 4 or more, 5 or more, or 6 or more, and may also be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1.

[0105] ·R 1 R 1Each is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may have a hydrogen atom or a substituent, and at least one R 1 This is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may have substituents.

[0106] R bonded to the above-Si 1 All of these may be aliphatic hydrocarbon groups having 1 to 10 carbon atoms, and may have substituents. In this embodiment, the alkylsilyl group corresponds to a trialkylsilyl group.

[0107] R bonded to the above-Si 1 Two of these are aliphatic hydrocarbon groups having 1 to 10 carbon atoms, which may have substituents, and the remaining R 1 This may be a hydrogen atom. In this embodiment, the alkylsilyl group corresponds to a dialkylsilyl group.

[0108] R bonded to the above-Si 1 One of them is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may have substituents, and the remaining R 1 This may be a hydrogen atom. In this embodiment, the alkylsilyl group corresponds to a trialkylsilyl group.

[0109] R 1 The aliphatic hydrocarbon group in this product may be a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. This aliphatic hydrocarbon group may be branched or linear, and is more preferably linear.

[0110] R 1 The number of carbon atoms in the aliphatic hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, preferably 1. The number of carbon atoms in the hydrocarbon group may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less, preferably 9 or less, 8 or less, or 7 or less.

[0111] R 1The aliphatic hydrocarbon group in the formula may have substituents, but is preferably unsubstituted. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms in each occurrence). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a substituted aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In a substituted aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0112] ○ Bonding position of alkylsilyl group -XR n In the Z group represented by , R is an aliphatic hydrocarbon group having 4 to 40 carbon atoms, which independently has at least one alkylsilyl group in each occurrence and may have substituents. The alkylsilyl group may be bonded to the carbon atoms constituting the aliphatic hydrocarbon group.

[0113] Specifically, if we consider the carbon atom directly bonded to X in the aliphatic hydrocarbon group of R as position 1, the alkylsilyl group may be bonded to any carbon atom from position 1 to the terminal of the aliphatic hydrocarbon group of R.

[0114] -XR n In this example, the aliphatic hydrocarbon group represented by R, having 4 to 40 carbon atoms, is bonded to the group represented by X. Preferably, the alkylsilyl group in the aliphatic hydrocarbon group is bonded to a carbon atom close to the group represented by X. When the alkylsilyl group is bonded to a carbon atom close to the group represented by X, the water-repellent and oil-repellent properties imparted by the compound to the substrate may be improved.

[0115] If we consider the carbon atom directly bonded to X as position 1 of the aliphatic hydrocarbon group of R, the alkylsilyl group may be bonded to at least one carbon atom between positions 1 and N / 2: [N is the number of carbon atoms in the main chain or the longest carbon chain of the aliphatic hydrocarbon group of R.]

[0116] If the aliphatic hydrocarbon group of R is considered to have a carbon atom directly bonded to X as position 1, the alkylsilyl group may be bonded to at least one carbon atom between positions 1 and N / 2, 1 and N / 3, 1 and N / 4, or 1 and N / 5.

[0117] The alkylsilyl group in the aliphatic hydrocarbon group may be bonded to carbon atoms at position 1 or higher, position 2 or higher, position 4 or higher, position 6 or higher, position 8 or higher, position 10 or higher, or position 11 or higher. The alkylsilyl group in the aliphatic hydrocarbon group may be at position 40 or lower, position 35 or lower, position 30 or lower, position 25 or lower, position 20 or lower, position 15 or lower, or position 10 or lower, preferably at position 30 or lower, position 25 or lower, or position 20 or lower. For example, the alkylsilyl group in the aliphatic hydrocarbon group may be bonded to carbon atoms at position 2, position 4, position 6, position 8, position 10, or position 11.

[0118] R n In this expression, n is the number of R elements that combine with X, and may be 1 or greater, 2 or greater, or 3 or greater. n may be 3 or less, 2 or less, or 1 or less, for example, 1, 2, or 3.

[0119] [Specific examples of compounds] Specific examples of the compounds disclosed herein are listed below.

[0120] 〇 Polycarboxylic acid The base compound may be a polycarboxylic acid. If the base compound is a polycarboxylic acid, the polycarboxylic acid is at least one selected from the group consisting of dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and carboxyl group-containing compound polymers. It is preferable that one or more hydroxyl groups of the polycarboxylic acid are substituted with Z groups.

[0121] If the base compound is a polycarboxylic acid, the polycarboxylic acid is Citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aldaric acid; Tricarbaryl acid, t-aconitic acid, trimellitic acid; It is preferable that the substance is at least one selected from the group consisting of pyromellitic acid and its derivatives.

[0122] The Z group is as described above.

[0123] 〇 Polyol The base compound may be a polyol. If the base compound is a polyol, the polyol is at least one selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, sugar alcohols, hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, and hydroxyl group-containing compound polymers. It is preferable that one or more hydroxyl groups of the polyol are substituted with Z groups.

[0124] The Z group is as described above.

[0125] When the base compound is a polyol, the polyol is Glucose, fructose, galactose, xylose; Sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; Sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; Starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomaltodextrin, gellan gum, tamarind seed gum; Kojic acid, quinic acid, chlorogenic acid, gluconic acid, aldonic acid, uronic acid; Glucosamine; Ascorbic acid, inositol; Catechins, quercetin, anthocyanins; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; It is preferable that the material is at least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer and derivatives thereof.

[0126] 〇 Polyamines The base compound may be a polyamine. When the base compound is a polyamine, the polyamine is composed of a 1-3 valent amino group and a chain-like saturated aliphatic hydrocarbon group or aromatic hydrocarbon group which may be cleaved by oxygen and / or sulfur atoms, and the molar ratio of carbon atoms to nitrogen atoms (C / N ratio) is 8 or less. Preferably, one or more hydrogen atoms bonded to the nitrogen atoms of the polyamine are substituted with Z groups.

[0127] The Z group is as described above.

[0128] 〇Aromatic compounds and nitrogen-containing cyclic compounds The base compound may be an aromatic compound or a nitrogen-containing cyclic compound. When the base compound is an aromatic compound or a nitrogen-containing cyclic compound, the compound of this disclosure is The following formula: A(-Z) m [In the formula, A is an m-valent group obtained by removing m hydrogen atoms from an aromatic compound having 7 or more carbon atoms, which may have substituents, or a nitrogen-containing cyclic compound having 5 or more carbon atoms. m is an integer between 1 and 6 (inclusive). It may be a compound represented by .

[0129] A is an m-valent group obtained by removing m hydrogen atoms from an aromatic compound having 7 or more carbon atoms, which may have substituents, or a nitrogen-containing cyclic compound having 5 or more carbon atoms. m may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, preferably 2 or more (for example, 3 or more). m may be 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less, preferably 4 or less.

[0130] Aromatic compounds with 7 or more carbon atoms include naphthalene, anthracene, phenanthrene, tetracene, pentacene, pyrene, and coronene.

[0131] Examples of nitrogen-containing cyclic compounds with 5 or more carbon atoms include pyridine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, benzimidazole, benzodriazole, benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaidene, imidazopyridine, pyrrolopyridine, thiadiazolopyridine, azepine, diazepine, thiazepine, dibenzazepine, tripenzazepine, and others.

[0132] The above aromatic compounds or nitrogen-containing cyclic compounds may have substituents. Examples of substituents on aromatic compounds or nitrogen-containing cyclic compounds are not particularly limited, but may include, for example, -OR', -N(R')2, -COOR' (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), halogen atoms, one or more halogen atoms, C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C3-10 Cycloalkyl groups, C 3-10 Unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl group, C 6-10 Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0133] The aromatic compound or nitrogen-containing heterocycle described above may be a 4-membered, 5-membered, 6-membered, 7-membered, or 8-membered ring. The aromatic compound or nitrogen-containing heterocycle may also be a condensed polycyclic ring containing 2 to 5 (preferably 2 to 3) 4 to 8-membered rings.

[0134] The number of carbon atoms in aromatic compounds may be 7 or more, 8 or more, or 10 or more. The number of carbon atoms in hydrocarbon aromatic compounds may be 30 or less, 20 or less, 16 or less, 12 or more, or 8 or less.

[0135] The aromatic compound may be a condensed polycyclic compound containing multiple aromatic ring carbons and / or non-aromatic hydrocarbons (e.g., 2 to 5, preferably 2 to 3).

[0136] The nitrogen-containing heterocycle may have 5 or more carbon atoms, 6 or more carbon atoms, 8 or more carbon atoms, or 10 or more carbon atoms. The hydrocarbon aromatic compound may have 30 or fewer carbon atoms, 20 or fewer carbon atoms, 16 or fewer carbon atoms, 12 or more carbon atoms, or 8 or fewer carbon atoms.

[0137] The compounds of this disclosure may be polymers (e.g., condensates or crosslinks) of the above-mentioned aromatic compounds or nitrogen-containing cyclic compounds. Polymerization may proceed via substituents of A in the polymer.

[0138] The condensation or crosslinking reaction to obtain the polymer is not limited, and known methods for carrying out polymerization at the functional groups of A can be used, and known catalysts, dehydrating condensing agents, crosslinking agents, etc. may be used. Examples of catalysts, dehydrating condensing agents, and crosslinking agents that can be used include: acids such as p-toluenesulfonic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, sulfuric acid, and boric acid fluoride; acid halides such as acetate chloride, propionic acid chloride, and benzoic acid chloride; bases such as sodium methoxide, potassium tert-butoxide, sodium hydride, potassium carbonate, cesium carbonate, triethylamine, and diisopropylamine; tetrabutylammonium bromide, sodium acetate, Burgess reagent, N,N'-dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (WSC) or its hydrochloride salt, N,N'-carbonyldiimidazole, and 1H-benzotriazole-1- Examples of condensing agents include yloxytris(dimethylamino)phosphonium hexafluorophosphate (BOP), O-(7-azabenzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HATU), 2-chloro-1,3-dimethylimidazolium chloride, bromotripyrrolidinophosphonium hexafluorophosphate (PyBrop), diethyl phosphocyanidate (diethyl cyanophosphate; DEPC), diphenyl phosphoryl azide (diphenyl phosphate azide; DPPA), 4-(4,6-dimethoxy[1,3,5]triazine-2-yl)-4-methylmorpholinium chloride (DMTMM), and Lawson's reagent.

[0139] The Z group is as described above.

[0140] 〇Isocyanate derivatives The base compound may be an isocyanate derivative. When the base compound is an isocyanate derivative, the compound of this disclosure is preferably a polyurethane obtained by reacting an isocyanate group-containing compound with an isocyanate-reactive compound. The isocyanate group-containing compound is preferably a triisocyanate.

[0141] The isocyanate derivative is the following formula containing the above Z group: L(-Z) m [In the formula, L is (a) one or more isocyanate group-containing compounds selected from the group consisting of isocyanates, diisocyanates and polyisocyanates, (b) One or more isocyanate-reactive compounds selected from the group consisting of compounds represented by the following general formulas (2a), (2b), and (2c): The reaction product is an m-valent urethane / amide skeleton, m is between 1 and 6 (inclusive). It may be a compound represented by .

[0142] [ka] [In general formulas (2a) and (2c): Rr is independently -H, -*, -C(O)-*, and -(CH2CH2O) in each occurrence. p (CH(CH3)CH2O) q H, -(CH2CH2O) p (CH(CH3)CH2O) q -*, or -(CH2CH2O) p (CH(CH3)CH2O) q C(O)-*, p is independently between 0 and 20 in each occurrence. q is independently between 0 and 20 in each occurrence. p+q is greater than 0, The symbol * is a combination of L, However, if the isocyanate-reactive compound is represented by general formula (2a) or (2c), then at least one of Rr is -H or -(CH2CH2O) p (CH(CH3)CH2O) q H is H, and at least one other Rr is -*, -C(O)-*, -(CH2CH2O) p (CH(CH3)CH2O) q -*, or -(CH2CH2O) p(CH(CH3)CH2O) q C(O)-*, In general formula (2b): Rr' is independently -H, -*, -C(O)-*, and -(CH2CH2O) in each occurrence. p’ (CH(CH3)CH2O) q’ H, -(CH2CH2O) p’ (CH(CH3)CH2O) q’ -*, or -(CH2CH2O) p’ (CH(CH3)CH2O) q’ C(O)-*, Rr'' is independently -H, -*, and -(CH2CH2O) in each occurrence. p’ (CH(CH3)CH2O) q’ H, -(CH2CH2O) p’ (CH(CH3)CH2O) q’ -*, or -(CH2CH2O) p’ (CH(CH3)CH2O) q’ C(O)-*, p' is independently between 0 and 20 in each occurrence. q' is independently between 0 and 20 in each occurrence. p'+q' is greater than 0, The symbol * is a combination of L, However, if the isocyanate-reactive compound is represented by general formula (2b), then at least one of Rr' and Rr'' is -H or -(CH2CH2O) p’ (CH(CH3)CH2O) q’ H is H, and at least one other of Rr' and Rr'' is -*, -C(O)-*, -(CH2CH2O) p’ (CH(CH3)CH2O) q’ -*, or -(CH2CH2O) p’ (CH(CH3)CH2O) q’ It is C(O)-*.

[0143] Note that p, q, p', and q' are integers between 0 and 20 for a single isocyanate derivative, but can be expressed as average values ​​when they are a collection of multiple isocyanate derivatives.

[0144] In this case, L in the isocyanate derivative is a urethane skeleton prepared by a process involving the reaction of an isocyanate group-containing compound (a) with an isocyanate-reactive compound (b), such a urethane / amide skeleton is usually polyvalent, but is not limited to this. When the isocyanate-reactive compound (b) is represented by general formula (2a) or (2c), it has at least one -OH group, and when represented by general formula (2b), it has at least one -OH group or -COOH group. Thus, by reacting the isocyanate group-containing compound (a) with the isocyanate-reactive compound (b), a reaction product can be obtained in which they are linked by a urethane bond or an amide bond. Such a reaction is known and can be carried out under any suitable conditions.

[0145] In such isocyanate derivatives, each of the m bonds (indicated by the symbol *) present in the moiety derived from the isocyanate-reactive compound (b) has a Z group -XR n The Z group is bonded (X is bonded to L's bond). n The part indicated by " is bonded to a bond (shown by the symbol *) present in the isocyanate-reactive compound (b) before the reaction. The isocyanate-reactive compound (b) may be one or any mixture of two or more compounds selected from the group consisting of compounds represented by general formulas (2a), (2b), and (2c), with the compound represented by general formula (2a) being preferred.

[0146] The isocyanate group-containing compound (a) may be one or any mixture of two or more selected from the group consisting of isocyanates, diisocyanates, and polyisocyanates. If the isocyanate group-containing compound (a) is a diisocyanate and / or polyisocyanate, and the isocyanate-reactive compound (b) has a total of two or more -OH groups and / or -COOH groups, the reaction product obtained therefrom may, but is not limited to, a polymer.

[0147] The isocyanate, diisocyanate, and polyisocyanate are preferably one or more selected from the group consisting of compounds represented by the following formulas (3a) to (3h).

[0148] [ka]

[0149] [ka]

[0150] Examples of isocyanate derivatives include those described in Japanese Patent Publication No. 2022-33218 (WO2016 / 049278), Japanese Patent No. 6987847 (WO2018 / 031534), and WO2021 / 251302, among others.

[0151] The Z group is as described above.

[0152] 〇Flag The compounds of this disclosure may be polymers. Polymers are compounds obtained by reacting monomers and contain repeating units derived from monomers. Polymers obtained by reacting monomers contain structural units derived from monomers.

[0153] The polymer may be an acrylic polymer. An acrylic polymer is a compound obtained by reacting acrylic monomers and contains repeating units derived from the acrylic monomers. An acrylic polymer obtained by reacting acrylic monomers contains structural units derived from the acrylic monomers and is a polymer having a chemical structure derived from ethylenically unsaturated groups in its main chain.

[0154] The acrylic monomer is not particularly limited as long as it contains an ethylenically unsaturated bond, and examples include monomers having an ethylenically unsaturated group such as a vinyl group, vinylene group, vinylidene group, (meth)acryloyl group, or (meth)acrylamide group. The hydrogen atom bonded to the carbon atom forming the above ethylenically unsaturated bond may be substituted with a monovalent organic group or a halogen atom.

[0155] The compounds disclosed herein are given by the following formula: EXR n [In the formula, E is an organic residue having an ethylenically unsaturated polymerizable group, X is a directly bonded or 1+n valence group, R is an aliphatic hydrocarbon group having 4 to 40 carbon atoms, which independently has at least one alkylsilyl group in each instance and may have substituents. n is between 1 and 3. The polymer may have repeating units derived from the monomer represented by .

[0156] E may be an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a carbon-carbon double bond. Specifically, CH2=C(-R 111 )-C(=O)-, CH2=C(-R 111 )-, CH2=C(-R 111 Examples include organic residues having ethylenically unsaturated polymerizable groups such as )-CH2-, and R 111 Examples of these include hydrogen atoms, methyl groups, or halogen atoms. In addition, E may have various organic groups other than ethylenically unsaturated polymerizable groups. Examples of such organic groups include chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents.

[0157] X is either a directly bonded group or a 1+n valence group, and the explanation of X in the Z group described above is used for further reference.

[0158] For E, the general formula is: CH2=C(-R 112 )-C(=O)-YQ- (In the formula, R 112 A preferred group is represented by (where is a hydrogen atom, a methyl group, or a halogen atom, Y is -O- or -NH-, and Q is a directly bonded or divalent organic group).

[0159] R 112 This is a hydrogen atom, a methyl group, or a halogen atom; therefore, the α-position of the acrylate or methacrylate may be a hydrogen atom or substituted with a halogen atom or the like.

[0160] Q may be a direct bond or a divalent organic group, and if it is a divalent organic group, Aliphatic groups with 1 to 10 carbon atoms, aromatic groups or cyclic aliphatic groups with 6 to 18 carbon atoms, -(CH2) m -N(R 1 )SO2-(CH2) n -Base (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 (A C1-C18 alkyl group) -CH2CH(OZ 1 )CH2- group (Z 1 is a hydrogen atom or R 1 C(=O)-, R 1 (A C1-C18 alkyl group) -CH2CH(OZ 1 )CH2-(Ph-O)- group (Z 1 is a hydrogen atom or R 1 C(=O)-, R 1 (where is an alkyl group having 1 to 18 carbon atoms, and Ph is a phenylene group), -(CH2) n -Ph-O- group (where Ph is a phenylene group and n is an integer from 0 to 10), -(CH2) m -SO2-(CH2) n -Base (m is an integer from 1 to 10, n is an integer from 0 to 10), -(CH2) m -OC(=O)N(R 1 )-(CH2)n -Base (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 (A C1-C18 alkyl group) -(CH2) m -N(R 1 )C(=O)O-(CH2) n -Base (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 (A C1-C18 alkyl group) -(CH2) m -C(=O)N(R 1 )-(CH2) n -Base (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 (A C1-C18 alkyl group) -(CH2) m -(R 1 )NC(=O)-(CH2) n -Base (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 (A C1-C18 alkyl group) -(CH2) m -(R 1 )NC(=O)N(R 1 )-(CH2) n -Base (m is an integer from 1 to 10, n is an integer from 0 to 10, R 1 (where C1 is an alkyl group with 1 to 18 carbon atoms), or -(CH2) m -S-(CH2) n -Base (m is an integer from 1 to 10, n is an integer from 0 to 10) These are some examples.

[0161] R is as described above.

[0162] The compounds disclosed herein include the following formula containing a Z group: CH2=C(-Q)-C(=O)-Z [In the formula, Q is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom. The polymer may contain repeating units derived from the compound represented by .

[0163] Examples of monovalent organic groups include cyano groups, aliphatic hydrocarbon groups having 1 to 6 carbon atoms (e.g., alkyl groups, alkenyl groups, etc.), and aromatic groups having 5 to 12 carbon atoms. Examples of halogen atoms other than fluorine atoms include chlorine, bromine, and iodine. Q may be a hydrogen atom, a halogen atom, a methyl group, a cyano group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, for example, a hydrogen atom, a methyl group, a chlorine atom, an iodine atom, or a cyano group, preferably a hydrogen atom, a methyl group, a chlorine atom, and especially a hydrogen atom or a methyl group.

[0164] The Z group is as described above.

[0165] From the viewpoint of liquid repellency, the polymer may be a polymer containing an amide group, a urea group, or a urethane group in X.

[0166] [Method for producing compounds] The compound may be produced by modifying the compound's pre-compound (i.e., the pre-compound compound of this disclosure) with a Z group. Specifically, the compound may be produced by modifying at least one functional group of the compound's pre-compound with a Z group. The functional group may be an active hydrogen-containing group, such as an amino group, a hydroxyl group, or a carboxyl group. The modification of the functional group with the Z group may involve substituting the functional group with the Z group, or substituting the active hydrogen contained in the functional group.

[0167] In one embodiment, the compound may be produced by substituting an active hydrogen in at least one functional group of the compound's base material with a Z group. For example, the compound may be produced by substituting a hydrogen atom of at least one amino group, hydroxyl group, or carboxyl group of the compound's base material with a Z group.

[0168] The base material of the compound may be one of the base material compounds exemplified above, or one or more functional groups such as a hydroxyl group, an amino group, an isocyanate group, or a carboxyl group bonded to one of the base material compounds exemplified above.

[0169] The method for modifying the Z group in the base compound is not particularly limited. For example, methods such as urethane bond formation reactions, urea bond formation reactions, ester bond formation reactions, amide bond formation reactions, and ether bond formation reactions can be used. In bond formation reactions, acylating agents, condensing agents, catalysts, etc., are used as appropriate.

[0170] A method for modifying the Z group in the base compound may be carried out by reacting the base compound with a hydrocarbon group-containing reactant having an alkylsilyl group. The hydrocarbon group-containing reactant having an alkylsilyl group is a compound having an aliphatic hydrocarbon group having an alkylsilyl group and a group that can react with the functional group of the base compound.

[0171] Examples of hydrocarbon group-containing reactants having alkylsilyl groups are as follows: H2N-R HO-R HO(O=)CR G(O=)CR RC(=O)OC(=O)R O=C=NR S=C=NR (CH2OCH)CH2OR GR [In the formula, R is an aliphatic hydrocarbon group with at least one alkylsilyl group and a power of 6 to 40, as defined above. G is a halogen atom (especially F, Cl, Br, or I).]

[0172] • Urethane bond formation The base compound and the hydrocarbon group having an alkylsilyl group may be bonded via a urethane bond. The urethane bond may be formed, for example, by reacting a hydroxyl group-containing base compound with an isocyanate containing an aliphatic hydrocarbon having an alkylsilyl group. A tin catalyst or an amine can be used as a catalyst during the reaction. For example, by reacting a hydroxyl group-containing base compound with an isocyanate containing an aliphatic hydrocarbon having an alkylsilyl group in an organic solvent for a certain period of time, the hydroxyl group reacts with the isocyanate group, and a base-modified compound is obtained in which the base compound and the hydrocarbon group having an alkylsilyl group are bonded via a urethane bond.

[0173] ·Urea bond formation The base compound and the hydrocarbon group having an alkylsilyl group may be bonded via a urea bond. The urea bond may be formed, for example, by reacting an amino group-containing base compound with an isocyanate group containing an aliphatic hydrocarbon group having an alkylsilyl group (or by reacting an isocyanate group-containing base compound with an amine containing an aliphatic hydrocarbon group having an alkylsilyl group). A catalyst may be used as appropriate during the reaction. For example, by reacting an amino group-containing base compound with an aliphatic hydrocarbon-containing isocyanate in an organic solvent for a certain period of time, the amino group reacts with the isocyanate group, and a base-modified compound is obtained in which the base compound and the hydrocarbon group having an alkylsilyl group are bonded via a urea bond.

[0174] • Ester bond formation The base compound and the hydrocarbon group having an alkylsilyl group may be bonded via an ester bond. The ester bond may be formed, for example, by reacting a hydroxyl group-containing base compound with a carboxylic acid containing an aliphatic hydrocarbon group having an alkylsilyl group (or by reacting a carboxylic acid-containing base compound with an alcohol containing an aliphatic hydrocarbon group having an alkylsilyl group). An acylation catalyst or condensing agent may be used during the reaction. For example, by reacting a hydroxyl group-containing base compound with a carboxylic acid containing an aliphatic hydrocarbon group having an alkylsilyl group in an organic solvent for a certain period of time, the hydroxyl group reacts with the carboxylic acid, and a base compound modified in which the base compound and the hydrocarbon group having an alkylsilyl group are bonded via an ester bond is obtained.

[0175] • Formation of amide bonds The base compound and the hydrocarbon group having an alkylsilyl group may be bonded via an amide bond. The amide bond may be formed, for example, by reacting an amino group-containing base compound with a carboxylic acid containing an aliphatic hydrocarbon group having an alkylsilyl group (or by reacting a carboxylic acid-containing base compound with an amine containing an aliphatic hydrocarbon group having an alkylsilyl group). An acylation catalyst or condensing agent may be used during the reaction. For example, by reacting an amino group-containing base compound with a carboxylic acid containing an aliphatic hydrocarbon group having an alkylsilyl group in an organic solvent for a certain period of time, the amino group reacts with the carboxylic acid, and a base-modified compound is obtained in which the base compound and the hydrocarbon group having an alkylsilyl group are bonded via an amide bond.

[0176] • Ether bond formation The base compound and the hydrocarbon group having an alkylsilyl group may be bonded via an ether bond. The ether bond may be formed, for example, by reacting a halogen-containing base compound with an alcohol containing an aliphatic hydrocarbon group having an alkylsilyl group (or by reacting a hydroxyl-containing base compound with a halide containing an aliphatic hydrocarbon group having an alkylsilyl group). Acid catalysts, base catalysts, etc., may be used during the reaction. For example, by heating and reacting a halogen-containing base compound and an alcohol containing an aliphatic hydrocarbon group having an alkylsilyl group in an organic solvent under catalyst, the alcohol containing the aliphatic hydrocarbon group having an alkylsilyl group acts as a nucleophile, and a base-modified compound is obtained in which the base compound and the hydrocarbon group having an alkylsilyl group are bonded via an ether bond.

[0177] ·Polymer formation The compounds of this disclosure may be obtained by polymerizing a monomer containing a Z group. The monomer containing a Z group may be an acrylic monomer such as acrylic acid or acryloyl chloride modified with a Z group. Such a monomer may be the Z-group modified monomer described above. (Polymerization method) Polymers containing Z groups can be produced by known polymerization methods, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0178] In solution polymerization, monomers are dissolved in an organic solvent in the presence of a polymerization initiator, followed by nitrogen purging and heating and stirring at a temperature of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of monomer.

[0179] Organic solvents are inert to monomers and dissolve them, and may include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, and methyl isobutyl ketone), and alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically ethanol, butanol, and isopropyl alcohol). Specific examples of organic solvents include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, per 100 parts by weight of the total monomers.

[0180] In emulsion polymerization, a method is employed in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and then polymerized by stirring at a temperature of 50-80°C for 1-20 hours after nitrogen purging. Polymerization initiators include water-soluble ones such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01-10 parts by weight per 100 parts by weight of monomer.

[0181] To obtain a polymer aqueous dispersion with excellent stability during storage, it is desirable to polymerize the monomers by micronizing them in water using an emulsifying device that can impart strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer. Various emulsifiers, including anionic, cationic, and nonionic types, can be used as emulsifiers, typically in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely miscible, it is preferable to add a compatibilizer that allows them to be sufficiently miscible, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsifying and copolymerizing properties.

[0182] As the water-soluble organic solvent, the organic solvents mentioned above may be used. For example, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc., may be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. In addition, as low molecular weight monomers, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., may be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0183] In polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially alkyl mercaptans (e.g., with 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomer.

[0184] <Liquid repellent composition> This disclosure provides a liquid-repellent composition comprising the compounds of this disclosure.

[0185] The compositions of this disclosure may contain the compounds of this disclosure alone or in combination of two or more compounds.

[0186] The compositions of this disclosure may be liquid or solid.

[0187] The amount of the compound of the Disclosure contained in the liquid-repellent composition of the Disclosure may be 0.01% by weight or more, 0.03% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less.

[0188] [Liquid media] The liquid-repellent composition in this disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The liquid-repellent composition may be a dispersion or a solution. The liquid-repellent composition in this disclosure is water-dispersible and may contain at least water.

[0189] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain compounds having at least one hydroxyl group (e.g., polyols such as alcohols and glycol-based solvents, ethers of polyols (e.g., monoethers)). These may be used individually or in combination of two or more.

[0190] [Amount of liquid medium] The amount of liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of the compound. The amount of liquid medium may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 1 part by weight of the compound.

[0191] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of the compound. The amount of water may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 1 part by weight of the compound.

[0192] The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of the compound. The amount of organic solvent may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 1 part by weight of the compound.

[0193] [Dispersant] The liquid-repellent compositions of this disclosure may contain a dispersant.

[0194] The dispersant is selected from organic dispersants and inorganic dispersants. There may be at least one of them. The dispersant may be non-anionic and may be at least one selected from nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants. The liquid-repellent composition does not need to contain anionic dispersants.

[0195] The dispersant may be either an organic dispersant or an inorganic dispersant, or a combination of both.

[0196] Organic dispersants may be used as dispersants. Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants, and the term "organic dispersant" may refer to surfactants.

[0197] The dispersant may be a fluorine-free compound.

[0198] [Nonionic dispersant] The dispersant may contain a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0199] The nonionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0200] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0201] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0202] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 10-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0203] Examples of ester ethers are compounds formed by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 3-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0204] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolaminos. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0205] The polyol may be a divalent to pentavalent alcohol with 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (a secondary amine or preferably a tertiary amine) (for example, having 5 to 50 carbon atoms).

[0206] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group of the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0207] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0208] The nonionic dispersant may be an alkylene oxide adduct of linear and / or branched aliphatic (saturated and / or unsaturated) groups, a polyalkylene glycol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sorbitan ester of linear and / or branched fatty acids (saturated and / or unsaturated), a glycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyglycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sucrose ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide addition portion and the polyalkylene glycol portion is polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not need to contain aromatic groups.

[0209] The nonionic dispersant is, formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 This is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms. R 2 Each of these is independently identical or distinct, an alkylene group having 3 or more carbon atoms (e.g., 3 to 10). R 3 These are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms. p is a number greater than or equal to 2. q is a number greater than or equal to 1, or 0. It may be a compound represented by [the formula shown].

[0210] R 1 The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. 1 Preferred specific examples include the lauryl group, tridecyl group, and oleyl group. R 2 Examples include the propylene group and the butylene group. In nonionic dispersants, p may be a number greater than or equal to 3 (e.g., 5 to 200). q may be a number greater than or equal to 2 (e.g., 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but oxypropylene chains are preferred among these.

[0211] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C 12 -C 16 ) Thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 This includes condensation products with amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc.

[0212] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example, 30 to 75% by weight, and especially 40 to 70% by weight, relative to the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of nonionic dispersants is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single agent or a mixture of two or more agents. The nonionic dispersant may be a mixture of a compound with an HLB (hydrophilic-hydrophobic balance) of less than 15 (especially 5 or less) and a compound with an HLB of 15 or more. [Cationic dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be of low molecular weight (e.g., molecular weight 2000 or less, particularly 10000 or less) or of high molecular weight (e.g., molecular weight 2000 or more). The cationic dispersant may be a compound that does not have an amide group.

[0213] The cationic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0214] The cationic dispersant may be an amine salt, a quaternary ammonium salt, or an oxyethylene-added ammonium salt. Specific examples of cationic dispersants are not particularly limited, but include alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt-type dispersants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, and quaternary ammonium salt-type dispersants such as benzethonium chloride.

[0215] Preferred examples of cationic dispersants are: R 21-N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 These are hydrocarbon groups with 1 to 40 carbon atoms. X is an anionic group. It is a compound represented by [formula]. R 21 , R 22 , R 23 and -R 24 Specific examples of X are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). The cationic dispersant is particularly preferably a monoalkyltrimethylammonium salt (alkyl group with 4 to 40 carbon atoms).

[0216] The cationic dispersant is preferably an ammonium salt. The cationic dispersant has the formula: R 1 p -N + R 2 q X - [In the formula, R 1 is C12 or higher (for example, C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 These are H or C1-C4 alkyl groups, benzyl groups, and polyoxyethylene groups (number of oxyethylene groups e.g., 1 (especially 2, particularly 3) to 50). (CH3 and C2H5 are particularly preferred.) X is a halogen atom (e.g., a chlorine atom), a C1-C4 fatty acid base, p is either 1 or 2, q is either 2 or 3, and p + q = 4. It may be an ammonium salt represented by R. 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[0217] Specific examples of cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0218] [Anionic dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant does not have to contain an anionic dispersant.

[0219] The anionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0220] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type dispersants, phosphate mono or diester type dispersants, and sulfosuccinate esters.

[0221] [Amphoteric dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0222] The amphoteric dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0223] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, these include lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

[0224] [Inorganic dispersants] The dispersant may contain an inorganic dispersant.

[0225] The average primary particle size of the inorganic dispersant may be 5 nm or larger, 30 nm or larger, 100 nm or larger, 1 μm or larger, 10 μm or larger, or 25 μm or larger. The average primary particle size of the inorganic dispersant may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may also be hydrophilic particles.

[0226] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0227] [Amount of dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the compound. The amount of dispersant may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less, per 100 parts by weight of the compound.

[0228] <Application> Examples of applications using the compounds and liquid-repellent compositions described herein include external treatment agents (surface treatment agents) or internal treatment agents, water-repellent compositions (water repellents, oil repellents, or water- and oil-repellent agents, particularly water repellents), antifouling agents, dirt removal agents, release agents, mold release agents (external or internal mold release agents), and the like.

[0229] Properties that can be improved by the above-mentioned examples of use include water repellency, oil repellency, anti-fogging, solvent resistance, stain resistance, fingerprint resistance, fingerprint removal, slipperiness, abrasion resistance, scratch resistance, chemical resistance, droplet sliding, snow sliding, ice sliding, mold release, and anti-reflective properties.

[0230] Examples of applications for the above-mentioned uses include ships (hulls, decks, propellers, etc.), houses (e.g., roofs, exterior walls, interior walls, floors, housing equipment, etc.), vehicles (automobiles, bicycles, motorcycles, construction vehicles, agricultural vehicles, railway vehicles, etc.), building materials, piping, equipment, tools, paper products, textile products, etc.

[0231] Specific applications include, but are not limited to, rust inhibitors for metal materials, de-icing agents for aerospace materials, anti-fogging agents for window glass and endoscopes, stain-resistant agents for exterior walls, snow-proofing agents for houses, stain-resistant agents for walls, frost-proofing agents for metal fins of heat exchangers, stain-resistant agents for bathtubs and toilets, stain-resistant treatment agents for resins used in optical applications such as lenses, mold release agents, water-repellent and waterproof treatment agents for printed circuit boards, fingerprint and stain-resistant agents for touch panels, mold release agents to provide release properties to films such as polyester, water-repellent and oil-repellent treatment agents for textiles and paper products, and water droplet-resistant agents for mirrors.

[0232] The substrates to be processed by the above-mentioned examples of applications are not particularly limited and include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, textiles, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0233] Examples of paper substrates that can be used include gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal laminated paper, and kraft paper. Other examples include neutral printing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper.

[0234] Examples of base materials for textile products include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics; fabrics in the form of clothing (e.g., water-repellent clothing, e.g., raincoats) and carpets; however, fibers, yarns, and intermediate textile products (e.g., slivers or rovings) in their pre-fabric state may also be treated.

[0235] The treatment of the target material for the above-mentioned example applications can be carried out using conventionally known methods. The treatment may be either an external addition treatment, in which the compound is attached to the surface of the substrate, or an internal addition treatment, in which the compound is incorporated into the substrate. An example of a treatment method is to prepare an organic solvent solution, organic solvent dispersion, or aqueous dispersion by diluting the compound in this disclosure by dissolving and dispersing it in an organic solvent or water as necessary, and then attaching it to the surface of the target material by a known method such as immersion coating, spray coating, or foam coating, and then drying it. Heating may be performed as needed, and the heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C.

[0236] If necessary, the compounds disclosed herein can also be used in combination with various additives such as anti-slip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insecticides, and defoamers.

[0237] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0238] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0239] Compounds A1 to A16 are compounds of the present disclosure. <Testing Method> [Water repellency evaluation: Measurement of water contact angle] The contact angle of the obtained compounds with water was measured. Specifically, a solution containing 1% by mass of the polymer in chloroform was prepared, and this solution was placed on a silicon substrate and spin-coated at 2000 rpm for 25 seconds to create a film. Water was dropped onto the obtained film and the contact angle was measured. The contact angle was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.) with 2 μL of water at a temperature of 25°C. A value of 95° or higher was marked with ○, and a value of less than 95° was marked with ×.

[0240] <Synthesis of Compound A1> First step

[0241] [ka] 177 mL of 1.06 M LDA in n-hexane-THF and THF were charged into a reaction vessel and stirred at -70°C. Subsequently, 30 g of ethyl (trimethylsilyl) acetate / THF was added at the same temperature. Then, while maintaining the internal temperature below -60°C, 16.8 g of HMPT and 42.3 g of 1-iodoheptane were added. After that, the temperature was raised to room temperature. After liquid-liquid separation and dehydration of the reaction solution, it was concentrated and purified by silica gel column to obtain 42 g of compound (A).

[0242] Second process

[0243] [ka] Et20 was placed in the reaction vessel, and while slightly cooling with ice, LiAlH4 (25g) was added. After raising the temperature to room temperature, compound (A) (40g) / Et20 was added. After liquid-liquid separation and dehydration of the reaction solution, it was concentrated and purified by silica gel column to obtain 22g of compound (B).

[0244] Third step

[0245] [ka] Compound (B) (20 g), / THF, and EtN (9.4 g) were charged into a reaction vessel and cooled with ice. Acryloyl chloride (8.36 g) was added dropwise to this solution. The mixture was then heated to room temperature. After liquid-liquid separation and dehydration of the reaction solution, it was concentrated and purified by silica gel column to obtain 12 g of compound (C).

[0246] Fourth step (polymerization step) 1.5 g of compound (C) was placed in a reaction vessel, toluene was added to dissolve it, and 1.2 mol% of 2,2-azobisisobutyronitrile was added. The reaction was carried out overnight at 69°C to obtain a crude polymer. The crude polymer was reprecipitated to obtain a purified polymer (polymer of compound A1) as a solid. The weight-average molecular weight of the polymer of compound A1 was 32,000 (polystyrene equivalent). The measured contact angle of water (°) was 95° or greater (〇). <Synthesis of Compound A2> 1st step

[0247] [ka] 11-Bromoundecanol (25g), dichloromethane, and 3,4-dihydro-2H-pyran (9.21g) were charged into a reaction vessel and stirred at room temperature. Then, pyridinium-p-toluenesulfonic acid (5.0g) was gradually added. After the addition was complete, stirring was continued at room temperature. After liquid-liquid separation and dehydration, the concentrated crude product was purified by silica gel column chromatography to obtain 27g of the target product, compA.

[0248] 2nd process

[0249] [ka] THF and CompA (1.0 g) were placed in a reaction vessel and stirred at -70°C. 1.5 M t-BuLi (4.0 mL) was gradually added to this solution. After the addition was complete, the temperature was raised from -10°C to 0°C. The mixture was cooled again to -70°C and TMS chloride (0.35 g) was added. After the addition was complete, the temperature was raised to room temperature. The reaction mixture was separated, dehydrated, and concentrated. The crude solution was purified by silica gel column chromatography to obtain 1.0 g of the target product, compB.

[0250] 3rd process

[0251] [ka] Reagents used (1) CompB: 1.0g (32 mmol) (2) Montmorillonite K10: 1.0g (3) Dehydrated methanol: 10 mL Reaction conditions CompB (1.0 g) and methanol were charged into a reaction vessel and stirred at room temperature. Montmorillonite K10 (1.0 g) was added to this reaction solution and heated and stirred at 40°C. After filtering off the insoluble matter, the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column and Kugel distillation to obtain 0.6 g of the target product, compC.

[0252] 4th step

[0253] [ka] CompC (0.3g), triethylamine (0.14g), and THF were added to a reaction vessel and stirred at 0°C. Acryloyl chloride (0.12g) was added to this solution. After the addition, the temperature was raised to room temperature. The reaction mixture was separated, dehydrated, and then concentrated to obtain 0.3g of the target product, compD.

[0254] Fifth step (polymerization step) 0.3 g of compD was placed in a reaction vessel, toluene was added and dissolved in it, the reaction flask was purged with nitrogen, and then 1.2 mol% of 2,2-azobisisobutyronitrile was added and the reaction was carried out overnight at 69°C to obtain a crude polymer. The crude polymer was reprecipitated to obtain a purified polymer (polymer of compound A2) as a solid. The weight-average molecular weight of the polymer of compound A2 was 28,000 (polystyrene equivalent). The measured contact angle of water (°) was 95° or greater (〇).

[0255] <Synthesis of Compound A3> 0.9 g of monoglycerin (10 mmol), 20 mL of pyridine, and compound (A) (40 mmol) were added to a reaction vessel and heated and stirred at an oil bath temperature of 60°C. Separation and purification were performed to obtain the desired monoglycerin derivative. The measured contact angle of water (°) was 95° or greater (〇).

[0256] <Synthesis of Compound A4> 5.0 g of polyglycerin (average molecular weight 500, 10 mmol), 20 mL of pyridine, and compound (A) (85 mmol) were added to a reaction vessel, and the mixture was heated and stirred at an oil bath temperature of 60°C. Separation and purification were performed to obtain the target polyglycerin derivative. The contact angle with water (°) was measured to be 95° or greater (〇).

[0257] <Synthesis of Compound A5> 1.8 g of sorbitol (10 mmol), 20 mL of pyridine, and compound (A) (50 mmol) were added to a reaction vessel and heated and stirred at an oil bath temperature of 60°C. Separation and purification were performed to obtain the target sorbitol derivative. The contact angle with water (°) was measured to be 95° or greater (〇).

[0258] <Synthesis of Compound A6> 15 mmol of trichloride citrate and 48 mmol of compound B were added to a reaction vessel, heated to an oil bath temperature of 70°C, toluene was added, and the mixture was further heated and stirred at 135°C. The reaction vessel was cooled to room temperature, and the mixture was separated and purified to obtain the target citric acid derivative (tris(2-(trimethylsilyl)nonyl)2-hydroxypropane-1,2,3-tricarboxylate). The contact angle with water (°) was measured to be 95° or greater (〇).

[0259] [ka]

[0260] <Synthesis of Compound A7> 15 mmol of trichloride citrate and 48 mmol of compC were added to a reaction vessel, heated to an oil bath temperature of 70°C, toluene was added, and the mixture was further heated and stirred at 135°C. The reaction vessel was cooled to room temperature, and the mixture was separated and purified to obtain the target citric acid derivative (tris(11-(trimethylsilyl)undecyl)2-hydroxypropane-1,2,3-tricarboxylate). The contact angle with water (°) was measured to be 95° or greater (〇).

[0261] [ka]

[0262] <Synthesis of Compound A8> 0.29 g (4.8 mmol) of ethylenediamine, 11 mmol of compound A, 0.12 g of 4,4-dimethylaminopyridine, and chloroform were added. The mixture was then heated and stirred in an oil bath at 50°C. After the reaction mixture cooled to room temperature, it was separated and purified to obtain the target ethylenediamine derivative (N,N'-(ethane-1,2-diyl)bis(2-(trimethylsilyl)nonanamide)). The contact angle with water (°) was measured to be 95° or greater (〇).

[0263] [ka]

[0264] <Synthesis of Compound A9> In the synthesis of compound A2, the same procedure and reaction were carried out, except that 18-bromooctadecane-1-ol was used instead of 11-bromoundecane-1-ol, to obtain a polymer of 18-(trimethylsilyl)octadecylacrylate. The weight-average molecular weight of this polymer was 25,000 (polystyrene equivalent). The contact angle with water (°) was measured to be 95° or greater (〇).

[0265] [ka]

[0266] <Synthesis of Compound A10> In the synthesis of compound A2, the same procedure and reaction were carried out, except that 6-bromohexane-1-ol was used instead of 11-bromoundecane-1-ol, to obtain a polymer of 6-(trimethylsilyl)hexyl acrylate. The weight-average molecular weight of this polymer was 20,000 (polystyrene equivalent). The contact angle with water (°) was measured to be 95° or greater (〇).

[0267] [ka]

[0268] <Synthesis of Compound A11> In the synthesis of compound A1, the same procedure and reaction were carried out, except that 1-iodohexadecane was used instead of 1-iodoheptane, to obtain a polymer of 2-(trimethylsilyl)octadecylacrylate. The weight-average molecular weight of this polymer was 30,000 (polystyrene equivalent). The measured contact angle with water (°) was 95° or greater (〇).

[0269] [ka]

[0270] <Synthesis of Compound A12> In the synthesis of compound A1, the same procedure and reaction were carried out, except that 1-iodobutane was used instead of 1-iodoheptane, to obtain a polymer of 2-(trimethylsilyl)hexyl acrylate. The weight-average molecular weight of this polymer was 32,000 (polystyrene equivalent). The measured contact angle with water (°) was 95° or greater (〇).

[0271] [ka] <Synthesis of Compound A13> CompC (10 mmol) was dissolved in tetrahydrofuran, then NaH (10 mmol) was added and the mixture was stirred for 1 hour. After 1 hour, cyanuric acid chloride (3 mmol) was added and the mixture was stirred overnight at an oil bath temperature of 72°C. After cooling to room temperature, the mixture was acidified with hydrochloric acid and concentrated. The target pyridine derivative was obtained by washing the residue. The contact angle with water (°) was measured to be 95° or greater (〇).

[0272] [ka] <Synthesis of Compound A14> Compound A4 (143g) was dissolved in MIBK, then desmodule N-100 (30g) and catalyst were added, and the mixture was heated and stirred at 80°C. Subsequently, liquid-liquid separation and purification were performed to obtain the target isocyanate derivative. The contact angle with water (°) was measured to be 95° or higher (〇).

[0273] <Synthesis of Compound A15> Compound A15 was obtained by the following procedure.

[0274] [ka]

[0275] 2-nonyn-1-ol (1.0 g), tributylsilane (1.57 g), and dichloromethane were added to a reaction vessel and stirred at room temperature. Karstedt's catalyst (27 mg) was then added. After stirring for 3 hours, the reaction mixture was passed through a silica gel-packed column, and the distillate was concentrated under reduced pressure. 2.2 g of crude product was obtained.

[0276] CompBu-1 (1.0 g), dry dichloromethane, and dry pyridine (0.28 g) were added to a reaction vessel and stirred at room temperature. TBSOTf (0.85 g) was added to this solution. The mixture was stirred at room temperature for 1 hour. Dichloromethane and distilled water were added to the reaction mixture and the mixture was separated. The organic layer was then washed with brine (20 mL) and dehydrated with sodium sulfate. The solvent was removed by vacuum distillation to obtain 1.3 g of crude product. The product was purified with silica gel to obtain 0.8 g of crude product.

[0277] CompBu-2 (1.0 g), ethanol, and 20 wt% Pd(OH)2on carbon (60 mg) were charged into a reaction vessel. After degassing under reduced pressure three times, hydrogen was added and the mixture was stirred at room temperature. After stirring for 1 hour, the solution was filtered using Celite and then concentrated under reduced pressure. Crude product: 0.8 g was obtained.

[0278] CompBu-3 (0.8g) and ethanol were charged into a reaction vessel and stirred at room temperature. Concentrated hydrochloric acid was added to this solution and stirred at room temperature. After stirring for 1 hour, the reaction mixture was concentrated under reduced pressure, then separated, dehydrated, and concentrated to obtain 0.5g of crude product.

[0279] CompBu-4 (0.5g), THF, and triethylamine (0.16g) were charged into a reaction vessel and stirred at approximately 5°C. Acryloyl chloride (0.14g) was gradually added dropwise to this solution. After the addition was complete, the temperature was raised to room temperature. The reaction mixture was analyzed, dehydrated, and concentrated to obtain 0.5g of crude product. Silica gel column purification confirmed that it was CompBu-5. (Yield: 0.43g, yield: 70%)

[0280] CompBu-5 (1.0 g), toluene, and AIBN (1.2 mol%) were charged into a reaction vessel and reacted overnight at 69°C to obtain a crude polymer. The crude polymer was reprecipitated to obtain the purified polymer (compound A15) as a solid. The contact angle with water (°) was measured to be 95° or greater (〇).

[0281] <Synthesis of Compound A16> Compound A16 was obtained by the following procedure.

[0282] [ka]

[0283] Compound A13 was obtained by performing the same procedure as in the synthesis of compound A15, except that tributylsilane was replaced with triethylsilane. The measured contact angle with water (°) was 95° or greater (〇). <Synthesis of compound Z1> 1.5 g of ethyl acrylate was placed in a reaction vessel, toluene was added to dissolve it, and 1.2 mol% of 2,2-azobisisobutyronitrile was added. The reaction was carried out overnight at 69°C to obtain a crude polymer. The crude polymer was reprecipitated to obtain a purified polymer (polymer of compound Z1) as a solid. The weight-average molecular weight of the polymer of compound Z1 was 30,000 (polystyrene equivalent). The measured water contact angle (°) was less than 95° (×). <Synthesis of compound Z2> 1.5 g of dodecyl acrylate was placed in a reaction vessel, toluene was added to dissolve it, and 1.2 mol% of 2,2-azobisisobutyronitrile was added. The reaction was carried out overnight at 69°C to obtain a crude polymer. The crude polymer was reprecipitated to obtain a purified polymer (polymer of compound Z2) as a solid. The weight-average molecular weight of the polymer of compound Z1 was 31,000 (polystyrene equivalent). The measured water contact angle (°) was less than 95° (×). <Synthesis of compound Z3> 0.9 g of monoglycerin (10 mmol), 20 mL of pyridine, and ethyl nonanoate (40 mmol) were added to a reaction vessel and heated and stirred at an oil bath temperature of 60°C. Separation and purification were performed to obtain the desired monoglycerin derivative. The contact angle with water (°) was measured to be less than 95° (×). <Synthesis of compound Z4> 5.0 g of polyglycerin (average molecular weight 500, 10 mmol), 20 mL of pyridine, and ethyl nonanoate (85 mmol) were added to a reaction vessel and heated and stirred at an oil bath temperature of 60°C. Separation and purification were performed to obtain the target polyglycerin derivative. The contact angle with water (°) was measured to be less than 95° (×). <Synthesis of compound Z5> 1.8 g of sorbitol (10 mmol), 20 mL of pyridine, and ethyl nonanoate were added to a reaction vessel and heated and stirred at an oil bath temperature of 60°C. Separation and purification were performed to obtain the desired sorbitol derivative. The contact angle with water (°) was measured to be less than 95° (×). <Synthesis of compound Z6> 15 mmol of trichloride citrate and 48 mmol of nonan-1-ol were added to a reaction vessel, heated to an oil bath temperature of 70°C, toluene was added, and the mixture was further heated and stirred at 135°C. The reaction vessel was cooled to room temperature, and the mixture was separated and purified to obtain the target citric acid derivative (tris(nonyl)2-hydroxypropane-1,2,3-tricarboxylate). The contact angle with water (°) was measured to be less than 95° (×).

[0284] Compounds A1-16 showed a larger contact angle and sufficiently high water repellency compared to compounds Z1-6.

[0285] The compounds disclosed herein can be used as water- and oil-repellent agents. Furthermore, these water- and oil-repellent agents can be used in various applications where liquid repellency (especially water repellency) is required. They can also be used to impart liquid repellency (especially water repellency) to textile products and the like. They can also be used as mold release agents.

Claims

1. A compound obtained by modifying at least one base compound selected from the group consisting of polycarboxylic acids, polyols, polyamines, aromatic compounds, nitrogen-containing cyclic compounds, isocyanate derivatives, and derivatives thereof with an aliphatic hydrocarbon group having 4 to 40 carbon atoms, which has at least one alkylsilyl group and may also have substituents.

2. The alkylsilyl group is defined by the following formula: -Si(R １ ) ３ [In the formula, R １ Each is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may have a hydrogen atom or a substituent, and at least one R １ This is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may have substituents. The compound according to claim 1, wherein the group is represented by

3. The aforementioned R １ The compound according to claim 2, wherein is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, which may have substituents.

4. The following formula: -X-R ｎ [In the formula, X is a direct bond or a 1+n valence group, R is an aliphatic hydrocarbon group having 4 to 40 carbon atoms, independently having at least one alkylsilyl group in each instance and possibly having substituents. n is between 1 and 3 (inclusive). The compound according to claim 3, having a Z group represented by .

5. X is selected from direct bond, -O-, -C(=O)-, -S(=O)- ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ , where R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and X is composed of one or more selected from the group consisting of １ and X is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents. ２ and, The compound according to claim 4, which is a 1+n valent group composed of one or more selected from the group consisting of the following.

6. X, -X １ -、 -X ２ -X １ -、 -X １ -X ２ -X １ -, or -X ２ -X １ -X ２ -X １ - [In the formula, X １ However, in each appearance independently, direct binding, -O-, -O-C(=O)-, -O-C(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)- -C(=O)-O-, -C(=O)-NR'-, -SO ２ -、 -SO ２ NR'-、 -C(OR')R'-, or -C(OR’)(-) ２ (In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each instance. It is a base represented by, X ２ This is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents. The compound according to claim 4, wherein the group is represented by .

7. The aforementioned base compound is a polycarboxylic acid. The polycarboxylic acid is at least one selected from the group consisting of dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and carboxyl group-containing compound polymers. The compound according to claim 4, wherein one or more hydroxyl groups of the polycarboxylic acid are substituted with the Z group.

8. The aforementioned polycarboxylic acid Citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aldaric acid; Tricarbaryl acid, t-aconitic acid, trimellitic acid; The compound according to claim 7, which is at least one selected from the group consisting of pyromellitic acid and derivatives thereof.

9. The following formula, including the aforementioned Z group: CH ２ =C(-Q)-C(=O)-Z [In the formula, Q is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom. The compound according to claim 4, which is a polymer containing repeating units derived from a compound represented by .

10. The aforementioned base material compound is a polyol. The polyol is at least one selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, sugar alcohols, hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, and hydroxy group-containing compound polymers. The compound according to claim 4, wherein one or more hydroxyl groups of the polyol are substituted with the Z group.

11. The polyol is glucose, fructose, galactose, or xylose; Sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; Sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; Starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomaltodextrin, gellan gum, tamarind seed gum; Kojic acid, quinic acid, chlorogenic acid, gluconic acid, aldonic acid, uronic acid; Glucosamine; Ascorbic acid, inositol; Catechins, quercetin, anthocyanins; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; The compound according to claim 10, which is at least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer and derivatives thereof.

12. The aforementioned matrix compound is a polyamine, The polyamine is composed of a 1-3 valent amino group and a chain-like saturated aliphatic hydrocarbon group or aromatic hydrocarbon group which may be cleaved by oxygen and / or sulfur atoms, and the molar ratio of carbon atoms to nitrogen atoms (C / N ratio) is 8 or less. The compound according to claim 4, wherein one or more hydrogen atoms bonded to the nitrogen atoms of the polyamine are substituted by the Z group.

13. The aforementioned base material compound is an aromatic compound or a nitrogen-containing cyclic compound. The following formula: A (-Z) ｍ [In the formula, A is an m-valent group obtained by removing m hydrogen atoms from an aromatic compound having 7 or more carbon atoms, which may have substituents, or a nitrogen-containing cyclic compound having 5 or more carbon atoms. m is an integer between 1 and 6 (inclusive). The compound according to claim 4, represented by [the specified compound].

14. The aforementioned base compound is an isocyanate derivative, The compound according to claim 1, wherein the isocyanate derivative is a polyurethane obtained by reacting an isocyanate group-containing compound with an isocyanate-reactive compound.

15. The compound according to claim 14, wherein the isocyanate group-containing compound is triisocyanate.

16. The compound according to claim 1, wherein the water contact angle of the compound is 95° or more.

17. A liquid-repellent composition comprising the compound described in any one of claims 1 to 16.

18. The liquid-repellent composition according to claim 17, which is an aqueous dispersion.

19. A liquid-repellent composition according to claim 17, used as a water-repellent agent, an oil-repellent agent, or a water-repellent and oil-repellent agent.

20. A liquid-repellent composition according to claim 17, which is used as a surface treatment agent, anti-fogging agent, rust inhibitor, or antifreeze agent.

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