Fluorine-containing compound

Abstract

To provide a novel fluorine-containing compound and a water- and oil-repellent agent containing the fluorine-containing compound.SOLUTION: The present invention discloses a novel fluorine-containing compound having a moiety derived from a compound (a) having one or more active hydrogen-containing groups selected from a hydroxy group, an amino group, a carboxyl group, and a thiol group, and a moiety derived from a compound (b) having Rf1 or Rf2, wherein Rf1 is -CF3, -CF2H, or -CFH2, Rf2 is -CF2- or -CFH-, and Rf1 and Rf2 are not parts of a fluoroalkyl group having 2 or more carbon atoms.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a fluorine-containing compound.

Background Art

[0002] It is known that certain non-fluorine polymers can impart oil resistance when used for surface treatment of a substrate (Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present disclosure is to provide a new fluorine-containing compound.

Means for Solving the Problems

[0005] The present disclosure includes the following aspects: [Item 1] A moiety derived from a compound (a) having one or more active hydrogen-containing groups selected from a hydroxy group, an amino group, a carboxyl group, and a thiol group, and R f1 or R f2 A moiety derived from a compound (b) having, A fluorine-containing compound having, R f1 is -CF3, -CF2H, or -CFH2, R f2 is -CF2- or -CFH-, R f1 and R f2 are not part of a fluoroalkyl group having 2 or more carbon atoms, a fluorine-containing compound. [Item 2] Said R f1The adjacent position is an oxygen atom or a nitrogen atom, said R f2 At least one of the adjacent positions of which is an oxygen atom or a nitrogen atom, the fluorine-containing compound according to claim 1. [Claim 3] said R f1 is CF3-, said R f2 is -CF2-, The fluorine-containing compound according to claim 1 or 2. [Claim 4] said compound (b) is Formula: -Y f -Z f α [In the formula, each symbol is independently in each occurrence, Y f is a 1+α-valent group composed of one or more selected from the group consisting of Y f1 and Y f2 ; Y f1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -NR’-, -C(OR’)R’-, and -C(OR’)(-)2, -N(-)2 (wherein R’ is a hydrogen atom or an organic group); Y f2 is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group; Z f is R f1 , or a hydrocarbon group having 2 to 40 carbon atoms containing R f1 or R f2 ; α is 1 to 3.] The fluorine-containing compound according to any one of claims 1 to 3, having a group represented by [Claim 5] said compound (b) is Formula: -Y f11 -(Y f21 -Y f12 ) β -Y f22 -Y f13 -Zf [In the formula, each symbol is independent at each occurrence, Y f11 is a direct bond, -O-, -NH-, -C(=O)-, -C(=O)-NH-, or -S-, Y f21 is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, Y f12 is a group composed of one or more selected from the group consisting of -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -NR’-, and -C(OR’)R’- (R’ is a hydrogen atom or an organic group.), β is from 0 to 3, Y f22 is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, Y f13 is -O-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-O-, -C(=O)-NR’-, or -SO2NR’- (R’ is a hydrogen atom or an organic group.). Z f is R f1 , or R f1 or R f2 is a hydrocarbon group having 2 to 40 carbon atoms including.] The fluorine-containing compound according to any one of items 1 to 4, having a group represented by. [Item 6] Y f22 is the formula -Y f221 -Y f222 - [In the formula, Y f221 is a direct bond or a hydrocarbon group having 2 to 40 carbon atoms, Y f222 is a direct bond or a phenyl group.] is a group represented by, Y f13 is -O- or -NR’- (R’ is a hydrogen atom or an organic group.), β is 0 or 1, Z f is R f1 The fluorine-containing compound according to item 5. [Item 7] The fluorine-containing compound according to any one of items 1 to 6, wherein the compound (b) is an active hydrogen-reactive compound; a polymerizable monomer or a polymer thereof. [Item 8] The fluorine-containing compound according to any one of items 1 to 7, wherein the compound (a) is a natural product. [Item 9] The fluorine-containing compound according to any one of items 1 to 8, wherein the compound (a) is a polyol, a polyamine or a polycarboxylic acid. [Item 10] The fluorine-containing compound according to any one of items 1 to 9, wherein the compound (a) is a monosaccharide, an oligosaccharide, a polysaccharide, a sugar alcohol, a hydroxy acid, an amino acid, a vitamin, a flavonol, a hydroxy hydrocarbon, and a polymer of a hydroxy group-containing compound, an organic acid, an organic amine, or a saturated / unsaturated aliphatic hydrocarbon compound. [Item 11] The compound (a) is glucose, fructose, galactose, xylose; sucrose, cyclodextrin, 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, isomalto-dextrin, gellan gum, tamarind seed gum; ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; glucosamine; inositol; catechin, quercetin, anthocyanin; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; Polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer; Citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aldic acid; Tricarballylic acid, t-aconitic acid, trimellitic acid; Pyromellitic acid; Alkylenediamine, alkylenetriamine, aromatic diamine; Or a fluorine-containing compound according to any one of items 1 to 10, which is a saturated / unsaturated aliphatic hydrocarbon compound having an active hydrogen group. [Item 12] A fluorine-containing compound according to any one of items 1 to 11, wherein the bio-based degree of the fluorine-containing compound is 20% or more. [Item 13] A fluorine-containing compound according to any one of items 1 to 12, wherein the weight average molecular weight is 1000 or more. [Item 14] A fluorine-containing compound according to any one of items 1 to 12, wherein the weight average molecular weight is less than 1000. [Item 15] -Y f -Z f n As a modifying group other than the above, having a monovalent hydrocarbon group having 6 to 40 carbon atoms, A fluorine-containing compound according to any one of items 1 to 14. [Item 16] The compound (b) is, Formula: -Y f11 -(Y f21 -Y f12 ) β -Y f22 -Y f13 -Zf [In the formula, each symbol is independent at each occurrence, Y f11 is a direct bond, -O-, -NH-, -C(=O)-, -C(=O)-NH-, or -S-, Y f21 is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, Y f12 is a group composed of one or more selected from the group consisting of -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -NR’-, and -C(OR’)R’- (R’ is a hydrogen atom or an organic group.), β is from 0 to 3, Y f22 is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, Y f13 is -O-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-O-, -C(=O)-NR’-, or -SO2NR’- (R’ is a hydrogen atom or an organic group.) Z f is -CF3.] The fluorine-containing compound according to item 11, which is a compound having a group represented by [Item 17] A dispersion containing the fluorine-containing compound according to any one of items 1 to 16 and a liquid medium. [Item 18] A water and oil repellent containing the fluorine-containing compound according to any one of items 1 to 16. [Item 19] The water and oil repellent according to item 18, which is for a fiber product or a paper product. [Item 20] A method for producing a treated substrate, which comprises treating a substrate with the water and oil repellent according to item 18 or 19. [Item 21] The production method according to item 20, wherein the substrate is a fiber product or a paper product. [Item 22] A product to which a fluorine-containing compound according to any one of items 1 to 16 is attached.

Advantages of the Invention

[0006] According to the present disclosure, a new fluorine-containing compound can be provided.

Modes for Carrying Out the Invention

[0007] <Definition of Terms> As used herein, the term "n-valent group" means a group having n bonds, that is, a group forming n bonds. Further, the term "n-valent organic group" means an n-valent group containing carbon. Such an organic group is not particularly limited, and may be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group 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 the hydrocarbon group.

[0008] As used herein, the term "hydrocarbon group" means a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but is C 1-40 Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Further, the hydrocarbon group may contain one or more ring structures. When the hydrocarbon group is explicitly described, it may be substituted with one or more substituents.

[0009] In this specification, regardless of whether the expression "independently at each occurrence", "independently of each other", "independently of each other" or a similar expression is explicitly described, unless there is a description to the contrary, when a term (symbol) that can appear multiple times in a chemical structure is defined, the definition is applied independently for each occurrence.

[0010] The chemical structures described in this specification should be understood not to include chemical structures that are recognized by those skilled in the art as being chemically impossible or extremely unstable.

[0011] <Fluorine-containing compound> The fluorine-containing compounds in the present disclosure are (a) a moiety derived from a compound having one or more groups selected from a hydroxy group, an amino group, a carboxyl group, and a thiol group, and (b) a moiety derived from a compound having R f1 or R f2 and having. have.

[0012] The fluorine-containing compound may be formed by the reaction of the active hydrogen of compound (a) with the active hydrogen-reactive group of compound (b). The fluorine-containing compound may be formed by graft-polymerizing compound (b) from the active sites on the molecular chain of compound (a).

[0013] [Properties, etc. of fluorine-containing compounds] The fluorine-containing compounds in the present disclosure can adhere to a substrate and impart liquid repellency (e.g., oil repellency, water repellency, oil resistance, water resistance) to the substrate.

[0014] The HD (n-hexadecane) contact angle of the fluorine-containing 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 20° or more, particularly 30° or more, and may also be 100° or less, 90° or less, or 75° or less. When the fluorine-containing compound has an HD contact angle of the above lower limit or more, it can impart good liquid repellency (particularly oil repellency) to the substrate. The HD contact angle refers to the static contact angle of the spin-coated film of the fluorine-containing compound, and is obtained by dropping 2 μL of HD on the spin-coated film and measuring the contact angle 1 second after droplet landing.

[0015] The water contact angle of the fluorine-containing compound may be 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may also be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By having a water contact angle of the fluorine-containing compound of the above lower limit or more, good liquid repellency (particularly water repellency) can be imparted to the substrate. The water contact angle refers to the static contact angle with respect to the spin-coated film of the fluorine-containing compound, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the droplet adheres.

[0016] The melting point or glass transition point (for example, melting point) of the fluorine-containing compound may be 0°C or more, 20°C or more, 30°C or more, 35°C or more, 40°C or more, 45°C or more, 50°C or more, or 55°C or more, and may also be 200°C or less, 150°C or less, 100°C or less, 80°C or less, or 70°C or less. The melting point is usually 30°C or more, preferably 40°C or more, for example 75°C or more.

[0017] The fluorine-containing compound is preferably a compound having bio-based origin carbon. The bio-based content is measured in accordance with ASTM D6866. The bio-based content of the fluorine-containing compound may be 20% or more, preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, still more preferably 70% or more, most preferably 80% or more or 90% or more, for example 100%. A high bio-based content means a small amount of use of fossil resource-based materials represented by petroleum and the like, and from such a viewpoint, it can be said that the higher the bio-based content of the fluorine-containing compound, the more preferable.

[0018] The fluorine-containing compound in the present disclosure is the above-described Rf 1 or Rf 2It has. On the other hand, the fluorine-containing compound in the present disclosure may not have any selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a fluoroalkyl group having 2 or more carbon atoms, and a perfluoroalkyl group having 2 or more carbon atoms. The fluorine-containing compound in the present disclosure can impart liquid repellency to the substrate even without containing these fluorine-containing groups. In the present specification, the fluoroalkyl group may be intended to be a group in which one or more hydrogen atoms at each carbon atom of the alkyl group are replaced by fluorine atoms.

[0019] The fluorine-containing compound may be low molecular weight (for example, having a weight average molecular weight of less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the fluorine-containing compound may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 3000000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0020] The substitution rate of active hydrogen in the fluorine-containing compound may be 0.01% or more, 0.1% or more, 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 10% or more, for example 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may also be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example 95% or less. Here, the "substitution rate" means the modified ratio (mol%) of the active hydrogen derived from compound (a), and may mean the modified ratio (mol%) by the structure derived from compound (b).

[0021] The residual rate of active hydrogen in the fluorine-containing compound may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example 5% or more, and may also be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example 50% or less, 30% or less, or 10% or less. Here, the "residual rate" means the unmodified ratio (mol%) of the active hydrogen derived from compound (a).

[0022] The number of modifying groups in the fluorine-containing compound may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, or 50 or more, and may also be 20000 or less, 10000 or less, 5000 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. Here, the modifying group may be a part derived from compound (b).

[0023] The equivalent weight of the fluorine-containing compound may be 100 or more, 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more, and may also be 10000 or less, 5000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the fluorine-containing compound by the number of modifying groups. Here, the modifying group may be a part derived from compound (b).

[0024] [R f1 and R f2 The fluorine-containing compound has R f1 or R f2 and, for example, has R f1 . Here, R f1 and R f2 are not part of a fluoroalkyl group having 2 or more carbon atoms. R f2 does not have to be part of -CH2-CF2-CH2-.

[0025] R f1 is -CF3, -CF2H, or -CFH2, preferably -CF3. The adjacent position of R f1 may be an oxygen atom or a nitrogen atom.

[0026] R f2 is -CF2- or -CFH-, preferably -CF2-. At least one of the adjacent positions of R f2 may be an oxygen atom or a nitrogen atom.

[0027] [Compound (a)] Compound (a) is a compound having one or more active hydrogen-containing groups selected from a hydroxy group, an amino group, a carboxyl group, and a thiol group, and is a compound that serves as a raw material for the fluorine-containing compound. Compound (a) may be aliphatic or aromatic, but is preferably aliphatic. Many compounds having one or more active hydrogen-containing groups selected from a hydroxy group, an amino group, a carboxyl group, and a thiol group are derived from natural products, and it is easy to increase the bio-based degree of the fluorine-containing compound. ​

[0028] Compound (a) preferably has carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content of the fluorine-containing compound may be 20% or more, preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, still more preferably 70% or more, most preferably 80% or more or 90% or more, for example 100%. A high biobased content means that the amount of fossil resource-based materials represented by petroleum and the like is small. From such a viewpoint, it can be said that the higher the biobased content of compound (a), the more preferable.

[0029] Compound (a) may be a low molecule (for example, a weight average molecular weight of less than 1000, 500 or less) and / or a high molecule. The weight average molecular weight of compound (a) may be 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, 300000 or more, or 500000 or more, and may also be 5000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 3000000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0030] The number of active hydrogen-containing groups that compound (a) has 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 20000 or less, 10000 or less, 5000 or less, 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.

[0031] The equivalent weight of the active hydrogen-containing group of compound (a) may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, 150 or more, and may also be 20000 or less, 10000 or less, 5000 or less, 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The equivalent weight of the active hydrogen-containing group of compound (a) is the value obtained by dividing the weight average molecular weight of compound (a) by the number of active hydrogen-containing groups.

[0032] Compound (a) may be a natural product. Compound (a) may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. Compounds converted from microorganisms are also included among the above natural products.

[0033] Compound (a) may be a compound having one active hydrogen-containing group selected from a hydroxy group, an amino group, a carboxyl group, and a thiol group, but is preferably a polyol, polyamine, polycarboxylic acid, or polythiol having a plurality of them. Compound (a) may be other than polythiol.

[0034] Examples of compound (a) include, but are not limited to, monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, other polyhydric alcohols, hydroxy group-containing compound polymers, polycarboxylic acids, polyamines, polywaxes, etc.

[0035] Examples of monosaccharides include glucose, fructose, galactose, xylose, etc.

[0036] Examples of oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose, etc.

[0037] Examples of sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, glycerin, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol, etc.

[0038] Examples of polysaccharides include starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomaltooligosaccharide, gellan gum, tamarind seed gum, and the like.

[0039] Examples of hydroxy acids include kojic acid, quinic acid, chlorogenic acid, gluconic acid, and the like.

[0040] Examples of amino acids include glucosamine and the like.

[0041] Examples of vitamins include ascorbic acid, inositol, and the like.

[0042] Examples of flavonols include catechin, quercetin, anthocyanin, and the like.

[0043] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, and the like. Hydroxyhydrocarbon is a hydrocarbon having a hydroxy group, which may be aromatic or aliphatic, preferably aliphatic. When referring to hydroxyhydrocarbon, it may mean hydroxyhydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxyhydrocarbons).

[0044] Examples of hydroxy group-containing compound polymers include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, hydroxybutyl (meth)acrylate polymer, and the like.

[0045] Examples of polycarboxylic acids include citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aldic acid; tricarballylic acid, t-aconitic acid, trimellitic acid; pyromellitic acid, itaconic acid, and the like. The polycarboxylic acid may be a polymer of a polymerizable compound such as (meth)acrylic acid.

[0046] Examples of polyamines include alkylenediamines, alkylenetriamines, aromatic diamines, etc. Specific examples include ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, 1,3-bis(aminomethylcyclohexane), xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, dimethylthiotoluenediamine, 4,4'-methylenebis[N-(1-methylpropyl)aniline], aminobenzylamine, bis[2-(4-aminophenyl)-2-propylbenzene, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-methylenebis[N-(1-methylpropyl)aniline], trimethylene-bis(4-aminobenzoate), diethylenetriamine, 2,2'-diamino-N-methyldiethylamine, triethylenetetramine, tris(2-aminoethyl)amine, and the like. The polyamine may be a polymer of a polymerizable compound such as allylamine.

[0047] Examples of saturated / unsaturated aliphatic hydrocarbon compounds having an active hydrogen group include aliphatic alcohols, amide group-containing aliphatic alcohols, aliphatic carboxylic acids, aliphatic hydroxy acids, aliphatic thiols, and the like.

[0048] [Compound (b)]

[0049] Compound (b) is R f1 or R f2It is a compound having [specific structure]. Compound (b) may have an active hydrogen reactive group that can react with the active hydrogen or active hydrogen-containing group of compound (a). Further, compound (b) may have polymerizability (graft polymerizability), for example, it may have an ethylenically unsaturated polymerizable group.

[0050] Compound (b) has the formula: -Y f -Z f α [In the formula, each symbol is independently, in each occurrence, Y f is a 1 + α-valent group composed of one or more selected from the group consisting of Y f1 and Y f2 ; Y f1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -NR’-, -C(OR’)R’-, and -C(OR’)(-)2, -N(-)2 (wherein R’ is a hydrogen atom or an organic group); Y f2 is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group; Z f is R f1 or a hydrocarbon group having 2 to 40 carbon atoms containing R f1 or R f2 ; α is 1 to 3.] It may have a group represented by [specific formula].

[0051] R f1 may be included in, for example, Z f . R f2 may be, for example, an organic group, Y f2 , Z f , R f2 .

[0052] -Y f -Z f α For Y of fAt the end of [[ID=]], a group reactive with the active hydrogen group of compound (a) such as acid halide, acid anhydride, carboxylic acid, isocyanate, thioisocyanate, epoxy, halide, amine, hydroxy, etc. may be formed. For example, compound (b) is X r -Y f -Z f α may be represented by. Here, X r is a group that forms a group reactive with the active hydrogen group of compound (a). For example, X r alone may form the group, or it may form the group jointly with Y f .

[0053] The polymerizable compound (b) is CH2=C(-X f )-Y f -Z f α [wherein each symbol is independently in each occurrence, X f is a hydrogen atom, a monovalent organic group or a halogen atom, and the others are as described above.] It may be a compound represented by. Here, X f is a hydrogen atom, a monovalent organic group or a halogen atom. X f is a hydrogen atom, a halogen other than a methyl group and a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, preferably a hydrogen atom, a methyl group or a chlorine atom. The polymerizable compound (b) may be an ethylenically unsaturated polymerizable compound such as an acrylic monomer, a styrene monomer or an allyl monomer.

[0054] However, compound (b) is not limited to the above structure, and any part in compound (b), particularly compound (b) having an active hydrogen reactive group or polymerizable compound (b), may be composed of -Y f -Z f α .

[0055] (Y f ) Y f is Y f1 and Y f2 is a 1+α-valent group consisting of one or more groups selected from the group consisting of Y f1 is a group consisting of one or more members selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (R' is a hydrogen atom or a monovalent organic group), Y f2 is a group composed of one or more groups selected from the group consisting of aliphatic groups and aromatic groups.

[0056] Y f The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0057] Below, Y f1 and Y f2 This article explains:

[0058] ○ Y f1 Y f1 is a non-hydrocarbon linker.

[0059] Y f1 is a direct bond or a divalent or higher valent group. f1 The valence of Y may be 2 to 4, 2 to 3, or 2. f1 is preferably not only a direct bond.

[0060] Y f1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0061] Y f1 is composed of one or more selected from the group consisting of -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a monovalent organic group).

[0062] R' is a hydrogen atom or a monovalent organic group. The organic group may be, for example, an aliphatic group or aromatic group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (e.g., a substituted or unsubstituted alkyl group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group). The same may apply to other R's in this specification.

[0063] Y f1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=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′—, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (wherein R′ in each occurrence is independently a hydrogen atom or a monovalent organic group.) Examples include:

[0064] ○ Y f2 Y f2 may be a group composed of one or more selected from the group consisting of aliphatic groups and aromatic groups.

[0065] Y f2 is a divalent or higher-valent group. Y f2 The valence number of Y may be, for example, 2 to 4, 2 to 3, or 2.

[0066] Y f2 The number of carbon atoms of Y 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, and may also 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.

[0067] Y f2 The molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may also be 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0068] Y f2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). Y f2 Y may be aliphatic or aromatic. Y f2 Y may be linear, branched, or cyclic.

[0069] Y f2 Y may be a linker of a hydrocarbon which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent, or a combination thereof. For example, Y f2 Y may be composed of one or more selected from the group consisting of a 2- to 4-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a 2- to 4-valent hydrocarbon aromatic ring which may have a substituent, and a 2- to 4-valent heterocyclic ring which may have a substituent.

[0070] The aliphatic hydrocarbon group having a valence of 2 to 4 and 1 to 20 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The aliphatic hydrocarbon group having a valence of 2 to 4 and 1 to 20 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may also be 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, and may also be 4 or less, 3 or less, or 2.

[0071] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein, R’ is, in each occurrence, independently a monovalent organic group). The substituent may or may not have an 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 the aliphatic hydrocarbon group having a substituent, 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, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0072] Examples of the hydrocarbon aromatic ring having a valence of 2 to 4 include groups obtained by removing 2 to 4 hydrogens from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may also be 4 or less, 3 or less, or 2.

[0073] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein R’ is, independently at each occurrence, a hydrogen atom or a monovalent organic group). The substituent may or may not have an 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 the hydrocarbon aromatic ring having a substituent, the amount of carbon atoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more with respect to the amount of carbon atoms and heteroatoms, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0074] The 2- to 4-valent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the 2- to 4-valent heterocyclic ring include a group obtained by removing 2 to 4 hydrogens from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocyclic ring may be 2 or more, 3 or more, or 4, and may also be 4 or less, 3 or less, or 2.

[0075] The heterocycle may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein, R’ is independently a hydrogen atom or a monovalent organic group at each occurrence). The substituent may or may not have an 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 the heterocycle having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example 65 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0076] Y f2 Examples of -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [Wherein, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or a heterocycle.] etc. are included.

[0077] Y f2 Specific examples of -(CH2) p -(p is 1 to 20, for example 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40 carbon atoms, for example 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40 carbon atoms, for example 1 to 10 carbon atoms, -(CH2) q-Cy-(CH2) r -(q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) and the like can be mentioned.

[0078] ○ Y f Examples of Y f will be described.

[0079] Y f As an example of Y f when Y is divalent, -Y f1 -, -Y f1 -Y f2 -, -Y f1 -Y f2 -Y f1 -, -Y f1 -Y f2 -Y f1 -Y f2 -, -Y f2 -, -Y f2 -Y f1 -, -Y f2 -Y f1 -Y f2 -, -Y f2 -Y f1 -Y f2 -Y f1 - and the like can be mentioned. Z f α The group adjacent to f1 may be Y.

[0080] Y f As an example of Y f when Y is trivalent, -Y f1 (-)2, -Y f1 -Y f2 (-)2, -Y f1 -(Y f2 -)2, -Y f1 -Y f2 -Y f1 (-)2, -Y f1 -Y f2 (-Y f1 -)2, -Y f1 -(Y f2 -Y f1 -)2, -Y f1 -Y f2 -Yf1 -Y f2 (-)2, -Y f1 -Y f2 -Y f1 -(Y f2 -) 2、 -Y f1 -Y f2 -(Y f1 -Y f2 -) 2、 -Y f1 -(Y f2 -Y f1 -Y f2 )2; -Y f2 (-)2, -Y f2 -Y f1 (-)2, -Y f2 -(Y f1 )2, -Y f2 -Y f1 -Y f2 (-)2, -Y f2 -Y f1 (-Y f2 )2, -Y f2 -(Y f1 -Y f2 )2, -Y f2 -Y f1 -Y f2 -Y f1 (-)2, -Y f2 -Y f1 -Y f2 -(Y f1 ) 2、 -Y f2 -Y f1 -(Y f2 -Y f1 ) 2、 -Y f2 -(Y f1 -Y f2 -Y f1 )2 etc. can be mentioned.

[0081] Y f As an example of Y f when it is tetravalent, -Y f1 (-)3, -Y f1 -Y f2 (-)3, -Y f1 -(Y f2 )3, -Y f1 -Y f2 -Yf1 (-)3, -Y f1 -Y f2 (-Y f1 -)3, -Y f1 -(Y f2 -Y f1 -)3, -Y f1 -Y f2 -Y f1 -Y k f2 (-)3, -Y f1 -Y f2 -Y f1 -(Y f2 -) 3、 -Y f1 -Y f2 -(Y f1 -Y f2 -) 3、 -Y f1 -(Y f2 -Y f1 -Y f2 -)3; -Y f2 (-)3, -Y f2 -Y f1 (-)3, -Y f2 -(Y f1 -)3, -Y f2 -Y f1 -Y f2 (-)3, -Y f2 -Y f1 (-Y f2 -)3, -Y f2 -(Y f1 -Y f2 -)3, -Y f2 -Y f1 -Y f2 -Y f1 (-)3, -Y f2 -Y f1 -Y f2 -(Y f1 -) 3、 -Y f2 -Y f1 -(Y f2 -Y f1 -) 3、 -Y f2 -(Y f1 -Y f2 -Y f1 -)3 etc. can be mentioned.

[0082] Y fPreferred examples include -Y f1 -,-Y f1 -Y f2 -,-Y f1 -Y f2 -Y f1 -,-Y f1 -Y f2 (-)2, -Y f2 -,-Y f2 -Y f1 -,-Y f2 -Y f1 -Y f2 -,-Y f2 -Y f1 (-)2 etc. can be mentioned.

[0083] (Z f ) Z f is a hydrocarbon group having 2 to 40 carbon atoms containing R f1 , or R f1 or R f2 and is, for example, R f1 . R f1 or R f2 The hydrocarbon group containing may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). R f1 or R f2 The hydrocarbon group containing is branched or linear, and more preferably linear. R f1 or R f2 The hydrocarbon group containing may be saturated or unsaturated. R f1 or R f2 The hydrocarbon group containing is preferably a saturated aliphatic hydrocarbon group (alkyl group). R f1 or R f2 The number of carbon atoms of the hydrocarbon group containing may be 2 or more, 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 10 or more, 12 or more, 14 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.

[0084] (α) α is 1 to 3 (1, 2, or 3), for example 1 or 2, for example 1.

[0085] (Example of compound (b)) Compound (b) is Formula: -Y f11 -(Y f21 -Y f12 ) β -Y f22 -Y f13 -Z f [In the formula, each symbol is independently at each occurrence Y f11 is a direct bond, -O-, -NH-, -C(=O)-, -C(=O)-NH-, or -S-, Y f21 is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, Y f12 is a group composed of one or more selected from the group consisting of -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -NR’-, and -C(OR’)R’- (R’ is a hydrogen atom or an organic group.), β is 0 to 3, Y f22 is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, Y f13 is -O-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-O-, -C(=O)-NR’-, or -SO2NR’- (R’ is a hydrogen atom or an organic group.) Z f is R f1 or, R f1 or R f2 or a hydrocarbon group having 2 to 40 carbon atoms containing R.] It may be a compound having a group represented by.

[0086] Y f11At the terminal on the side, an active hydrogen-reactive group such as an acid halide, acid anhydride, isocyanate, or epoxy may be formed.

[0087] Y f11 is a direct bond, -O-, -NH-, -C(=O)-, -C(=O)-NH-, or -S-.

[0088] Y f21 may be a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, and the above-described Y f2 can be applied with the same explanation. However, Y f21 is a divalent group.

[0089] Y f12 may be a group composed of one or more selected from the group consisting of -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -NR’-, and -C(OR’)R’-, and the above-described Y f1 can be applied with the same explanation. However, Y f12 is a divalent group.

[0090] β may be 0 to 3 (0, 1, 2, or 3), for example, 0 to 2, particularly 0 to 1.

[0091] Y f22 may be a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, and the above-described Y 2 can be applied with the same explanation. However, Y f22 is a divalent group. Y f22 is the formula -Y f221 -Y f222 - [wherein, Y f221 is a direct bond or a hydrocarbon group having 2 to 40 carbon atoms, Y f222 is a direct bond or a phenylene group.] It may be a group represented by. Here, the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and may be an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched or linear, for example, linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group may be a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms of the hydrocarbon group may be 2 or more, 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, 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.

[0092] Y f13 may be -O-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-O-, -C(=O)-NR’-, or -SO2NR’- (R’ is a hydrogen atom or a monovalent organic group). Y f13 is, for example, -O- or -NR’-.

[0093] Z f is R f1 or R f1 or R f2 is a hydrocarbon group having 2 to 40 carbon atoms including, as described above, and particularly R f1 is.

[0094] Alternatively, when compound (b) is polymerizable, the formula: CH2=C(-X f )-C(=O)-Y f11 -(Y f21 -Y f12 ) β -Y f22 -Y f13 -Z f or CH2=C(-X f )-CH2-Y f11 -(Y f21 -Y f12 ) β -Y f22 -Y f13 -Zf [In the formula, each symbol is independent at each occurrence, X f is a hydrogen atom, a monovalent organic group or a halogen atom, and the others are as described above.] It may be an acrylic monomer or an allyl monomer represented by

[0095] In one aspect, Y f22 is a formula -Y f221 -Y f222 - [In the formula, Y f221 is a direct bond or a hydrocarbon group having 2 to 40 carbon atoms, Y f222 is a direct bond or a phenylene group.] It may be a group represented by Here, Y f13 may be -O- or -NR'-(R' is a hydrogen atom or a monovalent organic group). β may be 0 or 1. Z f may be R f1 as described above.

[0096] (Specific examples of compound (b)) Specific examples of compound (b) are as follows: Acid halide G(O=)C-Y f -Z f α Acid anhydride O(C(=O)-Y f -Z f α )2 Carboxylic acid HO(O=)C-Y f -Z f α Isocyanate O=C=N-Y f -Z f α Thioisocyanate S=C=N-Y f -Z f α Epoxy (CH2OCH)CH2O-Yf -Z f α Halide G-Y f -Z f α Amine H2N-Y f -Z f α Hydroxy HO-Y f -Z f α [In the formula, Y f , Z f , α are as described above, and G is a halogen atom (e.g., F, Cl, Br, or I).] Note that in the above formula, the terminal functional group (such as G(O=)C etc.) adjacent to Y f -Z f α is expressed as not being included in -Y f -, but it is also possible to re-express it as a description in which a part of the structure of the terminal functional group (e.g., (O=)C) is incorporated into Y f .

[0097] Specific examples of compound (b) include the compounds listed in the above specific examples and compounds having an ethylenically unsaturated polymerizable group (e.g., (meth)acryloyl chloride, 2-((meth)acryloyloxy)ethyl isocyanate, glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl α-ethylacrylate, crotonyl glycidyl ether, (iso)crotonic acid glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, (meth)acrylic acid chloride, (meth)acryloyl chloride, (meth)acrylamide, (meth)acrylic acid, N,N-dimethylaminoethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allylamine, allyl alcohol, etc.) reacted therewith, and polymerizable compound (b) or its polymer obtained thereby are also included.

[0098] More specific examples of compound (b) include (for example, in the formula listed in the above specific examples) -Y f -Z fα is -Ali-O-R f1 , -Ali-Cy-O-R f1 , -Ali-Cy-Ali-O-R f1 , -Cy-O-R f1 , -Cy-Ali-O-R f1 , -Cy-Ali-Cy-O-R f1 , -Ali-N(R’)-R f1 , -Ali-Cy-N(R’)-R f1 , -Ali-Cy-Ali-N(R’)-R f1 , -Cy-N(R’)-R f1 , -Cy-Ali-N(R’)-R f1 , -Cy-Ali-Cy-N(R’)-R f1 , [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Cy is a hydrocarbon aromatic ring or a heterocyclic ring. R’ is a hydrogen atom or an organic group. R f1 is -CF3, -CF2H, or -CFH2.] is a compound, More specific examples of compound (b) include (for example, in the formula cited in the above specific examples) -Y f -Z f α is -(CH2) n -O-R f1 , -(CH2) n -Cy-O-R f1 , -(CH2) n -Cy-(CH2) n -O-R f1 , -Cy-O-R f1 , -Cy-(CH2) n -O-R f1 , -Cy-(CH2) n -Cy-O-R f1 、 -(CH2) n -N(R’)-R f1 、 -(CH2) n -Cy-N(R’)-R f1 、 -(CH2) n -Cy-(CH2)n-N(R’)-R f1 、 -Cy-N(R’)-R f1 、 -Cy-(CH2) n -N(R’)-R f1 、 -Cy-(CH2) n -Cy-N(R’)-R f1 、 [wherein, n is an integer of 1 to 40, Cy is a hydrocarbon aromatic ring or a heterocyclic ring, R’ is a hydrogen atom or an organic group, and R f1 is -CF3, -CF2H, or -CFH2.] Examples thereof include certain compounds and the like.

[0099] More specific examples of the compound (b) include trifluoromethoxyalkyl carboxylic acid, trifluoromethoxyalkyl carboxylic acid halide, trifluoromethoxybenzoic acid, trifluoromethoxybenzoic acid halide, trifluoromethoxyphenylacetic acid, trifluoromethoxyphenylacetic acid halide, trifluoromethoxyalkylamine, trifluoromethoxyaniline, trifluoromethoxyalkyl alcohol, trifluoromethoxyphenol, trifluoromethoxyalkyl isocyanate CF3-O-CF2-R 2 -OH CF3-O-R 1 -O-CF2-R 2 -OH CF3-O-R1 -CF2-O-R 2 -OH CF3-O-Ph-O-CF2-R 2 -OH CF3-O-Ph-CF2-O-R 2 -OH R 3 -O-CF2-R 2 -OH R 3 -CF2-O-R 2 -OH (Here, R1 to R3 are independently hydrocarbon groups having 1 to 40 carbon atoms.) etc. can be mentioned.

[0100] [Example of the production method of compound (b)] In this method, a compound (111) having a hydroxyl group and an olefin: HO-R j33 -CH=CH2 is used as a raw material to synthesize a trifluoromethoxy group-containing compound. Here, R j33 is an alkylene group, for example, a C1-30 alkylene group.

[0101] Examples of the olefin group-containing compound include 3-hydroxypropene, 4-hydroxy-1-butene, 5-hydroxy-1-pentene, 6-hydroxy-1-hexene, 7-hydroxy-1-heptene, 8-hydroxy-1-octene, 9-hydroxy-1-nonene, 10-hydroxy-1-decene, 11-hydroxy-1-undecene, 12-hydroxy-1-dodecene, 13-hydroxy-1-tridecene, 14-hydroxy-1-tetradecene, 15-hydroxy-1-pentadecene, 16-hydroxy-1-hexadecene, 17-hydroxy-1-heptadecene, 18-hydroxy-1-octadecene, 19-hydroxy-1-nonadecene, 20-hydroxy-1-icosene, 21-hydroxy-1-heneicosene, 24-hydroxy-1-tetracosene, 30-hydroxy-1-triacontene, etc.

[0102] To the hydroxyl group of compound (111), carbon disulfide is allowed to act in the presence of a base such as sodium hydride, and iodomethane is added to obtain xanthogenic acid ester (112): H3CS-C(=S)-O-R j33 -COOR j32 wherein R j32 is a lower alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, specifically a methyl group or a tert-butyl group. By allowing hydrogen fluoride pyridine and 1,3-dibromo-5,5-dimethylhydantoin to act on the above xanthogenic acid ester (102), the target trifluoromethoxy group-containing compound (113): F3CO-R j33 -CH=CH2 is obtained.

[0103] Alternatively, as another method, to the hydroxyl group of compound (111), in the presence of cesium fluoride, tetrabutylammonium bromide, etc., in an aprotic polar solvent such as NMP, DMF, HMPA (hexamethylphosphoric triamide), an arylsulfonic acid trifluoromethyl ester is allowed to act to obtain the target trifluoromethoxy group-containing compound (113): F3CO-R j33 -CH=CH2.

[0104] The obtained F3CO-R j33 -CH=CH2 can be converted to F3CO-R j33 CH2CH2-OH by a conventional method. Further, it may be reacted with a compound having an ethylenically unsaturated polymerizable group. For example, a (meth)acrylate monomer can be synthesized by reaction with (meth)acrylic acid. By reacting with a (meth)acrylate containing an isocyanate group, a (meth)acrylate monomer containing a urethane group can be synthesized. An alcohol and methyl acrylate may be reacted in the presence of a basic catalyst (for example, calcium hydroxide) to obtain a fluorine-containing acrylate.

[0105] Here, F3CO-R j33As other production methods of CH2CH2-OH, as described in WO2020 / 168011Al etc., silver triflate, potassium fluoride, 1-(chloromethyl)-4-fluoro-4-diazoniabicyclo[2.2.2]octane, a salt of tetrafluoroborate, and benzyloxy alcohol (for example, benzyloxyethanol) are reacted, and the resulting product (for example, [2-(trifluoromethoxy)ethoxy]methyl]benzene) is synthesized by performing hydrogen reduction under a palladium catalyst. F3CO-R j33 CH2CH2-OH can further synthesize a (meth)acrylate monomer by reaction with (meth)acrylic acid. By reacting with a (meth)acrylate containing an isocyanate group, a (meth)acrylate monomer containing a urethane group can be synthesized. An alcohol and methyl acrylate may be reacted in the presence of a basic catalyst (for example, calcium hydroxide) to obtain a fluorine-containing acrylate.

[0106] [Other parts] In addition to the above-described structure, the fluorine-containing compound may have a modifying group for compound (a) (for example, -Y f -Z f n or other modifying groups). Examples of the modifying group are an anionic group, a cationic group, and a monovalent hydrocarbon group having 2 or more and 40 or less carbon atoms.

[0107] Examples of the anionic group include monomers having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0108] Examples of the salt of the anionic group include an alkali metal salt, an alkaline earth metal salt, or an ammonium salt, for example, a methylammonium salt, an ethanolammonium salt, a triethanolammonium salt, etc.

[0109] Examples of the cationic group include an amino group, preferably a tertiary amino group and a quaternary amino group. In the tertiary amino group, the two groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an arylaliphatic group having 7 to 25 carbon atoms (especially an aralkyl group such as a benzyl group (C6H5-CH2-)). In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an arylaliphatic group having 7 to 25 carbon atoms (especially an aralkyl group such as a benzyl group (C6H5-CH2-)). In the tertiary amino group and the quaternary amino group, the remaining one group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0110] The cationic group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids such as carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred.

[0111] The monovalent hydrocarbon group having 2 or more and 40 or less carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and may be an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched or linear, for example, linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group may be a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms of the hydrocarbon group may be 2 or more, 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, 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.

[0112] 〔Method for producing fluorine-containing compound〕 The fluorine-containing compound can be obtained by reacting compound (a) with compound (b). The reaction conditions can be appropriately determined by those skilled in the art. The active hydrogen of compound (a) may react with the active hydrogen-reactive group of compound (b) to form a fluorine-containing compound. Alternatively, in the presence of compound (a), compound (b) may be graft polymerized together with an appropriate catalyst (for example, a polyvalent ion selected from Ce 4+ 、V 5+ 、Cr 6+ and Mn 3+ ). For example, the Grafting-to method, Grafting-from method, etc., well-known to those skilled in the art can be used. Regarding graft polymerization, reference can be made to textbooks such as "Principles of Polymerization" (G.G. Odian, Wiley Interscience, 1991, Third Edition, pages 715-725).

[0113] <Water and oil repellent> The water and oil repellent in the present disclosure imparts liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to a substrate (for example, a fiber substrate, a paper substrate), and can function as at least one selected from the group consisting of a water repellent, an oil repellent, an oil resistant agent, and a water resistant agent. The water and oil repellent in the present disclosure can preferably impart oil resistance (oil repellency) and / or water resistance (water repellency) to the substrate, and can preferably impart both oil resistance and water resistance, for example.

[0114] 〔Fluorine-containing compound〕 The water and oil repellent of the present disclosure contains the above-mentioned fluorine-containing compound. The fluorine-containing compound itself may be used as a water and oil repellent, or may be used as a water and oil repellent in combination with other components as described below.

[0115] The water and oil repellent in the present disclosure is the above-mentioned Rf 1 or Rf 2It contains a fluorine-containing compound having []. On the other hand, the water and oil repellent agent in the present disclosure may not have any selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 4 or more carbon atoms, a compound having a fluoroalkyl group with 2 or more carbon atoms, and a compound having a perfluoroalkyl group with 2 or more carbon atoms. The water and oil repellent agent in the present disclosure can impart liquid repellency to the substrate even without containing these fluorine compounds. In the present specification, the fluoroalkyl group may be intended to be a group in which one or more hydrogen atoms at each carbon atom of the alkyl group are substituted with fluorine atoms.

[0116] [Amount of fluorine-containing compound] The amount of the fluorine-containing compound 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 in the water and oil repellent agent, and may also be 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. The fluorine-containing compound itself may be used as the water and oil repellent agent.

[0117] [Other water and oil repellent agent components] The water and oil repellent agent of the present disclosure may contain other water and oil repellent agent components. As other water and oil repellent agents, known water and oil repellent agents can be used, for example, non-fluorine water and oil repellent agent components. Examples of non-fluorine water and oil repellent agent components include acrylic polymers described in, for example, WO / 2020 / 054856, WO / 2017 / 159754, WO / 2020 / 162547, etc., polyurethanes described in, for example, JP-T-2016-524628, JP-T-2017-533976, JP-T-2017-504730, WO / 2021 / 132170, WO / 2021 / 132172, etc., and natural product modifiers described in, for example, WO / 2022 / 065382 and WO / 2022 / 065385, etc., but are not limited thereto.

[0118] [Amount of other water- and oil-repellent agent components] The amount of other water- and oil-repellent agent components may be 0.01 part by weight or more, 0.1 part 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 with respect to 100 parts by weight of the fluorine-containing compound, and may also 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.

[0119] [Dispersant] The water- and oil-repellent agent of the present disclosure may contain a dispersant.

[0120] The dispersant is selected from an organic dispersant and an inorganic dispersant. It may be at least one kind. The dispersant may be nonionic, and may be at least one kind selected from a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant. The water- and oil-repellent agent may not contain an anionic dispersant.

[0121] Each of the organic dispersant and the inorganic dispersant may be used as the dispersant, or a combination of the organic dispersant and the inorganic dispersant may be used.

[0122] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may mean a surfactant.

[0123] The dispersant may be non-fluorine.

[0124] [Nonionic dispersant] The dispersant may contain a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant. ]

[0125] 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, and may also be 100000 or less, 50000 or less, 25000 or less, 10000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0126] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0127] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0128] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1- to 6-valent (especially 2- to 5-valent) alcohols having 1 to 50 carbon atoms (especially 10 to 30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0129] Examples of ester ethers are compounds obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1- to 6-valent (especially 2- to 5-valent) alcohols having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0130] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamine. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 1 to 3 amino groups and 1 to 5 hydroxyl groups and having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0131] The polyol may be an alcohol having 2 to 5 hydroxyl groups and 10 to 30 carbon atoms. The amine oxide may be an oxide (e.g., having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0132] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of the alkylene group in 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.

[0133] 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.

[0134] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (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 adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Also, the nonionic dispersant may not contain an aromatic group.

[0135] The nonionic dispersant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [wherein R 1 is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group, each of R 2 is independently the same or different and is an alkylene group having 3 or more (e.g., 3 to 10) carbon atoms, R 3 is 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 of 2 or more, q is 0 or a number of 1 or more.] It may be a compound represented by

[0136] R 1 is preferably 8 to 20, particularly 10 to 18 carbon atoms. Preferred specific examples of R 1 include a lauryl group, a tridecyl group, and an oleyl group. Examples of R 2 are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (e.g., 5 to 200). q may be a number of 2 or more (e.g., 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, among which an oxypropylene chain is preferred.

[0137] Specific examples of the nonionic dispersant include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C12 -C 16 ) Thiol, sorbitan mono-fatty acid (C7-C 19 ) or alkyl (C 12 -C 18 ) 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. are included.

[0138] The proportion of the polyoxyethylene block can be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single kind or a mixture of two or more kinds. The nonionic dispersant may be a mixture of a compound with an HLB (hydrophilic-lipophilic balance) of less than 15 (particularly 5 or less) and a compound with an HLB of 15 or more.

[0139] [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 type (for example, molecular weight 2000 or less, particularly 10000 or less) or of high molecular weight type (for example, molecular weight 2000 or more). The cationic dispersant may be a compound having no amide group.

[0140] 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, and may also be 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0141] The cationic dispersant may be an amine salt, a quaternary ammonium salt, or an oxyethylene-added type ammonium salt. Specific examples of the cationic dispersant are not particularly limited, and include amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc., and quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride.

[0142] Preferred examples of the cationic dispersant are R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 are hydrocarbon groups having 1 to 40 carbon atoms, X is an anionic group.] which is a compound represented by R 21 , R 22 , R 23 and -R 24 Specific examples of are alkyl groups (for example, methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogen (for example, chlorine), acid (for example, hydrochloric acid, acetic acid). The cationic dispersant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0143] The cationic dispersant is preferably an ammonium salt. The cationic dispersant has the formula: R 1 p -N + R 2 q X - [wherein, R 1 is a linear and / or branched aliphatic (saturated and / or unsaturated) group having 12 or more carbon atoms (for example, C 12 ~C 50 ), R 2 is H or an alkyl group having 1 to 4 carbon atoms, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (especially 2, particularly 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (for example,), a fatty acid base having 1 to C4,[[]] p is 1 or 2, q is 2 or 3, and p + q = 4.] It may be an ammonium salt represented by. The number of carbon atoms of R 1 may be 12 to 50, for example, 12 to 30.

[0144] Specific examples of the cationic dispersant 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.

[0145] [Anionic dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0146] 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, and may also be 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0147] Examples of the anionic dispersant include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonated fatty acid salts, N-acyl amino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinic acid esters.

[0148] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0149] 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, and may also be 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0150] Examples of the amphoteric dispersant include alanines, imidazolinium betaines, amide betaines, betaine acetates, etc. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, fatty acid amide propyl dimethylaminoacetic acid betaine, etc. may be mentioned.

[0151] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0152] The average primary particle diameter of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may also 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 diameter can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0153] Examples of the inorganic dispersant 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; hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0154] [Amount of dispersant] The amount of the dispersant may be 0.01 part by weight or more, 0.1 part 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, based on 100 parts by weight of the fluorine-containing compound, and may also 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.

[0155] [Liquid medium] The water and oil repellent in the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The water and oil repellent may be a dispersion or a solution. The water and oil repellent in the present disclosure may be a water-dispersed type and may contain at least water.

[0156] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically naphtha, kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., alcohols, polyols such as glycol solvents, ether forms of polyols (e.g., monoether forms), etc.). These may be used alone or in combination of two or more.

[0157] [Amount of liquid medium] The amount of the 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, with respect to 1 part by weight of the fluorine-containing compound, and may also 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.

[0158] 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, with respect to 1 part by weight of the fluorine-containing compound, and may also 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.

[0159] The amount of the 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 with respect to 1 part by weight of the fluorine-containing compound, and may also 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.

[0160] [Silicone] The water and oil repellent agent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, in addition to good liquid repellency, it can also have good texture and durability.

[0161] As the silicone, known silicones can be used. Examples of the silicone include polydimethylsiloxane, modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having a waxy property. These may be used alone or in combination of two or more.

[0162] The weight average molecular weight of the silicone may be 1000 or more, 10000 or more, or 50000 or more, and may also be 500000 or less, 250000 or less, 100000 or less, or 50000 or less.

[0163] [Amount of silicone] The amount of silicone may be 0.1 part 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 with respect to 100 parts by weight of the fluorine-containing compound, and may also 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, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0164] 〔Wax〕 The water and oil repellent in the present disclosure may contain wax. By containing wax, liquid repellency can be favorably imparted to the substrate.

[0165] Examples of wax include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (such as polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, and mineral wax. Paraffin wax is preferred. Specific examples of the compounds constituting the wax are normal alkanes (for example, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), normal alkenes (for example, 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 1-hentriacontene, 1-dotriacontene, 1-tritriacontene, 1-tetratriacontene, 1-pentatriacontene, 1-hexatriacontene). The carbon number of the compounds constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, 300 to 1000. These may be used alone or in combination of two or more.

[0166] The melting point of the wax may be 40°C or higher, 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher, preferably 55°C or higher, more preferably 60°C or higher, and may also be 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower, preferably 120°C or lower. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0167] [Amount of wax] The amount of wax may be 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more, and may also be 500 part by weight or less, 300 part by weight or less, 200 part by weight or less, 100 part by weight or less, 50 part by weight or less, 40 part by weight or less, 30 part by weight or less, 20 part by weight or less, 10 part by weight or less, 5 part by weight or less, based on 100 parts by weight of the fluorine-containing compound.

[0168] [Organic acid] The water and oil repellent of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred examples of the organic acid include carboxylic acids, sulfonic acids, sulfinic acids, etc., and carboxylic acids are particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., and formic acid or acetic acid is particularly preferred. In the present disclosure, one kind of organic acid may be used, or two or more kinds may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0169] [Amount of organic acid] The amount of the organic acid may be 0.1 part 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, based on 100 parts by weight of the fluorine-containing compound. Also, it 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, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of the organic acid may be adjusted so that the pH of the water and oil repellent is 3 to 10, for example 5 to 9, particularly 6 to 8. The water and oil repellent may be acidic (pH 7 or less, for example 6 or less).

[0170] 〔Hardening agent〕 The water and oil repellent of the present disclosure may contain a hardening agent (active hydrogen reactive compound or active hydrogen-containing compound).

[0171] The hardening agent (crosslinking agent) in the water and oil repellent can cure the fluorine-containing compound well. The hardening agent may be an active hydrogen reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen reactive group of the fluorine-containing compound. Examples of the active hydrogen reactive compound are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0172] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, it may be a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate groups of the isocyanate compound are masked with a blocking agent to suppress the reaction.

[0173] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as 2,6-diisocyanatomethyl caproate, and lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane and other aliphatic triisocyanates. These may be used alone or in combination of two or more.

[0174] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates are 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0175] Examples of araliphatic polyisocyanates are araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates are 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0176] Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc. These may be used alone or in combination of two or more.

[0177] Derivatives of polyisocyanates include, for example, various derivatives such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretoimines, isocyanurates, iminooxadiazinediones, etc. of the above-mentioned polyisocyanate compounds. These may be used alone or in combination of two or more.

[0178] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound obtained by blocking the isocyanate groups of the polyisocyanate compound with a blocking agent. It is preferable to use the blocked polyisocyanate compound because it is relatively stable in solution and can be used even in the same solution as the water and oil repellent.

[0179] The blocking agent blocks the free isocyanate groups. The blocked polyisocyanate compound can regenerate the isocyanate groups and react easily with hydroxyl groups, for example, by heating to 100 °C or higher, for example, 130 °C or higher. Examples of the blocking agent are phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compounds can be used alone or in combination of two or more.

[0180] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound are epoxy compounds having a polyoxyalkylene group, for example, polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether, etc. The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound are chloromethyl polystyrene, etc. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound are (poly)acrylic acid, (poly)methacrylic acid, etc.

[0181] Specific examples of the ketone group-containing compound include (poly) diacetone acrylamide, diacetone alcohol, and the like. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like. Specific examples of the melamine compound include melamine resin, methyl etherified melamine resin, and the like.

[0182] [Amount of curing agent] The amount of the curing agent may be 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, or 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more, based on 100 parts by weight of the fluorine-containing compound, and may also 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, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0183] [Other components] The water and oil repellent may contain other components other than the above components. Examples of other components include polysaccharides, paper strength enhancers, flocculants, yield improvers, coagulants, binder resins, slip preventers, sizing agents, paper strength enhancers, PVA, penetrants, organic acids, pigments, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, and the like. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components may include other water-repellent and / or oil-repellent agents, dispersants, texture modifiers, softeners, flame retardants, paint fixatives, anti-wrinkle agents, drying rate adjusters, crosslinking agents, film-forming aids, compatibilizers, anti-freezing agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, anti-shrinkage agents, anti-washing wrinkle agents, shape retainers, drape retention agents, ironing property improvers, brightening agents, whitening agents, fabric softening clay, migration inhibitors such as polyvinylpyrrolidone, polymer dispersants, soil release agents, scum dispersants, fluorescent brightening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, anti-foaming agents, silk protein powder, their surface modified products or emulsion dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical Co., Ltd.), hydrolyzed silk solution (Jomo), Silkgen G Soluble S (Ichimaru Pharcos)) that can impart silk-like texture and functions such as water absorption and release, anti-pollution agents (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Gohou Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan Co., Ltd., etc.). These may be used alone or in combination of two or more.

[0184] [Polysaccharides] Examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofiber, cellulose nanofiber, and pullulan, etc. The polysaccharides may be substituted modified polysaccharides, particularly modified polysaccharides into which a hydroxyl group or a cationic group has been introduced.

[0185] [Paper strength enhancer, flocculant, yield improver or coagulant] Examples of paper strength enhancers, flocculants, yield improvers or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamideamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide-formalin condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers, etc.

[0186] [Sizing agent] Examples of sizing agents include cellulose-reactive sizing agents, such as rosin-based sizing agents like rosin soap, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, such as emulsions / dispersions of acid anhydrides like alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and multimers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, such as copolymers of styrene and acrylate.

[0187] [Antistatic agent] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives, etc. Ion conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, and zwitterionic ion conductive groups may also be used. These may be used alone or in combination of two or more.

[0188] [Preservative] Preservatives can be mainly used to enhance the preservative power and bactericidal power and maintain the preservative property during long-term storage. Examples of preservatives include isothiazolone-based organosulfur compounds, benzisothiazolone-based organosulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, etc.

[0189] [UV absorber] UV absorbers are agents that have the effect of protecting against ultraviolet rays and are components that absorb ultraviolet rays and convert them into and emit infrared rays, visible light, etc. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole-based compounds, 4-t-butyl-4'-methoxybenzoylmethane, etc.

[0190] [Antibacterial agent] Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors derived from decomposition products of microorganisms. Examples of antibacterial agents include cationic bactericides such as quaternary ammonium salts, zinc bis-(2-pyridylthio-1-oxide), polyhexamethylene biguanide hydrochloride, 8-hydroxyquinoline, polylysine, etc.

[0191] [Deodorant] Examples of the deodorant include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, aminocarboxylic acid-based metal complexes (zinc complex of trisodium methylglycinediacetate described in International Publication No. 2012 / 090580), and the like.

[0192] [Amount of other components] The amount of each or the total amount of other components may be 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more, and may also be 500 part by weight or less, 300 part by weight or less, 200 part by weight or less, 100 part by weight or less, 50 part by weight or less, 40 part by weight or less, 30 part by weight or less, 20 part by weight or less, 10 part by weight or less, or 5 part by weight or less, based on 100 parts by weight of the fluorine-containing compound.

[0193] <Method for manufacturing a treated fiber product or paper product> The method for manufacturing a product treated with the water and oil repellent according to the present disclosure includes a treatment step of treating a substrate with the above-described water and oil repellent.

[0194] "Treatment" means applying the water and oil repellent to the substrate by dipping, spraying, coating, or the like. By the treatment, the fluorine-containing compound, which is the active ingredient of the water and oil repellent, adheres to the inside and / or surface of the substrate. Here, the adhesion may be physical adhesion or chemical adhesion. For example, the fluorine-containing compound may be physically or (reactively) chemically modified to the hydroxyl group of the substrate (fiber, paper, glass, etc.).

[0195] [Substrate] The substrate to be treated with the water and oil repellent according to the present disclosure is not limited, but is preferably a fiber product or a paper product, particularly a paper product.

[0196] The water and oil repellent agent in the present disclosure imparts liquid repellency to a substrate (e.g., a fiber substrate, a paper substrate), and can function as at least one selected from the group consisting of a water repellent agent, an oil repellent agent, an oil resistant agent, and a water resistant agent. The substrate treated with the water and oil repellent agent in the present disclosure is, for example, oil-resistant paper or water-resistant paper.

[0197] Examples of the substrate of a fiber product include animal and plant natural fibers such as cotton, hemp, 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 fiber, carbon fiber, and asbestos fiber, or mixed fibers thereof. Fiber products include woven fabrics, knitted fabrics, and non-woven fabrics, fabrics in the form of clothing (e.g., water-repellent clothing, e.g., raincoats), and carpets. However, the fibers, yarns, and intermediate fiber products (e.g., slivers or roving, etc.) in the state before being made into a fabric may also be treated.

[0198] Examples of the substrate of a paper product include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp, or thermomechanical pulp, waste paper pulp such as newspaper waste paper, magazine waste paper, cardboard waste paper, or deinked waste paper, paper containers made of paper, molded bodies made of paper, etc. Specific examples of paper products include food packaging materials, food containers, base paper for gypsum board, coated base paper, medium paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal laminated paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper, molded paper (molded containers), etc. Preferred examples include food packaging materials and food containers.

[0199] The base materials to be treated with the water- and oil-repellent agent of the present disclosure are not limited to textile products or paper products, and other examples include stone, filters (e.g., electrostatic filters), dust masks, parts of fuel cells (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster, etc.

[0200] When the base material is glass, the glass product to be manufactured may be an optical member. Some layer (or film), such as a hard coat layer or an antireflection layer, etc., may be formed on the surface (outermost layer) of the glass base material. Either a single-layer antireflection layer or a multilayer antireflection layer may be used for the antireflection layer. Examples of inorganic substances that can be used for the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic substances may be used alone or in combination of two or more thereof (e.g., as a mixture). When forming a multilayer antireflection layer, it is preferable to use SiO2 and / or SiO for its outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, etc., may be provided on a part of the surface of the base material (glass). Further, depending on its specific specifications, etc., the base material may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a fogging film layer, a hard coating film layer, a polarizing film, a retardation film, and a liquid crystal display module, etc.

[0201] [Treatment method] The water and oil repellent of the present disclosure can be applied to a substrate by a conventionally known method as a treatment agent (especially a surface treatment agent). As a treatment method, the water and oil repellent in the present disclosure can be dispersed and diluted in an organic solvent or water if necessary, and then adhered to the inside and / or surface of the substrate by a known method such as dip coating, spray coating, foam coating, etc., and then dried. After drying, a product with the solid component in the water and oil repellent adhered thereto can be obtained. Further, if necessary, it may be applied together with a suitable crosslinking agent and cured. To the water and oil repellent of the present disclosure, if necessary, further, a water and / or oil repellent, an anti-slip agent, an antistatic agent, a handle modifier, a softener, an antibacterial agent, a flame retardant, a paint fixing agent, an anti-wrinkle agent, a drying rate adjuster, a crosslinking agent, a film-forming aid, a compatibilizer, an antifreezing agent, a viscosity modifier, an ultraviolet absorber, an antioxidant, a pH adjuster, an insect repellent, an antifoaming agent, and other various additives can also be used in combination. Examples of the various additives may be the same as those described in the "other components" in the above description. The concentration of the water and oil repellent in the treatment agent in contact with the substrate may be appropriately changed depending on the use, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0202] The water and oil repellent can be applied to the substrate by any of the methods known for treating the substrate with a liquid. The substrate may be immersed in the water and oil repellent, or a solution may be adhered or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating in order to exhibit liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (for example, 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the substrate is paper, it may be coated on the paper, or a solution may be adhered or sprayed onto the paper, or it may be treated by mixing with the pulp slurry before papermaking. The treatment may be an external addition treatment or an internal addition treatment. Alternatively, the water and oil repellent may be applied to the fiber product by a cleaning method, for example, applied to the fiber product in a washing application or a dry cleaning method, etc.

[0203] [Treatment of Paper Products] Examples of the paper base material include paper, paper-made containers, and paper-made molded articles (e.g., pulp moldings). The fluorine-containing compound of the present disclosure adheres well to the paper base material.

[0204] Paper can be manufactured by a conventionally known papermaking method. An internal addition treatment method of adding a water and oil repellent to the pulp slurry before papermaking or an external addition treatment method of applying a water and oil repellent to the paper after papermaking can be used.

[0205] The size press of the external addition treatment method can also be classified as follows according to the coating method. One coating method is a so-called pond type two-roll size press in which a coating liquid (size liquid) is supplied to a nip portion formed by passing paper between two rubber rolls to create a coating liquid reservoir called a pond, and the size liquid is applied to both sides of the paper by passing the paper through this coating liquid reservoir. Another coating method is a gate roll type in which the size liquid is applied by a surface transfer type, and a rod metering size press. In the pond type two-roll size press, the size liquid easily penetrates into the paper, and in the surface transfer type, the size liquid components tend to remain on the surface of the paper. The surface transfer type has a coating layer that tends to remain on the surface of the paper compared to the pond type two-roll size press, and the coating layer formed on the surface is more than that of the pond type two-roll size press. In the present disclosure, the performance can be imparted to the paper even when the former pond type two-roll size press is used. The paper treated in this way can show excellent oil resistance and water resistance, etc. by undergoing a heat treatment that can optionally take a temperature range of up to 300°C, for example up to 200°C, particularly 80°C to 180°C, depending on the properties of the paper, after simple drying at room temperature or high temperature.

[0206] The internal addition treatment method may mean a treatment method of adding a water- and oil-repellent agent to the pulp slurry before papermaking. As the internal addition treatment method, it may include one or more of the steps of adding a water- and oil-repellent agent to the pulp slurry and stirring and mixing it, sucking and dehydrating the pulp composition prepared in the step through a reticular body of a predetermined shape to deposit the pulp composition to form an intermediate pulp mold, and molding and drying the intermediate pulp mold with a heated mold to obtain paper, a container made of paper, or a molded body made of paper, but it is not limited thereto. The treated paper may be optionally heat-treated depending on the properties of the paper after simple drying at room temperature or high temperature. The temperature of the heat treatment may be 150 °C or higher, 180 °C or higher, or 210 °C or higher, and may also be 300 °C or lower, 250 °C or lower, or 200 °C or lower, particularly 80 °C to 180 °C. By performing the heat treatment within such a temperature range, excellent oil resistance, water resistance, etc. can be exhibited.

[0207] The present disclosure can be used in gypsum board base paper, coated base paper, medium paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner and metal laminated paper, kraft paper, etc. It can also be used in neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper.

[0208] As the pulp raw material, bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp or thermomechanical pulp, etc. Either bleached or unbleached high-yield pulp, waste paper pulp such as newspaper waste paper, magazine waste paper, cardboard waste paper or deinked waste paper can be used. In addition, a mixture of the above pulp raw materials and synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, polyvinyl alcohol, etc. can also be used.

[0209] The water resistance of paper can be improved by adding a sizing agent. Examples of sizing agents are cationic sizing agents, anionic sizing agents, rosin sizing agents (e.g., acidic rosin sizing agents, neutral rosin sizing agents). The amount of the sizing agent may be 0.01 to 5% by weight based on the pulp.

[0210] If necessary, for paper, as papermaking chemicals used to a normal extent, additives used in the production of paper such as starch, modified starch, carboxymethyl cellulose, paper strength enhancers such as polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, yield improvers, dyes, fluorescent dyes, slime control agents, defoaming agents, etc. can be used. It is preferable to use starch and modified starch. If necessary, a water and oil repellent can be applied to the paper by a size press, a gate roll coater, a blade coater, a calendar, etc. using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc.

[0211] In external addition, the amount of the fluorine-containing compound contained in the coating layer is 0.01 to 2.0 g / m 2 and particularly preferably 0.1 to 1.0 g / m 2 . The coating layer is preferably formed by a water and oil repellent, starch and / or modified starch. The solid content of the water and oil repellent for paper in the coating layer is preferably 2 g / m 2 or less. In internal addition, it is preferable to mix a water and oil repellent with the pulp so that the amount of the water and oil repellent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, particularly 0.2 to 5.0 parts by weight, based on 100 parts by weight of the pulp forming the paper.

[0212] In external addition, by storing a treatment liquid between rolls and passing the base paper through the treatment liquid between the rolls at an arbitrary roll speed and nip pressure using a so-called pond type two-roll size press treatment, oil resistance can also be imparted to the paper.

[0213] In the external addition treatment, the paper base material may contain additives such as sizing agents, paper strength enhancers, flocculants, yield improvers, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives is -10000 to 10000 μeq / g, preferably -4000 to 8000 μeq / g, and more preferably -1000 to 7000 μeq / g. The additives (for example, sizing agents, paper strength enhancers, flocculants, yield improvers, or coagulants, etc., for example, solids or active ingredients) can generally be used in an amount of 0.1 to 10% by weight (for example, from 0.2 to 5.0% by weight) based on the pulp. In the case of a paper base material containing a cationic additive (for example, sizing agent, paper strength enhancer, flocculant, yield improver, or coagulant), the water and oil repellent may be anionic, and in the case of containing anionic additives, the water and oil repellency may be cationic, but it is not limited thereto.

[0214] In the internal addition treatment, it is preferable to form paper from a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight). Additives (for example, sizing agents, paper strength enhancers, flocculants, yield improvers, or coagulants, etc.) and fluorine-containing compounds can be added to the pulp slurry. Examples of the additives (for example, sizing agents, paper strength enhancers, flocculants, yield improvers, or coagulants, etc.) include alkyl ketene dimer, alkenyl succinic anhydride, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamideamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide-formalin condensates, dimethyldiallylammonium chloride polymers, olefin / maleic anhydride polymers.

[0215] In the internal addition treatment, the paper base material may contain additives such as sizing agents, paper strength enhancers, flocculants, yield agents or coagulants. The additives may be nonionic, cationic, anionic or amphoteric. The ionic charge density of the additives may be -10000 to 10000 μeq / g, preferably -4000 to 8000 μeq / g, and more preferably -1000 to 7000 μeq / g. The additives (for example, sizing agents, paper strength enhancers, flocculants, yield agents or coagulants, etc. For example, solid content or active ingredient) can generally be used in an amount of 0.1 to 10% by weight (for example, 0.2 to 5.0% by weight) with respect to the pulp. In the case of a paper base material containing a cationic additive (for example, sizing agent, paper strength enhancer, flocculant, yield agent or coagulant), the water and oil repellent may be anionic, and in the case of containing an anionic additive, the water and oil repellent may be cationic, but it is not limited thereto.

[0216] [Pretreatment of Fiber Products] The fiber product may be pretreated before being treated with the water and oil repellent of the present disclosure. By performing the pretreatment of the fiber product, excellent fastness can be imparted to the fiber product after being treated with the water and oil repellent.

[0217] Examples of the pretreatment of the fiber product include cationization treatment by reaction with a reactive quaternary ammonium salt, anionic treatment such as sulfonation, carboxylation, phosphorylation, etc., acetylation treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, polymer coating treatment, etc. after the anionic treatment.

[0218] As a method for pretreating the fiber product, although not limited, the fiber product can be pretreated by a conventionally known method. The pretreatment liquid is dispersed and diluted in an organic solvent or water as necessary, and adhered to the inside and / or surface of the fiber product by a known method such as dipping coating, spray coating, foam coating, etc., and then dried. The pH and temperature of the pretreatment liquid may be adjusted according to the required degree of treatment. As an example of the method for pretreating the fiber product, the method for pretreating the fiber product with the above-mentioned treatment agent will be described in detail.

[0219] The pretreatment method of the fiber product is to attach -SO3M 1 (wherein M 1 represents a monovalent cation), a monovalent group represented by -COOM 2 (wherein M 2 represents a monovalent cation), and -O-P(O)(OX 1 )(OX 2 (wherein X 1 and X 2 each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms)), and one or more functional groups selected from the group consisting of monovalent groups (hereinafter, may also be referred to as "specific functional groups") may be provided.

[0220] Examples of M 1 include H, K, Na, or an ammonium ion which may have a substituent. Examples of M 2 include H, K, Na, or an ammonium ion which may have a substituent. When X 1 or X 2 is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0221] The fiber containing the above specific functional group (hereinafter, may also be referred to as "functional group-containing fiber") can be prepared, for example, by the following method. (i) A compound having the above specific functional group is attached to the fiber material. Note that the attachment of the compound may be in a state where a part of the compound and a part of the fiber are chemically bonded within a range where a sufficient amount of the above specific functional group remains. (ii) A fiber in which the above specific functional group is directly introduced into the material constituting the fiber is prepared.

[0222] In the case of (i), for example, a functional group-containing fiber can be obtained by a functional group introduction step of treating the fiber material with a pretreatment liquid containing one or more compounds having the above specific functional group.

[0223] The material of the fiber material is not particularly limited, and examples include natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any form such as fiber (tow, sliver, etc.), yarn, knitted fabric (including interlaced knitting), woven fabric (including interlacing), and non-woven fabric.

[0224] In this embodiment, from the viewpoint of improving the water repellency of the obtained fiber product, it is preferable to use a fiber material containing polyamide and polyester as materials, and in particular, nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these are preferably used.

[0225] The above -SO3M 1 As the compound having, a phenolic polymer can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.

[0226] TIFF2025111538000001.tif4770 [In the formula, X 2 represents -SO3M 3 (in the formula, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000. ]

[0227] TIFF2025111538000002.tif2758 [In the formula, M 4 represents a monovalent cation. ]

[0228] The above M 3 Examples of include H, K, Na, or an ammonium ion which may have a substituent.

[0229] The above M 4Examples thereof include H, K, Na, or an ammonium ion which may have a substituent.

[0230] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0231] Examples of the compound having the above -COOM 2 include polycarboxylic acid polymers.

[0232] Examples of the polycarboxylic acid polymer include polymers synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or commercially available products.

[0233] Examples of the method for producing the polycarboxylic acid polymer include a method in which a radical polymerization initiator is added to an aqueous solution of the above monomer and / or its salt, and the mixture is heated and reacted at 30 to 150°C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, and isopropyl alcohol, or aqueous solvents such as acetone may be added to the aqueous solution of the above monomer and / or its salt. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators obtained by combining persulfates with sodium bisulfite, etc., hydrogen peroxide, water-soluble azo polymerization initiators, etc. These radical polymerization initiators may be used alone or in combination of two or more. Further, a chain transfer agent (for example, octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization during radical polymerization.

[0234] In radical polymerization, copolymerizable monomers can be used in addition to the above monomers. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Acrylates and methacrylates preferably have a hydrocarbon group with 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination of two or more.

[0235] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by an alkali metal, an amine compound, or the like. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0236] From the viewpoint of obtaining a fiber product with good water repellency, the weight average molecular weight of the polycarboxylic acid polymer is preferably 1000 to 20000, more preferably 3000 to 15000.

[0237] As the polycarboxylic acid polymer, commercially available products such as "Neocrystar 770" (trade name, manufactured by Nihon Kayaku Co., Ltd.) and "Cellopol PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0238] Examples of the compound having -O-P(O)(OX 1 )(OX 2 ) include, for example, phosphate ester compounds represented by the following general formula. TIFF2025111538000003.tif3136[wherein, X 1 or X 2 has the same meaning as above, X3 represents an alkyl group having 1 to 22 carbon atoms.

[0239] As the above phosphate ester compound, a monoester, diester, and triester of phosphoric acid in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and a mixture thereof can be used.

[0240] From the viewpoint of obtaining a fiber product with good water repellency, it is preferable to use lauryl phosphate ester and decyl phosphate ester.

[0241] As the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.

[0242] The pretreatment liquid containing one or more of the above compounds having a specific functional group can be, for example, an aqueous solution of the above-described compounds. Further, the pretreatment liquid may contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0243] Examples of the method for treating the fiber material with the above pretreatment liquid include padding treatment, dipping treatment, spraying treatment, and coating treatment. Examples of the padding treatment include methods using a padding apparatus described on pages 396 to 397 of the Fiber Dyeing and Finishing Dictionary (published in 1963 by Nikkansen) and pages 256 to 260 of Color Dyeing Chemistry III (published in 1975 by Jitsumyo Publishing Co., Ltd.). Examples of the coating treatment include methods using a coating machine described on pages 473 to 477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Sen'i Shuppan Co., Ltd.). Examples of the dipping treatment include methods using a batch dyeing machine described on pages 196 to 247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Sen'i Shuppan Co., Ltd.), and a liquid flow dyeing machine, an air flow dyeing machine, a drum dyeing machine, a winch dyeing machine, a washer dyeing machine, a cheese dyeing machine, etc. can be used. Examples of the spraying treatment include an air spray in which the treatment liquid is atomized with compressed air and sprayed, and a method using a hydraulic atomization type air spray. The treatment conditions such as the concentration of the treatment liquid at this time and the heat treatment after application can be appropriately adjusted in consideration of various conditions such as the purpose and performance. When the pretreatment liquid contains water, it is preferably dried to remove the water after adhering to the fiber material. The drying method is not particularly limited, and either a dry heat method or a wet heat method may be used. The drying temperature is not particularly limited either, but for example, it may be dried at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes after drying.

[0244] When the fiber material is to be dyed, the treatment with the pretreatment liquid may be performed before dyeing or in the same bath as dyeing. However, when performing reduction soaping, since the compound having the above specific functional group adsorbed in the process (for example, a phenolic polymer compound, etc.) may fall off, it is preferably performed after reduction soaping after dyeing.

[0245] The treatment temperature in the dipping treatment can be 60 to 130°C. The treatment time can be 5 to 60 minutes.

[0246] In the functional group introduction step using the pretreatment liquid, it is preferable to perform the treatment in such an amount that the adhesion amount of the compound having the specific functional group is 1.0 to 7.0 parts by weight with respect to 100 parts by weight of the fiber material. When it is within this range, excellent durable water repellency and texture can be achieved simultaneously.

[0247] The pretreatment liquid may have its pH adjusted to less than 7, for example, to 3 - 5. For pH adjustment, pH adjusters such as acetic acid and malic acid can be used.

[0248] In the pretreatment liquid, salts can also be used in combination to effectively adsorb the compound having the specific functional group to the fiber material by the salting - out effect. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0249] In the functional group introduction step using the pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. Examples of the removal method include washing with water. By performing sufficient removal, it is possible to suppress the inhibition of the development of water repellency in the subsequent water - repellent processing. In addition, the texture of the resulting fiber product becomes good. Also, the obtained functional - group - containing fiber is preferably dried sufficiently before being brought into contact with the above - mentioned treatment agent.

[0250] (ii) Examples of fibers in which the specific functional group is directly introduced into the material constituting the fiber include cation - dyeable polyester (CD - PET).

[0251] From the viewpoint of the excellent water repellency of the resulting fiber product, the zeta potential of the surface of the functional - group - containing fiber is preferably - 100 to - 0.1 mV, and more preferably - 50 to - 1 mV. The zeta potential of the fiber surface can be measured, for example, using a zeta potential - particle size measurement system ELSZ - 1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0252] As described above, although the embodiments have been explained, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

Example

[0253] Hereinafter, the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to these examples.

[0254] <Test method> The test procedure is as follows.

[0255] [Water repellency evaluation (droplet fall test)] A PET cloth (basis weight: 88 g / m 2 , 70 denier, gray) was immersed in a dispersion or solution containing a fluorine-containing compound (fluorine-containing compound concentration: 0.2 g / ml), then passed through a mangle, heated at 70°C for 1 hour to prepare a treated PET cloth. The treated PET cloth was fixed to a base inclined at 30° from the horizontal by a fully automatic contact angle meter (DropMaster701 manufactured by Kyowa Interface Science Co., Ltd.). 20 μL of water was dropped onto the PET cloth from a microsyringe, and it was confirmed whether the dropped water would fall. The case where the droplet falls is evaluated as ○, and the case where the droplet does not move from the dropped position or penetrates into the cloth is evaluated as ×.

[0256] [Oil repellency evaluation (oil resistance test)] (Preparation of treated paper) As wood pulp, a pulp slurry with a weight ratio of LBKP (hardwood bleached kraft pulp) to NBKP (softwood bleached kraft pulp) of 60% by weight and 40% by weight, and a drainage degree of the pulp of 400 ml (Canadian Standard Freeness) was prepared. A wet strength agent and a sizing agent were added to this pulp slurry, and paper with a basis weight of 45 g / m 3 and a paper density of 0.58 g / cm 2 was used as the base paper for external sizing treatment (size press treatment). The oil resistance (KIT value) of this base paper was 0, and the water resistance (Cobb value) was 52 g / m 2 . For this base paper, an aqueous dispersion or aqueous solution containing 1.0 wt% of a fluorine-containing compound was prepared, and the coating was applied using a Baker applicator with a gap set to 0 mil (0 μm) or 7 mil (170 μm), and the drying operation was repeated three times, followed by annealing at 100 °C for 10 minutes to produce a treated paper.

[0257] (Corn oil resistance evaluation) Corn oil was placed on the surface of the treated paper, and when the test oil was wiped off 15 seconds later, it was evaluated based on the presence or absence of oil stain on the treated paper. When there is no back staining, it is marked as 〇, and when back staining is observed, it is marked as ×.

[0258] [Example 1] 5.0 g of polyglycerin (average molecular weight 500, 10 mmol), 20 mL of pyridine, and 7-(trifluoromethoxy)heptanoyl chloride (85 mmol) were added to a reaction vessel, and the mixture was heated and stirred at an oil bath temperature of 60 °C. Liquid separation and purification were performed to obtain a fluorine-containing compound, which is the target polyglycerin derivative. TIFF2025111538000004.tif2035

[0259] [Example 2] The same operations as in Example 1 were performed except that 7-(trifluoromethoxy)heptanoyl chloride was changed to 3-(trifluoromethoxy)propanoyl chloride to obtain a fluorine-containing compound, which is the target polyglycerin derivative. TIFF2025111538000005.tif2028

[0260] [Example 3] The same operations as in Example 1 were performed except that 7-(trifluoromethoxy)heptanoyl chloride was changed to 2-(4-(trifluoromethoxy)phenyl)acetyl chloride to obtain a fluorine-containing compound, which is the target polyglycerin derivative. TIFF2025111538000006.tif2032

[0261] [Example 4] The same operations were carried out as in Example 1, except that 7-(trifluoromethoxy)heptanoyl chloride was changed to 4-(trifluoromethoxy)benzoyl chloride, to obtain the target fluorine-containing compound, which is a polyglycerol derivative. TIFF2025111538000007.tif2531

[0262] [Example 5] The same operations were carried out as in Example 1, except that 7-(trifluoromethoxy)heptanoyl chloride was changed to 7-chloro-7-oxoheptyl (trifluoromethyl)carbamate, to obtain the target fluorine-containing compound, which is a polyglycerol derivative. TIFF2025111538000008.tif2039

[0263] [Example 6] The same operations were carried out as in Example 1, except that 7-(trifluoromethoxy)heptanoyl chloride was changed to 7-((trifluoromethyl)amino)heptanoyl chloride, to obtain the target fluorine-containing compound, which is a polyglycerol derivative. TIFF2025111538000009.tif2545

[0264] [Example 7] 1.8 g of sorbitol (10 mmol), 20 mL of pyridine, and 7-(trifluoromethoxy)heptanoyl chloride (60 mmol) were added to a reaction vessel, and the mixture was heated and stirred at an oil bath temperature of 60 °C. Liquid separation and purification treatments were carried out to obtain the target fluorine-containing compound, which is a sorbitol derivative. TIFF2025111538000010.tif2039

[0265] [Example 8] In Example 7, the same procedure was carried out except that 7-(trifluoromethoxy)heptanoyl chloride was changed to 3-(trifluoromethoxy)propanoyl chloride, and a fluorine-containing compound, which is the target sorbitol derivative, was obtained. TIFF2025111538000011.tif2533

[0266] [Example 9] 2.8 g (15 mmol) of citric acid and 6-(trifluoromethoxy)hexan-1-amine (48 mmol) were added to a reaction vessel equipped with a reflux condenser and a Dean-Stark apparatus, 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, subjected to liquid separation and purification treatments, and a fluorine-containing compound, which is the target citric acid derivative, was obtained. TIFF2025111538000012.tif2036

[0267] [Example 10] In Example 9, the same procedure was carried out except that 6-(trifluoromethoxy)hexan-1-amine was changed to 2-(trifluoromethoxy)ethan-1-amine, and a fluorine-containing compound, which is the target citric acid derivative, was obtained. TIFF2025111538000013.tif2028

[0268] [Example 11] In Example 9, the same procedure was carried out except that 6-(trifluoromethoxy)hexan-1-amine was changed to 4-(trifluoromethoxy)aniline, and a fluorine-containing compound, which is the target citric acid derivative, was obtained. TIFF2025111538000014.tif2530

[0269] [Example 12] The same operations were carried out as in Example 9, except that 6-(trifluoromethoxy)hexan-1-amine was changed to 6-aminohexyl (trifluoromethyl)carbamate, and a fluorine-containing compound, which is the target citric acid derivative, was obtained. TIFF2025111538000015.tif2041

[0270] [Example 13] The same operations were carried out as in Example 9, except that 6-(trifluoromethoxy)hexan-1-amine was changed to N-(trifluoromethyl)hexane-1,6-diamine, and a fluorine-containing compound, which is the target citric acid derivative, was obtained. TIFF2025111538000016.tif2552

[0271] [Example 14] 0.29 g (4.8 mmol) of ethylenediamine, 11 mmol of 7-(trifluoromethoxy)heptanoic acid, 0.12 g of 4,4-dimethylaminopyridine, and chloroform were added, and then 2.1 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide was added. Thereafter, the mixture was heated and stirred at an oil bath temperature of 50°C. After the reaction solution was cooled to room temperature, liquid separation and purification were carried out to obtain a fluorine-containing compound, which is the target ethylenediamine derivative (diamide form). TIFF2025111538000017.tif2043

[0272] [Example 15] The same operations were carried out as in Example 14, except that 7-(trifluoromethoxy)heptanoic acid was changed to 3-(trifluoromethoxy)propanoic acid, and a fluorine-containing compound, which is the target ethylenediamine derivative, was obtained. TIFF2025111538000018.tif2033

[0273] [Example 16] The same procedures were carried out as in Example 14, except that 7-(trifluoromethoxy)heptanoic acid was changed to 2-(4-(trifluoromethoxy)phenyl)acetic acid, to obtain the target fluorine-containing compound, an ethylenediamine derivative. TIFF2025111538000019.tif2037

[0274] [Example 17] The same procedures were carried out as in Example 14, except that 7-(trifluoromethoxy)heptanoic acid was changed to 4-(trifluoromethoxy)benzoic acid, to obtain the target fluorine-containing compound, an ethylenediamine derivative. For this compound, a droplet falling test and an oil resistance test were carried out, and it was confirmed that the results were ○. TIFF2025111538000020.tif3041

[0275] [Example 18] The same procedures were carried out as in Example 14, except that 7-(trifluoromethoxy)heptanoic acid was changed to 7-(((trifluoromethyl)carbamoyl)oxy)heptanoic acid, to obtain the target fluorine-containing compound, an ethylenediamine derivative. TIFF2025111538000021.tif2051

[0276] [Example 19] The same procedures were carried out as in Example 14, except that 7-(trifluoromethoxy)heptanoic acid was changed to 7-((trifluoromethyl)amino)heptanoic acid, to obtain the target fluorine-containing compound, an ethylenediamine derivative. TIFF2025111538000022.tif2044

[0277] [Example 20] 4-(Trifluoromethoxy)phenylacetic Acid (Tokyo Chemical Industry Co., Ltd.), glycerin, and 4,4-dimethylaminopyridine were dissolved in dehydrated toluene, and then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide was added, followed by stirring overnight at an oil bath temperature of 50 °C. After cooling the reaction solution to room temperature and concentrating it, the obtained solid was washed with methanol and diethyl ether, and the solid was dried to obtain a fluorine-containing compound which is a polyol modified product obtained by modifying glycerin with 4-(Trifluoromethoxy)phenylacetic Acid (Tokyo Chemical Industry Co., Ltd.). TIFF2025111538000023.tif2541

[0278] [Example 21] 4-(Trifluoromethoxy)benzoic Acid (Tokyo Chemical Industry Co., Ltd.), glycerin, and 4,4-dimethylaminopyridine were dissolved in dehydrated toluene, and then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide was added, followed by stirring overnight at an oil bath temperature of 50 °C. After cooling the reaction solution to room temperature and concentrating it, the obtained solid was washed with methanol and diethyl ether, and the solid was dried to obtain a fluorine-containing compound which is a polyol modified product obtained by modifying glycerin with 4-(Trifluoromethoxy)benzoic Acid. TIFF2025111538000024.tif3040

[0279] [Example 22] Glycerin, dehydrated toluene, and 4-(Trifluoromethoxy)phenyl Isocyanate (Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60 °C for 1 hour. After confirming the disappearance of 4-(Trifluoromethoxy)phenyl Isocyanate (Tokyo Chemical Industry Co., Ltd.), it was added dropwise to hexane to precipitate a solid. The precipitated solid was collected by suction filtration to obtain a fluorine-containing compound which is a polyol modified product obtained by modifying glycerin with 4-(Trifluoromethoxy)phenyl Isocyanate. TIFF20,251,115,380,000,25.tif3041

[0280] [Example 23] A stir bar, ethylenediamine, toluene, and 4-(Trifluoromethoxy)phenyl Isocyanate were added to a reaction vessel, and 1 drop of dibutyltin dilaurate was added, followed by stirring at 60 °C for 1 hour. After confirming the disappearance of 4-(Trifluoromethoxy)phenyl Isocyanate, it was added dropwise to hexane to precipitate a solid. The precipitated solid was collected by suction filtration to obtain a fluorine-containing compound which is a polyvalent amine modified product obtained by modifying ethylenediamine with 4-(Trifluoromethoxy)phenyl Isocyanate (Tokyo Chemical Industry Co., Ltd.). TIFF20,251,115,380,000,26.tif2536

[0281] [Example 24] After dissolving 4-(Trifluoromethoxy)phenol, citric acid, and 4,4-dimethylaminopyridine in toluene, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide was added, and the mixture was stirred overnight at an oil bath temperature of 50 °C. After cooling the reaction solution to room temperature and concentrating it, the obtained solid was washed with methanol and diethyl ether, and the solid was dried to obtain a fluorine-containing compound which is a polyvalent carboxylic acid modified product obtained by modifying citric acid with 4-(Trifluoromethoxy)phenol. TIFF20,251,115,380,000,27.tif3035

[0282] [Example 25] 5.0 g of monoglycerin, 20 mL of pyridine, and 4-(trifluoromethoxy)benzoyl chloride (85 mmol) are added to a reaction vessel, and the mixture is heated and stirred at an oil bath temperature of 60°C. Liquid separation and purification treatments are performed to obtain a fluorine-containing compound, which is a monoglycerin derivative of the target fluorine-containing compound. A droplet falling test and an oil resistance test are conducted on this compound, and it is confirmed that the result is ○. TIFF2025111538000028.tif2635

[0283] The fluorine-containing compound of the present disclosure imparts good liquid repellency to a substrate.

Claims

1. A moiety derived from a compound (a) having one or more active hydrogen-containing groups selected from a hydroxy group, an amino group, a carboxyl group, and a thiol group, and R ｆ１ or R ｆ２ a moiety derived from compound (b) having A fluorine-containing compound having, R ｆ１ is -CF ３ , -CF ２ H, or -CFH ２ and is R ｆ２ is -CF ２ - or -CFH-, and R ｆ１ and R ｆ２ is a fluorine-containing compound that is not part of a fluoroalkyl group having 2 or more carbon atoms.

2. The aforementioned R ｆ１ has an adjacent position that is an oxygen atom or a nitrogen atom, The aforementioned R ｆ２ The fluorine-containing compound according to claim 1, wherein at least one of the adjacent positions of

3. The aforementioned R ｆ１ is CF ３ -. Said R ｆ２ is -CF ２ -, The fluorine-containing compound according to claim 1 or 2.

4. wherein the compound (b) is Formula: -Y ｆ -Z ｆ α [In the formula, each symbol is independently at each occurrence, Y ｆ is a 1+α-valent group composed of one or more selected from the group consisting of Y ｆ１ and Y ｆ２ and is a 1+α-valent group composed of one or more selected from the group consisting of Y ｆ１ is a group consisting of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ , -N(-) ２ (wherein R' is a hydrogen atom or an organic group), and is a group composed of one or more selected from the group consisting of Y ｆ２ is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, Z ｆ is a hydrocarbon group having 2 to 40 carbon atoms containing R ｆ１ , or R ｆ１ or R ｆ２ and having 2 to 40 carbon atoms α is 1 to 3.] The fluorine-containing compound according to claim 1 or 2, having a group represented by

5. wherein the compound (b) is Formula: -Y ｆ１１ -(Y ｆ２１ -Y ｆ１２ ) β -Y ｆ２２ -Y ｆ１３ -Z ｆ [In the formula, each symbol is independently at each occurrence, Y ｆ１１ is a direct bond, -O-, -NH-, -C(=O)-, -C(=O)-NH- or -S-, Y ｆ２１ is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, Y ｆ１２ is a group composed of one or more selected from the group consisting of -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -NR'-, and -C(OR')R'- (wherein R' is a hydrogen atom or an organic group). β is from 0 to 3, Y ｆ２２ is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, Y ｆ１３ is -O-, -O-C(=O)-O-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-O-, -C(=O)-NR'-, or -SO ２ NR'- (wherein R' is a hydrogen atom or an organic group). Z ｆ is a hydrocarbon group having 2 to 40 carbon atoms and containing R ｆ１ , or R ｆ１ or R ｆ２ . The fluorine-containing compound according to claim 1 or 2, having a group represented by

6. Y ｆ２２ is the formula -Y ｆ２２１ -Y ｆ２２２ - [In the formula, Y ｆ２２１ is either directly bonded or a hydrocarbon group having 2 to 40 carbon atoms, Y ｆ２２２ is a direct bond or a phenylene group. is a group represented by, Y ｆ１３ is -O- or -NR'-(where R' is a hydrogen atom or an organic group), β is 0 or 1, Z ｆ is R ｆ１ The fluorine-containing compound according to claim 5, wherein

7. The fluorine-containing compound according to claim 1 or 2, wherein the compound (b) is an active hydrogen-reactive compound; a polymerizable monomer or a polymer thereof.

8. The fluorine-containing compound according to claim 1 or 2, wherein the compound (a) is a natural product.

9. The fluorine-containing compound according to claim 1 or 2, wherein the compound (a) is a polyol, a polyamine or a polycarboxylic acid.

10. The fluorine-containing compound according to claim 1 or 2, wherein the compound (a) is a monosaccharide, an oligosaccharide, a polysaccharide, a sugar alcohol, a hydroxy acid, an amino acid, a vitamin, a flavonol, a hydroxy hydrocarbon, and a polymer of a hydroxy group-containing compound, an organic acid, an organic amine, or a saturated / unsaturated aliphatic hydrocarbon compound.

11. wherein the compound (a) 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, isomalto-dextrin, gellan gum, tamarind seed gum; ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; glucosamine; inositol; catechin, quercetin, anthocyanin; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; Polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer; Citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aldic acid; Tricarballylic acid, t - aconitic acid, trimellitic acid; Pyromellitic acid, itaconic acid; Alkylenediamine, alkylenetriamine, aromatic diamine; The fluorine - containing compound according to claim 1 or 2, which is a saturated / unsaturated aliphatic hydrocarbon compound having an active hydrogen group.

12. The fluorine - containing compound according to claim 1 or 2, wherein the bio - based degree of the fluorine - containing compound is 20% or more.

13. The fluorine - containing compound according to claim 1 or 2, wherein the weight - average molecular weight is 1000 or more.

14. The fluorine - containing compound according to claim 1 or 2, wherein the weight - average molecular weight is less than 1000.

15. -Y ｆ -Z ｆ ｎ As a modifying group other than the above, having a monovalent hydrocarbon group with 2 to 40 carbon atoms The fluorine - containing compound according to claim 1 or 2.

16. The compound (b) is Formula: -Y ｆ１１ -(Y ｆ２１ -Y ｆ１２ ) β -Y ｆ２２ -Y ｆ１３ -Z ｆ [In the formula, each symbol is independently at each occurrence, Y ｆ１１ is a direct bond, -O-, -NH-, -C(=O)-, -C(=O)-NH- or -S-, Y ｆ２１ is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, Y ｆ１２ is a group composed of one or more selected from the group consisting of -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -NR'-, and -C(OR')R'- (where R' is a hydrogen atom or an organic group). β is from 0 to 3, Y ｆ２２ is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group, Y ｆ１３ is -O-, -O-C(=O)-O-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-O-, -C(=O)-NR'-, or -SO ２ NR'-(wherein R' is a hydrogen atom or an organic group). Z ｆ is -CF ３ .] The fluorine - containing compound according to claim 11, which is a compound having a group represented by.

17. A dispersion containing the fluorine - containing compound according to claim 1 or 2 and a liquid medium.

18. A water - and oil - repellent containing the fluorine - containing compound according to claim 1 or 2.

19. The water - and oil - repellent according to claim 18, which is for fiber products or paper products.

20. A method for producing a treated substrate, which comprises treating a substrate with the water - and oil - repellent according to claim 18.

21. The production method according to claim 20, wherein the substrate is a fiber product or a paper product.

22. A product to which the fluorine - containing compound according to claim 1 or 2 is attached.

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