Fluorine-containing compound

Abstract

This fluorine-containing compound has a moiety derived from an active hydrogen-containing compound (a), a moiety derived from an active hydrogen-reactive compound (b), and-NHCO-derived from the compound (a) and the compound (b). The compound (a) contains a compound (a1) having Rf1 or Rf2, or the compound (b) contains a compound (b1) having Rf1 or Rf2, Rf1 is-CF3,-CF2H, or-CFH2, Rf2 is-CF2-or-CFH-, and Rf1 and Rf2 are not some of a fluoroalkyl group having 2 or more carbon atoms. According to the fluorine-containing compound, a novel fluorine-containing compound is provided.

Description

TECHNICAL FIELD

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

[0002] It is known that certain kinds of non-fluorine polymers are capable of imparting oil resistance when used for surface treatment of a substrate (Patent Literature 1).

[0003] PRIOR ART DOCUMENTS PATENT LITERATURE Patent Literature 1: International Publication No. 2020-054856 SUMMARY

[0004] PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present application is to provide a novel fluorine-containing compound.

[0005] TECHNICAL MEANS FOR SOLVING THE PROBLEMS The present application includes the following modes.

[0006] [Item 1] A fluorine-containing compound having a moiety derived from a compound (a) containing a reactive hydrogen, a moiety derived from a compound (b) reactive to the reactive hydrogen, and -NHCO- derived from the above-mentioned compound (a) and the above-mentioned compound (b), The above-mentioned compound (a) contains a compound (a1) having R f1 or R f2 , or the above-mentioned compound (b) contains a compound (b1) having R f1 or R f2 , 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.

[0007] [Item 2] The fluorine-containing compound according to Item 1, wherein The adjacent position of the above-mentioned R f1 is an oxygen atom or a nitrogen atom, At least one side of the adjacent position of the above-mentioned R f2 is an oxygen atom or a nitrogen atom.

[0008] [Item 3] The fluorine-containing compound according to Item 1 or 2, wherein The above-mentioned R f1 is CF3-, The above-mentioned R f2 is -CF2-.

[0009] [Para 4] The fluorine-containing compound according to any one of Paras 1 to 3, wherein The compound (a) contains an alcohol, The compound (b) contains an isocyanate, The fluorine-containing compound is a polyurethane.

[0010] [Para 5] The fluorine-containing compound according to any one of Paras 1 to 4, wherein The compound (al) or the compound (bl) has a formula: -Y f -Z f α group.

[0011] [Para 6] The fluorine-containing compound according to any one of Paras 1 to 5, wherein Y f is a 1+α-valent group composed of one or more selected from Y f1 and Y f2 , Y f1 is a direct bond, a group composed of one or more selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'- and -C(OR' )2, -N(-)2 (where R' is a hydrogen atom or an organic group), Y f2 is a group composed of one or more selected from an aliphatic group and an aromatic group, Z f is R f1 , or a hydrocarbon group having 2 or more and 40 or less carbon atoms containing R f1 or R f2 , α is 1 to 3. [Para 6] The fluorine-containing compound according to any one of Paras 1 to 5, wherein The compound (al) or the compound (bl) is a compound having a formula: -Y f11 -(Y f21 -Y f12 ) β -Y f22 -Y f13 -Z f group.

[0012] [Para 6] The fluorine-containing compound according to any one of Paras 1 to 5, wherein Y f11 is a direct bond, -O-, -NH- or -C(=O)-, Y f21 is a group composed of one or more selected from an aliphatic group and an aromatic group, Y f12 is a group consisting 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 consisting of one or more selected from the group consisting of aliphatic groups and aromatic groups, 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 a hydrocarbon group having 2 or more and 40 or less carbon atoms containing R f1 or R f2 . [Item 7] The fluorine-containing compound according to Item 6, wherein, Y f22 is a group represented by the formula -Y f221 -Y f222 -Y [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. 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 .

[0013] [Item 8] The fluorine-containing compound according to any one of Items 1 to 7, wherein, the above-mentioned compound (a) comprises the above-mentioned compound (al).

[0014] [Item 9] The fluorine-containing compound according to Item 1 or 2, wherein, the above-mentioned compound (a) comprises a compound having a reactive hydrogen (a2) having a hydrocarbon group having 6 or more and 40 or less carbon atoms.

[0015] [Item 10] The fluorine-containing compound according to Item 9, wherein, the above-mentioned compound (a2) is a sugar alcohol and / or a hydroxy acid modified with a hydrocarbon group having 6 or more and 40 or less carbon atoms.

[0016] [Item 11] The fluorine-containing compound according to any one of Items 1 to 10, wherein The above compound (a) contains other active hydrogen-containing compound (a3).

[0017] [Item 12] The fluorine-containing compound according to Item 11, wherein the above compound (a3) contains a chain extender.

[0018] [Item 13] The fluorine-containing compound according to any one of Items 1 to 12, wherein the above compound (b) is selected from the group consisting of: aromatic polyisocyanate selected from the group consisting of toluene diisocyanate (2,4-toluene diisocyanate, 2,6-toluene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-phenylene diisocyanate, p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-dimethyl diphenyl diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylene diisocyanate (1,3-xylene diisocyanate, 1,4-xylene diisocyanate or a mixture thereof) (XDI), tetramethyl xylene diisocyanate (1,3-tetramethyl xylene diisocyanate, 1,4-tetramethyl xylene diisocyanate or a mixture thereof) (TMXDI), omega, omega'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl) thiophosphate, polymethylene polyphenylene polyisocyanate, nitro diphenyl-4,4'-diisocyanate, 3,3'-dimethyl diphenylmethane-4,4'-diisocyanate, 4,4'-diphenyl propane diisocyanate and 3,3'-dimethoxy diphenyl-4,4'-diisocyanate; non-cyclic aliphatic polyisocyanate selected from the group consisting of trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 2,6-diisocyanate methyl hexanoate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethyl hexamethylene diisocyanate, decamethylene diisocyanate; cycloaliphatic polyisocyanate selected from the group consisting of 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene bis(cyclohexyl isocyanate) (4,4'-methylene bis(cyclohexyl isocyanate), 2,4'-methylene bis(cyclohexyl isocyanate), 2,2'-methylene bis(cyclohexyl isocyanate), or a mixture thereof) (hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, trans-cyclohexane-1,4-diisocyanate, hydrogenated toluene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI); bridged cycloaliphatic polyisocyanate selected from the group consisting of norbornene diisocyanate, methyl norbornane diisocyanate, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, di(diisocyanatomethyl)tricyclodecane; a compound selected from the group consisting of the following structural formulas: a compound selected from the group consisting of the above compounds (dimer, trimer, pentamer, heptamer, uretdione, uretonimine, isocyanurate modifier, polycarbodiimide, etc.), biuret modifier, other derivatives.

[0019] [Item 14] The compound according to Item 13, wherein, the above compound (a) comprises a compound (al), the above compound (al) is a compound having a formula: -Y f11 - (Y f21 - Y f12 ) β - Y f22 - Y f13 - Z f

[0020] [In the formula, each symbol is independent at each occurrence, Y f11 is a direct bond, -O-, -NH-, or -C(=O)-, Y f21 is a group consisting of one or more selected from the group consisting of aliphatic groups and aromatic groups, Y​f12 R is a group consisting of one or more selected from the group consisting of -0-, -C(=0)-, -C(=NR')-, -S-, -S(=0)2-, -NR'- and -C(OR')R' (R' is a hydrogen atom or an organic group), β is 0 to 3, Y f22 R is a group consisting of one or more selected from the group consisting of aliphatic groups and aromatic groups, Y f13 R is -0-, -0-C(=0)-0-, -0-C(=0)-NR'-, -NR'-, -NR'-C(=0)-0-, -NR'-C(=0)-NR'-, -C(=0)-0-, -C(=0)-NR'- or -SO2NR'- (R' is a hydrogen atom or an organic group), Z f R is -CF3. [Item 15] A dispersion liquid containing the fluorine-containing compound according to any one of items 1 to 14 and a liquid medium.

[0021] [Item 16] A water- and oil-repellent agent containing the fluorine-containing compound according to any one of items 1 to 14.

[0022] [Item 17] The water- and oil-repellent agent according to item 16, which contains other non-fluorine water- and oil-repellent agent components.

[0023] [Item 18] The water- and oil-repellent agent according to item 16 or 17, which is a water- and oil-repellent agent for a fiber product or a paper product.

[0024] [Item 19] A method for producing a treated substrate, which treats a substrate with the water- and oil-repellent agent according to any one of items 16 to 18.

[0025] [Item 20] The method for producing according to item 19, wherein the substrate is a fiber product or a paper product.

[0026] [Item 21] An article to which the fluorine-containing compound according to any one of items 1 to 14 is attached.

[0027] Effects of the Invention According to the present application, it is possible to provide a novel fluorine-containing compound. DETAILED DESCRIPTION

[0028] <Definitions of Terms> In the present specification, "an n-valent group" means a group having n valence, that is, a group forming n bonds. Further, "an n-valent organic group" means an n-valent group containing carbon. As such an organic group, there is no particular limitation, and it can be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group means a group having 1 or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, or the like at the end or in the molecular chain of a hydrocarbon group.

[0029] In the present specification, "a hydrocarbon group" is a group containing carbon and hydrogen, and is a group in which a hydrogen atom is removed from a hydrocarbon. As such a hydrocarbon group, there is no particular limitation, and a C 1－40 A hydrocarbon group, such as an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or the like. The above "aliphatic hydrocarbon group" can be any one of a straight chain, a branched chain, or a ring, and can be any one of saturated or unsaturated. Further, the hydrocarbon group can include 1 or more ring structures. In the case where it is explicitly described, the hydrocarbon group can be substituted with 1 or more substituents.

[0030] In the present specification, regardless of whether "independently at each occurrence", "each independently of one another", "independently of one another", or the like is explicitly described, unless otherwise specified, the definition is applied independently at each occurrence in the chemical structure in which a term (symbol) that occurs multiple times is defined.

[0031] It should be understood that the chemical structures described in the present specification do not include chemical structures that are considered to be chemically impossible or extremely unstable by a person skilled in the art.

[0032] <Fluorine-containing compound> The fluorine-containing compound of the present application has: (a) a portion derived from a compound containing a reactive hydrogen, (b) a portion derived from a compound reactive to a reactive hydrogen, and -NHCO- derived from the above compound (a) and the above compound (b).

[0033] [Properties of fluorine-containing compound, etc.] The fluorine-containing compound of the present application can be attached to a substrate, and imparts liquid repellency (for example, oil repellency, water repellency, oil resistance, water resistance) to the substrate.

[0034] The HD (n-hexadecane) contact angle of the fluorine-containing compound can 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, and preferably 30° or more; and can be 100° or less, 90° or less, or 75° or more. By the fluorine-containing compound having the HD contact angle of 30° or more, the substrate can be imparted with a liquid repellency (particularly, oil repellency) favorably. The HD contact angle is a static contact angle of a spin-coated film of the fluorine-containing compound, and refers to a value obtained by dropping 2 μL of HD on the spin-coated film and measuring the contact angle after 1 second of dropping.

[0035] The water contact angle of the fluorine-containing compound can be 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 can be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By the fluorine-containing compound having the water contact angle of 100° or more, the substrate can be imparted with a liquid repellency (particularly, water repellency) favorably. The water contact angle is a static contact angle of a spin-coated film of the fluorine-containing compound, and refers to a value obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle after 1 second of dropping.

[0036] The weight average molecular weight of the fluorine-containing compound can be 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and can be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, or 5000 or less.

[0037] The melting point or glass transition temperature (e.g., melting point) of the fluorine-containing compound can 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 can 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, and preferably 40°C or more, for example, 75°C or more.

[0038] The fluorine-containing compound is preferably a compound having a carbon of a bio-based origin. The bio-based content is determined based on ASTM D6866. The bio-based content of the fluorine-containing compound can be 20% or more, preferably 30% or more, more preferably 50% or more, further preferably 60% or more, further 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 resources such as petroleum, and in this respect, the bio-based content of the fluorine-containing compound can be said to be higher the better.

[0039] The fluorine-containing compound of the present application has the Rf 1 or Rf 2 . On the other hand, the fluorine-containing compound of the present application can not have any one of a fluorinated alkyl group having 8 or more carbon atoms, a perfluorinated alkyl group having 8 or more carbon atoms, a fluorinated alkyl group having 4 or more carbon atoms, a perfluorinated alkyl group having 4 or more carbon atoms, a fluorinated alkyl group having 2 or more carbon atoms, and a perfluorinated alkyl group having 2 or more carbon atoms. The fluorine-containing compound of the present application can impart liquid repellency to a substrate even if it does not contain these fluorine-containing groups. In the present specification, a fluorinated alkyl group means a group in which one or more hydrogen atoms on each carbon atom of an alkyl group is replaced with a fluorine atom.

[0040] 〔R f1 and R f2 〕 The fluorine-containing compound has R f1 or R f2 , for example, R f1 . Here, R f1 and R f2 are not part of a fluorinated alkyl group having 2 or more carbon atoms. R f2 may not be part of -CH2-CF2-CH2-.

[0041] R f1 is -CF3, -CF2H, or -CFH2, preferably -CF3. The adjacent position of R f1 is an oxygen atom or a nitrogen atom.

[0042] R f2 is -CF2- or -CFH-, preferably -CF2-. The adjacent position of R f2 may be an oxygen atom or a nitrogen atom at least on one side.

[0043] 〔(a) compound containing active hydrogen〕 The fluorine-containing compound has a moiety derived from the compound containing active hydrogen (a).

[0044] The compound (a) is a compound having a group containing a reactive hydrogen. As examples, monofunctional, difunctional, and polyfunctional alcohols, mercaptans, and amines, and the like can be cited. The alcohol in the present invention is an alcohol in the broad sense, including phenols.

[0045] The compound (a) is preferably a compound having a bio-based source carbon. The bio-based content is determined based on ASTM D6866. The bio-based content of the fluorine-containing compound can be 20% or more, preferably 30% or more, more preferably 50% or more, further preferably 60% or more, further more preferably 70% or more, most preferably 80% or more or 90% or more, for example, 100%. A high bio-based content means that the amount of fossil resource-based materials represented by petroleum and the like is small, and in this view, it can be said that the higher the bio-based content of the compound (a) is, the better.

[0046] The compound (a) contains: one or more of a compound (a1) having R f1 or R f2 , a reactive hydrogen-containing compound (a2) having a hydrocarbon group having 6 or more and 40 or less carbon atoms, and another reactive hydrogen-containing compound (a3).

[0047] [Compound (a1)] The compound (a1) is a compound having R f1 or R f2 . The compound (a1) can have a group represented by the formula: -Y f -Z f α .

[0048] [In the formula, each symbol is independent at each occurrence, Y f is a 1+α-valent group composed of one or more selected from Y f1 and Y f2 , Y f1 is a group composed of one or more selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'- and -C(OR' )2, -N(-)2 (in which R' is a hydrogen atom or an organic group), Y f2 is a group composed of one or more selected from an aliphatic group and an aromatic group, Z f is R f1 , or a hydrocarbon group having 2 or more and 40 or less carbon atoms containing R f1 or R f2 , α is 1 to 3.] Rf1 For example, Z f may be contained in R f2 For example, the organic group, Y f2 , Z f , R f2 may be contained.

[0049] Y f Z f α The terminal of Y f may be bonded to -H, -OH, -NH2, or COOH to form a reactive hydrogen terminal. For example, compound (al) can be represented by the following formula: H-Y f Z f α HO-Y f Z f α H2N-Y f Z f α HOOC-Y f Z f α .

[0050] Here, the terminal H is a reactive hydrogen.

[0051] However, compound (al) is not limited to this structure, Y f Z f α may constitute any portion of compound (al).

[0052] (Y f ) Y f is a 1+α-valent group composed of one or more selected from Y f1 and Y f2 , Y f1 is a group directly bonded, composed of one or more selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'- and -C(OR'X2, -N(-)2(R' is a hydrogen atom or a monovalent organic group), Y f2 is a group composed of one or more selected from aliphatic groups and aromatic groups.

[0053] Y fThe molecular weight of Y can be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and can 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.

[0054] Y is described below. f1 and Y f2 are described.

[0055] Y f1 Y f1 is a non-hydrocarbon linking group.

[0056] Y f1 is a direct bond or a divalent or greater group. Y f1 The valence of Y can be 2 to 4, 2 to 3, or 2. Preferably, Y f1 is not only a direct bond.

[0057] Y f1 The molecular weight of Y can be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and can be 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0058] Y f1 consists 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' is independently at each occurrence a hydrogen atom or a monovalent organic group).

[0059] R' is a hydrogen atom or a monovalent organic group. The organic group can be, for example, an aliphatic group or an aromatic group (e.g., a substituted or unsubstituted alkyl group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group) having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The same applies to other R' in the specification.

[0060] Examples of Y f1 include: a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'- -C(=O)- -C(=O)-O- -C(=O)-NR'- -SO2- -SO2NR'- -C(OR')R'- -C(OR')(— )2, etc.

[0061] (In the formula, R' is independently at each occurrence a hydrogen atom or a monovalent organic group.) o Y f2 Y f2 may be a group composed of one or more of an aliphatic group and an aromatic group.

[0062] Y f2 is a divalent or higher valent group. Y f2 may have a valence of 2 to 4, 2 to 3, or 2, for example.

[0063] Y f2 may have a carbon atom number of 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 have 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.

[0064] Y f2 may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may have 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.

[0065] Y f2 may be a hydrocarbon group or a non-hydrocarbon group (containing a heteroatom). Y f2 may be aliphatic or aromatic. Y f2 may be linear, branched, cyclic.

[0066] Y f2 may be a linking group of a hydrocarbon that can have a substituent, an aromatic hydrocarbon ring that can have a substituent, or a heterocyclic ring that can have a substituent, or a combination thereof. For example, Y f2 may be composed of one or more of a 1 to 20 carbon atom number aliphatic hydrocarbon group that can have a substituent, a 2 to 4 valent aromatic hydrocarbon ring that can have a substituent, and a 2 to 4 valent heterocyclic ring that can have a substituent.

[0067] The aliphatic hydrocarbon group having 1 to 20 carbon atoms and 2 to 4 valences can be a cyclic, branched, or linear hydrocarbon group. The aliphatic hydrocarbon group having 1 to 20 carbon atoms and 2 to 4 valences can 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 can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and can be 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0068] The aliphatic hydrocarbon group can have a substituent. As examples of the substituent, -OR', -N(R')2, -COOR', a halogen atom, and the like (in the formula, R' is independently a monovalent organic group at each occurrence) can be given. The substituent can have a reactive hydrogen or can not have. The number of substituents can 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 can be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and preferably 75 mol% or more, relative to the amount of carbon atoms and heteroatoms; and can be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0069] As examples of the aromatic hydrocarbon ring having 2 to 4 valences, groups in which 2 to 4 hydrogens are removed from aromatic hydrocarbon rings of benzene, naphthalene, anthracene, phenanthrene, tetracene, naphthacene (anthracylene), pentacene, pyrene, coronene, and the like can be given. The number of ring-forming atoms of the aromatic hydrocarbon ring can be 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the aromatic hydrocarbon ring can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0070] The aromatic hydrocarbon ring can have a substituent. As examples of the substituent, -R', -OR', -N(R')2, -COOR', a halogen atom, and the like (in the formula, R' is independently a hydrogen atom or a monovalent organic group at each occurrence) can be given. The substituent can have a reactive hydrogen or can not have. The number of substituents can be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aromatic hydrocarbon ring having a substituent, the amount of carbon atoms can be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and preferably 75 mol% or more, relative to the amount of carbon atoms and heteroatoms; and can be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0071] The divalent to tetravalent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of divalent to tetravalent heterocyclic rings include groups obtained by removing 2 to 4 hydrogen atoms 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, imidazoline, thiazoline, and the like. The number of ring atoms in 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 be 4 or less, 3 or less, or 2.

[0072] Heterocyclic rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein each occurrence of R' is independently a hydrogen atom or a monovalent organic group). Substituents may or may not have active hydrogen atoms. The number of substituents may be 6 or fewer, 5 or fewer, 4 or fewer, 3 or fewer, 2 or fewer, 1 or fewer, or 0. In heterocyclic rings with substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or greater, 70 mol% or greater, 80 mol% or greater, 90 mol% or greater, 95 mol% or greater, or 99 mol% or greater, for example, 65 mol% or greater; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0073] As Y f2 Examples include: -Ali- -Cy- -Ali (-) 2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali (-)2 (-)2Cy (-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali-etc.

[0074] [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring.] As Y f2 Specific examples include: -(CH2) p - (p is 1 to 20, for example, 1 to 10), a linear hydrocarbon group having an unsaturated bond having 1 to 40, for example, 1 to 10 carbon atoms, a branched hydrocarbon group having 1 to 40, 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 an aromatic ring or a heterocyclic ring), and the like.

[0075] o Y f Examples of Y Examples of Y f are described.

[0076] Examples of Y f , in the case where Y f is divalent, are -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. The group adjacent to Z f α may be Y f1 .

[0077] Examples of Y f , in the case where Y f is trivalent, are: -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 -Yf1 - )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 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.

[0078] As examples of Y f , in the case where Y f is tetravalent, the following can be listed: - Y f1 ( - )3, -Y f1 - Y f2 ( - )3, -Y f1 - (Yf2 - )3, -Y f1 - Y f2 - Y f1 ( - )3, -Y f1 - Y f2 ( -Y f1 - )3, -Y f1 - (Y f2 - Y f1 - )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 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.

[0079] as 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.

[0080] (Z f ) Z f R f1 , or containing R f1 or R f2 The hydrocarbon group having 2 or more and 40 or less carbon atoms, for example, R f1 . Contains R f1 or R f2 The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group (alkyl group). f1 or R f2 The hydrocarbon group is branched or linear, more preferably linear. f1 or R f2 The hydrocarbon group may be saturated or unsaturated. f1 or R f2 The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). f1 or R f2 The number of carbon atoms of the hydrocarbon group can 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 can 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.

[0081] (α) α is 1 to 3 (1, 2, or 3), for example, 1 or 2, for example, 1.

[0082] (Example of compound (a1)) Compound (a1) may be of the formula: -Y f11 - (Y f21 -Y f12 ) β— Y f22 — Y f13 — Z f the group shown.

[0083] [In the formula, each symbol is independent at each occurrence, Y f11 is a direct bond, — O —, — NH —, or — C(=O) —, Y f21 is a group consisting of one or more selected from the group consisting of aliphatic groups and aromatic groups, Y f12 is a group consisting 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 consisting of one or more selected from the group consisting of aliphatic groups and aromatic groups, 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 a hydrocarbon group having 2 or more and 40 or less carbon atoms containing R f1 or R f2 . — H or — OH can be bonded at the terminal of Y f11 side to form a reactive hydrogen terminal.

[0084] Y f11 may be a direct bond, — O —, — NH —, or — C(=O) —.

[0085] Y f21 may be a group consisting of one or more selected from the group consisting of aliphatic groups and aromatic groups, and the same explanation as Y f2 above can be applied. Here, Y f21 is a divalent group.

[0086] Y f12 may be a group consisting 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 same explanation as Y f1 above can be applied. Here, Y f12It is a divalent group.

[0087] β may be 0-3 (0, 1, 2 or 3), for example, 0-2, particularly 0-1.

[0088] Y f22 It can be a group consisting of one or more selected from aliphatic groups and aromatic groups, and can be used in conjunction with the above Y 2 The same explanation applies. f22 Y is a divalent group. f22 It can be expressed as: -Y f221 -Y f222 - the group shown.

[0089] [Where, 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.] 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 in 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 be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less.

[0090] Y f13 It 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). f13 For example, -O- or -NR'-.

[0091] Z f R f1 , or containing R f1 or R f2 The hydrocarbon group having 2 or more and 40 or less carbon atoms is as described above, and is particularly R f1 .

[0092] In one approach, Y f22 It can be expressed as -Y f221 -Y f222 - the group shown.

[0093] [Where, 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. Here, Y f13 may be -O- or -NR'- (R' is a hydrogen atom or a monovalent organic group). β can be 0 or 1. Z f may be R f1 .

[0094] (Specific examples of compound (al)) Specific examples of compound (al) are as follows: hydroxyl group HO-Y f -Z f α carboxylic acid HO(O=)C-Y f -Z f α amine H2N-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).) where, in the above formula, the functional group (G(O=)C, etc.) at the end adjacent to Y f -Z f α is expressed in a manner not included in -Y f -, but can also be expressed in a manner in which the partial structure of the functional group (e.g., (O=)C) at the end is integrated into Y f .

[0095] As more specific examples of compound (al), there are (e.g., in the formulae listed in the above specific examples) -Y f -Z f α compounds in which -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 .

[0096] [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Cy is an aromatic hydrocarbon ring or a heterocyclic ring. R' is a hydrogen atom or an organic group. R f1 is -CF3, -CF2H or -CFH2.] More specific examples of the compound (a1) include (for example, in the formula listed in the above specific examples) -Y f -Z f α Compounds of the following groups: -(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 .

[0097] (wherein n is an integer of 1 to 40, Cy is an aromatic hydrocarbon ring or a heterocyclic ring, R' is a hydrogen atom or an organic group, and R f1 is -CF3, -CF2H or -CFH2.) As more specific examples of the compound (al), there can be mentioned: trifluoromethoxyalkyl carboxylic acid, trifluoromethoxyalkyl carboxylic acid halide, trifluoromethoxybenzoic acid, trifluoromethoxybenzoic acid halide, trifluoromethoxyphenylacetic acid, trifluoromethoxyphenylacetic acid halide, trifluoromethoxyalkyl amine, trifluoromethoxyaniline, trifluoromethoxyalkyl alcohol, trifluoromethoxyphenol, CF3-O-CF2-R 2 -OH CF3-O-R 1 -O-CF2-R 2 -OH CF3-O-R 1 -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, etc.

[0098] (wherein R1to R3are independently a hydrocarbon group having 1 to 40 carbon atoms.) [Example of the method for producing the compound (al)] In this method, a compound (111) having a hydroxyl group and an olefin: HO-R j33 -CH=CH2is used as a starting material, and a trifluoromethoxy-containing compound is synthesized. Here, R j33alkylene, for example, C1-30 alkylene.

[0099] As the compound containing an olefinic group, for example, 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-icocene, 21-hydroxy-1-heneicosene, 24-hydroxy-1-tetracosene, 30-hydroxy-1-triacontene, and the like can be exemplified.

[0100] By reacting carbon disulfide with the hydroxyl group of the compound (111) in the presence of an alkali such as sodium hydride, and then adding methyl iodide, a xanthate (112) can be obtained: H3CS-C(=S)-O-R j33 -COOR j32 . In the formula, R j32 is a lower alkyl group, for example, methyl, ethyl, propyl, butyl, t-butyl, specifically, methyl, t-butyl. By reacting hydrogen fluoride pyridine and 1,3-dibromo-5,5-dimethylhydantoin with the above xanthate (102), a target compound (113) containing a trifluoromethoxy group: F3CO-R j33 -CH=CH2.

[0101] Further, as another method, by reacting trifluoromethyl aryl sulfonate with the hydroxyl group of the compound (111) in the presence of cesium fluoride, tetrabutylammonium bromide, or the like, in a non-protic polar solvent such as NMP, DMF, HMPA (hexamethylphosphoric acid triamide), a target compound (113) containing a trifluoromethoxy group: F3CO-R j33 -CH=CH2.

[0102] The obtained F3CO-R j33 -CH=CH2can be made into F3CO-R j33 CH2CH2-OH by a conventional method.

[0103] Here, as F3CO-R j33Other production methods of CH2CH2-OH can also be performed according to the method described in WO2020 / 168011A1 or the like, using a method of synthesizing by reacting silver triflate, potassium fluoride, 1-(chloromethyl)-4-fluoro-4-diazabicyclo[2.2.2]octane, tetrafluoroborate, and a benzyloxy alcohol (e.g., benzyloxyethanol), and then performing hydrogen reduction of the resulting product (e.g., [2-(trifluoromethoxy)ethoxy]methyl]benzene) under a palladium catalyst.

[0104] [Compound (a2)] Compound (a2) is a compound containing active hydrogen having a hydrocarbon group with a carbon number of 6 or more and 40 or less. Among them, the hydrocarbon group can 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). The hydrocarbon group can be branched or linear, and is more preferably linear. The hydrocarbon group can be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms of the hydrocarbon group can be 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 is preferably 10 or more, 12 or more, 14 or more, or 16 or more; and can be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and is preferably 30 or less, 25 or less, or 20 or less.

[0105] (Sugar alcohol / hydroxy acid modifier) The compound (a2) can be a sugar alcohol / hydroxy acid modifier which is a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) modified with a hydrocarbon group having 6 or more and 40 or less carbon atoms. The kind of the sugar alcohol / hydroxy acid is not limited, and can be cyclic or acyclic, and as examples of the sugar alcohol, monosaccharides, reducing sugars, amino sugars, aldonic acids, aldonic acid lactones can be listed; and as examples of the hydroxy acid, hydroxy polybasic carboxylic acids and the like can be listed. The sugar alcohol / hydroxy acid can be a substance present in a living body. As examples of the sugar alcohol / hydroxy acid, compounds derived from aldoses and ketoses, such as, for example, tetratomic sugars, pentatomic sugars, hexatomic sugars and heptatomic sugars, but are not limited to these, and as specific examples, glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, gulose, galactose, talose, fructose, ribulose, sedohexulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, mannopyranose, talopyranose, allopynarose, altropyranose, idopyranose, gulopyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol, pentaerythritol, dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconolactone, glycerolactone, xylolactone, glucosamine, galactosamine or a mixture thereof can be listed. The number of carbon atoms of the sugar alcohol / hydroxy acid can be 2 or more, 4 or more or 6 or more, and can be 30 or less, 20 or less or 10 or less. The average OH value of the compound (a2) can be in the range of more than 0 and about 230 or less, preferably in the range of about 10 to about 175, and most preferably in the range of about 25 to about 140.

[0106] The number of hydrocarbon groups having 6 or more and 40 or less carbon atoms possessed by the sugar alcohol / hydroxy acid modifier can be 1 or more, 2 or more, 3 or more, 4 or more or 5 or more, and can be 12 or less, 9 or less, 6 or less or 3 or less.

[0107] In the sugar alcohol / hydroxy acid modifier, at least one active hydrogen (for example, OH group, hydrogen of carboxyl group) possessed by the sugar alcohol and / or the hydroxy acid can be substituted with an active hydrogen substituent selected from the group consisting of -R a2 , -C(O)R a2 , - (CH2CH2O) n (CH (CH3) CH2O) m R a2 , - (CH2CH2O) n (CH (CH3) CH2O) m C(O)R a2 or a mixture thereof. Among them, R a2R is a hydrocarbon group having 6 or more and 40 or less carbon atoms, each n is independently 0 to 20, each m is independently 0 to 20, and m + n can be greater than 0. Among them, the compound (a2) has at least one active hydrogen, and for example, in the sugar alcohol / hydroxy acid modifier, at least one active hydrogen (1 or more) of the sugar alcohol / hydroxy acid can not be modified, and the active hydrogen (for example, -OH group) can react with the active hydrogen reactive group (particularly, isocyanate group) of the compound (b) to form -NHCO-.

[0108] (sorbitol modifier) The sugar alcohol / hydroxy acid modifier is a sorbitol modifier in which a hydrocarbon group having 6 or more and 40 or less carbon atoms is modified to sorbitol, and particularly, can be an alkyl sorbitol, and can be a compound in which -R a2 , -C(O)R a2 , -(CH2CH2O) n (CH(CH3)CH2O) m R a2 , -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R a2 or a mixture thereof is substituted to sorbitol (here, R a2 is a hydrocarbon group having 6 or more and 40 or less carbon atoms). For example, a compound in which -C(O)R a2 is mono-, di- or tri-substituted to sorbitol. Here, the sorbitol can contain sorbitol, isosorbide or other intermediates, or by-products. A commercially available sorbitol such as SPAN or the like can be used as the above alkyl sorbitol.

[0109] In one mode, at least one active hydrogen substituent can be -C(O)R a2 , and R a2 may be a linear / branched alkyl group having 6 to 40, more preferably 7 to 21, most preferably 11 to 21 carbon atoms. As preferred compounds, mono-, di- and tri-substituted sorbitols derived from octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and a mixture thereof can be exemplified. As particularly preferred compounds, mono-, di- and tri-substituted sorbitol stearates or sorbitol behenates can be exemplified.

[0110] In one mode, R a2 may include at least one unsaturated bond. As examples of such compounds (at least one active hydrogen substituent is selected from -C(O)R a2 , R a2Contains at least one unsaturated bond), sorbitan trioleate (ie, wherein R a2 -C7H 14 CH=CHC8H 17 As other examples, mono-, di- and tri-substituted sorbitans derived from palmitic acid, linoleic acid, arachidic acid and erucic acid may be cited, but are not limited thereto.

[0111] In one embodiment, the modified sorbitan has at least one active hydrogen substituent, and the active hydrogen substituent can be independently -(CH2CH2O) n (CH(CH3)CH2O) m R a2 or -(CH2CH2O) n (Can be CH(CH3)CH2O) m C(O)R a2 , each m is independently 0 to 20, each n is independently 0 to 20, and m + n is greater than 0). Such compounds are called polysorbates and are sold on the market under the trademark TWEEN. a2 These sorbitols are monosubstituted, disubstituted or trisubstituted. 2 H (unsubstituted) various polysorbates to various R a2 Polysorbates having a linear or branched alkyl group with 6 to 40 carbon atoms (completely substituted), including various mixtures and mixtures of these various substitutions. Examples of such modified sorbitan include polysorbates such as polysorbate tristearate and polysorbate monostearate. a2 Examples of modified sorbitan containing at least one unsaturated bond include, but are not limited to, polysorbate trioleate (herein R a2 C7H 14 CH=CHC8H 17 ), which is sold on the market under the name of polysorbate 80. Sorbitan modified forms may contain a mixture of various compounds having active hydrogen substituents, and may contain R a2 Compounds containing at least one unsaturated bond and R a2 A mixture of completely saturated compounds.

[0112] (Citrate modified form) The sugar alcohol / hydroxy acid modifier can be a citric acid modifier in which a hydrocarbon group having 6 or more and 40 or less carbon atoms is modified on citric acid, and specifically can be an alkyl citrate. For example, the citric acid modifier can exist in the form of a mono-substituted body, a di-substituted body, or a tri-substituted body having an alkyl group. The active hydrogen substituent can use a mixture of citric acid esters having various values, and also can contain R a2 a compound having a hydrocarbon group containing at least 1 unsaturated bond, and R a2 a mixture of compounds that are completely saturated hydrocarbon groups. The citric acid modifier can have an active hydrogen substituent selected from - (CH2CH2O) n (CH(CH3)CH2O) m R a2 or - (CH2CH2O) n (CH(CH3)CH2O) m C(O)R a2 wherein R a2 is a hydrocarbon group having 6 or more and 40 or less carbon atoms. As examples of the citric acid modifier, trialkyl citrates can be cited, but are not limited to these.

[0113] (pentaerythritol) The sugar alcohol / hydroxy acid modifier can be a pentaerythritol modifier in which a hydrocarbon group having 6 or more and 40 or less carbon atoms is modified on pentaerythritol, and can be a mono-substituted body, a di-substituted body, or a tri-substituted body having a hydrocarbon group (particularly an alkyl group) having 6 or more and 40 or less carbon atoms, for example, a dipentaerythritol ester. In the formula, the active hydrogen substituent can contain -CH2C[CH2OR a2 ]3 (wherein R a2 is a hydrocarbon group having 6 or more and 40 or less carbon atoms). Also, the pentaerythritol modifier can contain a compound having a mixture of chain lengths of the hydrocarbon group or R a2 a compound having at least 1 unsaturated bond, and R a2 a mixture of compounds that are completely saturated.

[0114] R a2 [Compound (a3)] The above compound (a) can contain other active hydrogen-containing compounds (a3).

[0115] (compound (a31)) The compound (a3) can be a compound represented by the formula: R a31 -X a31 .

[0116] [In the formula, R 31 is: C1-C20 alkyl groups which can contain at least one unsaturated group 30 linear or branched alkyl groups, hydroxy-functional C1-C20 30 linear or branched alkyl groups, hydroxy-functional linear or branched C1-C20 30 polyethers, hydroxy-functional linear or branched polyesters, hydroxy-functional linear or branched organosiloxanes, thiol-functional C1-C20 30 linear or branched alkyl groups, amine-functional C1-C20 30 linear or branched alkyl groups, Y － R a311 R a312 R a313 N ＋ — R a314 — (where Y is a halide ion, e.g., Cl － ), HOS(=O)2— R a314 — or R a311 R a312 C=N— (where R a311 , R a312 , R a313 are each independently —H, C1-C6 alkyl, and R a314 is a divalent alkyl group having 1 to 20 carbon atoms, X a31 is —OH, —C(O)OH, —SH, —NH(R'), —O— (CH2CH2O) s (CH(CH3)CH2O) t —H, or —C(O)— O— (CH2CH2O) s (CH(CH3)CH2O) t —H, etc. (where R' is —H or a monovalent organic group, s is an integer from 0 to 50, t is an integer from 0 to 50, and s+t is greater than 0). Compound (a31) can be a hydrophilic, water-soluble material comprising at least one hydroxyl-terminated polyether, where X a31 is —O— (CH2CH2O) s (CH(CH3)CH2O) t —H, or —C(O)— O— (CH2CH2O) t —H. —(CH2CH2O)— represents oxyethylene (EO), and —(CH(CH3)CH2O)— represents oxypropylene (PO). These polyethers can contain only EO groups, only PO groups, or a mixture containing both. In addition, these polyethers can also exist in the form of a specified PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymer.

[0117] In one mode, X a31 is -OH, -C(O)OH, -SH, -NH(R'), R a31 is optionally selected from C1-C20 alkyl diols or polyols comprising at least 1 unsaturated group (R 30 linear or branched alkyl, hydroxyl functional C1-C20 linear or branched alkyl, (R 30 linear or branched alkyl, hydroxyl functional linear or branched C1-C20 alkyl, (R 30 polyether, hydroxyl functional linear or branched polyester, hydroxyl or amine functional linear or branched organosiloxane, thiol functional C1-C20 linear or branched alkyl, (R 30 linear or branched alkyl, amine functional C1-C20 linear or branched alkyl, (R 30 linear or branched alkyl.

[0118] X a31 may be -OH, as examples of such compounds (a31), one can cite alkyl alcohols such as propanol, butanol, or aliphatic alcohols including stearyl alcohol (R a31 is optionally selected from C1-C20 alkyl diols or polyols comprising at least 1 unsaturated group (R 30 linear or branched alkyl), ethylene glycol, propylene glycol, butylene glycol, or hexanediol, or other alkyl diols or polyols comprising at least 1 unsaturated group (R 5 is hydroxyl functional C1-C20 linear or branched alkyl, (R 30 linear or branched alkyl), triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or other alkylene glycol ethers comprising at least 1 unsaturated group (R a31 is hydroxyl functional linear or branched C1-C20 alkyl, (R 30 polyether), polyester polyols (R a31 is hydroxyl functional linear or branched polyester), silicone prepolymer polyols (R a31 is hydroxyl functional linear or branched organosiloxane), N,N-dimethylaminoethanol (R 5 is amine functional C1-C20 linear or branched alkyl, (R 30 linear or branched alkyl), choline chloride or betaine HCl (R a31 is Y － R a311 R a312 R a313 N ＋ -R a314 -), butanone oxime (R 5 is R a311 R a312C=N-, but are not limited to these. The polyether polyols can contain only EO groups, only PO groups, THF groups, or a mixture thereof. In addition, these polyethers can exist in the form of block copolymers designated as PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol), and the like. The polyether diols preferably have an average molecular weight of about 200 or more, most preferably 350 to 2000.

[0119] X a31 may be -C(O)OH, as examples of such compounds (a31), fatty acids (R a31 optionally C1-C 30 linear or branched alkyl), hydroxyoctanoic acid, hydroxydecanoic acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxy-behenic acid, hydroxy-palmitic acid, hydroxy-linoleic acid, hydroxy-arachidic acid, hydroxy-oleic acid, or hydroxy-erucic acid, and the like hydroxyl-containing acids (R a31 hydroxyl-functional C1-C 30 linear or branched alkyl), and mercaptopropionic acid, and the like mercaptoalkane acids (R a31 mercapto-functional C1-C 30 linear or branched alkyl), but are not limited to these.

[0120] X a31 may be -SH, as examples of such compounds (a31), alkyl mercaptans (R a31 optionally C1-C 30 linear or branched alkyl), but are not limited to these.

[0121] X a31 may be -NH(R'), as examples of such compounds (a31), alkyl amines (R a31 optionally C1-C 30 linear or branched alkyl), alkanol amines (R a31 hydroxyl-functional C1-C 30 linear or branched alkyl), silicone prepolymer polyamines (R a31 amine-functional linear or branched organosiloxanes), alkyl diamines (R a31 amine-functional C1-C 30 linear or branched alkyl), and aminoalkane sulfonic acids (Ra31 is HO-S(O)2R 314 -), but are not limited to these.

[0122] (Compound (a32)) Compound (a32) is of the formula: R a321 -(OCH2CH(OR a322 )CH2) z -OR a323 .

[0123] [Where, R a321 、R a322 and R a323 At least 1 R a321 、R a322 or R a323 is -H, and each independently is -H, -R a324 , -C(O)R a324 , R a324 Each is independently a linear or branched alkyl group having 5 to 29 carbon atoms which may contain at least one unsaturated bond, and z is 1 to 15.] Compound (a32) may be a compound generally referred to as polyglycerol. Specific examples include, but are not limited to, triglycerol monostearate, triglycerol distearate, hexaglycerol monostearate, hexaglycerol distearate, decaglycerol mono(caprylate / caprate), decaglycerol di(caprylate / caprate), decaglycerol, polyglycerol-3, and C18 diglyceride.

[0124] (Chain Extender) Compound (a3) ​​may be a chain extender. A chain extender is a compound having two or more (eg, two) active hydrogen-containing functional groups in its molecule. As the chain extender, a known chain extender can be used, and examples thereof include: aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; phenolic hydroxyl group-containing compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbisphenol, and o,o'-diallyl-bisphenol A; and alcoholamines such as aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, and aminohexylpropanolamine.

[0125] [(b) Active hydrogen-reactive compounds] The fluorine-containing compound has a moiety derived from the active hydrogen-reactive compound (b).

[0126] The active hydrogen reactive compound (b) has an active hydrogen reactive group. As examples of the active hydrogen reactive group, an epoxy group, an isocyanate group, a thioisocyanate group, a carbodiimide group, an acyl halide group, a maleic anhydride group, and the like can be listed, and typically an isocyanate. The active hydrogen reactive compound (b) is typically a polyisocyanate, and can be a diisocyanate, a triisocyanate, or a polyvalent isocyanate, and can be aliphatic or aromatic.

[0127] As examples of the compound (b), the following compounds can be selected: an aromatic polyisocyanate selected from the group consisting of toluene diisocyanate (2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or a mixture thereof) (TDI), phenylene diisocyanate (m-phenylene diisocyanate, p-phenylene diisocyanate, or a mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, or a mixture thereof) (MDI), 4,4'-dimethyl diphenyl diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylene diisocyanate (1,3-xylene diisocyanate, 1,4-xylene diisocyanate, or a mixture thereof) (XDI), tetramethyl xylene diisocyanate (1,3-tetramethyl xylene diisocyanate, 1,4-tetramethyl xylene diisocyanate, or a mixture thereof) (TMXDI), omega, omega'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 1,8-naphthalene diisocyanate, or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl) thiophosphate, polymethylene polyphenylene polyisocyanate, nitro diphenyl-4,4'-diisocyanate, 3,3'-dimethyl diphenylmethane-4,4'-diisocyanate, 4,4'-diphenyl propane diisocyanate, and 3,3'-dimethoxy diphenyl-4,4'-diisocyanate; a non-cyclic aliphatic polyisocyanate selected from the group consisting of trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 2,6-diisocyanate methyl hexanoate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethyl hexamethylene diisocyanate, decamethylene diisocyanate; Cyclic alicyclic polyisocyanates selected from 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate (4,4'-methylenebis(cyclohexyl isocyanate), 2,4'-methylenebis(cyclohexyl isocyanate), 2,2'-methylenebis(cyclohexyl isocyanate) esters) or mixtures thereof) (hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatemethyl)cyclohexane (1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane or mixtures thereof) (hydrogenated XDI), dimer acid diisocyanate, trans-cyclohexane-1,4-diisocyanate, hydrogenated toluene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylene diisocyanate (hydrogenated TMXDI); a bridged alicyclic polyisocyanate selected from norbornene diisocyanate, methyl norbornane diisocyanate, bicycloheptane triisocyanate, diisocyanate methylbicycloheptane, and bis(diisocyanate methyl)tricyclodecane; A compound selected from the following structural formulas: Compounds selected from polymers (dimers, trimers, pentamers, heptamers, uretdione, uretonimine, isocyanurate-modified products, polycarbodiimide, etc.), biuret-modified products, and other derivatives of the above-mentioned compounds.

[0128] [(b1) Compound] Compound (b) may contain R f1 or R f2 Compound (b1).

[0129] With R f1 or R f2 The compound (b1) may have the formula: -Y f -Z f α The groups shown.

[0130] [In the formula, each symbol is independent at each occurrence, Y f Selected from Y f1 and Y f2 A 1+α-valent group consisting of one or more of Y f1a group consisting of one or more selected from the group consisting of -0-, -C(=0)-, -C(=NR')-, -S-, -S(=0)2-, -NR'-, -C(OR')R'- and -C(OR')(-)2, -N(-)2 (where R' is a hydrogen atom or an organic group), Y f2 a group consisting of one or more selected from the group consisting of aliphatic groups and aromatic groups, Z f R f1 , or a hydrocarbon group having 2 or more and 40 or less carbon atoms containing R f1 or R f2 , α is 1 to 3. R f1 may be contained in, for example, Z f . R f2 may be contained in, for example, an organic group, Y f2 , Z f , R f2 .

[0131] The description of -Y f -Z f α of the compound (bl) is applied to the description of -Y f -Z f α of the compound (al).

[0132] wherein the compound (bl) can form a reactive group of active hydrogen at the end of the Y f side. For example, the compound (bl) can be represented by X f -Y f -Z f α Here, X f is a group forming a reactive group of active hydrogen, and is particularly an isocyanate group. However, the compound (bl) is not limited to this structure, and Y f -Z f α may constitute any part of the compound (bl).

[0133] (Specific examples of the compound (bl)) The specific examples of the compound (bl) are as follows, but are not particularly limited. The compound (bl) can be an isocyanate.

[0134] The specific examples of the compound (bl) are as follows: carboxylic acid HO(O=)C-Y f -Zf α Acyl halide G(O=)C-Y f -Z f α Acid anhydride O(C(=O)-Y f -Z f α Isocyanate O=C=N-Y f -Z f α Thioisocyanate S=C=N-Y f -Z f α Epoxide (CH2OCH)CH2O-Y f -Z f α Halide G-Y f -Z f α .

[0135] [In the formula, Y f , Z f , and α are as described above, and G is a halogen atom (e.g., F, Cl, Br, or I).] wherein, in the above formula, the functional group (G(O=)C, etc.) at the end adjacent to Y f -Z f α is expressed in a manner not included in -Y f -, but can also be expressed in a manner in which the moiety of the functional group (e.g., (O=)C) at the end is integrated into Y f .

[0136] As more specific examples of the compound (b1), there are compounds in which, for example, -Y f -Z f α in the formulae listed in the above specific examples is the following group: -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 .

[0137] [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Cy is an aromatic hydrocarbon ring or a heterocyclic ring. R' is a hydrogen atom or an organic group. R f1 is -CF3, -CF2H or -CFH2.] More specific examples of the compound (b1) include (for example, in the formula listed in the above specific examples) -Y f -Z f α Compounds of the following groups: -(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')-Rf1 、 -Cy-N(R')-R f1 、 -Cy-(CH2) n -N(R')-R f1 、 -Cy-(CH2) n -Cy-N(R')-R f1 .

[0138] [Wherein, n is an integer from 1 to 40, Cy is an aromatic hydrocarbon ring or a heterocyclic ring, R' is a hydrogen atom or an organic group, R f1 is -CF3, -CF2H or -CFH2.] More specific examples of compound (b1) include: trifluoromethoxyalkylcarboxylic acid, trifluoromethoxyalkylcarboxylic acid halide, Trifluoromethoxybenzoic acid, trifluoromethoxybenzoyl halide, Trifluoromethoxyphenylacetic acid, trifluoromethoxyphenylacetyl halide, Trifluoromethoxyalkyl isocyanate, F3CO-Ph-NCO, etc.

[0139] 〔-NHCO-〕 The fluorinated compound has an -NHCO- group derived from compound (a) and compound (b). -NHCO- is a group formed by the reaction of an active hydrogen-containing group (typically a hydroxyl group) in compound (a) and an active hydrogen-reactive group (typically an isocyanate group) in compound (b). The fluorinated compound is typically polyurethane.

[0140] [Composition of fluorine-containing compounds] The amount of the portion derived from compound (a) relative to the fluorine-containing compound may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less.

[0141] The amount of the portion derived from compound (a1) relative to the portion derived from compound (a) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less.

[0142] The amount of the portion derived from compound (a2) can be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and can be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, relative to the portion derived from compound (a).

[0143] The amount of the portion derived from compound (a3) can be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and can be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, relative to the portion derived from compound (a).

[0144] The amount of the portion derived from compound (a31) can be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and can be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, relative to the portion derived from compound (a).

[0145] The amount of the portion derived from compound (a32) can be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and can be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, relative to the portion derived from compound (a).

[0146] The amount of the portion derived from the chain extender can be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and can be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, relative to the portion derived from compound (a).

[0147] The amount of the moiety derived from the compound (b) can be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and can be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, relative to the fluorine-containing compound.

[0148] The amount of the moiety derived from the compound (b1) can be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and can be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, relative to the moiety derived from the compound (b).

[0149] [Method for producing fluorine-containing compound] The fluorine-containing compound can be obtained by reacting the compound (a) with the compound (b). The reaction can be performed in one step or can be performed in a plurality of steps. For example, in the case where an unreacted active hydrogen group or an active hydrogen reactive group is present in the product, the synthesis can be performed in a plurality of steps. The stepwise reaction is particularly effective when a substituted sugar alcohol having a high OH number or the like is used. The reaction conditions and the like are not particularly limited and can be determined by those skilled in the art. Specifically, the compound (a) and the compound (b) can be combined in an equivalent ratio (active hydrogen reactive group / active hydrogen group) of the active hydrogen reactive group to the active hydrogen group, for example, 1.2 or more, preferably 1.5 or more, and for example, 2.0 or less.

[0150] <Water-and oil-repellent agent> The water-and oil-repellent agent of the present application can impart water repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to a substrate (for example, a fiber substrate, a paper substrate), and can exhibit at least one function selected from a water-repellent agent, an oil-repellent agent, an oil-resistant agent, and a water-resistant agent. The water-and oil-repellent agent of the present application can impart oil resistance (oil repellency) and / or water resistance (water repellency) to a substrate well, for example, can impart both oil resistance and water resistance well.

[0151] [Fluorine-containing compound] The water-and oil-repellent agent of the present application contains the above-described fluorine-containing polymer. The fluorine-containing polymer itself can be used as the water-and oil-repellent agent, or can be used as the water-and oil-repellent agent in combination with other components described below.

[0152] The water-and oil-repellent agent of the present application contains the above-described fluorine-containing polymer having Rf 1 or Rf 2The water- and oil-repellent agent of the present application can not contain any of a compound 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 water- and oil-repellent agent of the present application can impart liquid repellency to a substrate even if it does not contain these fluorine compounds. In the present specification, the fluoroalkyl group can mean a group in which one or more hydrogen atoms on each carbon atom of an alkyl group is replaced with a fluorine atom.

[0153] [Amount of fluorine-containing compound] The amount of the fluorine-containing compound in the water- and oil-repellent agent can 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, and can 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 polymer itself can be used as the water- and oil-repellent agent.

[0154] [Other water- and oil-repellent agent components] The water- and oil-repellent agent of the present application can contain other water- and oil-repellent agent components. As the other water- and oil-repellent agent, a known water- and oil-repellent agent, such as a non-fluorine water- and oil-repellent agent component, can be used. As examples of the non-fluorine water- and oil-repellent agent component, for example, an acrylic acid polymer described in WO / 2020 / 054856, WO / 2017 / 159754, WO / 2020 / 162547, and the like, a polyurethane described in Japanese Patent Application Publication No. 2016-524628, Japanese Patent Application Publication No. 2017-533976, Japanese Patent Application Publication No. 2017-504730, WO / 2021 / 132170, WO / 2021 / 132172, and the like, a natural substance modifier described in WO / 2022 / 065382, WO / 2022 / 065385, and the like, and the like can be listed, but are not limited to these.

[0155] [Amount of other water- and oil-repellent agent components] The amount of the other water- and oil-repellent agent component can be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the fluorine-containing compound, and can 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.

[0156] [Dispersant] The water- and oil-repellent agent of the present application can contain a dispersant.

[0157] The dispersant can be at least one selected from organic dispersants and inorganic dispersants. The dispersant can be non-anionic, and can be at least one selected from nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants. The water- and oil-repellent agent can not contain an anionic dispersant.

[0158] The dispersant can use an organic dispersant and an inorganic dispersant respectively, or can be a combination of an organic dispersant and an inorganic dispersant.

[0159] As the dispersant, an organic dispersant can be used. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant means a surfactant.

[0160] The dispersant can be a non-fluorine dispersant.

[0161] [Nonionic dispersant] The dispersant can contain a nonionic dispersant. The nonionic dispersant can be a nonionic surfactant.

[0162] The nonionic dispersant can be low-molecular or high-molecular. The molecular weight can be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and can 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.

[0163] As examples of the nonionic dispersant, ethers, esters, ester ethers, alkylol amides, polyhydric alcohols, and amine oxides can be listed.

[0164] Examples of the ether include compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0165] Examples of the ester are esters of an alcohol and a fatty acid. Examples of the alcohol are alcohols of valence 1 to 6, particularly 2 to 5, and carbon number 1 to 50, particularly 10 to 30 (e.g., aliphatic alcohols). Examples of the fatty acid are saturated or unsaturated fatty acids of carbon number 2 to 50, particularly 5 to 30.

[0166] Examples of the ester ether are compounds in which an alkylene oxide, particularly ethylene oxide, is added to an ester of an alcohol and a fatty acid. Examples of the alcohol are alcohols of valence 1 to 6, particularly 2 to 5, and carbon number 1 to 50, particularly 3 to 30 (e.g., aliphatic alcohols). Examples of the fatty acid are saturated or unsaturated fatty acids of carbon number 2 to 50, particularly 5 to 30.

[0167] Examples of the alkanolamide are formed from a fatty acid and an alkanolamine. The alkanolamide can be monoalkanolamide or dialkanolamide. Examples of the fatty acid are saturated or unsaturated fatty acids of carbon number 2 to 50, particularly 5 to 30. The alkanolamine can be an alkanol of carbon number 2 to 50, particularly 5 to 30, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0168] The polyol can be an alcohol of valence 2 to 5 and carbon number 10 to 30.

[0169] The amine oxide can be an oxide of an amine (secondary amine or preferably tertiary amine) (e.g., carbon number 5 to 50).

[0170] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably polyoxyethylene). The carbon number of the alkylene group of the oxyalkylene group is preferably 2 to 10. The number of the oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0171] The nonionic dispersant is selected from the group consisting of an ether, an ester, an ester ether, an alkanolamide, a polyol, and an amine oxide, and is preferably a nonionic dispersant having an oxyalkylene group.

[0172] The nonionic dispersant can be an alkylene oxide adduct of a straight-chain and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a straight-chain and / or branched aliphatic acid (saturated and / or unsaturated), a sorbitan ester of a straight-chain and / or branched aliphatic acid (saturated and / or unsaturated), a glycerin ester of a straight-chain and / or branched aliphatic acid (saturated and / or unsaturated), a polyglycerin ester of a straight-chain and / or branched aliphatic acid (saturated and / or unsaturated), a sucrose ester of a straight-chain and / or branched aliphatic acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of an acetylenic diol, or the like. Among these, the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is preferably polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which can be a random copolymer or a block copolymer).

[0173] In addition, the nonionic dispersant can be free of an aromatic group.

[0174] The nonionic dispersant can be a compound represented by the formula: 1 O— (CH2CH2O) p — (R 2 O) q — R 3

[0175] [In the formula, 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 R 2 is independently the same or different and is an alkylene group having 3 or more (for example, 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.] R 1 is preferably 8 to 20, and particularly 10 to 18. As a preferred specific example of R 1 , lauryl, tridecyl, oleyl can be given.

[0176] Examples of R 2 include propylene, butylene.

[0177] In the nonionic dispersant, p can be a number of 3 or more (for example, 5 to 200). q can be a number of 2 or more (for example, 5 to 200). That is, — (R 2 O) q — can form a polyoxyalkylene chain. ​

[0178] The nonionic dispersant can be a polyoxyethylene alkylene alkyl ether having a central polyoxyethylene chain that is hydrophilic and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain). As the hydrophobic oxyalkylene chain, a propylene oxide chain, a butylene oxide chain, a styrene chain, or the like can be exemplified, of which a propylene oxide chain is preferred.

[0179] Specific examples of the nonionic dispersant include: condensation products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkyl (C 12 - C 16 )thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 - C 18 )amine, 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.

[0180] The proportion of the polyoxyethylene block with respect to the molecular weight of the nonionic dispersant (copolymer) can be 5 to 80% by weight, for example, 30 to 75% by weight, particularly 40 to 70% by weight.

[0181] The average molecular weight of the nonionic dispersant is generally 300 to 5000, for example, 500 to 3000.

[0182] The nonionic dispersant can be a single one or a mixture of two or more. The nonionic dispersant can be a mixture of a compound having an HLB (hydrophilic-lipophilic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more.

[0183] [Nonionic Dispersant] The dispersant can contain a nonionic dispersant. The nonionic dispersant can be a nonionic surfactant. The nonionic dispersant can be a low-molecular type (for example, a molecular weight of 2000 or less, particularly 10000 or less) or a high-molecular type (for example, a molecular weight of 2000 or more). The nonionic dispersant can be a compound having no amide group.

[0184] The nonionic dispersant can be a low-molecular type or a high-molecular type. The molecular weight can be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and can 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.

[0185] The cationic dispersant can be an amine salt, a quaternary ammonium salt, an oxyethylene-addition type ammonium salt. As specific examples of the cationic dispersant, there are no particular limitations, and examples that can be listed are: amine salt type dispersants of alkyl amine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like; quaternary ammonium salt type dispersants of alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts, benzalkonium chloride, benzethonium chloride, and the like.

[0186] Preferred examples of the cationic dispersant are compounds represented by the formula: 21 — N ＋ (— R 22 )(— R 23 )(— R 24 )X － .

[0187] [In the formula, R 21 , R 22 , R 23 , and R 24 are hydrocarbon groups having a carbon atom number of 1 to 40, X is an anionic group.] R 21 , R 22 , R 23 , and — R 24 are specific examples of alkyl groups (e.g., methyl, butyl, stearyl, palmitoyl). Specific examples of X are halogens (e.g., chlorine), acids (e.g., hydrochloric acid, acetic acid).

[0188] The cationic dispersant is particularly preferably a monoalkyl trimethyl ammonium salt (the carbon atom number of the alkyl group is 4 to 40).

[0189] The cationic dispersant is preferably an ammonium salt. The cationic dispersant can be an ammonium salt represented by the formula: R 1 p — N ＋ R 2 q X － .

[0190] [In the formula, R 1 is a linear and / or branched aliphatic (saturated and / or unsaturated) group of C12 or more (e.g., C 12 ~ C 50 ), R 2 is H or an alkyl group of C1~4, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, especially 3) to 50) (particularly preferably CH3, C2H5), X is a halogen atom (e.g., Cl), a C1~C4 fatty acid salt group, p is 1 or 2, q is 2 or 3, and p + q = 4. R 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[0191] Specific examples of the cationic dispersant include: dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydroxypolyoxyethylene)ammonium chloride, benzyldodecyldi(hydroxypolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0192] [Anionic dispersant] The dispersant can contain an anionic dispersant. The anionic dispersant can be an anionic surfactant. The dispersant can also not contain an anionic dispersant.

[0193] The anionic dispersant can be low-molecular or high-molecular. The molecular weight can be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and can 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.

[0194] As examples of the anionic dispersant, alkyl ether sulfate salts, alkyl sulfate salts, alkenyl ether sulfate salts, alkenyl sulfate salts, olefin sulfonate salts, alkane sulfonate salts, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylic acid salts, α-fatty sulfonic acid salts, N-acyl amino acid type dispersants, phosphoric acid monoester or diester type dispersants, and sulfosuccinates can be listed.

[0195] [Amphoteric dispersant] The dispersant can contain an amphoteric dispersant. The amphoteric dispersant can be an amphoteric surfactant.

[0196] The amphoteric dispersant can be low-molecular or high-molecular. The molecular weight can be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and can 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.

[0197] As examples of the amphoteric dispersants, there can be mentioned alanine type, imidazolinium betaine type, amido betaine type, and betaine acetate, and specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amido propyl dimethylamino acetic acid betaine.

[0198] [Inorganic dispersant] The dispersant can contain an inorganic dispersant.

[0199] The average primary particle diameter of the inorganic dispersant can 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 can 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 can be a hydrophilic particle.

[0200] As examples of the inorganic dispersant, there can be mentioned: phosphoric acid polyvalent metal salts 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, and the like.

[0201] [Amount of dispersant] The amount of the dispersant can be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and can 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, relative to 100 parts by weight of the fluorine-containing compound.

[0202] [liquid medium] The water- and oil-repellent agent of the present application can contain a liquid medium. The liquid medium can be water, an organic solvent, or a mixture of water and an organic solvent. The water- and oil-repellent agent can be a dispersion or a solution. The water- and oil-repellent agent of the present application can be water-dispersible, and can contain at least water.

[0203] Examples of the organic solvent are 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), 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 can contain a compound having at least one hydroxyl group (e.g., alcohols, glycol solvents, and the like, ethers of polyhydric alcohols (e.g., monoethers), and the like). They can be used alone or in combination of two or more.

[0204] [Amount of liquid medium] The amount of the liquid medium can 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, and can 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, relative to 1 part by weight of the fluorine-containing compound 1.

[0205] The amount of water can 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, and can 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, relative to 1 part by weight of the fluorine-containing compound 1.

[0206] The amount of the organic solvent can 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, relative to 1 part by weight of the fluorine-containing compound, and can 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.

[0207] 〔Silicone〕 The water- and oil-repellent agent of the present application can contain a silicone (polyorganosiloxane). By containing a silicone, in addition to good liquid repellency, good hand and durability can also be achieved.

[0208] As the silicone, known silicones can be used, and as examples of the silicone, polydimethylsiloxane, modified silicones (amino-modified, epoxy-modified silicone, carboxyl-modified silicone, methyl hydrogen silicone, etc.) can be listed. The silicone can be a silicone wax having a waxy property. They can be used alone or two or more kinds can be used in combination.

[0209] The weight average molecular weight of the silicone can be 1000 or more, 10000 or more, or 50000 or more, and can be 500000 or less, 250000 or less, 100000 or less, or 50000 or less.

[0210] [Amount of Silicone] The amount of the silicone can 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, relative to 100 parts by weight of the fluorine-containing compound, and can 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.

[0211] 〔Wax〕 The water- and oil-repellent agent of the present application can contain a wax. By containing a wax, good liquid repellency can be imparted to the substrate.

[0212] As examples of the wax, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and plant wax, and mineral wax, etc. can be listed. Paraffin wax is preferred. Specific examples of the compound constituting the wax are n-alkane (e.g., n-tricosane, n-tetracosane, n-pentacosane, n-hexacosane, n-heptacosane, n-octacosane, n-nonacosane, n-triacontane, n-hentriacontane, n-dotriacontane, n-tritriacontane, n-tetratriacontane, n-pentatriacontane, n-hexatriacontane), n-alkene (e.g., 1-n-eicosene, 1-n-docosene, 1-n-tricosene, 1-n-tetracosene, 1-n-pentacosene, 1-n-hexacosene, 1-n-heptacosene, 1-n-octacosene, 1-n-nonacosene, 1-n-triacontene, 1-n-hentriacontene, 1-n-dotriacontene, 1-n-tritriacontene, 1-n-tetratriacontene, 1-n-pentatriacontene, 1-n-hexatriacontene). The number of carbon atoms of the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax can be 200 to 2000, for example, 250 to 1500, 300 to 1000. They can be used alone or two or more of them can be used in combination.

[0213] The melting point of the wax can 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 can 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 can be measured in accordance with JIS K 2235-1991.

[0214] [Amount of wax] The amount of the wax can be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and can 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, with respect to 100 parts by weight of the fluoropolymer.

[0215] [Organic acid] The water- and oil-repellent agent of the present application can contain an organic acid. As the organic acid, a publicly known organic acid can be used. As the organic acid, carboxylic acids, sulfonic acids, sulfinic acids and the like are preferably mentioned, with carboxylic acids being particularly preferred. As the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid and the like can be mentioned, with formic acid or acetic acid being particularly preferred. In the present application, one kind of organic acid can be used or two or more kinds of organic acids can be used in combination. For example, formic acid and acetic acid can be used in combination.

[0216] [Amount of organic acid] The amount of the organic acid can be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more or 100 parts by weight or more, and can 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, relative to 100 parts by weight of the fluorine-containing compound. The amount of the organic acid can be adjusted so that the pH of the water- and oil-repellent agent becomes 3 to 10, for example, 5 to 9, particularly 6 to 8. The water- and oil-repellent agent can be acidic (pH of 7 or less, for example, 6 or less).

[0217] [Hardening agent] The water- and oil-repellent agent of the present application can contain a hardening agent (a reactive hydrogen reactive compound or a reactive hydrogen-containing compound).

[0218] The hardening agent (crosslinking agent) in the water- and oil-repellent agent can allow the fluorine-containing polymer to be well cured. The hardening agent can be a reactive hydrogen reactive compound or a reactive hydrogen-containing compound which reacts with the reactive hydrogen or the reactive hydrogen reactive group possessed by the fluorine-containing compound. Examples of the reactive hydrogen reactive compound are isocyanate compounds, epoxy compounds, chlorine-methyl-containing compounds, carboxyl-containing compounds and hydrazide compounds. Examples of the reactive hydrogen-containing compound are hydroxyl-containing compounds, amino-containing compounds and carboxyl-containing compounds, ketone-containing compounds, hydrazide compounds and melamine compounds.

[0219] The curing agent can contain an isocyanate compound. The isocyanate compound can be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of the polyisocyanate compound can include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound can be a blocked isocyanate compound (e.g., a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked with a blocking agent to inhibit reaction.

[0220] Examples of the aliphatic polyisocyanate 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 methyl 2,6-diisocyanatohexanoate, and aliphatic triisocyanates such as 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 the like. They can be used alone or in combination of two or more.

[0221] Examples of the alicyclic polyisocyanate include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of the alicyclic polyisocyanate include 1,3-cyclopentylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3,5-triisocyanatocyclohexane. They can be used alone or in combination of two or more.

[0222] Examples of the aromatic aliphatic polyisocyanate include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of the aromatic aliphatic polyisocyanate include 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, 1,3,5-triisocyanatomethylbenzene. They can be used alone or in combination of two or more.

[0223] Examples of the aromatic polyisocyanate include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of the aromatic polyisocyanate include 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, and the like. They can be used alone or in combination of two or more.

[0224] Examples of the derivative of the polyisocyanate include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, urethdiones, isocyanurates, iminooxadiazinediones, and the like. They can be used alone or in combination of two or more.

[0225] These polyisocyanates can be used alone or in combination of two or more.

[0226] As the polyisocyanate compound, it is preferable to use a compound in which the isocyanate group of the polyisocyanate compound is blocked with a blocking agent, i.e., a blocked polyisocyanate compound (blocked isocyanate). The blocked polyisocyanate compound is preferable because it is stable in a solution, can be used in the same solution as the water- and oil-repellent agent, and the like. The blocked polyisocyanate compound is preferable.

[0227] The blocking agent is a substance that blocks the free isocyanate group. The blocked polyisocyanate compound regenerates the isocyanate group when heated to, for example, 100°C or higher, for example, 130°C or higher, and can easily react with the hydroxyl group. Examples of the blocking agent include phenol-based compounds, lactam-based compounds, aliphatic alcohol-based compounds, oxime-based compounds, and the like. The polyisocyanate compound can be used alone or in combination of two or more.

[0228] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether, and sorbitol polyglycidyl ether, and the like.

[0229] The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include chloromethyl polystyrene, and the like.

[0230] The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid, (poly)methacrylic acid, and the like.

[0231] As specific examples of the ketone group-containing compound, (poly)diketone acrylamide, diketone alcohol, and the like can be listed.

[0232] As specific examples of the hydrazine compound, hydrazine, carbohydrazide, adipic acid hydrazide, and the like can be given.

[0233] As specific examples of the melamine compound, melamine resin, methyl etherified melamine resin, and the like can be given.

[0234] [Amount of curing agent] The amount of the curing agent can be 0.1 parts by weight or more, 1 parts 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, or 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, and can 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, relative to 100 parts by weight of the fluorine-containing compound.

[0235] [Other components] The water- and oil-repellent agent can contain other components in addition to the above components. As examples of the other components, polysaccharides, paper strength enhancers, coagulants, retention aids, coagulants, adhesive resins, anti-slip agents, sizing agents, paper strength enhancers, PVA, penetrants, organic acids, pigments, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, perfumes, and the like can be given. They can be used alone or two or more of them can be used in combination.

[0236] In addition to the above-mentioned components, as other components, other water- and / or oil-repellents, dispersants, hand adjusters, softening agents, flame retardants, coating fixatives, anti-wrinkling agents, drying speed adjusters, crosslinking agents, film-forming aids, solubilizers, antifreezes, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, antifoaming agents, shrinkage preventives, wash-and-wrinkle preventives, shape retainers, drape retainers, ironing property improvers, whitening agents, whitening agents, clay for softening of cloth, anti-migration agents such as polyvinylpyrrolidone, high-molecular dispersants, soil release agents, scum dispersants, fluorescent whitening 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, bleaching agents, enzymes such as cellulase, amylase, protease, lipase, cutinase, as fiber surface modifiers, antifoaming agents, silk fibroin powder, surface-modified products thereof, or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (Kamoi), SILKGEN G Soluble S (ICHIMARU PHARCOS Co., Ltd.)), anti-pollution agents (e.g., nonionic high-molecular compounds composed of alkylene glycol terephthalate and / or alkylene glycol isophthalate units, and polyoxyalkylene units (e.g., FR627 manufactured by Mutsumi Chemical Industry), SRC-1 manufactured by CLARIANT Japan, and the like) and the like can be compounded. They can be used alone or two or more of them can be used in combination.

[0237] [Polysaccharides] As examples of the polysaccharides, starch, xanthan gum, gum karaya, gum temoleo, 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 nanofilament, cellulose nanofilament, and pullulan, and the like can be given. The polysaccharides can also be substituted modified polysaccharides, and in particular, modified polysaccharides into which a hydroxyl group or a cationic group has been introduced.

[0238] [Paper strength enhancers, coagulants, retention aids, or coagulants] As examples of the paper strength enhancer, coagulant, retention aid, or coagulating agent, there can be mentioned styrene-based polymers (styrene / maleic acid-based polymers, styrene / acrylic acid-based polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide-based polymers, polyamine-based polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamine, dicyandiamide-aldehyde condensates, dimethyldiallyl ammonium chloride polymers, and olefin / maleic anhydride polymers, and the like.

[0239] [Size] As examples of the size, there can be mentioned cellulose-reactive sizes, rosin-based sizes such as rosin-based soaps and the like, rosin-based emulsions / dispersions, emulsions / dispersions of anhydrides such as alkyl and alkenyl succinic anhydride (ASA) and the like, 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.

[0240] [Antistatic agent] As examples of the antistatic agent, there can be mentioned quaternary ammonium salts, pyridinium salts, cationic antistatic agents having cationic functional groups such as primary amino groups, secondary amino groups, tertiary amino groups, and the like; anionic antistatic agents having anionic functional groups such as sulfonate salts or sulfate salts, phosphonate salts, phosphate salts, and the like; amphoteric antistatic agents such as alkyl betaines and derivatives thereof, imidazolines and derivatives thereof, alanines and derivatives thereof, and the like; nonionic antistatic agents such as amino alcohols and derivatives thereof, glycerol and derivatives thereof, polyethylene glycol and derivatives thereof, and the like. There can also be mentioned ion conductive polymers obtained by polymerizing or copolymerizing monomers having ion conductive groups of the cationic, anionic, and zwitterionic types. These can be used alone or in combination of two or more.

[0241] [Preservative] The preservative is mainly used to enhance the preservative and bactericidal power, and to ensure the preservative property in long-term storage. As the preservative, there can be mentioned, for example, isothiazolinone-based organic sulfur compounds, benzisothiazolinone-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, and the like.

[0242] [UV absorber] The UV absorber is an agent having the effect of defending against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays or visible light and releases them. As the UV absorber, there can be mentioned, for example, aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole-based compounds, 4-tert-butyl-4'-methoxybenzoylmethane, and the like.

[0243] [Antibacterial agent] The antibacterial agent is a component having an effect of inhibiting the proliferation of bacteria on a fiber and inhibiting the generation of an odor from a decomposition product of microorganisms. As the antibacterial agent, for example, a cationic bactericide such as a quaternary ammonium salt, bis(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanide hydrochloride, 8-oxoquinoline, polylysine, and the like can be listed.

[0244] [Deodorant] As the deodorant, highly branched cyclic dextrin (Cluster Dextrin), methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamide propyl dimethyl amine oxide, amino carboxylic acid-based metal complex (zinc complex of trisodium methyl glycine diacetate described in International Publication No. 2012 / 090580), and the like can be listed.

[0245] [Amount of other components] The amount of each of the other components or the total amount thereof can be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and can 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, with respect to 100 parts by weight of the fluorine-containing polymer.

[0246] <Manufacturing method of treated fiber product or paper product> The manufacturing method of a treated product using a water- and oil-repellent agent in the present application includes a treatment step of treating a base material with the water- and oil-repellent agent described above.

[0247] The "treatment" means that the water- and oil-repellent agent is applied to the base material by dipping, spraying, coating, or the like. By the treatment, the fluorine-containing polymer as an effective component of the water- and oil-repellent agent is attached to the inside and / or surface of the base material. Among them, the attachment can be physical attachment or chemical attachment, and for example, the fluorine-containing polymer can be physically modified or (reactively) chemically modified by the hydroxyl group possessed by the base material (fiber, paper, glass, or the like).

[0248] [Base material] The base material treated with the water- and oil-repellent agent in the present application is not limited, and is preferably a fiber product or a paper product, particularly a paper product.

[0249] The water- and oil-repellent agent in the present application can impart water repellency to a substrate (e.g., a fiber substrate, a paper substrate), and can exert at least one function selected from water-repellent agents, oil-repellent agents, oil-resistant agents, and water-resistant agents. The substrate treated with the water- and oil-repellent agent in the present application is, for example, an oil-resistant paper or a water-resistant paper.

[0250] As examples of the substrate of the fiber product, there can be mentioned natural fibers of plants and animals such as cotton, hemp, wool, silk, and the like; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, and the like; semisynthetic fibers such as rayon, acetate fiber, and the like; inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, and the like; or mixed fibers thereof. The fiber product includes woven fabric, knitted fabric, and nonwoven fabric, cloth in clothing form (e.g., water-repellent clothing such as rainwear), and carpet, but can also be applied to fibers, filaments, and intermediate fiber products (e.g., slivers or roving, and the like) in a state before being made into cloth.

[0251] As examples of the substrate of the paper product, there can be mentioned paper formed of 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 waste newspaper, waste magazine paper, waste corrugated paper, or deinked waste paper, and the like, containers formed of paper, molded bodies formed of paper, and the like. As specific examples of the paper product, there can be mentioned food packaging materials, food containers, plaster board base paper, coating base paper, medium weight paper, ordinary liner and medium core, neutral pure white roll paper, neutral liner, rust-proof liner and metal composite paper, kraft paper, neutral printing and writing paper, neutral coating base paper, neutral PPC paper, neutral heat-sensitive paper, neutral pressure-sensitive base paper, neutral ink-jet paper, and neutral information paper, molded paper (molded container), and the like. As preferred examples, there can be mentioned food packaging materials and food containers.

[0252] As the substrate treated with the water- and oil-repellent agent of the present application, it is not limited to the fiber product or the paper product, and in addition to these, there can be mentioned stone, filters (e.g., electrostatic filters), dust masks, components of fuel cells (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, kiln products, plastics, painted surfaces, and plaster, and the like.

[0253] In the case where the substrate is glass, the manufactured glass product can be an optical member. The surface (the outermost layer) of the glass substrate can be formed with certain layers (or films), such as a hard coat layer or an antireflection layer. The antireflection layer can use either of a single-layer antireflection layer and a multilayer antireflection layer. As examples of inorganic substances that can be used as the antireflection layer, SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, and the like can be listed. These inorganic substances can be used alone, or two or more of them can be used in combination (e.g., in the form of a mixture). In the case where a multilayer antireflection layer is formed, it is preferable that the outermost layer thereof use SiO2and / or SiO. In the case where the article to be manufactured is an optical glass member for a touch panel, a part of the surface of the substrate (glass) can have a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide, or the like. In addition, the substrate can have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a haze film layer, a hard coat film layer, a polarizing film, a phase difference film, a liquid crystal display module, and the like, depending on the specific style thereof or the like.

[0254] [Method of treatment] The water- and oil-repellent agent of the present application can be applied to a substrate as a treatment agent (particularly, a surface treatment agent) by a publicly known method. As the method of treatment, there can be a method of diluting the water- and oil-repellent agent of the present application as needed by dispersing it in an organic solvent or water, and then adhering it to the inside and / or surface of a substrate by a publicly known method such as dip coating, spray coating, or sponge coating, and then drying. After drying, an article to which a solid component of the water- and oil-repellent agent is adhered can be obtained. Also, it can be applied together with a suitable crosslinking agent as needed, and cured. The water- and oil-repellent agent of the present application can also be used further with various additives such as a water- and / or oil-repellent agent, an antislip agent, an antistatic agent, a hand adjuster, a softening agent, an antibacterial agent, a flame retardant, a paint fixing agent, a wrinkle preventing agent, a drying speed adjuster, a crosslinking agent, a film forming aid, a solubilizing agent, an antifreezing agent, a viscosity adjuster, an ultraviolet absorber, an antioxidant, a pH adjuster, an insect repellent, an antifoaming agent, and the like, as needed. As examples of the various additives, there can be the same substances as those described in the description of "other components" in the above description. The concentration of the water- and oil-repellent agent in the treatment agent that comes into contact with the substrate can be changed as appropriate depending on the use, and can be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0255] The water- and oil-repellent agent can be applied to the substrate by any known method for treating a substrate with a liquid. The substrate can be immersed in the water- and oil-repellent agent, or the solution can be attached or sprayed to the substrate. In order to impart water repellency to the treated substrate, drying and curing are preferably performed by heating. The heating temperature is, for example, 100 to 200°C, 100 to 170°C, or 100 to 120°C. In the present application, even with low-temperature heating (for example, 100 to 140°C), good performance can be obtained. The heating time in the present application can be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the substrate is paper, the water- and oil-repellent agent can be applied by coating on the paper, or the solution can be attached or sprayed to the paper, or the treatment can be performed by mixing with a paper pulp slurry before papermaking. The treatment can be an external treatment or an internal treatment. Alternatively, the water- and oil-repellent agent can be applied to a fibrous product by a cleaning method, for example, by washing or using a dry cleaning method, and the like.

[0256] [Processing of paper products] As the paper substrate, paper, a container formed of paper, a molded body formed of paper (for example, a pulp molded product), and the like can be mentioned. The fluorine-containing compound of the present application can be attached to the paper substrate favorably.

[0257] The paper can be manufactured by a publicly known papermaking method. An internal treatment method in which the water- and oil-repellent agent is added to a paper pulp slurry before papermaking, or an external treatment method in which the water- and oil-repellent agent is applied to paper after papermaking can be employed.

[0258] The sizing of the external treatment method can also be classified according to the coating method as follows.

[0259] One of the coating methods is a so-called size pond type double roll sizing in which a coating liquid (sizing liquid) is supplied to a nip portion formed by passing paper between two rubber rolls, a coating liquid storage portion called a size pond is formed, and the paper is passed through the coating liquid storage portion to coat the sizing liquid on both sides of the paper. Other coating methods include a gate roll type in which the sizing liquid is coated using a surface transfer die, and a film transfer sizing. In the size pond type double roll sizing, the sizing liquid easily penetrates into the inside of the paper; in the surface transfer die, the components of the sizing liquid easily remain on the surface of the paper. The surface transfer die is such that the coating layer easily remains on the surface of the paper, and the coating layer formed on the surface is more than that in the size pond type double roll sizing. In the present application, in the case where the former size pond type double roll sizing is used, the paper can be imparted with performance. The paper treated in this way can exhibit excellent oil and water resistance, and the like by simple drying at room temperature or at a high temperature, and optionally, heat treatment at a temperature of 300°C or lower, for example, 200°C or lower, particularly, in the range of 80 to 180°C, depending on the properties of the paper.

[0260] The internal addition treatment method can mean a treatment method in which a water / oil repellent is added to a pulp slurry before papermaking. As the internal addition treatment method, one or more of the following processes can be included, but is not limited thereto: a process in which a water / oil repellent is added to a pulp slurry and mixed by stirring; a process in which a pulp composition prepared in the process is suction-dewatered using a mesh body having a predetermined shape, and the pulp composition is stacked to form a pulp molded intermediate; and a process in which the pulp molded intermediate is formed and dried by using a heated forming mold to obtain paper, a container formed of paper, or a formed body formed of paper. The treated paper can be optionally subjected to heat treatment after being simply dried at room temperature or at a high temperature, depending on the properties of the paper. The temperature of the heat treatment can be 150°C or higher, 180°C or higher, or 210°C or higher, and can be 300°C or lower, 250°C or lower, or 200°C or lower, and in particular, can be 80°C to 180°C. By performing heat treatment in such a temperature range, excellent oil resistance and water resistance, and the like can be exhibited.

[0261] The present application can be used in gypsum board base paper, coating base paper, medium paper, ordinary liner and medium core, neutral pure white web, neutral liner, anti-rust liner and metal composite paper, kraft paper, and the like. Furthermore, it can also be used in neutral printing and writing paper, neutral coating base paper, neutral PPC paper, neutral heat-sensitive paper, neutral pressure-sensitive base paper, neutral ink-jet paper, and neutral information paper.

[0262] As the pulp raw material, any of waste paper pulp such as bleached or unbleached chemical pulp of kraft pulp or sulfite pulp, bleached or unbleached high yield pulp of groundwood pulp, mechanical pulp, or thermomechanical pulp, waste newspaper, waste magazine paper, waste corrugated paper, or deinked waste paper can be used. In addition, a mixture of the above-mentioned pulp raw material and synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, polyvinyl alcohol, or the like can also be used.

[0263] The addition of a sizing agent can improve the water resistance of the paper. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, rosin-based sizing agents (for example, acidic rosin-based sizing agents, neutral rosin-based sizing agents). The amount of the sizing agent can be 0.01 to 5% by weight with respect to the pulp.

[0264] The paper can use, as needed, paper strength agents such as starch, modified starch, carboxymethyl cellulose, polyamide polyamine-epichlorohydrin resin, or the like, coagulants, fixatives, retention aids, dyes, fluorescent dyes, viscosity control agents, defoaming agents, and the like, which are papermaking reagents used to the extent of being generally used, as additives used at the time of papermaking. Starch and modified starch are preferably used. As needed, starch, polyvinyl alcohol, dyes, color coating agents, anti-slip agents, and the like can be used, and the water / oil repellent can be applied to the paper using a size press, a gate roll coater, a blade coater, a calender, or the like.

[0265] The amount of the fluorine-containing compound contained in the coating layer is preferably 0.01 to 2.0 g / m 2 , more preferably 0.1 to 1.0 g / m 2 . The coating layer is preferably formed of a water- and oil-repellent agent and starch and / or modified starch. The amount of the solid content of the water- and oil-repellent agent in the coating layer is preferably 2 g / m 2 or less.

[0266] In the internal addition, the water- and oil-repellent agent is preferably mixed with the pulp in an amount of 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, relative to 100 parts by weight of the pulp for forming paper.

[0267] In the external addition, the oil resistance can be imparted to the paper by using a so-called size press double roll application process in which the raw paper is passed through the treatment liquid held between rolls at an arbitrary roll speed and nip pressure.

[0268] In the external addition process, the paper base material can contain an additive such as a sizing agent, a paper strength enhancer, a coagulant, a retention aid, or a coagulant. The additive can be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additive can be -10,000 to 10,000 μeq / g, preferably -4,000 to 8,000 μeq / g, more preferably -1,000 to 7,000 μeq / g. The amount of the additive (e.g., a sizing agent, a paper strength enhancer, a coagulant, a retention aid, or a coagulant, such as a solid content or an active ingredient) used relative to the pulp is usually 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight). In the case of a paper base material containing a cationic additive (e.g., a sizing agent, a paper strength enhancer, a coagulant, a retention aid, or a coagulant), the water- and oil-repellent agent can be anionic; in the case of containing an anionic additive, the water- and oil-repellent agent can be cationic, but is not limited to these.

[0269] In the internal addition treatment, a paper pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (e.g., 2.5 to 4.0% by weight) is preferably used for papermaking. Additives (e.g., a sizing agent, a paper strength enhancer, a coagulant, a retention aid, or a coagulant, etc.) and a fluorine-containing compound can be added to the paper pulp slurry. Examples of the additives (e.g., a sizing agent, a paper strength enhancer, a coagulant, a retention aid, or a coagulant, etc.) include alkylalkeneketene dimer, alkenyl succinic anhydride, a styrene-based polymer (styrene / maleic acid-based polymer, styrene / acrylic acid-based polymer), urea-formaldehyde polymer, polyethylene imine, melamine-formaldehyde polymer, polyamidoamine-epichlorohydrin polymer, polyacrylamide-based polymer, polyamine-based polymer, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensate, condensate of alkylene dichloride and polyalkylene polyamine, dicyandiamide-aldehyde condensate, dimethyldiallyl ammonium chloride polymer, olefin / maleic anhydride polymer.

[0270] In the internal addition treatment, the paper base material can contain additives such as a sizing agent, a paper strength enhancer, a coagulant, a retention aid, or a coagulant. The additives can be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives can be -10,000 to 10,000 μeq / g, preferably -4,000 to 8,000 μeq / g, and more preferably -1,000 to 7,000 μeq / g. The amount of the additives (e.g., a sizing agent, a paper strength enhancer, a coagulant, a retention aid, or a coagulant, such as a solid content or an active ingredient) used with respect to the pulp is usually 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight). In the case of a paper base material containing a cationic additive (e.g., a sizing agent, a paper strength enhancer, a coagulant, a retention aid, or a coagulant), the water- and oil-repellent agent can be anionic; in the case of a paper base material containing an anionic additive, the water- and oil-repellent agent can be cationic, but is not limited to these.

[0271] The oil resistance (KIT method) of the treated paper product can be measured in accordance with TAPPI T-559 cm-02. The paper product can be an externally treated product. The KIT test solution is a test solution prepared by mixing castor oil, toluene, and heptane at the ratios shown in the table below. One drop of the test solution shown in the table is placed on the paper, and the state of penetration of the oil is observed after 15 seconds. The highest score for the oil resistance degree imparted by the KIT test solution that does not show penetration is taken as the oil resistance. The larger the number of the KIT test solution, the higher the oil resistance. The high-temperature oil resistance of the treated paper product is measured as follows. The paper product can be an internally treated product. In a paper pulp molded product formed on a container, 100 ml of corn oil at 65°C is added, and after 30 minutes, the corn oil is poured out, and the degree of penetration of the oil into the paper pulp molded product is evaluated in accordance with the following criteria.

[0272] 4: Almost no oil stain is observed on the inner side of the bottom of the container 3: No oil stain is observed on the outer side of the bottom of the container 2: The area of the oil stain observed on the outer side of the bottom of the container is less than 5% 1: The area of the oil stain observed on the outer side of the bottom of the container is 5% or more but less than 50% 0: The area of the oil stain observed on the outer side of the bottom of the container is 5% or more The high-temperature water resistance of the treated paper product is determined as follows. The paper product can be a product treated by internal addition. In a paper pulp molded product formed on a container, 100 ml of warm water at 80°C is added, and after 30 minutes, the warm water is poured out, and the degree of penetration of oil into the paper pulp molded product is evaluated according to the following criteria.

[0273] 4: Almost no oil stain is observed on the inner side of the bottom of the container 3: No oil stain is observed on the outer side of the bottom of the container 2: The area of the oil stain observed on the outer side of the bottom of the container is less than 5% 1: The area of the oil stain observed on the outer side of the bottom of the container is 5% or more but less than 50% 0: The area of the oil stain observed on the outer side of the bottom of the container is 5% or more [Pre-treatment of fiber product] The fiber product can be subjected to pre-treatment before being treated with the water- and oil-repellent agent of the present application. By subjecting the fiber product to pre-treatment, the treated fiber product can be imparted with excellent fastness by the water- and oil-repellent agent.

[0274] Examples of the pre-treatment of the fiber product can include cationization treatment using reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, phosphonation, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannin treatment, high molecular coating treatment, and the like.

[0275] As the method of pre-treating the fiber product, there is no limitation, and the fiber product can be pre-treated using a publicly known method. The pre-treatment liquid can be diluted by being dispersed in an organic solvent or water as needed, and attached to the inside and / or surface of the fiber product by a publicly known method such as dip coating, spray coating, and sponge coating, followed by drying. The pH and temperature of the pre-treatment liquid can be adjusted according to the desired degree of treatment. As an example of the method of pre-treating the fiber product, the method of pre-treating the fiber product with the above-mentioned treatment agent is described in detail.

[0276] The pre-treatment method of the fiber product can include providing the fiber with a monovalent group selected from -SO3M 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M2 a monovalent group represented by -O-P(O)(OX 1 )(OX 2 (in the formula, X 1 and X 2 independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) and a monovalent group represented by -O-P(O)(OX

[0277] As M 1 , H, K, Na or an ammonium ion which can have a substituent can be given. As M 2 , H, K, Na or an ammonium ion which can have a substituent can be given. In the case where X 1 or X 2 is an alkyl group, an alkyl group having 1 to 22 carbon atoms is preferred, and an alkyl group having 4 to 12 carbon atoms is more preferred.

[0278] A fiber containing the above-described specific functional group (hereinafter also referred to as "functional group-containing fiber" in some cases) can be prepared, for example, by the following method.

[0279] (i) A compound having the above-described specific functional group is attached to a fiber material. Here, the attachment of the compound can be in a state where a part of the compound is chemically bound to a part of the fiber in a range where a sufficient amount of the above-described specific functional group remains.

[0280] (ii) A fiber in which the above-described specific functional group is directly introduced into a material constituting the fiber is prepared.

[0281] In the case of (i), for example, a fiber material is treated with a pretreatment liquid containing one or more compounds having the above-described specific functional group, and a functional group-introducing step is performed, whereby a functional group-containing fiber can be obtained.

[0282] As a raw material of the fiber material, there is no particular limitation, and natural fibers such as cotton, hemp, silk, wool, semi-synthetic fibers such as rayon, acetate fibers, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, polypropylene, and composite fibers, blended fibers, and the like thereof can be given. The form of the fiber material can be any form of fiber (tow, sliver, etc.), yarn, woven fabric (including mixed weaving), nonwoven fabric, and the like.

[0283] In the present embodiment, from the viewpoint of water repellency of the obtained fiber product, it is preferred to use a fiber material containing polyamide and polyester as a raw material, and particularly preferably nylon 6, nylon 6,6, and the like, polyethylene terephthalate (PET), polytrimethyl terephthalate, polylactic acid, and the like, and a blended fiber containing the same.

[0284] As the compound having the above -SO3M 1 , a phenol-based polymer can be used. As such a phenol-based polymer, for example, a substance containing at least one compound represented by the following general formula can be listed. [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.] [In the formula, M 4 represents a monovalent cation.] As the above M 3 , H, K, Na or an ammonium ion which can have a substituent can be listed.

[0285] As the above M 4 , H, K, Na or an ammonium ion which can have a substituent can be listed.

[0286] The compound represented by the above general formula can be, for example, a formalin condensate of phenol sulfonic acid, a formalin condensate of sulfonated bisphenol S.

[0287] As the compound having the above -COOM 2 , a polycarboxylic acid-based polymer can be listed.

[0288] As the polycarboxylic acid-based polymer, for example, a polymer synthesized by using acrylic acid, methacrylic acid, maleic acid or the like as a monomer according to a radical polymerization method which is publicly known at present, or a commercial product can be used.

[0289] As a method of producing the polycarboxylic acid-based polymer, for example, a method of adding a radical polymerization initiator to an aqueous solution of the above monomer and / or a salt thereof, and performing a heating reaction at 30 to 150°C for 2 to 5 hours can be listed. At this time, an alcohol such as methanol, ethanol, isopropyl alcohol or an aqueous solvent such as acetone can also be added to the aqueous solution of the above monomer and / or a salt thereof. As the radical polymerization initiator, for example, a persulfate salt such as potassium persulfate, sodium persulfate, ammonium persulfate, a redox-based polymerization initiator using a combination of a persulfate salt and sodium bisulfite or the like, hydrogen peroxide, a water-soluble azo-based polymerization initiator or the like can be listed. These radical polymerization initiators can be used alone or two or more kinds can be used in combination. In addition, in the radical polymerization, in order to adjust the degree of polymerization, a chain transfer agent (for example, octyl mercaptoacetate) can be added.

[0290] In addition to the above-mentioned monomers, a copolymerizable monomer can be used in the radical polymerization. As the copolymerizable monomer, ethylene-based monomers such as ethylene, vinyl chloride, vinyl acetate, and the like; acrylamide, acrylate esters, methacrylate esters, and the like can be exemplified. The acrylate esters and methacrylate esters preferably have a hydrocarbon group having 1 to 3 carbon atoms which can have a substituent group such as a hydroxyl group. As such acrylate esters or methacrylate esters, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, propyl methacrylate, and the like can be exemplified. These copolymerizable monomers can be used alone or two or more kinds thereof can be used in combination.

[0291] The carboxyl group in the polycarboxylic acid-based polymer can be free or can be neutralized by an alkali metal or an amine-based compound or the like. As the alkali metal, sodium, potassium, lithium, and the like can be exemplified; as the amine-based compound, ammonia, monoethanolamine, diethanolamine, triethanolamine, and the like can be exemplified.

[0292] The weight average molecular weight of the polycarboxylic acid-based polymer is preferably 1000 to 20000, more preferably 3000 to 15000, from the viewpoint of good water repellency of the resulting fiber product.

[0293] As the polycarboxylic acid-based polymer, commercially available products such as "NEOCRYSTAL 770" (manufactured by Nippon Shokubai Co., Ltd., trade name), "Celopol PC-300" (manufactured by Sanko Chemical Industry Co., Ltd., trade name), and the like can be used.

[0294] As the compound having the above -O-P(O)(OX 1 )(OX 2 , for example, phosphate ester compounds represented by the following general formula can be exemplified. [In the formula, X 1 or X 2 have the same meanings as above, and X 3 represents an alkyl group having 1 to 22 carbon atoms.] As the above phosphate ester compound, monoesters, diesters, and triesters of phosphoric acid in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0295] From the viewpoint of good water repellency of the resulting fiber product, lauryl phosphate, decyl phosphate are preferably used.

[0296] The phosphate ester compound can be used, for example, commercially available products such as "PHOSPHANOL ML-200" (manufactured by Toyobo Co., Ltd., trade name), and the like.

[0297] The pretreatment liquid containing one or more compounds having the above specific functional group can be, for example, an aqueous solution of the above compound. In addition, the pretreatment liquid can also contain an acid, a base, a surfactant, a chelating agent, and the like.

[0298] As the method of treating the fiber material with the above pretreatment liquid, for example, there can be mentioned pad treatment, immersion treatment, spray treatment, and coating treatment. As the pad treatment, for example, there can be mentioned a method using a pad mangle described on pages 396 to 397 of the Fiber Dyeing Processing Dictionary (Showa 38, published by Nippon Kogyo Shimbunsha) or pages 256 to 260 of the Color Dye Chemistry III (1975, published by Jitsugyo no Kai). As the coating treatment, for example, there can be mentioned a method using a coating machine described on pages 473 to 477 of the Dyeing Finishing Equipment Guide (Showa 56, published by The Fiber Society). As the immersion treatment, for example, there can be mentioned a method using a batch dyeing machine described on pages 196 to 247 of the Dyeing Finishing Equipment Guide (Showa 56, published by The Fiber Society), and a liquid flow dyeing machine, an air flow dyeing machine, a drum dyeing machine, a skein dyeing machine, a washing dyeing machine, a package dyeing machine, and the like can also be used. As the spray treatment, for example, there can be mentioned a method of spraying the treatment liquid in a mist form using compressed air or a method of spraying the treatment liquid in a mist form using a hydraulic atomization method. The concentration of the treatment liquid at this time and the treatment conditions such as the heat treatment after the application can be appropriately adjusted in consideration of various conditions such as the purpose and the performance. Also, in the case where the pretreatment liquid contains water, it is preferable to perform drying after the application to the fiber material to remove the water. As the drying method, there is no particular limitation, and any of a dry heat method and a wet heat method can be used. The drying temperature is also not particularly limited, and, for example, drying can be performed at room temperature to 200°C for 10 seconds to several days. If necessary, heating treatment can also be performed at a temperature of 100 to 180°C for 10 seconds to about 5 minutes after the drying.

[0299] In the case where the fiber material is a dyed article, the treatment with the pretreatment liquid can be performed before the dyeing, or can be performed in the same bath as the dyeing, but in the case where reduction soaping is performed, since the adsorbed compound having the above specific functional group (for example, a phenolic polymer compound or the like) can be detached in this process, it is preferable to perform the treatment after the reduction soaping after the dyeing.

[0300] The treatment temperature in the immersion treatment can be set to 60 to 130°C. The treatment time can be set to 5 to 60 minutes.

[0301] In the functional group introduction step using the pretreatment liquid, it is preferable to perform the treatment in an amount in which the attached amount of the compound having the above specific functional group is 1.0 to 7.0 parts by weight with respect to 100 parts by weight of the fiber material. When in this range, it is possible to achieve both durable water repellency and hand feeling at a high level.

[0302] The pre-treatment liquid can be adjusted to a pH of less than 7, for example, 3 to 5. The pH adjustment can use a pH adjuster such as acetic acid, malic acid, or the like.

[0303] In the pre-treatment liquid, a salt can also be used at the same time in order to effectively adsorb the compound having the above specific functional group to the fiber material through a salting-out effect. As a salt that can be used, for example, sodium chloride, sodium carbonate, ammonium sulfate, sodium sulfate can be listed.

[0304] In the functional group introduction process using the pre-treatment liquid, it is preferable to remove the compound having the above specific functional group that has been excessively treated. As a removal method, a method using water washing can be listed. By performing sufficient removal, it is possible to inhibit hindrance of the manifestation of water repellency in the subsequent water repellent processing, and the obtained fiber product has a good hand feeling. Furthermore, the obtained functional group-containing fiber is preferably sufficiently dried before being brought into contact with the above treatment agent.

[0305] (ii) As a fiber in which the above specific functional group is directly introduced into a material constituting the fiber, for example, cationic dyeable polyester (CD-PET) can be listed.

[0306] From the viewpoint of the water repellency of the obtained fiber product being good, the surface Zeta potential of the functional group-containing fiber is preferably -100 to -0.1 mV, and more preferably -50 to -1 mV. The surface Zeta potential of the fiber can be measured, for example, using a Zeta potential / particle size measuring system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0307] The embodiments have been described above, but it should be understood that various modifications in form and details can be made without departing from the spirit and scope of the claimed invention.

[0308] Examples The present invention is explained in detail below using examples, but the present invention is not limited to these examples.

[0309] <Manufacturing Method> [Manufacturing Example 1] A 50-ml three-necked flask equipped with a stirrer, a thermometer, and a condenser was charged with 4-trifluoromethoxyphenol 4.0 g and 4-methyl-2-pentanone (MIBK, 16 g). Thereafter, the solution was cooled to 50°C, Desmodur N3200A (manufactured by Sumika Bayer Urethane Co., Ltd.) 3.8 g was added, and then dibutyltin dilaurate 1 drop was added, and the solution was heated at 80°C for 4 hours to obtain a synthetic product 1 having a solid content of 33%.

[0310] [Manufacturing Example 2] In a 50-ml three-necked flask equipped with a stirrer, a thermometer, and a condenser, 4- trifluoromethoxyphenol 3.4 g, sorbitan monostearate 6.0 g, and 4-methyl-2-pentanone (MIBK, 16 g) were placed. Thereafter, the solution was cooled to 50°C, Desmodur N3200A (manufactured by Sumika Bayer Urethane Co., Ltd.) 6.6 g was added, and then dibutyltin dilaurate 1 drop was added, and the solution was heated at 80°C for 4 hours to obtain a synthetic product 2 having a solid content of 50%.

[0311] [Production Example 3] In a 50-ml three-necked flask equipped with a stirrer, a thermometer, and a condenser, 4- trifluoromethoxyphenol 3.4 g, sorbitan monostearate 6.0 g, and 4-methyl-2-pentanone (MIBK, 16 g) were placed. Thereafter, the solution was cooled to 50°C, Desmodur N3200A (manufactured by Sumika Bayer Urethane Co., Ltd.) 6.6 g was added, and then dibutyltin dilaurate 1 drop was added, and the solution was heated at 80°C for 4 hours to obtain a synthetic product 2 having a solid content of 50%.

[0312] [Comparative Example 1] In a 50-ml three-necked flask equipped with a stirrer, a thermometer, and a condenser, 4- trifluoromethoxyphenol 3.4 g, sorbitan monostearate 6.0 g, and 4-methyl-2-pentanone (MIBK, 16 g) were placed. Thereafter, the solution was cooled to 50°C, Desmodur N3200A (manufactured by Sumika Bayer Urethane Co., Ltd.) 6.6 g was added, and then dibutyltin dilaurate 1 drop was added, and the solution was heated at 80°C for 4 hours to obtain a synthetic product 2 having a solid content of 50%.

[0313] [Comparative Example 2] In a 50-ml three-necked flask equipped with a stirrer, a thermometer, and a condenser, 4- trifluoromethoxyphenol 3.4 g, sorbitan monostearate 6.0 g, and 4-methyl-2-pentanone (MIBK, 16 g) were placed. Thereafter, the solution was cooled to 50°C, Desmodur N3200A (manufactured by Sumika Bayer Urethane Co., Ltd.) 6.6 g was added, and then dibutyltin dilaurate 1 drop was added, and the solution was heated at 80°C for 4 hours to obtain a synthetic product 2 having a solid content of 50%.

[0314] [Comparative Example 3] In a 50 ml three-necked flask equipped with a stirrer, a thermometer, and a condenser, 4-methoxyphenol 3.6 g, N-methyldiethanolamine 1.7 g, and 4-methyl-2-pentanone (MIBK, 15 g) were charged. Thereafter, the solution was cooled to 50°C, Desmodur N3200A (manufactured by Sumika Bayer Urethane Co., Ltd.) 10.1 g was added, and then dibutyltin dilaurate 1 drop was added, and the solution was heated at 80°C for 4 hours to obtain a composition 6 having a solid content of 51%.

[0315] <Preparation method of treatment liquid> The solutions prepared in Production Examples 1 to 3 were diluted with methyl ethyl ketone (MEK) to prepare treatment liquids 1 to 6 each at 200 g at a solid content concentration of 1.0, 2.0%.

[0316] The solutions prepared in Comparative Examples 1 to 3 were diluted with methyl ethyl ketone (MEK) to prepare treatment liquids 7 to 12 each at 200 g at a solid content concentration of 1.0, 2.0%.

[0317] The treatment liquids were listed in Table 1.

[0318] <Evaluation of treated cloth> <Method of treatment of cloth> As the cloth used, nylon-based cloth and PET-based cloth were used.

[0319] The two kinds of cloth were put into 500 ml plastic bottles each containing 200 g of the prepared treatment liquids 1 to 12, and the plastic bottles were shaken for 10 seconds to allow the treatment liquid to adhere. After the cloth was taken out of the treatment liquid, the cloth was put into a centrifugal device and treated at 1000 rpm for 30 seconds. Thereafter, the cloth was dried at room temperature for 24 hours and then heated at 160°C for 2 minutes.

[0320] <Water repellency test> The water repellency of the treated cloth was evaluated in accordance with the spray method of (JIS-L-1092 (AATCC-22) based on the following criteria to visually evaluate the wet state. As shown in the following table, the evaluation results were expressed in terms of water repellency No. The higher the score, the better the water repellency. The results are shown in Table 2.

[0321] ◎ (100): The surface was not wet or water droplets were not adhered O (90): The surface was not wet, but small water droplets were adhered Δ (80): The surface showed a small wetness in the form of individual water droplets X (70 or less): More than half of the surface showed wetness, and penetration was observed in some parts <Oil repellency test> The IPA / water = 10 / 90 solution was used to drop the liquid droplet on the treated cloth, and the state after 30 seconds was visually evaluated based on the following criteria.

[0322] The results are shown in Table 3.

[0323] ◎: The liquid droplet did not penetrate, and the shape of the round liquid droplet was maintained O: The liquid droplet hardly penetrated, and the state of the liquid droplet was maintained Δ: The liquid droplet slightly penetrated, but the liquid droplet remained X: The liquid droplet completely penetrated, and the liquid stain spread < Evaluation of treated paper > [Preparation of treated paper] The treated liquids 1 to 12 were applied 3 times on the thin paper having water resistance (Cobb value) of 52 g / m 2 , basis weight of 45 g / m 2 , and density of 0.60 g / m 3 using a BAKER applicator with a gap set to 0 mil, and then annealed at 140°C for 1 minute, thereby preparing the treated paper.

[0324] [Kit test (oil resistance)] The test was performed using a 3M kit (TAPPI T-559 cm-02). In the 3M kit method, the test oil in which castor oil, toluene, and heptane were mixed was placed on the surface of the treated paper, and the test oil was wiped off after 15 seconds, and the presence or absence of an oil stain on the treated paper at that time was evaluated. The test was performed using test oils having reagent numbers 1 to 6, and the largest reagent number in which no oil stain was found was used as the evaluation result of the oil resistance. The evaluation results are shown in Table 4.

Claims

1. A fluorine-containing compound characterized by comprising a moiety derived from a compound (a) containing a reactive hydrogen, a moiety derived from a compound (b) reactive to the reactive hydrogen, and -NHCO- derived from the compound (a) and the compound (b).

2. The fluorine-containing compound according to claim 1, characterized in that the compound (a) contains an alcohol. The compound (a) comprises a compound (a1) having R f1 or R f2 The compound (b) comprises a compound (b1) having R f1 or R f2 ​ R f1 is -CF3, -CF2H or -CFH2, R f2 is -CF2- or -CFH-, R f1 and R f2 is not part of a fluoroalkyl group having 2 or more carbon atoms.

3. The fluorine-containing compound according to claim 1 or 2, characterized in that the compound (b) contains an isocyanate. The R f1 The adjacent position of the R is an oxygen atom or a nitrogen atom, The R f2 at least one side of the position adjacent to the position is an oxygen atom or a nitrogen atom.

4. The fluorine-containing compound according to any one of claims 1 to 3, characterized in that the compound (a) contains a hydroxyl group. R1is CF3, f1 CF3, R1is -CF2-. f2 -CH2-. -CH2-.

5. The fluorine-containing compound according to any one of claims 1 to 4, characterized in that the compound (b) contains a hydroxyl group.

6. The fluorine-containing compound according to any one of claims 1 to 5, characterized in that the compound (a) contains a hydroxyl group.

7. The fluorine-containing compound according to claim 6, characterized in that the compound (a) contains a hydroxyl group.

8. The fluorine-containing compound according to any one of claims 1 to 7, characterized in that the compound (a) contains the compound (al).

9. The fluorine-containing compound according to any one of claims 1 to 8, characterized in that the compound (a) contains a compound (a2) containing a hydrocarbon group having 6 or more and 40 or less carbon atoms. The compound (a1) or the compound (b1) has the formula: -Y f -Z f α the groups shown, 10. The fluorine-containing compound according to claim 9, characterized in that the compound (a2) is a sugar alcohol and / or a hydroxy acid modified with a hydrocarbon group having 6 or more and 40 or less carbon atoms. Y f is a 1+α-valent group consisting of one or more selected from the group consisting of f1 and Y f2 is a 1+α-valent group consisting of one or more selected from the group consisting of Y f1 a group consisting of one or more selected from the group consisting of -0-, -C(=0)-, -C(=NR')-, -S-, -S(=0)2-, -NR'-, -C(OR')R'- and -C(OR')(-)2, -N(-)2, wherein R' is a hydrogen atom or an organic group, Y f2 R is a group consisting of one or more selected from aliphatic groups and aromatic groups, Z f For R f1 , or a hydrocarbon group having 2 or more and 40 or less carbon atoms containing R f1 or R f2 , 11. The fluorine-containing compound according to any one of claims 1 to 10, characterized in that the compound (a) contains another compound (a3) containing a reactive hydrogen.

12. The fluorine-containing compound according to claim 11, characterized in that the compound (a3) contains a chain extender. said compound (a1) or said compound (b1) is a compound of formula: -Y f11 - (Y f21 - Y f12 ) β - Y f22 - Y f13 - Z f a group represented by 13. The fluorine-containing compound according to any one of claims 1 to 12, characterized in that the compound (b) is selected from the following compounds: Y f11 is a direct bond, -O-, -NH- or -C(=O)-, Y f21 R is a group consisting of one or more selected from an aliphatic group and an aromatic group, Y f12 a group consisting of one or more selected from the group consisting of -0-, -C(=0)-, -C(=NR')-, -S-, -S(=0)2-, -NR'- and -C(OR')R'- wherein R' is a hydrogen atom or an organic group, ​ Y f22 R is a group consisting of one or more selected from aliphatic groups and aromatic groups, 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'-, wherein R' is a hydrogen atom or an organic group, Z f For R f1 , or a hydrocarbon group having 2 or more and 40 or less carbon atoms containing R f1 or R f2 . ​ Y f22 is of the formula -Y f221 -Y f222 the group shown in the formula -Y, ​ Y f221 R is a direct bond or a hydrocarbon group having 2 to 40 carbon atoms, Y f222 is a direct bond or phenylene, Y f13 is -O- or -NR'- wherein R' is a hydrogen atom or an organic group, ​ Z f for R f1 . ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ aromatic polyisocyanate selected from the group consisting of toluene diisocyanate (TDI), phenylene diisocyanate, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (MDI), 4,4'-dimethyl diphenyl diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylene diisocyanate (XDI), tetramethyl xylene diisocyanate (TMXDI), omega, omega'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl) thiophosphate, polymethylene polyphenylene polyisocyanate, nitro diphenyl-4,4'-diisocyanate, 3,3'-dimethyl diphenylmethane-4,4'-diisocyanate, 4,4'-diphenyl propane diisocyanate, and 3,3'-dimethoxy diphenyl-4,4'-diisocyanate, wherein toluene diisocyanate (TDI) is 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or a mixture thereof, phenylene diisocyanate is m-phenylene diisocyanate, p-phenylene diisocyanate, or a mixture thereof, diphenylmethane diisocyanate (MDI) is 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, or a mixture thereof, xylene diisocyanate (XDI) is 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, or a mixture thereof, tetramethyl xylene diisocyanate (TMXDI) is 1,3-tetramethyl xylene diisocyanate, 1,4-tetramethyl xylene diisocyanate, or a mixture thereof, naphthalene diisocyanate (NDI) is 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 1,8-naphthalene diisocyanate, or a mixture thereof; non-cyclic aliphatic polyisocyanate selected from the group consisting of trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethyl hexamethylene diisocyanate, decamethylene diisocyanate, wherein butylene diisocyanate is tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate; cycloaliphatic polyisocyanate selected from 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), methylene bis(cyclohexyl isocyanate) (hydrogenated MDI), methylcyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (hydrogenated XDI), dimer acid diisocyanate, trans-cyclohexane-1,4-diisocyanate, hydrogenated toluene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI), wherein the cyclohexane diisocyanate is 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, the 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) is isophorone diisocyanate, the methylene bis(cyclohexyl isocyanate) (hydrogenated MDI) is 4,4'-methylene bis(cyclohexyl isocyanate), 2,4'-methylene bis(cyclohexyl isocyanate), 2,2'-methylene bis(cyclohexyl isocyanate), or a mixture thereof, the methylcyclohexane diisocyanate is methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, the bis(isocyanatomethyl)cyclohexane (hydrogenated XDI) is 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, or a mixture thereof; bridged cycloaliphatic polyisocyanate selected from norbornene diisocyanate, methyl norbornane diisocyanate, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, di(diisocyanatomethyl)tricyclodecane; a compound selected from the following structural formula: a compound selected from a multimer, a biuret-modified compound, other derivative of the above-mentioned compound, wherein the above-mentioned multimer is a dimer, a trimer, a pentamer, a heptamer, an uretdione, an uretonimine, an isocyanurate-modified compound, a polycarbodiimide, or the like.

14. The compound according to claim 13, wherein the compound (a) comprises a compound (al), the compound (a) comprises a compound (al), said compound (a1) is a compound of formula: -Y f11 - (Y f21 - Y f12 ) β - Y f22 - Y f13 - Z f a group represented by -Z in the formula, each symbol is independently at each occurrence, Y f11 is a direct bond, -O-, -NH- or -C(=O)-, Y f21 R is a group consisting of one or more selected from aliphatic groups and aromatic groups, Y f12 a group consisting of one or more selected from the group consisting of -0-, -C(=0)-, -C(=NR')-, -S-, -S(=0)2-, -NR'- and -C(OR')R'- wherein R' is a hydrogen atom or an organic group, β is 0 to 3, Y f22 R is a group consisting of one or more selected from aliphatic groups and aromatic groups, 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'-, wherein R' is a hydrogen atom or an organic group, Z f is -CF3.

15. A dispersion, comprising: the fluorine-containing compound according to any one of claims 1 to 14; and a liquid medium.

16. A water- and oil-repellent agent, comprising: the fluorine-containing compound according to any one of claims 1 to 14.

17. The water- and oil-repellent agent according to claim 16, further comprising: another water- and oil-repellent agent component other than the fluorine-containing compound.

18. The water- and oil-repellent agent according to claim 16 or 17, wherein the water- and oil-repellent agent is a water- and oil-repellent agent for a fiber product or a paper product.

19. A method for producing a treated substrate, comprising: treating a substrate with the water- and oil-repellent agent according to any one of claims 16 to 18.

20. The method for producing according to claim 19, wherein the substrate is a fiber product or a paper product.

21. An article, comprising: the fluorine-containing compound according to any one of claims 1 to 14 attached thereto. ​ ​ ​ ​ ​ ​ ​

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