Folic acid compounds

Abstract

To provide a novel fluorine-containing compound.SOLUTION: A fluorine-containing compound has a part derived from an active hydrogen-containing compound (a), a part derived from an active hydrogen-reactive compound (b), and -NHCO- derived from the compound (a) and the compound (b), where the compound (a) includes a compound (a1) having Rf1 or Rf2, or the compound (b) includes a compound (b1) having Rf1 or Rf2, Rf1 is -CF3, -CF2H, or -CFH2, Rf2 is -CF2-, or -CFH-, and Rf1 and Rf2 are not parts of ≥2C fluoroalkyl groups.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to fluorine-containing compounds. [Background technology]

[0002] Certain non-fluorinated polymers are known to impart oil resistance when used for surface treatment of substrates (Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2020-054856 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] This disclosure aims to provide novel fluorine-containing compounds. [Means for solving the problem]

[0005] This disclosure includes the following aspects: [Section 1] The portion derived from the active hydrogen-containing compound (a), The moiety derived from the active hydrogen-reactive compound (b), and -NHCO- derived from compound (a) and compound (b), A fluorine-containing compound having, The above compound (a) is R f1 or R f2 A compound (a1) having R f1 or R f2 The compound (b1) contains the following: R f1 is -CF3, -CF2H, or -CFH2, R f2 is -CF2- or -CFH-, R f1 and Rf2 A fluorine-containing compound that is not part of a fluoroalkyl group having 2 or more carbon atoms. [Item 2] The adjacent position of the said R f1 is an oxygen atom or a nitrogen atom, The adjacent position of the said R f2 The fluorine-containing compound according to Item 1, wherein at least one of the adjacent positions of the said R is an oxygen atom or a nitrogen atom. [Item 3] The said R f1 is CF3-, The said R f2 is -CF2-, The fluorine-containing compound according to Item 1 or 2. [Item 4] The said compound (a) contains alcohol, The said compound (b) contains isocyanate, The fluorine-containing compound according to any one of Items 1 to Item 3, wherein the said fluorine-containing compound is polyurethane. [Item 5] The said compound (a1) or the said compound (b1) is Formula: -Y f -Z f α [In the formula, each symbol is independently in each occurrence, Y f is a 1 + α-valent group composed of one or more selected from the group consisting of Y f1 and Y f2 ; Y f1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' is a hydrogen atom or an organic group). <所 Y f2 is a group composed of one or more selected from the group consisting of an aliphatic group and an aromatic group. Z f is R f1 or, R f1 or R f2A hydrocarbon group having 2 to 40 carbon atoms, α is between 1 and 3. A fluorine-containing compound according to any one of items 1 to 4, having a group represented by . [Section 6] The compound (a1) or the compound (b1) is formula: -Y f11 -(Y f21 -Y f12 ) β -Y f22 -Y f13 -Z f [In the formula, each symbol is independent in each occurrence.] Y f11 These are direct bonds, -O-, -NH-, or -C(=O)-, Y f21 This is a group composed of one or more groups selected from the group consisting of aliphatic groups and aromatic groups. Y f12 This is a group composed of one or more elements selected from the group consisting of -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, and -C(OR')R'- (where R' is a hydrogen atom or an organic group). β is between 0 and 3. Y f22 This is a group composed of one or more groups selected from the group consisting of aliphatic groups and aromatic groups. Y f13 These are -O-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-O-, -C(=O)-NR'-, or -SO2NR'- (where R' is a hydrogen atom or an organic group). Z f R f1 , or R f1 or R f2 It is a hydrocarbon group containing 2 to 40 carbon atoms. A fluorine-containing compound according to any one of items 1 to 5, which has a group represented by . [Section 7] Y f22 is, formula -Y f221 -Y f222 - [wherein Y f221 is a direct bond or a hydrocarbon group having 2 to 40 carbon atoms, Y f222 is a direct bond or a phenylene group.] is a group represented by Y f13 is -O- or -NR'-(where R' is a hydrogen atom or an organic group.), β is 0 or 1, Z f is R f1 The fluorine-containing compound according to item 6, which is [Item 8] The fluorine-containing compound according to any one of items 1 to 7, wherein the compound (a) contains the compound (a1). [Item 9] The fluorine-containing compound according to item 1 or 2, wherein the compound (a) contains an active hydrogen-containing compound (a2) having a hydrocarbon group with 6 to 40 carbon atoms. [Item 10][[ID=__]] The fluorine-containing compound according to item 9, wherein the compound (a2) is a sugar alcohol and / or a hydroxy acid modified with a hydrocarbon group having 6 to 40 carbon atoms. [Item 11] The fluorine-containing compound according to any one of items 1 to 10, wherein the compound (a) contains another active hydrogen-containing compound (a3). [Item 12] The fluorine-containing compound according to item 11, wherein the compound (a3) contains a chain extender. [Item 13] The fluorine-containing compound according to any one of items 1 to 12, wherein the compound (b) is selected from the compounds described below. Tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixture thereof) (TDI), phenylene diisocyanate (m-,p-phenylene diisocyanate or mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4' or 2,2'-diphenylmethane diisocyanate or mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixture thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or 1,4-tetramethyl Aromatic polyisocyanates selected from tylxylylene diisocyanate or a mixture thereof (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; Acyclic aliphatic polyisocyanates selected from 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-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capeate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate; 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’-, 2,4’- or 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 - or 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), a cyclic alicyclic polyisocyanate selected from; A bridged alicyclic polyisocyanate selected from norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, di(diisocyanatomethyl)tricyclodecane; TIFF0007866209000001.tif15383 A compound selected from TIFF0007866209000002.tif14370; And compounds selected from the above multimers (dimers, trimers, pentamers, heptamers, uretdione, uretonimine, isocyanurate modified forms, polycarbodiimide, etc.), biuret modified forms, and other derivatives [Item 14] The compound (a) contains the compound (a1), The compound (a1) is Formula: -Y f11 -(Y f21 -Y f12 ) β -Yf22 -Y f13 -Z f [In the formula, each symbol is independent in each occurrence.] Y f11 These are direct bonds, -O-, -NH-, or -C(=O)-, Y f21 This is a group composed of one or more groups selected from the group consisting of aliphatic groups and aromatic groups. Y f12 This is a group composed of one or more elements selected from the group consisting of -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, and -C(OR')R'- (where R' is a hydrogen atom or an organic group). β is between 0 and 3. Y f22 This is a group composed of one or more groups selected from the group consisting of aliphatic groups and aromatic groups. Y f13 These are -O-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-O-, -C(=O)-NR'-, or -SO2NR'- (where R' is a hydrogen atom or an organic group). Z f This is -CF3. The compound described in item 13, which has a group represented by . [Section 15] A dispersion comprising a fluorine-containing compound and a liquid medium as described in any one of items 1 to 14. [Section 16] A water-repellent and oil-repellent agent containing a fluorine-containing compound as described in any one of items 1 to 14. [Section 17] The water-repellent and oil-repellent agent according to item 16, comprising other non-fluorine water-repellent and oil-repellent components. [Section 18] A water- and oil-repellent agent according to item 16 or 17, for use in textile or paper products. [Section 19] A method for producing a treated substrate, comprising treating the substrate with a water-repellent and oil-repellent agent described in any one of items 16 to 18. [Section 20] The manufacturing method according to item 19, wherein the substrate is a textile product or a paper product. [Section 21] Products to which any of the fluorine-containing compounds described in items 1 to 14 are attached. [Effects of the Invention]

[0006] According to this disclosure, it is possible to provide novel fluorine-containing compounds. [Modes for carrying out the invention]

[0007] <Definition of Terms> As used herein, "n-valent group" means a group having n bonds, that is, a group that forms n bonds. Furthermore, "n-valent organic group" means an n-valent group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A hydrocarbon group derivative means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the terminal or molecular chain of a hydrocarbon group.

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

[0009] In this specification, unless otherwise stated, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition is applied independently for each appearance, regardless of whether expressions such as "independently in each occurrence", "independently of each other", "independently respectively" or similar expressions are explicitly stated.

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

[0011] <Fluorine-containing compound> The fluorine-containing compounds in the present disclosure (a) a moiety derived from an active hydrogen-containing compound, (b) a moiety derived from an active hydrogen-reactive compound, and -NHCO- derived from the compound (a) and the compound (b), and have.

[0012] [Properties of fluorine-containing compounds, etc.] The fluorine-containing compounds in the present disclosure can adhere to a substrate and impart liquid repellency (e.g., oil repellency, water repellency, oil resistance, water resistance) to the substrate.

[0013] The HD (n-hexadecane) contact angle of the fluorine-containing compound may be 10° or more, 15° or more, 25° or more, 35° or more, 40° or more, 45° or more, 55° or more, or 65° or more, preferably 30° or more, and may also be 100° or less, 90° or less, or 75° or less. When the fluorine-containing compound has an HD contact angle of not less than the above lower limit, it can impart good liquid repellency (especially oil repellency) to the substrate. The HD contact angle is the static contact angle of the spin-coated film of the fluorine-containing compound, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after droplet landing.

[0014] The water contact angle of the fluorine-containing compound is 35° or higher, 40° or higher, 45° or higher, 50° or higher, 55° or higher, 65° or higher, 75° or higher, 85° or higher, 90° or higher, or 100° or higher, and may also be 160° or lower, 140° or lower, 130° or lower, 120° or lower, 110° or lower, 100° or lower, or 90° or lower. By having a water contact angle of the fluorine-containing compound above the lower limit, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle is the static contact angle of the fluorine-containing compound with respect to the spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop.

[0015] The weight-average molecular weight of the fluorine-containing compound is 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, or 5000 or less.

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

[0017] The fluorine-containing compound is preferably a compound having carbon of bio-based origin. The degree of bio-basedness is measured in accordance with ASTM D6866. The degree of bio-basedness of the fluorine-containing compound may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example 100%. A high degree of bio-basedness means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this viewpoint, a higher degree of bio-basedness of the fluorine-containing compound is preferable.

[0018] The fluorine-containing compounds in this disclosure are Rf as described above. 1 or Rf 2 The fluorine-containing compounds in this disclosure do not necessarily have to contain any of the group selected from the group consisting of fluoroalkyl groups having 8 or more carbon atoms, perfluoroalkyl groups having 8 or more carbon atoms, fluoroalkyl groups having 4 or more carbon atoms, perfluoroalkyl groups having 4 or more carbon atoms, fluoroalkyl groups having 2 or more carbon atoms, and perfluoroalkyl groups having 2 or more carbon atoms. The fluorine-containing compounds in this disclosure can impart liquid repellency to a substrate even without containing these fluorine-containing groups. In this specification, fluoroalkyl groups may refer to groups in which one or more hydrogen atoms at each carbon atom of the alkyl group are substituted with fluorine atoms.

[0019] [R f1 and R f2 ] Fluorine-containing compounds are R f1 or R f2 It has, for example, R f1 It has R f1 and R f2 It is not part of a fluoroalkyl group having 2 or more carbon atoms. f2 It does not have to be part of -CH2-CF2-CH2-.

[0020] R f1 is -CF3, -CF2H, or -CFH2, preferably -CF3. f1 The adjacent positions may be oxygen atoms or nitrogen atoms.

[0021] R f2 is -CF2- or -CFH-, preferably -CF2-. f2 At least one of the adjacent positions may be an oxygen atom or a nitrogen atom.

[0022] [(a) Compounds containing active hydrogen] The fluorine-containing compound has a portion derived from the active hydrogen-containing compound (a).

[0023] Compound (a) is a compound containing an active hydrogen-containing group, and examples include monofunctional, difunctional, and polyfunctional alcohols, thiols, and amines. In this disclosure, alcohol is a broad term and includes phenol.

[0024] Compound (a) is preferably a compound having carbon of bio-based origin. The degree of bio-basedness is measured in accordance with ASTM D6866. The degree of bio-basedness of the fluorine-containing compound may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example 100%. A high degree of bio-basedness means that the amount of fossil resource-based materials represented by petroleum etc. is small, and from this viewpoint, a higher degree of bio-basedness of compound (a) is preferable.

[0025] Compound (a) is, R f1 or R f2 Compound (a1) having, A compound containing active hydrogen having a hydrocarbon group with 6 to 40 carbon atoms (a2), and Other active hydrogen-containing compounds (a3) It may include one or more of the following:

[0026] [Compound (a1)] Compound (a1) is R f1 or R f2 It is a compound having . Compound (a1) is formula: -Y f -Z f α [In the formula, each symbol is independent in each occurrence.] Y f Y f1 and Y f2 A 1+α valency group consisting of one or more selected from the group comprising: Y f1is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -NR’-, -C(OR’)R’-, and -C(OR’)(-)2, where R’ is a hydrogen atom or an organic group. Y f2 is a group composed of one or more selected from the group consisting of aliphatic group and aromatic group. Z f is R f1 or R f1 or R f2 is a hydrocarbon group having 2 to 40 carbon atoms including α is 1 to 3.] may have a group represented by

[0027] R f1 For example, may be included in Z f R f2 For example, may be an organic group, Y f2 Z f R f2 and may be included in.

[0028] -Y f -Z f α At the end of Y f -H, -OH, -NH2, or -COOH may be bonded to form an active hydrogen terminal. For example, compound (a1) is H-Y<00001​​​​​​​​​​​​​​​​​​​​​​​​​​However, compound (a1) is not limited to the said structure, and any part of compound (a1) can be Y f -Z f α It may be composed of these.

[0030] (Y f ) Y f Y f1 and Y f2 A 1+α valency group consisting of one or more selected from the group comprising: Y f1 This group is composed of one or more elements selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (where R' is a hydrogen atom or a monovalent organic group). Y f2 This group is composed of one or more groups selected from the group consisting of aliphatic groups and aromatic groups.

[0031] Y f The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may also 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.

[0032] Below, Y f1 and Y f2 I will explain this.

[0033] ○ Y f1 Y f1 It is a non-hydrocarbon linker.

[0034] Y f1 This is a directly bonded or divalent or more group. f1 The valence of Y may be 2-4, 2-3, or 2. f1 It is preferable that the bonding is not solely direct.

[0035] Y f1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may also be 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0036] Y f1 It 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 a hydrogen atom or a monovalent organic group in each occurrence).

[0037] R' is a hydrogen atom or a monovalent organic group. The organic group may be, for example, an aliphatic group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) 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). The same applies to other R's in this specification.

[0038] Y f1 Examples include, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2nd class (In the formula, R' is independently a hydrogen atom or a monovalent organic group in each instance.) These are some examples.

[0039] ○ Y f2 Y f2 This group may consist of one or more groups selected from the group comprising aliphatic groups and aromatic groups.

[0040] Y f2 Y is a group with two or more valent values. f2 The valence may be, for example, 2-4, 2-3, or 2.

[0041] Y f2 The number of carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0042] Y f2 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may also be 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0043] Y f2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). f2 Y may be aliphatic or aromatic. f2 The chain may be linear, branched, or annular.

[0044] Y f2 This may be a linker of an optionally substituted hydrocarbon, an optionally substituted hydrocarbon aromatic ring, or an optionally substituted heterocyclic linker, or a combination thereof. For example, Y f2 This may consist of one or more selected from the group comprising a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have substituents; a di- to tetravalent hydrocarbon aromatic ring, which may have substituents; and a di- to tetravalent heterocycle, which may have substituents.

[0045] A divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a cyclic, branched, or linear hydrocarbon group. A divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in a divalent to 2 to 20 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 15 or less, 10 or less, or 5 or less. The valency of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0046] Aliphatic hydrocarbon groups may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a monovalent organic group in each occurrence). Substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a substituent-containing aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0047] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring constituent atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valency of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0048] The hydrocarbon aromatic ring may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a monovalent organic group in each occurrence). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic ring having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0049] The 2-4 valent heterocycle may be an aliphatic group or an aromatic group. Examples of 2-4 valent heterocycles include groups obtained by removing 2-4 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, imidazolidine, thiazoline, etc. The number of ring constituent atoms of the heterocycle is 3-20, 4-16, or 5-12, preferably 5-12. The valency of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0050] The heterocycle may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a monovalent organic group in each occurrence). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0051] 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- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] These are some examples.

[0052] Y f2 Specific examples include: -(CH2) p -(p is between 1 and 20, for example, between 1 and 10) A linear hydrocarbon group having 1 to 40 carbon atoms, for example, 1 to 10 unsaturated bonds, A hydrocarbon group having 1 to 40 carbon atoms, for example, a branched structure with 1 to 10 carbon atoms. -(CH2) q-Cy-(CH2) r -(q and r are each independently between 0 and 20, for example between 1 and 10, and Cy is a hydrocarbon aromatic ring or heterocycle) These are some examples.

[0053] ○ Y f Examples Y f Let's explain an example.

[0054] Y f An example is Y f If it is divalent, -Y f1 -, -Y f1 -Y f2 -, -Y f1 -Y f2 -Y f1 -, -Y f1 -Y f2 -Y f1 -Y f2 -, -Y f2 -, -Y f2 -Y f1 -, -Y f2 -Y f1 -Y f2 -, -Y f2 -Y f1 -Y f2 -Y f1 -, etc. are examples. f α The adjacent base is Y f1 That's fine.

[0055] Y f An example is Y f If it is trivalent, -Y f1 (-)2, -Y f1 -Y f2 (-)2, -Y f1 -(Y f2 -)2, -Y f1 -Y f2 -Y f1 (-)2, -Y f1 -Y f2 (-Y f1 -)2, -Y f1 -(Y f2 -Y f1 -)2, -Y f1 -Y f2 -Yf1 -Y f2 (-)2, -Y f1 -Y f2 -Y f1 -(Y f2 -) 2、 -Y f1 -Y f2 -(Y f1 -Y f2 -) 2、 -Y f1 -(Y f2 -Y f1 -Y f2 -)2; -Y f2 (-)2, -Y f2 -Y f1 (-)2, -Y f2 -(Y f1 (-)2, -Y f2 -Y f1 -Y f2 (-)2, -Y f2 -Y f1 (-Y f2 (-)2, -Y f2 -(Y f1 -Y f2 (-)2, -Y f2 -Y f1 -Y f2 -Y f1 (-)2, -Y f2 -Y f1 -Y f2 -(Y f1 -) 2、 -Y f2 -Y f1 -(Y f2 -Y f1 -) <00002​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​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. can be mentioned.

[0057] Yf A preferred example of this is -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, These are some examples.

[0058] (Z f ) Z f R f1 , or R f1 or R f2 A hydrocarbon group having 2 to 40 carbon atoms, for example, R f1 That is. R f1 or R f2 The hydrocarbon group containing may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). f1 or R f2 The hydrocarbon group containing is branched or linear, more preferably linear. f1 or R f2 The hydrocarbon group containing R may be saturated or unsaturated. f1 or R f2 The hydrocarbon group containing is preferably a saturated aliphatic hydrocarbon group (alkyl group). f1 or R f2The number of carbon atoms in the hydrocarbon group containing may be 2 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0059] (α) α is 1 to 3 (1, 2, or 3), for example, 1 or 2, for example, 1.

[0060] (Example of compound (a1)) Compound (a1) is, formula: -Y f11 -(Y f21 -Y f12 ) β -Y f22 -Y f13 -Z f [In the formula, each symbol is independent in each occurrence.] Y f11 These are direct bonds, -O-, -NH-, or -C(=O)-, Y f21 This is a group composed of one or more groups selected from the group consisting of aliphatic groups and aromatic groups. Y f12 This is a group composed of one or more elements selected from the group consisting of -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, and -C(OR')R'- (where R' is a hydrogen atom or an organic group). β is between 0 and 3. Y f22 This is a group composed of one or more groups selected from the group consisting of aliphatic groups and aromatic groups. Y f13 These are -O-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-O-, -C(=O)-NR'-, or -SO2NR'- (where R' is a hydrogen atom or an organic group). Zf R f1 , or R f1 or R f2 It is a hydrocarbon group containing 2 to 40 carbon atoms. The compound may have a group represented by .

[0061] Y f11 An active hydrogen terminus may be formed by the bonding of -H or -OH to the terminal end of the side.

[0062] Y f11 The bond may be a direct bond, -O-, -NH-, or -C(=O)-.

[0063] Y f21 This may be a group composed of one or more selected from the group consisting of aliphatic groups and aromatic groups, and the above Y f2 A similar explanation can be used. However, Y f21 It is a divalent group.

[0064] Y f12 The group may consist of one or more selected from the group consisting of -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, and -C(OR')R'-, and the above Y f1 A similar explanation can be used. However, Y f12 It is a divalent group.

[0065] β can be 0 to 3 (0, 1, 2, or 3), for example, 0 to 2, and especially 0 to 1.

[0066] Y f22 This may be a group composed of one or more selected from the group consisting of aliphatic groups and aromatic groups, and the above Y 2 A similar explanation can be used. However, Y f22 Y is a divalent group. f22 is, formula -Y f221 -Y f222 - [In the formula, Y f221 These are directly bonded or hydrocarbon groups having 2 to 40 carbon atoms. Y f222 This is either a direct bond or a phenylene group. The group may be represented by . Here, the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and may be an aliphatic hydrocarbon group, in particular 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 also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less.

[0067] Y f13 R' may be -O-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-O-, -C(=O)-NR'-, or -SO2NR'- (where R' is a hydrogen atom or a monovalent organic group). f13 For example, -O- or -NR'-.

[0068] Z f R f1 , or R f1 or R f2 A hydrocarbon group having 2 to 40 carbon atoms, as described above, and especially R f1 That is the case.

[0069] In one aspect, Y f22 is, formula -Y f221 -Y f222 - [In the formula, Y f221 These are directly bonded or hydrocarbon groups having 2 to 40 carbon atoms. Y f222 This is either a direct bond or a phenylene group. It may be a base represented by . Here, Yf13 β may be -O- or -NR'- (where R' is a hydrogen atom or a monovalent organic group). β may be 0 or 1. Z f is R f1 That's fine.

[0070] (Specific example of compound (a1)) Specific examples of compound (a1) are as follows: Hydroxy HO-Y f -Z f α Carboxylic acid HO(O=)CY f -Z f α Amine H2N-Y f -Z f α [In the formula, Y f , Z f α is as described above, and G is a halogen atom (e.g., F, Cl, Br, or I). Note that the above formula is Y f -Z f α The terminal functional group adjacent to it (G(O=)C, etc.) is -Y f -Although it is expressed as something not included in Y f It is also possible to rewrite it as a description incorporated into the text.

[0071] A more specific example of compound (a1) is (for example, in the formula given in the example above) -Y f -Z f α but -Ali-OR f1 , -Ali-Cy-OR f1 , -Ali-Cy-Ali-OR f1 , -Cy-OR f1 , -Cy-Ali-OR f1 , -Cy-Ali-Cy-ORf1 , -Ali-N(R')-R f1 , -Ali-Cy-N(R')-R f1 , -Ali-Cy-Ali-N(R')-R f1 , -Cy-N(R')-R f1 , -Cy-Ali-N(R')-R f1 , -Cy-Ali-Cy-N(R')-R f1 , [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Cy is a hydrocarbon aromatic ring or heterocycle, and R' is a hydrogen atom or an organic group. f1 This is -CF3, -CF2H, or -CFH2. It is a compound that is A more specific example of compound (a1) is (for example, in the formula given in the example above) -Y f -Z f α but -(CH2) n -OR f1 , -(CH2) n -Cy-OR f1 , -(CH2) n -Cy-(CH2) n -OR f1 , -Cy-OR f1 , -Cy-(CH2) n -OR f1 , -Cy-(CH2) n -Cy-OR f1 , -(CH2) n -N(R')-R f1 , -(CH2) n -Cy-N(R')-R f1 , -(CH2) n -Cy-(CH2)nN(R')-R f1 , -Cy-N(R')-R f1 , -Cy-(CH2) n -N(R')-R f1 , -Cy-(CH2) n -Cy-N(R')-R f1 , [In the formula, n is an integer from 1 to 40, Cy is a hydrocarbon aromatic ring or heterocycle, R' is a hydrogen atom or organic group, R f1 This is -CF3, -CF2H, or -CFH2. Examples include certain compounds.

[0072] A more specific example of compound (a1) is: Trifluoromethoxyalkyl carboxylic acid, trifluoromethoxyalkyl carboxylic acid halogenated compounds, Trifluoromethoxybenzoic acid, trifluoromethoxybenzoic acid halogens, Trifluoromethoxyphenylacetic acid, trifluoromethoxyphenyl acetate halogenated compounds, Trifluoromethoxyalkylamine, Trifluoromethoxyaniline, Trifluoromethoxyalkyl alcohol, Trifluoromethoxyphenol, CF3-O-CF2-R 2 -OH CF3-OR 1 -O-CF2-R 2 -OH CF3-OR 1 -CF2-OR 2 -OH CF3-O-Ph-O-CF2-R 2 -OH CF3-O-Ph-CF2-OR 2 -OH R 3 -O-CF2-R 2 -OH R 3 -CF2-OR 2 -OH (Here, R1 to R3 are independently hydrocarbon groups having 1 to 40 carbon atoms.) These are some examples.

[0073] [Example of a method for producing compound (a1)] In this method, compounds having a hydroxyl group and an olefin (111): HO-R j33 A trifluoromethoxy group-containing compound is synthesized using -CH=CH2 as a starting material. Here, R j33 This is an alkylene group, for example, a C1-30 alkylene group.

[0074] Examples of olefin group-containing compounds include 3-hydroxypropene, 4-hydroxy-1-butene, 5-hydroxy-1-pentene, 6-hydroxy-1-hexene, 7-hydroxy-1-heptene, 8-hydroxy-1-octene, 9-hydroxy-1-nonene, 10-hydroxy-1-decene, 11-hydroxy-1-undecene, 12-hydroxy-1-dodecene, 13-hydroxy-1-tridecene, 14-hydroxy-1-tetradecene, 15-hydroxy-1-pentadekene, 16-hydroxy-1-hexadekene, 17-hydroxy-1-heptadekene, 18-hydroxy-1-octadekene, 19-hydroxy-1-nonadekene, 20-hydroxy-1-icosene, 21-hydroxy-1-henicosene, 24-hydroxy-1-tetracosene, and 30-hydroxy-1-triacontene.

[0075] By reacting the hydroxyl group of compound (111) with carbon disulfide in the presence of a base such as sodium hydride, and then adding iodomethane, xanthogenic acid ester (112): H3CS-C(=S)-OR j33 -COOR j32 This is obtained. Here, R j32The lower alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a tert-butyl group, specifically a methyl group or a tert-butyl group. The target trifluoromethoxy group-containing compound (113):F3CO-R is obtained by reacting the above xanthogenic acid ester (102) with pyridine hydrogen fluoride and 1,3-dibromo-5,5-dimethylhydantoin. j33 -CH=CH2 is obtained.

[0076] Alternatively, by reacting the hydroxyl group of compound (111) with aryl sulfonic acid trifluoromethyl ester in a non-protonate polar solvent such as NMP, DMF, or HMPA (hexamethyl phosphate triamide) in the presence of cesium fluoride or tetrabutylammonium bromide, the desired trifluoromethoxy group-containing compound (113):F3CO-R j33 -CH=CH2 is obtained.

[0077] The obtained F3CO-R j33 -CH=CH2 is converted to F3CO-R by standard method. j33 It can be formed as CH2CH2-OH.

[0078] Here, F3CO-R j33 Another method for producing CH2CH2-OH is to react silver triflate, potassium fluoride, a salt of 1-(chloromethyl)-4-fluoro-4-diazoniabicyclo[2.2.2]octane, tetrafluoroborate, and benzyloxy alcohol (e.g., benzyloxyethanol), and then synthesize the product (e.g., [2-(trifluoromethoxy)ethoxy]methyl]benzene) by hydrogen reduction under palladium catalyst, as described in WO2020 / 168011Al, etc.

[0079] [Compound (a2)] Compound (a2) is an active hydrogen-containing compound having a hydrocarbon group with 6 to 40 carbon atoms. Here, the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group is branched or linear, more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 12 or more, 14 or more, or 16 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and is preferably 30 or less, 25 or less, or 20 or less.

[0080] (Sugar alcohol / hydroxy acid modified product) Compound (a2) may be a sugar alcohol / hydroxy acid modified product, which is a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) modified with a hydrocarbon group having 6 to 40 carbon atoms. The type of sugar alcohol / hydroxy acid is not limited and may be cyclic or acyclic. Examples of sugar alcohols include monosaccharides, reducing sugars, amino sugars, aldonic acids, and aldonic acid lactones, and examples of hydroxy acids include hydroxypolycarboxylic acids, etc. The sugar alcohol / hydroxy acid may be a substance that exists in living organisms. Examples of sugar alcohols / hydroxy acids include compounds derived from aldoses and ketoses, such as tetrose, pentose, hexose, and heptose, but are not limited to these. Specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, glycerol, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, and mannopyranose. Examples include sugar alcohols, taropyranose, allopyranose, altropyranose, idopyranose, globyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fusitol, iditol, inositol, pentaerythritol, dipentaerythritol, boremitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconate lactone, glyceric acid lactone, xylonate lactone, glucosamine, galactosamine, or mixtures thereof. The number of carbon atoms in the sugar alcohol / hydroxy acid may be 2 or more, 4 or more, or 6 or more, and may be 30 or less, 20 or less, or 10 or less. The average OH value of compound (a2) may be in the range of greater than 0 to about 230, preferably about 10 to about 175, most preferably about 25 to about 140.

[0081] The number of hydrocarbon groups having 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified product may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may also be 12 or less, 9 or less, 6 or less, or 3 or less.

[0082] In sugar alcohol / hydroxy acid modified products, at least one active hydrogen (e.g., hydrogen in an OH group or carboxyl group) of the sugar alcohol and / or hydroxy acid is -R a2 , -C(O)R a2 -(CH2CH2O) n (CH(CH3)CH2O) m R a2 -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R a2 R may be substituted with an active hydrogen substituent selected from a mixture thereof. a2 n is a hydrogen atom or a hydrocarbon group having 6 to 40 carbon atoms, each n is independently 0 to 20, each m is independently 0 to 20, and m+n may be greater than 0. Compound (a2) has at least one active hydrogen, and for example, in a sugar alcohol / hydroxy acid modified product, at least one (1 or more) of the active hydrogens of the sugar alcohol / hydroxy acid may be unmodified, and this active hydrogen (e.g., an -OH group) may react with the active hydrogen reactant group (especially an isocyanate group) of compound (b) to form -NHCO-.

[0083] (Sorbitan modified compound) The sugar alcohol / hydroxy acid modified product may be a sorbitan modified product obtained by modifying sorbitan with a hydrocarbon group having 6 to 40 carbon atoms, and may particularly be an alkylsorbitan, where sorbitan is -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 compounds substituted with a mixture thereof (where R a2 (A hydrocarbon group has 6 to 40 carbon atoms). For example, sorbitan is -C(O)R a2The compound may be monosubstituted, disubstituted, or trisubstituted. Here, sorbitan may contain amounts of sorbitol, isosorbide, or other intermediates or by-products. Commercially available sorbitan such as SPAN can be used as the alkylsorbitan.

[0084] In one embodiment, at least one active hydrogen substituent is -C(O)R a2 It is fine if R a2 The C1 is a linear or branched alkyl group having 6 to 40 carbon atoms, more preferably 7 to 21, and most preferably 11 to 21 carbon atoms. Preferred compounds include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and monosubstituted, disubstituted, and trisubstituted sorbitans derived from mixtures thereof. Particularly preferred compounds include monosubstituted, disubstituted, and trisubstituted sorbitan stearates, or sorbitan behenin.

[0085] In one embodiment, R a2 It may contain at least one unsaturated bond. An example of such a compound (at least one active hydrogen substituent is -C(O)R a2 Selected from, R a2 As an example of a compound containing at least one unsaturated bond, sorbitan trioleate (i.e., in the formula, R a2 -C7H 14 CH=CHC8H 17 Examples include, but are not limited to, palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid, which are monosubstituted, disubstituted, and trisubstituted sorbitans.

[0086] In one embodiment, the sorbitan modified product has at least one active hydrogen substituent, and the active hydrogen substituent is independently -(CH2CH2O) n (CH(CH3)CH2O) m R a2 or -(CH2CH2O) n (CH(CH3)CH2O) mC(O)R a2 (where m is independently between 0 and 20, and n is independently between 0 and 20, and m+n is greater than 0). Such compounds are known as polysorbates and are marketed under the trademark name TWEEN. These sorbitans are R a2 Therefore, monosubstituted, disubstituted, or trisubstituted compounds can be used. Commercially available polysorbates have each R 2 From various polysorbates where H is unsubstituted, each R a2 It is known to contain a wide range of mixtures, from polysorbates in which the linear or branched alkyl group has 6 to 40 carbon atoms (fully substituted), to mixtures of various substitutions thereof. Examples of such sorbitan modifications include polysorbates such as polysorbate tristearate and polysorbate monostearate. m+n is greater than 0, and R a2 Examples of sorbitan modifications containing at least one unsaturated bond include, but are not limited to, polysorbate trioleates (where R a2 C7H 14 CH=CHC8H 17 Examples include (which are commercially available under the name polysorbate 80). The sorbitan modified material may contain a mixture of compounds having various active hydrogen substituents, and R a2 A compound containing at least one unsaturated bond, and R a2 It may also contain a mixture with a completely saturated compound.

[0087] (Citrate-modified) The sugar alcohol / hydroxy acid modified product may be a citrate modified product obtained by modifying citrate with a hydrocarbon group having 6 to 40 carbon atoms, and may be an alkyl citrate in particular. For example, the citrate modified product may exist as a monosubstituted, disubstituted, or trisubstituted product having an alkyl group. A mixture of citrates having active hydrogen substituents of various values ​​may be used, and R a2 A compound having a hydrocarbon group having at least one unsaturated bond, and R a2It may also contain a mixture with a compound that is a completely saturated hydrocarbon. The citrate-modified compound is -(CH2CH2O) n (CH(CH3)CH2O) m R a2 Alternatively, -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R a2 It may have an active hydrogen substituent selected from (where R a2 (A hydrocarbon group has 6 to 40 carbon atoms). Examples of citrate-modified compounds include, but are not limited to, trialkyl citrates.

[0088] (Pentaerythritol) The sugar alcohol / hydroxy acid modified product may be a pentaerythritol modified product obtained by modifying pentaerythritol with a hydrocarbon group having 6 to 40 carbon atoms, and may be a monosubstituted, disubstituted, or trisubstituted product having a hydrocarbon group (especially an alkyl group) having 6 to 40 carbon atoms, for example, a dipentaerythriol ester. In the formula, the active hydrogen substituent is -CH2C[CH2OR a2 ]3 may be included (where R a2 ( is a hydrocarbon group with 6 to 40 carbon atoms). Also, pentaerythritol modified compounds are compounds having a mixture of hydrocarbon groups with different chain lengths, or R a2 A compound containing at least one unsaturated bond, and R a2 It may also contain a mixture with a completely saturated compound.

[0089] R a2 [Compound (a3)] The compound (a) may also contain other active hydrogen-containing compounds (a3).

[0090] (Compound (a31)) Compound (a3) ​​is, R a31 -X a31 [In the formula, In the formula, R 31 teeth, C1-C may contain at least one unsaturated group. 30 Linear or branched alkyl, hydroxy-functional C1-C 30 Linear or branched alkyl, hydroxy-functional linear or branched C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Linear or branched alkyl, amine-functionalized C1-C 30 Linear or branched alkyl, Y - R a311 R a312 R a313 N + -R a314 -(Here, Y is a halide ion, for example, Cl - It is. ), HOS(=O)2-R a314 -, or R a311 R a312 C = N - (where R a311 , R a312 , R a313 Each of them is independently -H and C1-C6 alkyl, and R a314 It 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 is an isocyanate-reactive functional group (where R ’ is a -H or monovalent organic group, s is an integer between 0 and 50, t is an integer between 0 and 50, and s+t is greater than 0. It may be a compound represented by .

[0091] Compound (a31) may be a hydrophilic water-soluble material containing at least one hydroxy-terminated polyether, where X a31 is -O-(CH2CH2O) s (CH(CH3)CH2O) t-H or -C(O)-O-(CH2CH2O)s(CH(CH3)CH2O) t -H. -(CH2CH2O)- represents an oxyethylene group (EO), and -(CH(CH3)CH2O)- represents an oxypropylene group (PO). These polyethers may contain only EO groups, only PO groups, or mixtures thereof. These polyethers may also exist as the specified PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymer.

[0092] In one embodiment, X a31 -OH, -C(O)OH, -SH, -NH(R ’ ) and R a31 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Linear or branched alkyl, hydroxy-functional C1-C 30 Linear or branched alkyl, hydroxy-functional linear or branched C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy or amine-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Linear or branched alkyl, amine-functionalized C1-C 30 Selected from linear or branched alkyl groups.

[0093] X a31 (a31) may be an -OH group, and examples of such compounds include alkyl alcohols such as propanol and butanol, or aliphatic alcohols including stearyl alcohol (R a31 It optionally contains at least one unsaturated group, C1-C 30 Alkyl diols or polyols (R) such as linear or branched alkyls, ethanediol, propanediol, butanediol, or hexanediol. 5 These are hydroxy-functional C1-C 30Alkylene glycol ethers such as linear or branched alkyl triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or glycol ethers having a mixture of PEG, PPG, or THF units (R a31 These are hydroxy-functional linear or branched C1-C chains. 30 Polyether, polyester polyol (R a31 (These are hydroxy-functional linear or branched polyesters), silicone prepolymer polyols (R a31 (These are hydroxy-functional linear or branched organosiloxanes), N,N-dimethylaminoethanol (R 5 This is amine functional C1~C 30 (Straight-chain or branched-chain alkyl), choline chloride or betaine HCl (R a31 Y - R a311 R a312 R a313 N + -R a314 -is), butanone oxime (R 5 R a311 R a312 Examples include, but are not limited to, polyether polyols (where C=N-). Polyether polyols may contain only EO groups, only PO groups, only THF groups, or mixtures thereof. These polyethers may also exist as block copolymers, such as those specified by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). Polyether glycols preferably have an average molecular weight of about 200 or more, most preferably 350 to 2000.

[0094] X a31 This may be -C(O)OH, and examples of such compounds (a31) include fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, or erucic acid (R a31C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Hydroxy-containing acids (R) such as linear or branched alkyl, hydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybehenic acid, hydroxylignoceric acid, hydroxypalmitoleic acid, hydroxylinoleic acid, hydroxyarachidonic acid, hydroxyoleic acid, or hydroxyerucic acid. a31 These are hydroxy-functional C1-C 30 (Linear or branched alkyl), and mercaptoalkanoic acids such as mercaptopropionic acid (R a31 This is thiol functionality C1~C 30 Examples include, but are not limited to, linear or branched alkyl groups.

[0095] X a31 This may be -SH, and examples of such compounds (a31) include alkylthiols such as lauryl mercaptan or dodecyl mercaptan (R a31 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Examples include, but are not limited to, linear or branched alkyl groups.

[0096] X a31 This may be -NH(R'), and examples of such compounds (a31) include alkylamines such as diisopropylamine, propylamine, hexylamine, or laurylamine (R a31 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Alkanolamines such as linear or branched alkyl groups, ethanolamine, or propanolamine (R a31 These are hydroxy-functional C1-C 30 (Linear or branched alkyl), silicone prepolymer polyamine (R a31 (These are amine-functional linear or branched organosiloxanes), alkyldiamines (R a31 This is amine functional C1~C 30(R) are linear or branched alkyl groups, and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid. a31 HO-S(O)2R 314 - is one example, but is not limited to these.

[0097] (Compound (a32)) Compound (a32) is, formula R a321 -(OCH2CH(OR a322 )CH2) z -OR a323 [In the formula, R a321 , R a322 and R a323 is at least one R a321 , R a322 or R a323 -H is -H, and independently of each other, -H and -R a324 , -C(O)R a324 And R a324 This is a linear or branched alkyl group having 5 to 29 carbon atoms, which may independently contain at least one unsaturated bond, and z is 1 to 15.

[0098] Compound (a32) may be a compound generally known as polyglycerol. Other specific examples include, but are not limited to, triglycerol monostearate, triglycerol distearate, hexaglycerol monostearate, hexaglycerol distearate, decaglyceryl mono(caprylate / capate), decaglyceryl di(caprylate / capate), decaglycerol, polyglycerol-3, and C18 diglycerides.

[0099] (Chain extender) Compound (a3) ​​may also be a chain extender. The chain extender is a compound having two or more (e.g., two) functional groups containing active hydrogen within its molecule. Known chain extenders can be used as chain extenders, and examples include aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; phenol hydroxyl group-containing compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, and o,o'-diallyl-bisphenol A; and alcohol amines such as aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, and aminohexylpropanolamine.

[0100] [(b) Active hydrogen reactive compounds] The fluorine-containing compound has a moiety derived from the active hydrogen-reactive compound (b).

[0101] The active hydrogen-reactive compound (b) has an active hydrogen-reactive group. Examples of active hydrogen-reactive groups include epoxy groups, isocyanate groups, thioisocyanate groups, carbodiimide groups, acid halide groups, maleic anhydride groups, etc., but is typically an isocyanate. The active hydrogen-reactive compound (b) is typically a polyisocyanate, which may be a diisocyanate, triisocyanate, or polyvalent isocyanate, and may be aliphatic or aromatic.

[0102] Examples of compound (b) include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-,p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1, Aromatic polyisocyanates selected from 4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; Acyclic aliphatic polyisocyanates selected from 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-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capeate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate; 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'-, 2,4'- or 2,2'-methylenebis(Cyclohexyl isocyanate or mixtures thereof) (Hydrogenated MDI), Methylcyclohex Cyclic alicyclic polyisocyanates selected from diisocyanates (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate-methyl)cyclohexane (1,3- or 1,4-bis(isocyanate-methyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanates, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); Bridged cyclic alicyclic polyisocyanates selected from norbornene diisocyanate, norbornene diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane; TIFF0007866209000003.tif14478 Compounds selected from TIFF0007866209000004.tif14370; Examples include compounds selected from the above-mentioned polymers (dimers, trimers, pentamers, heptamers, urethidinedione, uretonimine, isocynurate modified compounds, polycarbodiimides, etc.), biuret modified compounds, and other derivatives.

[0103] [(b1) compound] Compound (b) is R f1 or R f2 The compound (b1) may also contain the following:

[0104] R f1 or R f2 Compound (b1) having is formula: -Y f -Z f α [In the formula, each symbol is independent in each occurrence.] Y f Y f1 and Y f2 A 1+α valency group consisting of one or more selected from the group comprising: Y f1 This group is composed of one or more elements selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' is a hydrogen atom or an organic group). Y f2 This is a group composed of one or more groups selected from the group consisting of aliphatic groups and aromatic groups. Z f R f1 , or R f1 or R f2 A hydrocarbon group having 2 to 40 carbon atoms, α is between 1 and 3. It may have a group represented by .

[0105] R f1 For example, Z f It may be included in R. f2 For example, an organic group, Y f2 , Z f , R f2 It can be included.

[0106] Compound (b1) possesses -Y f -Z f α The explanation for this is the -Y possessed by the above compound (a1). f -Z f α We will use the explanation regarding this matter.

[0107] However, compound (b1) is Y f Active hydrogen-reactive groups such as acid halides, acid anhydrides, isocyanates, and epoxys may be formed at the terminal end. For example, compound (b1) is X f -Y f -Z f α It may also be expressed as follows: where X f Y is a group that forms an active hydrogen reaction group, and is particularly an isocyanate group. However, compound (b1) is not limited to this structure, and any part of compound (b1) can be Y f -Z f α It may be composed of these.

[0108] (Specific example of compound (b1)) The specific examples of compound (b1) are not particularly limited, but are as follows. Compound (b1) may be an isocyanate.

[0109] Specific examples of compound (b1) are as follows: Carboxylic acid HO(O=)CY f -Z f α Acid halide G(O=)CY f -Z f α Acid anhydride O(C(=O)-Y f -Z f α )2 Isocyanate O=C=NY f -Z f α Thioisocyanate S=C=NY f -Z f α Epoxy (CH2OCH)CH2O-Y f -Z f α Halides GY f -Z f α [In the formula, Y f , Z f α is as described above, and G is a halogen atom (e.g., F, Cl, Br, or I). Note that the above formula is Y f -Z f α The terminal functional group adjacent to it (G(O=)C, etc.) is -Y f -Although it is expressed as something not included in Y f It is also possible to rewrite it as a description incorporated into the text.

[0110] A more specific example of compound (b1) is (for example, in the formula given in the example above) -Y f -Z f α but -Ali-OR f1 , -Ali-Cy-OR f1 , -Ali-Cy-Ali-OR f1 , -Cy-OR f1 , -Cy-Ali-OR f1 , -Cy-Ali-Cy-OR f1 , -Ali-N(R')-R f1 , -Ali-Cy-N(R')-R f1 , -Ali-Cy-Ali-N(R')-R f1 , -Cy-N(R')-R f1 , -Cy-Ali-N(R')-R f1 , -Cy-Ali-Cy-N(R')-R f1 , [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Cy is a hydrocarbon aromatic ring or heterocycle, and R' is a hydrogen atom or an organic group. f1 This is -CF3, -CF2H, or -CFH2. It is a compound that is A more specific example of compound (b1) is (for example, in the formula given in the example above) -Y f -Z f α but -(CH2) n -OR f1 , -(CH2) n -Cy-OR f1 , -(CH2) n -Cy-(CH2) n -OR f1 , -Cy-OR f1 , -Cy-(CH2) n -OR f1 , -Cy-(CH2) n -Cy-OR f1 , -(CH2) n -N(R')-R f1 , -(CH2) n -Cy-N(R')-R f1 , -(CH2) n -Cy-(CH2)nN(R')-R f1 , -Cy-N(R')-R f1 , -Cy-(CH2)n -N(R')-R f1 , -Cy-(CH2) n -Cy-N(R')-R f1 , [In the formula, n is an integer from 1 to 40, Cy is a hydrocarbon aromatic ring or heterocycle, R' is a hydrogen atom or organic group, R f1 This is -CF3, -CF2H, or -CFH2. Examples include certain compounds.

[0111] A more specific example of compound (b1) is: Trifluoromethoxyalkyl carboxylic acid, trifluoromethoxyalkyl carboxylic acid halogenated compounds, Trifluoromethoxybenzoic acid, trifluoromethoxybenzoic acid halogens, Trifluoromethoxyphenylacetic acid, trifluoromethoxyphenyl acetate halogenated compounds, Trifluoromethoxyalkyl isocyanate, F3CO-Ph-NCO These are some examples.

[0112] [-NHCO-] Fluorine-containing compounds have an -NHCO- group derived from compound (a) and compound (b). The -NHCO- group is 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). Fluorine-containing compounds are typically polyurethanes.

[0113] [Composition of fluorine-containing compounds] The amount of 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, relative to the fluorine-containing compound, and may also 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.

[0114] The amount of the portion derived from compound (a1) 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 relative to the portion derived from compound (a), and may also 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.

[0115] The amount of the portion derived from compound (a2) may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight relative to the portion derived from compound (a), and may also be 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, or 15% or less by weight.

[0116] The amount of the portion derived from compound (a3) ​​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, relative to the portion derived from compound (a), and may also 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.

[0117] The amount of the portion derived from compound (a31) may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight relative to the portion derived from compound (a), and may also be 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, or 15% or less by weight.

[0118] The amount of the portion derived from compound (a32) may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight relative to the portion derived from compound (a), and may also be 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, or 15% or less by weight.

[0119] The amount of the portion derived from the chain extender may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight relative to the portion derived from compound (a), and may also be 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, or 15% or less by weight.

[0120] The amount of the portion derived from compound (b) 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, relative to the fluorine-containing compound, and may also 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.

[0121] The amount of the portion derived from compound (b1) 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, relative to the portion derived from compound (b), and may also 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.

[0122] [Method for producing fluorine-containing compounds] Fluorine-containing compounds can be obtained by reacting compound (a) and compound (b). The reaction may be carried out in one step or sequentially in multiple steps. For example, if the product contains unreacted active hydrogen groups or active hydrogen reactive groups, the synthesis may be carried out sequentially. Sequential reactions are particularly useful when using substituted sugar alcohols with a high number of OH groups. The reaction conditions are not particularly limited and can be determined by those skilled in the art. Specifically, compounds (a) and (b) may be blended such that the equivalent ratio of the active hydrogen reactive group (isocyanate group) to the active hydrogen group (active hydrogen reactive group / active hydrogen group) is, for example, 1.2 or more, preferably 1.5 or more, and for example, 2.0 or less.

[0123] <Water and oil repellent> The water- and oil-repellent agents in this disclosure impart liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to a substrate (e.g., a textile substrate, a paper substrate), and can function as at least one selected from the group consisting of water repellents, oil repellents, oil-resistant agents, and water-resistant agents. The water- and oil-repellent agents in this disclosure can impart good oil resistance (oil repellency) and / or water resistance (water repellency) to a substrate, and can, for example, impart good oil resistance and water resistance.

[0124] [Fluorine-containing compound] The water-repellent and oil-repellent agent of this disclosure includes the fluorine-containing compound described above. The fluorine-containing compound itself may be used as a water-repellent and oil-repellent agent, or it may be used in combination with other components as described below.

[0125] The water-repellent and oil-repellent agent in this disclosure is Rf as described above. 1 or Rf 2The present disclosure includes a fluorine-containing compound having the following properties. On the other hand, the water- and oil-repellent agent in this disclosure does not have to contain any of the compounds selected from the group consisting of compounds having 8 or more carbon atoms in a fluoroalkyl group, compounds having 8 or more carbon atoms in a perfluoroalkyl group, compounds having 4 or more carbon atoms in a fluoroalkyl group, compounds having 2 or more carbon atoms in a fluoroalkyl group, and compounds having 2 or more carbon atoms in a perfluoroalkyl group. The water- and oil-repellent agent in this disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds. In this specification, a fluoroalkyl group may refer to a group in which one or more hydrogen atoms at each carbon atom of the alkyl group are substituted with fluorine atoms.

[0126] [Amount of fluorine-containing compounds] The amount of fluorine-containing compound may be 0.01% or more by weight, 0.03% or more by weight, 0.5% or more by weight, 1% or more by weight, 3% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, or 30% or more by weight in the water-repellent and oil-repellent agent, or 60% or less by weight, 50% or less by weight, 40% or less by weight, 30% or less by weight, 20% or less by weight, 10% or less by weight, 5% or less by weight, or 3% or less by weight. The fluorine-containing compound itself may also be used as a water-repellent and oil-repellent agent.

[0127] [Other water-repellent and oil-repellent ingredients] The water- and oil-repellent agents of this disclosure may contain other water- and oil-repellent components. Other water- and oil-repellent agents that are known may be used, for example, non-fluorine water- and oil-repellent components. Examples of non-fluorine water- and oil-repellent components include, but are not limited to, acrylic polymers described in WO / 2020 / 054856, WO / 2017 / 159754, WO / 2020 / 162547, etc., polyurethanes described in JP 2016-524628, JP 2017-533976, JP 2017-504730, WO / 2021 / 132170, WO / 2021 / 132172, etc., and natural product modifiers described in WO / 2022 / 065382 and WO / 2022 / 065385, etc.

[0128] [Amount of other water-repellent and oil-repellent components] The amount of other water-repellent and oil-repellent components may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the fluorine-containing compound, or 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.

[0129] [Dispersant] The water-repellent and oil-repellent agents of this disclosure may include a dispersant.

[0130] The dispersant is selected from organic dispersants and inorganic dispersants. There may be at least one of them. The dispersant may be non-anionic and may be at least one selected from nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants. The water-repellent and oil-repellent agent does not have to contain anionic dispersants.

[0131] The dispersant may be either an organic dispersant or an inorganic dispersant, or a combination of both.

[0132] Organic dispersants may be used as dispersants. Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants, and the term "organic dispersant" may refer to surfactants.

[0133] The dispersant may be non-fluorinated.

[0134] [Nonionic dispersant] The dispersant may contain a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0135] The nonionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 50000 or less, 25000 or less, 10000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0136] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0137] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0138] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 10-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0139] Examples of ester ethers are compounds formed by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 3-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0140] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolaminos. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0141] The polyol may be a divalent to pentavalent alcohol with 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (a secondary amine or preferably a tertiary amine) (for example, having 5 to 50 carbon atoms).

[0142] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group of the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0143] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0144] The nonionic dispersant may be an alkylene oxide adduct of linear and / or branched aliphatic (saturated and / or unsaturated) groups, a polyalkylene glycol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sorbitan ester of linear and / or branched fatty acids (saturated and / or unsaturated), a glycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyglycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sucrose ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide addition portion and the polyalkylene glycol portion is polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not need to contain aromatic groups.

[0145] The nonionic dispersant is, formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 This is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms. R 2 Each of these is independently identical or distinct, an alkylene group having 3 or more carbon atoms (e.g., 3 to 10). R 3 These are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms. p is a number greater than or equal to 2. q is a number greater than or equal to 1, or 0. It may be a compound represented by [the formula shown].

[0146] R 1 The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. 1 Preferred specific examples include the lauryl group, tridecyl group, and oleyl group. R 2 Examples include the propylene group and the butylene group. In nonionic dispersants, p may be a number greater than or equal to 3 (e.g., 5 to 200). q may be a number greater than or equal to 2 (e.g., 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but oxypropylene chains are preferred among these.

[0147] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C12 -C 16 ) Thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl(C 12 -C 18 This includes condensation products with amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc.

[0148] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example, 30 to 75% by weight, and especially 40 to 70% by weight, relative to the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of nonionic dispersants is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single agent or a mixture of two or more agents. The nonionic dispersant may be a mixture of a compound with an HLB (hydrophilic-hydrophobic balance) of less than 15 (especially 5 or less) and a compound with an HLB of 15 or more.

[0149] [Cationic dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be of low molecular weight (e.g., molecular weight 2000 or less, particularly 10000 or less) or of high molecular weight (e.g., molecular weight 2000 or more). The cationic dispersant may be a compound that does not have an amide group.

[0150] The cationic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 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.

[0151] The cationic dispersant may be an amine salt, a quaternary ammonium salt, or an oxyethylene-added ammonium salt. Specific examples of cationic dispersants are not particularly limited, but include alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt-type dispersants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, benzethonium chloride, and other quaternary ammonium salt-type dispersants.

[0152] Preferred examples of cationic dispersants are: R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 These are hydrocarbon groups with 1 to 40 carbon atoms. X is an anionic group. It is a compound represented by [formula]. R 21 , R 22 , R 23 and -R 24 Specific examples of X are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). The cationic dispersant is particularly preferably a monoalkyltrimethylammonium salt (alkyl group with 4 to 40 carbon atoms).

[0153] The cationic dispersant is preferably an ammonium salt. The cationic dispersant has the formula: R 1 p -N + R 2 q X - [In the formula, R 1 is C12 or higher (for example, C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 These are H or C1-C4 alkyl groups, benzyl groups, and polyoxyethylene groups (number of oxyethylene groups e.g., 1 (especially 2, particularly 3) to 50). (CH3 and C2H5 are particularly preferred.) X is a halogen atom (for example), a C1-C4 fatty acid base, p is either 1 or 2, q is either 2 or 3, and p + q = 4. It may be an ammonium salt represented by R. 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[0154] Specific examples of cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0155] [Anionic dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant does not have to contain an anionic dispersant.

[0156] The anionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 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.

[0157] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type dispersants, phosphate mono or diester type dispersants, and sulfosuccinate esters.

[0158] [Amphoteric dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0159] The amphoteric dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 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.

[0160] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, examples include lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

[0161] [Inorganic dispersants] The dispersant may contain an inorganic dispersant.

[0162] The average primary particle size of the inorganic dispersant may be 5 nm or larger, 30 nm or larger, 100 nm or larger, 1 μm or larger, 10 μm or larger, or 25 μm or larger, and may also be 100 μm or smaller, 50 μm or smaller, 10 μm or smaller, 1 μm or smaller, 500 nm or smaller, or 300 nm or smaller. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may also be hydrophilic particles.

[0163] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0164] [Amount of dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the fluorine-containing compound, or 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.

[0165] [Liquid media] The water- and oil-repellent agents in this disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The water- and oil-repellent agents may be a dispersion or a solution. The water- and oil-repellent agents in this disclosure may be water-dispersible and may contain at least water.

[0166] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain compounds having at least one hydroxyl group (e.g., polyols such as alcohols and glycol-based solvents, ethers of polyols (e.g., monoethers)). These may be used individually or in combination of two or more.

[0167] [Amount of liquid medium] The amount of liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 1 part by weight of the fluorine-containing compound.

[0168] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 1 part by weight of the fluorine-containing compound.

[0169] The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of the fluorine-containing compound, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0170] 〔silicone〕 The water- and oil-repellent agent in this disclosure may contain silicone (polyorganosiloxane). By including silicone, it is possible to achieve good liquid repellency in addition to good texture and durability.

[0171] As the silicone, known silicones can be used. Examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified, carboxy-modified, methylhydrogen silicones, etc.). The silicone may also be a silicone wax having waxy properties. These may be used alone or in combination of two or more.

[0172] The weight-average molecular weight of the silicone may be 1000 or more, 10000 or more, or 50000 or more, and may also be 500000 or less, 250000 or less, 100000 or less, or 50000 or less.

[0173] [Amount of silicone] The amount of silicone may 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, per 100 parts by weight of the fluorine-containing compound, or 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.

[0174] 〔wax〕 The water- and oil-repellent agent in this disclosure may contain wax. Including wax can effectively impart liquid repellency to the substrate.

[0175] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and plant waxes, and mineral waxes. Paraffin wax is preferred. Specific examples of compounds that constitute the wax include n-alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane) and n-alkenes (e.g., 1-eicosene, 1-docosene, 1-tricocene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontane, 1-hentriacontane, 1-dotriacontane, 1-tritriacontane, 1-tetratriacontane, 1-pentatriacontane, 1-hexatriacontane). The number of carbon atoms in the compounds that constitute the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500 or 300 to 1000. These may be used alone or in combination of two or more.

[0176] The melting point of the wax may be 40°C or higher, 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher, preferably 55°C or higher, more preferably 60°C or higher, and may also be 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower, preferably 120°C or lower. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0177] [Amount of wax] The amount of wax may 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, per 100 parts by weight of the fluorine-containing compound, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0178] [Organic acid] The water- and oil-repellent agent of this disclosure may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, and sulfinic acids, with carboxylic acids being particularly preferred. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, and citric acid, with formic acid or acetic acid being particularly preferred. In this disclosure, one organic acid may be used, or two or more may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0179] [Amount of organic acids] The amount of organic acid may 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, per 100 parts by weight of the fluorine-containing compound, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the water-repellent and oil-repellent agent is 3 to 10, for example 5 to 9, and especially 6 to 8. The water-repellent and oil-repellent agent may be acidic (pH 7 or less, for example 6 or less).

[0180] [Hardening agent] The water-repellent and oil-repellent agents of this disclosure may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound).

[0181] The curing agent (crosslinking agent) in water-repellent and oil-repellent agents can effectively cure fluorine-containing compounds. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group present in the fluorine-containing compound. Examples of active hydrogen-reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0182] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). A blocked isocyanate compound is a compound in which the isocyanate groups of an isocyanate compound are masked with a blocking agent to suppress the reaction.

[0183] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diiso These include aliphatic diisocyanates such as cyanatomethyl caproate, 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, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0184] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used individually or in combination of two or more.

[0185] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used individually or in combination of two or more.

[0186] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate or mixtures thereof, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used individually or in combination of two or more.

[0187] Examples of polyisocyanate derivatives include various derivatives of the polyisocyanate compounds described above, such as dimers, trimers, biuretes, allophanates, carbodiimides, uretodiones, uretoimines, isocyanurates, and iminooxadiazinediones. These may be used individually or in combination of two or more.

[0188] These polyisocyanates can be used individually or in combination of two or more types. It is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent, as the polyisocyanate compound. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as water-repellent and oil-repellent agents.

[0189] Blocking agents sequester free isocyanate groups. Blocked polyisocyanate compounds can be easily reacted with hydroxyl groups by heating them to, for example, 100°C or higher, such as 130°C or higher, which regenerates the isocyanate groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0190] Epoxy compounds are compounds that have an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound that has a chloromethyl group. Examples of chloromethyl group-containing compounds include chloromethyl polystyrene. Carboxyl group-containing compounds are compounds that have a carboxyl group. Examples of carboxyl group-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

[0191] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resin and methyl etherified melamine resin.

[0192] [Amount of hardener] The amount of curing agent may 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, 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, per 100 parts by weight of the fluorine-containing compound, or it may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0193] [Other ingredients] Water- and oil-repellent agents may contain other components besides those listed above. Examples of other components include polysaccharides, paper strength enhancers, flocculants, yield enhancers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength enhancers, PVA, penetrating agents, organic acids, pigments, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used individually or in combination of two or more. In addition to the above-mentioned components, other components include other water-repellent and / or oil-repellent agents, dispersants, texture modifiers, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, wrinkle inhibitors, shape-retaining agents, drape-retaining agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, color transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyldisodium (Chinopearl CBS-X, manufactured by Ciba Specialty Chemicals), dye fixatives, and color-fading inhibitors such as 1,4-bis(3-aminopropyl)piperazine. In addition, enzymes such as cellulase, amylase, protease, lipase, and keratinase can be used as stain removers and fiber surface modifiers; silk protein powder can be used as a foam inhibitor and to impart the texture and functionality of silk, such as moisture absorption and release properties; surface modifiers or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Solubble S (Ichimaru Falcos)); and anti-fouling agents (e.g., nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Go-o Chemical Industry), SRC-1 manufactured by Clariant Japan, etc.). These may be used individually or in combination of two or more.

[0194] [Polysaccharide] Examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofibers, cellulose nanofibers, and pullulan. The polysaccharides may be substituted or modified polysaccharides, and in particular, modified polysaccharides to which hydroxyl groups or cationic groups have been introduced.

[0195] [Paper strength enhancers, flocculants, yield improvers, or coagulants] Examples of paper strength enhancers, flocculants, yield improvers, or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, alkylenedichloride-polyalkylene polyamine condensates, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0196] [Cyssing agent] Examples of sizing agents include cellulose-reactive sizing agents, such as rosin-based sizing agents like rosin soap, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, such as emulsions / dispersions of acid anhydrides like alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, such as copolymers of styrene and acrylate.

[0197] [Antistatic agent] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives. These may also be ion-conductive polymers obtained by polymerizing or copolymerizing monomers having cationic, anionic, or amphoteric ion-conductive groups. These may be used individually or in combination of two or more.

[0198] [Preservatives] Preservatives are primarily used to enhance preservative and bactericidal properties and maintain preservation during long-term storage. Examples of preservatives include isothiazolone-type organosulfur compounds, benzisothiazolone-type organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol.

[0199] [UV absorber] UV absorbers are chemicals that have the effect of protecting against ultraviolet rays. They absorb ultraviolet rays and convert them into infrared rays, visible light, etc., and release them. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0200] [Antibacterial agent] Antibacterial agents are components that suppress the growth of bacteria on fibers and also suppress the generation of unpleasant odors derived from microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0201] [Deodorizer] Examples of deodorizers include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of trisodium methylglycinediacetate described in International Publication No. 2012 / 090580).

[0202] [Amount of other ingredients] The individual or total amounts of the other components may 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, per 100 parts by weight of the fluorine-containing compound, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0203] <Method for manufacturing processed textile or paper products> The method for manufacturing a product treated with a water-repellent and oil-repellent agent in this disclosure includes a processing step of treating a substrate with the water-repellent and oil-repellent agent described above.

[0204] "Treatment" means applying a water-repellent and oil-repellent agent to a substrate by immersion, spraying, coating, etc. Through treatment, the fluorine-containing compound, which is the active ingredient of the water-repellent and oil-repellent agent, adheres to the interior and / or surface of the substrate. Here, adhesion may be physical or chemical, and for example, the fluorine-containing compound may be physically or chemically modified (by reaction) the hydroxyl groups present in the substrate (fiber, paper, glass, etc.).

[0205] [Base material] The substrates treated with the water- and oil-repellent agents in this disclosure are not limited, but are preferably textile products or paper products, particularly paper products.

[0206] The water- and oil-repellent agents in this disclosure impart liquid repellency to a substrate (e.g., a fibrous substrate, a paper substrate) and can function as at least one selected from the group consisting of water-repellent agents, oil-repellent agents, oil-resistant agents, and water-resistant agents. A substrate treated with the water- and oil-repellent agent in this disclosure is, for example, oil-resistant paper or water-resistant paper.

[0207] Examples of base materials for textile products include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics; fabrics in the form of clothing (e.g., water-repellent clothing, e.g., raincoats) and carpets; however, fibers, yarns, and intermediate textile products (e.g., slivers or rovings) in their pre-fabric state may also be treated.

[0208] Examples of base materials for paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as crushed wood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine, recycled corrugated cardboard or deinked paper, as well as containers and molded bodies made of paper. Specific examples of paper products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal interleaving paper, kraft paper, neutral printing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc. Preferred examples include food packaging materials and food containers.

[0209] Substrates treated with the water- and oil-repellent agent of this disclosure are not limited to textile or paper products, but can also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0210] When the substrate is glass, the manufactured glass product may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflective layer, may be formed on the surface (outermost layer) of the glass substrate. Either a single-layer anti-reflective layer or a multi-layer anti-reflective layer may be used for the anti-reflective layer. Examples of inorganic materials that can be used for the anti-reflective layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic materials may be used individually or in combination of two or more (for example, as a mixture). When a multi-layer anti-reflective layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, may be present on part of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, depending on its specific specifications.

[0211] [Processing method] The water- and oil-repellent agent of this disclosure can be applied to a substrate by conventionally known methods as a treatment agent (particularly a surface treatment agent). The treatment method may involve diluting the water- and oil-repellent agent of this disclosure by dispersing it in an organic solvent or water as needed, and then applying it to the interior and / or surface of the substrate by known methods such as immersion coating, spray coating, or foam coating, followed by drying. After drying, a product with the solid components of the water- and oil-repellent agent attached is obtained. Furthermore, if necessary, it may be applied together with a suitable crosslinking agent and cured. The water- and oil-repellent agent of this disclosure can also be used in combination with various additives as needed, such as water- and / or oil-repellent agents, anti-slip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insecticides, and defoaming agents. Examples of various additives may be the same as those described under "other components" in the above explanation. The concentration of the water-repellent and oil-repellent agent in the treatment agent that comes into contact with the substrate may be changed as appropriate depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0212] The water- and oil-repellent agent can be applied to a substrate by any known method for treating the substrate with a liquid. The substrate may be immersed in the water- and oil-repellent agent, or the solution may be applied to or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating to exhibit liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In this disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In this disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the substrate is paper, it may be coated onto the paper, or the solution may be applied to or sprayed onto the paper, or it may be mixed with the pulp slurry before papermaking. The treatment may be an external or internal addition. Alternatively, the water- and oil-repellent agent may be applied to textile products by cleaning methods, for example, by washing or dry cleaning methods.

[0213] [Disposal of paper products] Examples of paper substrates include paper, paper containers, and paper molded products (e.g., pulp molds). The fluorine-containing compounds of this disclosure adhere well to paper substrates.

[0214] Paper can be manufactured using conventionally known papermaking methods. Either an internal additive method, in which a water- and oil-repellent agent is added to the pulp slurry before papermaking, or an external additive method, in which a water- and oil-repellent agent is applied to the paper after papermaking, can be used.

[0215] The size press for external additive processing can also be classified as follows, depending on the application method. One coating method is the so-called pound-type two-roll sizing press, in which a coating liquid (sizing liquid) is supplied to a nip formed by passing paper between two rubber rolls, creating a coating liquid reservoir called a pound, and the sizing liquid is applied to both sides of the paper by passing it through this reservoir. Other coating methods include the gate-roll type and the rod-metering sizing press, which apply the sizing liquid by surface transfer. In the pound-type two-roll sizing press, the sizing liquid easily penetrates into the interior of the paper, while in the surface transfer type, the sizing liquid components tend to remain on the surface of the paper. Compared to the pound-type two-roll sizing press, the surface transfer type allows the coating layer to remain on the surface of the paper more easily, and the coating layer formed on the surface is greater than that of the pound-type two-roll sizing press. In this disclosure, performance can be imparted to the paper even when the former pound-type two-roll sizing press is used. Paper treated in this way can exhibit excellent oil resistance and water resistance, etc., after simple drying at room temperature or high temperature, and optionally with heat treatment that can be performed at temperatures up to 300°C, for example up to 200°C, particularly in the temperature range of 80°C to 180°C, depending on the properties of the paper.

[0216] The internal additive treatment method may refer to a treatment method in which a water-repellent and oil-repellent agent is added to the pulp slurry before papermaking. The internal additive treatment method may include, but is not limited to, one or more of the following steps: adding a water-repellent and oil-repellent agent to the pulp slurry and stirring and mixing it; dewatering the pulp composition prepared in the first step by suction through a mesh-like body of a predetermined shape to deposit the pulp composition and form a pulp mold intermediate; and molding and drying the pulp mold intermediate using a heated mold to obtain paper, a paper container, or a paper molded body. After simple drying at room temperature or high temperature, the treated paper may optionally be heat-treated depending on the properties of the paper. The heat treatment temperature may be 150°C or higher, 180°C or higher, or 210°C or higher, and may also be 300°C or lower, 250°C or lower, or 200°C or lower, and particularly 80°C to 180°C. By performing heat treatment in such a temperature range, excellent oil resistance and water resistance can be obtained.

[0217] This disclosure can be used in gypsum board base paper, coated base paper, medium quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal laminates, kraft paper, and the like. It can also be used in neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper.

[0218] Pulp raw materials include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, wood pulp, mechanical pulp or thermomechanical pulp, etc. Any type of recycled paper pulp can be used, including bleached or unbleached high-yield pulp, recycled newspaper, recycled magazine, recycled corrugated cardboard, or deinked recycled paper. Mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.

[0219] The water resistance of paper can be improved by adding a sizing agent. Examples of sizing agents include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents). The amount of sizing agent may be 0.01 to 5% by weight relative to the pulp.

[0220] If necessary, the paper may contain additives used in papermaking, such as starch, modified starch, carboxymethylcellulose, polyamide polyamine-epichlorohydrin resin (paper strength enhancers), flocculants, fixatives, yield enhancers, dyes, fluorescent dyes, slime control agents, and defoamers, in amounts commonly used in papermaking. Starch and modified starch are preferred. If necessary, water and oil repellents can be applied to the paper using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc., by a size press, gate roll coater, bill blade coater, calender, etc.

[0221] In external additions, the amount of fluorine-containing compound in the coating layer is 0.01 to 2.0 g / m². 2 Especially 0.1~1.0g / m 2 Preferably, the coating layer is formed of a water-repellent and oil-repellent agent and starch and / or modified starch. The solid content of the water-repellent and oil-repellent agent for paper in the coating layer is 2 g / m². 2 The following is preferable: In the internal addition process, it is preferable to mix the water-repellent and oil-repellent agent with the pulp such that the amount of the water-repellent and oil-repellent agent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example, 0.01 to 10 parts by weight, and particularly 0.2 to 5.0 parts by weight, per 100 parts by weight of pulp used to form the paper.

[0222] In external application, oil resistance can also be imparted to paper by using a so-called pound-type two-roll size press process, in which the processing liquid is stored between the rolls and the base paper is passed through the processing liquid between the rolls at an arbitrary roll speed and nip pressure.

[0223] In external additive processing, the paper substrate may contain additives such as sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additive is -10000 to 10000 μeq / g, preferably -4000 to 8000 μeq / g, and more preferably -1000 to 7000 μeq / g. Additives (e.g., sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants, e.g., solids or active ingredients) can generally be used in an amount of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) relative to the pulp. In the case of a paper substrate containing a cationic additive (e.g., sizing agent, paper strength enhancer, flocculant, yield enhancer, or coagulant), the water-repellent and oil-repellent agent may be anionic, and in the case of an anionic additive, the water-repellent and oil-repellent agent may be cationic, but is not limited to these.

[0224] In the internal additive processing, it is preferable to papermake a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight). Additives (for example, sizing agents, paper strength enhancers, flocculants, yield enhancers or coagulants, etc.) and fluorine-containing compounds can be added to the pulp slurry. Examples of additives (e.g., sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants) include alkyl ketene dimers, alkenyl succinic anhydride, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimines, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, alkylenedichloride-polyalkylene polyamine condensates, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0225] In internal additive processing, the paper substrate may contain additives such as sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additive may 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. Additives (e.g., sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants, e.g., solids or active ingredients) can generally be used in an amount of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) relative to the pulp. In the case of a paper substrate containing a cationic additive (e.g., sizing agent, paper strength enhancer, flocculant, yield enhancer, or coagulant), the water-repellent and oil-repellent agent may be anionic, and in the case of an anionic additive, the water-repellent and oil-repellent agent may be cationic, but are not limited to these.

[0226] The oil resistance (KIT method) of treated paper products can be measured according to TAPPI T-559cm-02. Here, the paper product may be an externally treated product. The KIT test solution is a mixture of castor oil, toluene, and heptane in the ratios shown in the table below. Place one drop of the test solution shown in the table onto the paper and observe the oil penetration after 15 seconds. The highest oil resistance score given by the KIT test solution that shows no penetration is defined as the oil resistance. A higher KIT test solution number indicates higher oil resistance. TIFF0007866209000005.tif7596

[0227] The high-temperature oil resistance of the treated paper product can be measured as follows. Here, the paper product may be one that has undergone internal additive treatment. 100 ml of corn oil at 65°C is placed in a molded pulp mold product on a container, left for 30 minutes, and then the corn oil is removed. The degree to which the oil has penetrated the pulp mold is evaluated according to the following criteria. 4: There are almost no oil stains visible on the inside of the bottom of the container. 3: No oil stains are visible on the outside of the bottom of the container. 2: Oil stains are visible on less than 5% of the outer surface area of ​​the container bottom. 1: Oil stains are visible on 5% to less than 50% of the outer surface area of ​​the container bottom. 0: Oil stains are visible on more than 5% of the outer surface area of ​​the container bottom.

[0228] The high-temperature water resistance of the treated paper product can be measured as follows. Here, the paper product may be one that has undergone internal additive treatment. 100 ml of 80°C hot water is placed in a container with the molded pulp mold product, left for 30 minutes, and then the hot water is removed. The degree to which the oil has penetrated the pulp mold is evaluated according to the following criteria. 4: There are almost no oil stains visible on the inside of the bottom of the container. 3: No oil stains are visible on the outside of the bottom of the container. 2: Oil stains are visible on less than 5% of the outer surface area of ​​the container bottom. 1: Oil stains are visible on 5% to less than 50% of the outer surface area of ​​the container bottom. 0: Oil stains are visible on more than 5% of the outer surface area of ​​the container bottom.

[0229] [Pretreatment of textile products] Textile products may be pre-treated before being treated with the water- and oil-repellent agents of this disclosure. Pre-treating textile products can impart excellent durability to them after treatment with the water- and oil-repellent agents.

[0230] Examples of pretreatments for textile products include cationization by reaction with reactive quaternary ammonium salts, anionization by sulfonation, carboxylation, phosphorylation, etc., acetylation, benzoylation, carboxymethylation, grafting, tannic acid treatment, and polymer coating after anionization.

[0231] The method for pre-treating textile products is not limited, but conventionally known methods can be used. The pre-treatment solution may be diluted by dispersing it in an organic solvent or water as needed, and then applied to the interior and / or surface of the textile product by known methods such as immersion coating, spray coating, or foam coating, followed by drying. The pH and temperature of the pre-treatment solution may be adjusted according to the desired degree of treatment. As an example of a method for pre-treating textile products, a method of pre-treating textile products with the above-mentioned treatment agent will be described in detail.

[0232] The pretreatment method for textile products involves applying -SO3M to the fibers. 1 (In the formula, M 1 (represents a monovalent cation) a monovalent group represented by -COOM 2 (In the formula, M 2 A monovalent group represented by (where is a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 The process may include a step of adding one or more functional groups (hereinafter sometimes referred to as "specific functional groups") selected from the group consisting of monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0233] M 1 Examples include H, K, Na, or ammonium ions which may have substituents. 2 Examples include H, K, Na, or ammonium ions which may have substituents. 1 or X 2 If it is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0234] Fibers containing the above-mentioned specific functional groups (hereinafter sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following method. (i) A compound having the above-mentioned specific functional group is attached to the fiber material. The attachment of the compound may be such that a portion of the compound and a portion of the fiber are chemically bonded, as long as a sufficient amount of the above-mentioned specific functional group remains. (ii) Prepare a fiber in which the above-mentioned specific functional group is directly introduced into the material constituting the fiber.

[0235] (i) For example, a functional group-containing fiber can be obtained by a functional group introduction step in which the fiber material is treated with a pretreatment solution containing one or more compounds having the above-mentioned specific functional group.

[0236] There are no particular restrictions on the material of the fiber material, and examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene; and composite fibers and blended fibers thereof. The fiber material may take any form, such as fibers (tow, sliver, etc.), yarn, knitted fabrics (including interwoven fabrics), woven fabrics (including interwoven fabrics), and nonwoven fabrics.

[0237] In this embodiment, from the viewpoint of obtaining good water repellency in the resulting textile product, it is preferable to use a fiber material containing polyamide and polyester as a base material. In particular, it is preferable to use nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0238] The above -SO3M 1 As a compound having this property, phenolic polymers can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.

[0239] TIFF0007866209000006.tif4770 [where, X 2 ha-SO3M 3 (In the formula, M 3 (where represents a monovalent cation) or a group represented by the following general formula, where n is an integer between 20 and 3000.

[0240] TIFF0007866209000007.tif2758 [In the formula, M 4 This represents a monovalent cation.

[0241] The above M 3 Examples include H, K, Na, or ammonium ions which may have substituents.

[0242] The above M 4Examples include H, K, Na, or ammonium ions which may have substituents.

[0243] The compound represented by the above general formula may, for example, be a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0244] The above-COOM 2 Examples of compounds having this property include polycarboxylic acid polymers.

[0245] As polycarboxylic acid polymers, for example, polymers synthesized by conventionally known radical polymerization methods using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or commercially available polymers can be used.

[0246] One method for producing polycarboxylic acid polymers is to add a radical polymerization initiator to an aqueous solution of the monomer and / or its salt, and heat the reaction at 30 to 150°C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, isopropyl alcohol, or aqueous solvents such as acetone may be added to the aqueous solution of the monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators using combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0247] In radical polymerization, copolymerizable monomers can be used in addition to the monomers mentioned above. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, as well as acrylamide, acrylates, and methacrylates. Acrylates and methacrylates are preferably those having a hydrocarbon group with 1 to 3 carbon atoms, which may have substituents such as hydroxyl groups. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used individually or in combination of two or more.

[0248] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0249] The weight-average molecular weight of the polycarboxylic acid polymer is preferably 1,000 to 20,000, and more preferably 3,000 to 15,000, from the viewpoint of obtaining good water repellency in the resulting textile product.

[0250] For polycarboxylic acid polymers, commercially available products such as "NeoCrystal 770" (manufactured by Nikka Chemical Co., Ltd., product name) and "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., product name) can be used.

[0251] The above - OP(O)(OX 1 )(OX 2 Examples of compounds having the following general formula include phosphate ester compounds. TIFF0007866209000008.tif3136[where, X 1 or X 2 This is synonymous with the above, X3 This represents an alkyl group with 1 to 22 carbon atoms.

[0252] As the phosphate ester compound mentioned above, phosphate monoesters, diesters, and triesters in which the alkyl ester portion has an alkyl group having 1 to 22 carbon atoms, as well as mixtures thereof, can be used.

[0253] From the viewpoint of obtaining good water repellency in the resulting textile product, it is preferable to use lauryl phosphate esters and decyl phosphate esters.

[0254] For the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.

[0255] The pretreatment solution containing one or more compounds having the above-mentioned specific functional groups can, for example, be an aqueous solution of the compounds described above. The pretreatment solution may also contain acids, alkalis, surfactants, chelating agents, etc.

[0256] Methods for treating fibrous materials with the above-mentioned pretreatment solution include, for example, padding, immersion, spraying, and coating. For padding, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used. For immersion, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. Examples of spray treatments include air sprays that atomize the treatment solution using compressed air, and air sprays that use a hydraulic atomization system. The concentration of the treatment solution and the treatment conditions such as heat treatment after application can be adjusted as appropriate, taking into account the purpose, performance, and other conditions. If the pretreatment solution contains water, it is preferable to dry it to remove the water after it has been applied to the fiber material. There are no particular restrictions on the drying method, and either a dry heat method or a wet heat method may be used. There are no particular restrictions on the drying temperature, but for example, drying at room temperature to 200°C for 10 seconds to several days is sufficient. If necessary, after drying, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes.

[0257] Furthermore, if the fiber material is to be dyed, the pretreatment with the pretreatment solution may be performed before dyeing or in the same bath as the dyeing. However, if reducing soaping is performed, there is a risk that the compounds having the specific functional groups (e.g., phenolic polymer compounds, etc.) that have been adsorbed during the process may be removed. Therefore, it is preferable to perform the pretreatment after reducing soaping following dyeing.

[0258] The treatment temperature during the immersion process can be 60 to 130°C. The treatment time can be 5 to 60 minutes.

[0259] In the functional group introduction step using the pretreatment solution, it is preferable to treat the material in such an amount that the amount of compound having the specified functional group attached is 1.0 to 7.0 parts by weight per 100 parts by weight of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0260] The pretreatment solution may be adjusted to a pH of less than 7, for example, 3 to 5. pH adjustment can be done using pH adjusting agents such as acetic acid or malic acid.

[0261] In the pretreatment solution, salt can also be used in combination to effectively adsorb the compound having the above-mentioned specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0262] In the functional group introduction step using the pretreatment solution, it is preferable to remove any compounds having the specified functional groups that have been excessively treated. One method of removal is washing with water. By performing sufficient removal, it is possible to suppress the inhibition of the development of water repellency in the subsequent water-repellent treatment, and in addition, the texture of the resulting textile product will be good. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fibers before contacting them with the above-mentioned treatment agent.

[0263] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fiber include cationic dyeable polyester (CD-PET).

[0264] From the viewpoint of obtaining good water repellency in the resulting textile product, the functional group-containing fibers preferably have a surface zeta potential of -100 to -0.1 mV, and more preferably -50 to -1 mV. The surface zeta potential of the fibers can be measured, for example, using the zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0265] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0266] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0267] <Manufacturing method> [Manufacturing Example 1] 4.0 g of 4-trifluoromethoxyphenol and 16 g of 4-methyl-2-pentanone (MIBK) were added to a 50 ml three-necked flask equipped with a stirrer, thermometer, and condenser. The solution was then cooled to 50°C, and 3.8 g of desmodule N3200A (manufactured by Sumika Bayer Urethane) and then 1 drop of dibutyltin dilaurate were added. The solution was heated to 80°C for 4 hours to obtain compound 1 with a 33% solid content.

[0268] [Manufacturing Example 2] In a 50 ml three-necked flask equipped with a stirrer, thermometer, and condenser, 3.4 g of 4-trifluoromethoxyphenol, 6.0 g of sorbitan monostearate, and 16 g of 4-methyl-2-pentanone (MIBK) were added. The solution was then cooled to 50°C, and 6.6 g of desmodule N3200A (manufactured by Sumika Bayer Urethane) and then 1 drop of dibutyltin dilaurate were added. The solution was heated to 80°C for 4 hours to obtain compound 2 with a 50% solid content.

[0269] [Manufacturing Example 3] In a 50 ml three-necked flask equipped with a stirrer, thermometer, and condenser, 4.0 g of 4-trifluoromethoxyphenol, 1.3 g of N-methyldiethanolamine, and 19 g of 4-methyl-2-pentanone (MIBK) were added. The solution was then cooled to 50°C, and 7.6 g of desmodule N3200A (manufactured by Sumika Bayer Urethane) and then 1 drop of dibutyltin dilaurate were added. The solution was heated to 80°C for 4 hours to obtain compound 3 with a 40% solid content.

[0270] [Comparative Example 1] 5.0 g of 4-methoxyphenol and 12 g of 4-methyl-2-pentanone (MIBK) were added to a 50 ml three-necked flask equipped with a stirrer, thermometer, and condenser. The solution was then cooled to 50°C, and 7.0 g of desmodule N3200A (manufactured by Sumika Bayer Urethane) and then 1 drop of dibutyltin dilaurate were added. The solution was heated to 80°C for 4 hours to obtain compound 4 with a 50% solid content.

[0271] [Comparative Example 2] In a 50 ml three-necked flask equipped with a stirrer, thermometer, and condenser, 2.7 g of 4-methoxyphenol, 7.0 g of sorbitan monostearate, and 17 g of 4-methyl-2-pentanone (MIBK) were added. The solution was then cooled to 50°C, and 7.6 g of desmodule N3200A (manufactured by Sumika Bayer Urethane) and then 1 drop of dibutyltin dilaurate were added. The solution was heated to 80°C for 4 hours to obtain compound 5 with a 50% solid content.

[0272] [Comparative Example 3] In a 50 ml three-necked flask equipped with a stirrer, thermometer, and condenser, 3.6 g of 4-methoxyphenol, 1.7 g of N-methyldiethanolamine, and 15 g of 4-methyl-2-pentanone (MIBK) were added. The solution was then cooled to 50°C, and 10.1 g of desmodule N3200A (manufactured by Sumika Bayer Urethane) was added, followed by 1 drop of dibutyltin dilaurate. The solution was then heated to 80°C for 4 hours to obtain compound 6 with a 51% solid content.

[0273] <Method for preparing the processing solution> The solutions prepared in Production Examples 1-3 were diluted with methyl ethyl ketone (MEK) to prepare 200g each of treatment solutions 1-6 with solid content concentrations of 1.0% and 2.0%, respectively. The solutions prepared in Comparative Examples 1-3 were diluted with methyl ethyl ketone (MEK) to prepare 200g each of treatment solutions 7-12, with solid content concentrations of 1.0% and 2.0%, respectively. A list of the treatment solutions is shown in Table 1.

[0274] <Evaluation of treated fabric> [How to treat fabric] Two types of fabric were used: nylon and PET. Two types of cloth were placed in 500 ml poly bottles containing 200 g each of the prepared treatment solutions (1-12), and the poly bottles were shaken for 10 seconds to allow the treatment solution to adhere to the cloth. After removing the cloth from the treatment solution, it was placed in a centrifuge and centrifugated at 1000 rpm for 30 seconds. The cloth was then dried at room temperature for 24 hours and then heated at 160°C for 2 minutes.

[0275] [Water repellency test] The water repellency of the treated fabric was evaluated by visually assessing its wet state according to the following criteria, in accordance with the spray method of JIS-L-1092 (AATCC-22). The evaluation results are expressed by a water repellency number as shown in the table below. A higher score indicates better water repellency. The results are shown in Table 2. ◎(100): No moisture or water droplets on the surface. ○(90): The surface does not become wet, but small water droplets are present. △(80): Shows wetting on the surface in the form of small individual water droplets. ×(70 or less): More than half of the surface is wet, and partial penetration is observed. [Oil repellency test] A droplet of IPA / water = 10 / 90 solution is placed on the treated cloth, and the condition after 30 seconds is visually evaluated according to the following criteria. The results are shown in Table 3. ◎: No liquid droplet seepage occurs, and the droplet maintains its round shape. ○: There is almost no seepage of the droplet, and the droplet remains intact. △: Some liquid seepage is visible, but the liquid droplets remain. ×: The liquid droplet has completely soaked in, and the liquid stain has spread. <Evaluation of processed paper> [Preparation of processed paper] Water resistance (Cobb value): 52g / m 2 , basis weight 45g / m 2 , density 0.60g / m 3Treated paper was created by applying treatment solutions 1 to 12 to thin paper three times using a Baker-type applicator with a gap set to 0 mil, and then annealing it at 140°C for 1 minute. [KIT Test (Oil Resistance)] The results were measured using the 3M Kit Test (TAPPI T-559cm-02). The 3M Kit Test method involves placing a test oil containing castor oil, toluene, and heptane on the surface of treated paper, wiping off the test oil after 15 seconds, and evaluating the oil resistance based on whether or not an oil stain remains on the treated paper. Tests were conducted with test oils numbered 1 to 6, and the kit number with the highest percentage of unstained test oil was used as the oil resistance evaluation result. The evaluation results are shown in Table 4.

[0276] Table 1: List of Processing Solutions TIFF0007866209000009.tif7084

[0277] Table 2: Evaluation of water repellency of treated fabric TIFF0007866209000010.tif5688

[0278] Table 3: Evaluation of oil repellency of treated fabric TIFF0007866209000011.tif5690

[0279] Table 4: Evaluation of oil resistance of treated paper TIFF0007866209000012.tif7580

Claims

1. A fluorine-containing compound, The fluorine-containing compound is The portion derived from the active hydrogen-containing compound (a), The moiety derived from the active hydrogen-reactive compound (b), and -NHCO- derived from compound (a) and compound (b), It has, Perfluoroalkyl groups with 2 or more carbon atoms It does not have, -NHCO- is a group formed by the reaction of the active hydrogen-containing group of compound (a) and the active hydrogen-reactive group of compound (b), The compound (a) is R ｆ１ The compound (a1) contains the following: The compound (a1) Hydroxy HO-Y ｆ -Z ｆ α [In the formula, each symbol is independent in each occurrence.] Y ｆ Y ｆ１ and Y ｆ２ A group consisting of one or more selected from the group comprising the above, having a 1+α valency and a molecular weight of 500 or less, Y ｆ１ is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ , -N(-) ２ (wherein, R' is a hydrocarbon group having 1 to 20 carbon atoms), and is a group composed of one or more selected from the group consisting of) Y ｆ２ This is a group composed of one or more groups selected from the group consisting of aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Z ｆ R ｆ１ , or R ｆ１ A hydrocarbon group having 2 to 40 carbon atoms (however, the hydrocarbon group contains R in addition to carbon and hydrogen) ｆ１ (Contains a fluoro group that it has) R ｆ１ Ha-CF ３ , -CF ２ H, or -CFH ２ And, R ｆ１ It is not part of a fluoroalkyl group having 2 or more carbon atoms, R ｆ１ Its adjacent positions are oxygen atoms or nitrogen atoms. α is between 1 and 3. And, The compound (b) is a polyisocyanate, The aforementioned fluorine-containing compound is a fluorine-containing compound that is not a mercapto-Michael adduct.

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

3. The compound (a) contains an alcohol, The fluorine-containing compound according to claim 1 or 2, wherein the fluorine-containing compound is polyurethane.

4. The aforementioned compound (a1) is formula: -Y ｆ１１ —(Y ｆ２１ -Y ｆ１２ ( β -Y ｆ２２ -Y ｆ１３ -Z ｆ [In the formula, each symbol is independent in each occurrence.] Y ｆ１１ These are direct bonds, -O-, or -C(=O)-, Y ｆ２１ This is a group composed of one or more groups selected from the group consisting of aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Y ｆ１２ are -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ It is a group composed of one or more selected from the group consisting of -, -NR'-, and -C(OR')R'- (where R' is a hydrocarbon group having 1 to 20 carbon atoms). β is between 0 and 3. Y ｆ２２ This is a group composed of one or more groups selected from the group consisting of aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Y ｆ１３ is -O-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-O-, -C(=O)-NR'-, or -SO ２ It is NR'- (where R' is a hydrocarbon group with 1 to 20 carbon atoms). Z ｆ R ｆ１ , or R ｆ１ A hydrocarbon group having 2 to 40 carbon atoms (however, the hydrocarbon group contains R in addition to carbon and hydrogen) ｆ１ (It contains the fluoro group that it possesses.) The fluorine-containing compound according to claim 1 or 2, which is a compound having a group represented by .

5. Y ｆ２２ is, formula -Y ｆ２２１ -Y ｆ２２２ — [In the formula, Y ｆ２２１ These are directly bonded or hydrocarbon groups having 2 to 40 carbon atoms. Y ｆ２２２ This is either a direct bond or a phenylene group. It is a base represented by, Y ｆ１３ is -O- or -NR'- (where R' is a hydrocarbon group having 1 to 20 carbon atoms), β is either 0 or 1. Z ｆ is R ｆ１ The fluorine-containing compound according to claim 4.

6. The fluorine-containing compound according to claim 1 or 2, wherein the compound (a) comprises an active hydrogen-containing compound (a2) having a hydrocarbon group with 6 to 40 carbon atoms.

7. The fluorine-containing compound according to claim 6, wherein the compound (a2) is a sugar alcohol and / or hydroxy acid modified with a hydrocarbon group having 6 to 40 carbon atoms.

8. The fluorine-containing compound according to claim 1 or 2, wherein the compound (a) comprises another active hydrogen-containing compound (a3).

9. The fluorine-containing compound according to claim 8, wherein the compound (a3) ​​contains a chain extender.

10. The fluorine-containing compound according to claim 1 or 2, wherein the compound (b) is selected from the compounds listed below. Tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixture thereof) (TDI), phenylene diisocyanate (m-,p-phenylene diisocyanate or mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4' or 2,2'-diphenylmethane diisocyanate or mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixture thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or 1,4-tetramethyl Aromatic polyisocyanates selected from tylxylylene diisocyanate or a mixture thereof (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; Acyclic aliphatic polyisocyanates selected from 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-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capeate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate; 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'-, 2,4'- or 2,2'-Methylenebis(Cyclohexyl isocyanate or mixtures thereof) (Hydrogenated MDI), Methylcyclohex Cyclic alicyclic polyisocyanates selected from diisocyanates (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate-methyl)cyclohexane (1,3- or 1,4-bis(isocyanate-methyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanates, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); Bridged cyclic alicyclic polyisocyanates selected from norbornene diisocyanate, norbornene diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane; Compounds selected from; and compounds selected from the above-mentioned polymers (dimers, trimers, pentamers, heptamers, urethidinedione, uretonimine, isocynurate modified, polycarbodiimide, etc.) and biuret modified compounds.

11. The compound (a1) formula: -Y ｆ１１ —(Y ｆ２１ -Y ｆ１２ ( β -Y ｆ２２ -Y ｆ１３ -Z ｆ [In the formula, each symbol is independent in each occurrence.] Y ｆ１１ These are direct bonds, -O-, or -C(=O)-, Y ｆ２１ This is a group composed of one or more groups selected from the group consisting of aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Y ｆ１２ are -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ It is a group composed of one or more selected from the group consisting of -, -NR'-, and -C(OR')R'- (where R' is a hydrocarbon group having 1 to 20 carbon atoms). β is between 0 and 3. Y ｆ２２ This is a group composed of one or more groups selected from the group consisting of aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Y ｆ１３ is -O-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-O-, -C(=O)-NR'-, or -SO ２ It is NR'- (where R' is a hydrocarbon group with 1 to 20 carbon atoms). Z ｆ -CF ３ That is the case. The fluorine-containing compound according to claim 10, which is a compound having a group represented by .

12. A dispersion comprising the fluorine-containing compound and a liquid medium as described in claim 1 or 2.

13. A water-repellent and oil-repellent agent comprising the fluorine-containing compound described in claim 1 or 2.

14. The water-repellent and oil-repellent agent according to claim 13, further comprising other non-fluorine water-repellent and oil-repellent components.

15. The water-repellent and oil-repellent agent according to claim 13, for use in textile products or paper products.

16. A method for producing a treated substrate, comprising treating the substrate with the water-repellent and oil-repellent agent described in claim 13.

17. The manufacturing method according to claim 16, wherein the base material is a textile product or a paper product.

18. A product to which the fluorine-containing compound described in claim 1 or 2 is attached.

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