Liquid repellent

Abstract

To provide a novel liquid repellent.SOLUTION: A liquid repellent includes a poly(hydrocarbylamine) derivative, which is poly(hydrocarbylamine) substituted by one or more substituents, wherein at least one of the substituents is a substituent on an amine nitrogen in the poly(hydrocarbylamine), and is represented by the formula: -Ray [where Ray is a hydroxyethyl group optionally having one or more substituents (at least one of the substituents is an alkyl group optionally having one or more substituents)].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a liquid repellent agent and the like. [Background technology]

[0002] Conventionally, various fluorine-containing compounds having excellent oil repellency have been used. is provided. However, such fluorine-containing compounds have low solubility in general-purpose solvents (fluorine-free organic solvents), and therefore need to be dissolved in an expensive fluorine-containing organic solvent when applied. In contrast, Patent Document 1 discloses an oil- and / or water-repellent composition that is highly soluble in general-purpose solvents. Coating agents have been proposed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2013 / 115380 Brochure Summary of the Invention [Problem to be solved by the invention]

[0004] It would be useful to provide a liquid repellent which reduces the use of expensive fluorine-containing solvents, and in particular which can be dissolved in water and then applied. Therefore, an object of the present invention is to provide a new liquid repellent agent, particularly a liquid repellent agent that can be dissolved in water and then applied. In particular, an object of the present invention is to provide a liquid repellent agent that can impart liquid repellency to the surface of an article by applying it to the surface of the article. [Means for solving the problem]

[0005] As a result of extensive investigation, the present inventors have found that A poly(hydrocarbylamine) substituted with one or more substituents, at least one of which is substituted on an amine nitrogen of the poly(hydrocarbylamine), having the formula: -R ay : [In the formula, R ay has one or more substituents (at least one of which has one or more substituents and an alkyl group optionally having one or more -O- portions inserted therein, or an aryl group optionally having one or more substituents). A poly(hydrocarbylamine) derivative having a substituent represented by the formula: Contains Liquid repellent The present invention has been completed based on the discovery that the above problems can be solved by the above method.

[0006] The present invention includes the following aspects. Section 1. A poly(hydrocarbylamine) substituted with one or more substituents, at least one of which is substituted on an amine nitrogen of the poly(hydrocarbylamine), having the formula: -R ay : [In the formula, R ay has one or more substituents (at least one of which has one or more substituents and optionally having one or more -O- moieties inserted therein; or (an aryl group optionally having one or more substituents) represents a hydroxyethyl group. A poly(hydrocarbylamine) derivative having a substituent represented by the formula: Contains Liquid repellent. Section 2. The poly(hydrocarbylamine) derivative is A polyethyleneimine substituted with one or more substituents, at least one of which is substituted on the amine nitrogen of the polyethyleneimine. Formula:-R ay : [In the formula, R ay has one or more substituents (at least one of which has one or more substituents and an alkyl group optionally having one or more -O- portions inserted therein, or an aryl group optionally having one or more substituents). A polyethyleneimine derivative having a substituent represented by the formula: That is, Item 1. The liquid repellent according to item 1. Section 3. Item 3. The liquid repellent according to item 1 or 2, wherein the poly(hydrocarbylamine) derivative has a branched or cyclic structure, or a combination thereof. Section 4. R ay has one or more substituents, at least one of which is R fa R f a is an alkyl group which may have one or more substituents and into which one or more -O- moieties may be inserted, or an aryl group which may have one or more substituents. Section 5. The poly(hydrocarbylamine) derivative is Formula (U1): -Acyclic hydrocarbons -N(-R ay )- (U1) [The symbols in the formula are as defined above.] A poly(hydrocarbylamine) derivative having one or more structural units represented by the formula: Item 5. The liquid repellent according to any one of items 1 to 4. Section 6. The poly(hydrocarbylamine) derivative is ne end groups E, np building blocks G p , nqf building blocks G qf, and nr building blocks G r Includes; Building block G p may be the same or different in each occurrence, Formula (Up1): -CH2CH2-NH- (Up1) It is a structural unit represented by Building block G qf may be the same or different in each occurrence, Formula (Uq1): -CH2CH2-N(-R qfy )-(Uq1) [In the formula, R qfy is one or more substituents (at least one of which is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or (an aryl group optionally having one or more substituents) represents a hydroxyethyl group. It is a structural unit represented by Building block G r may be the same or different in each occurrence, Expression (Ur1): -CH2CH2-N(-R ot )-(Ur1) [In the formula, R ot is R qfy represents a substituent different from that shown. is a building block represented by; ne is an integer in the range of 0 to 50000, np is an integer in the range of 0 to 50000, nqf is an integer in the range of 0 to 50000, nr is an integer in the range of 0 to 50000, The sum of np and nqf is an integer equal to or greater than 100, The ratio of nqf / (np+nqf) is in the range of 0.02 to 100%. The structural unit G p , G qf , and G reach of the joins is of any type, and The structural unit G p , G qf , and G r may be linked to other structural units via a portion that does not constitute the main chain.] A polymer represented by the formula: Item 6. The liquid repellent according to any one of Items 1 to 5. Section 7. R qfy is a hydroxyethyl group optionally having one or more substituents (at least one of the substituents is a fluoroalkyl group which may have one or more substituents and may have one or more -O- moieties inserted therein). Section 8. Item 8. The liquid repellent according to any one of items 1 to 7, which is for surface treatment. Section 9. Item 9. The liquid repellent according to any one of items 1 to 8, which is used to impart liquid repellency to a surface of an article. Section 10. Item 10. A liquid-repellent film comprising the liquid-repellent agent according to any one of items 1 to 9. Section 11. Item 10. A method for producing a liquid-repellent film according to item 10, 1) a step of applying a liquid containing a poly(hydrocarbylamine) onto the surface of an article, and 2) a step of applying a liquid containing an oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents) onto the surface of the article, and reacting at least a part of the liquid to form the liquid-repellent film according to item 10. A manufacturing method comprising: Section 12. Item 10. A method for producing a liquid-repellent film according to item 10, Poly(hydrocarbylamines), and an oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents); A liquid containing Item 11. A method for producing a liquid-repellent film according to item 10, comprising applying the composition to a surface of an article and reacting at least a portion of the composition to form the liquid-repellent film according to item 10. Section 13. Item 11. An article comprising the liquid-repellent film according to item 10. Section 14. A method for producing an article having the liquid-repellent film according to item 10, Poly(hydrocarbylamines), and An oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents). A liquid containing Item 11. A method for producing a liquid-repellent film according to item 10, comprising applying the composition to a surface of an article and reacting at least a portion of the composition to form the liquid-repellent film according to item 10. Section 15. A polyethyleneimine substituted with one or more substituents, at least one of which is substituted on the amine nitrogen of the polyethyleneimine. Formula: -C2R4OH [In the formula, R, in each occurrence, is the same or different and represents a hydrogen atom or a substituent. However, at least one of the four R's is a fluoroalkyl group, optionally bearing one or more substituents and optionally containing one or more -O- moieties; or It is a fluoroaryl group which may have one or more substituents.] A polyethyleneimine derivative, wherein the substituent is represented by the following formula: Section 16. Item 16. A liquid repellent agent comprising the polyethyleneimine derivative according to item 15. Section 17. 1) Polyethylenimine; and 2) Contains an oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents). Repellent kit including: Effect of the Invention

[0007] According to the present invention, a new liquid repellent agent is provided. [Brief description of the drawings]

[0008] [Figure 1] 1 is a DSC thermogram of a PEI-Ex2 thin film (Test Example 2). [Diagram 2] IR spectrum of PEI-Ex2 thin film (Test Example 3) [Diagram 3] NMR spectrum of PEI-Ex2 thin film (Test Example 4) DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] 1. Terminology Unless otherwise specified, the symbols and abbreviations in this specification should be understood to have the meanings commonly used in the technical field to which the present invention pertains, in accordance with the context of this specification.

[0010] As used herein, the phrase "comprising" is intended to encompass the phrases "consisting essentially of" and "consisting of."

[0011] Unless specifically limited, the steps, processes, or operations described herein may be carried out at room temperature.

[0012] In this specification, room temperature means a temperature within the range of 10 to 40°C.

[0013] In this specification, the notation "Cn-Cm" (wherein n and m are numbers) indicates that the number of carbon atoms is n or more and m or less, as is commonly understood by those skilled in the art.

[0014] In this specification, the term "liquid repellent agent" refers to an agent that can impart liquid repellency to the surface of an article by applying (eg, coating) to the surface of the article. As used herein, the term "liquid repellency" can mean water repellency, oil repellency, or both. As used herein, the term "liquid repellency" can mean water repellency, oil repellency, or both. As used herein, the term "article surface" can refer to all or a portion of the surface of an article.

[0015] In this specification, unless otherwise limited, examples of the "halo (group)" can include fluoro (group), chloro (group), bromo (group), and iodo (group). In this specification, unless otherwise specified, examples of "halogen (atom)" include fluorine (atom), chlorine (atom), bromine (atom), and iodine (atom).

[0016] As used herein, "organic group" means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound).

[0017] In the present specification, the term "organic group" refers to, for example, a hydrocarbon group which may have one or more substituents [such a hydrocarbon group includes, for example, -NR o -, =N-, -N=, -O-, -S-, -C(=O)O-, -OC(=O)-, -C(=O)-, -S(=O)-, -S(=O)2-, -S(=O)2-NR o -, -NR o -S(=O)2-, -S(=O)-, -S(=O)-NR o - and -NR o -S(=O)-(wherein R o are independently a hydrogen atom or an organic group.) may be inserted with one or more moieties selected from the group consisting of:

[0018] As is commonly understood based on common knowledge in the chemical field, examples of such heteroatom-inserted hydrocarbon groups can include non-aromatic heterocyclic groups and heteroaryl groups.

[0019] In this specification, the number of carbon atoms in the "hydrocarbon group which may have one or more substituents" can be, for example, 1 to 100, 1 to 80, 1 to 60, 1 to 40, 1 to 30, 1 to 20, or 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10).

[0020] Examples of the "organic group" are: an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents, a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group which may have one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, a heteroaryl group optionally having one or more substituents, Cyano group, Aldehyde groups, R r O-, R r CO-, R r SO2-, R r OCO-, and R r OSO2- (In these formulas, R r is, independently, an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents, a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group which may have one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, or is a heteroaryl group which may have one or more substituents. can be included.

[0021] In this specification, "A hydrocarbon group which may have one or more substituents", "An alkyl group which may have one or more substituents and may have one or more -O- portions inserted therein" "An alkenyl group optionally having one or more substituents", "an alkynyl group optionally having one or more substituents" "Cycloalkyl group optionally having one or more substituents" "A cycloalkenyl group optionally having one or more substituents", "A cycloalkadienyl group optionally having one or more substituents", "An aryl group which may have one or more substituents", and "Aralkyl group optionally having one or more substituents" Examples of the "substituents" in the above formulae can include a halo group, a nitro group, a cyano group, an oxo group, a thioxo group, a sulfo group, a sulfamoyl group, a sulfinamoyl group, and a sulfenamoyl group, respectively. The number of the substituents can be within the range from 1 to the maximum number of possible substitutions (eg, 1, 2, 3, 4, 5, 6).

[0022] As used herein, the terms "hydrocarbon group" and "hydrocarbyl (group)" may be used interchangeably. As one of ordinary skill in the art would generally understand, the hydrocarbon group may have a linear structure (acyclic structure), or a cyclic structure, or a structure which is a combination of one or more of these. In this specification, examples of the "hydrocarbon group" can include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, aralkyl groups, and groups that are combinations thereof.

[0023] In this specification, unless otherwise limited, examples of the "alkyl group" include straight-chain or branched-chain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, and docosyl.

[0024] In the present specification, the term "alkyl group" refers to, for example, an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 2 ... It can be an alkyl group having from 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 6 carbon atoms, 5 carbon atoms, 4 carbon atoms, 3 carbon atoms, 2 carbon atoms, or 1 carbon atom.

[0025] In this specification, unless otherwise specified, the term "(halo)alkyl group" means an alkyl group or a haloalkyl group.

[0026] As used herein, a "haloalkyl group" is an alkyl group in which at least one hydrogen atom is replaced with a halogen atom.

[0027] In this specification, the number of halogen atoms in a "haloalkyl group" can be 1 or more (for example, 1 to 3, 1 to 6, 1 to 12, or 1 to the maximum number that can be substituted).

[0028] In this specification, the "haloalkyl group" can be, for example, a haloalkyl group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, 6 to 20 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 6 carbon atoms, 5 carbon atoms, 4 carbon atoms, 3 carbon atoms, 2 carbon atoms, or 1 carbon atom.

[0029] Examples of "(halo)alkyl groups" include (fluoro)alkyl groups. In this specification, unless otherwise specified, the (fluoro)alkyl group means an alkyl group or a fluoroalkyl group.

[0030] As used herein, a "fluoroalkyl group" is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.

[0031] In this specification, the number of fluorine atoms that a "fluoroalkyl group" has can be 1 or more (for example: 1 to 3, 1 to 6, 1 to 12, or 1 to the maximum number that can be substituted).

[0032] In this specification, the "fluoroalkyl group" can be, for example, a fluoroalkyl group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, 6 to 20 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 6 carbon atoms, 5 carbon atoms, 4 carbon atoms, 3 carbon atoms, 2 carbon atoms, or 1 carbon atom.

[0033] In this specification, unless otherwise specified, the (fluoro)alkyl group means an alkyl group or a fluoroalkyl group.

[0034] As used herein, a "fluoroalkyl group" is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. In this specification, the number of fluorine atoms that a "fluoroalkyl group" has can be 1 or more (for example: 1 to 3, 1 to 6, 1 to 12, or 1 to the maximum number that can be substituted). In this specification, the "fluoroalkyl group" can be, for example, a fluoroalkyl group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, 6 to 20 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 6 carbon atoms, 5 carbon atoms, 4 carbon atoms, 3 carbon atoms, 2 carbon atoms, or 1 carbon atom.

[0035] As one of ordinary skill in the art would commonly understand, the suffix "perhalogeno" means that all hydrogen atoms have been replaced with halo groups. As one of ordinary skill in the art would commonly understand, the suffix "perfluoro" means that all hydrogen atoms have been replaced with halo groups.

[0036] The term "fluoroalkyl group" encompasses perfluoroalkyl groups.

[0037] A "perfluoroalkyl group" is an alkyl group in which all hydrogen atoms are replaced with fluorine atoms. Specific examples of the perfluoroalkyl group include a trifluoromethyl group (CF3-) and a pentafluoroethyl group (C2F5-).

[0038] In this specification, the "fluoroalkyl group" can be, for example, a fluoroalkyl group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, 6 to 20 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 6 carbon atoms, 5 carbon atoms, 4 carbon atoms, 3 carbon atoms, 2 carbon atoms, or 1 carbon atom.

[0039] In this specification, a "fluoroalkyl group" can be a straight-chain or branched-chain fluoroalkyl group. In the present specification, specific examples of a "fluoroalkyl group" include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group (CF3-), a 2,2,2-trifluoroethyl group, a pentafluoroethyl group (C2F5-), a tetrafluoropropyl group (e.g., HCF2CF2CH2-), a hexafluoropropyl group (e.g., (CF3)2CH-), a nonafluorobutyl group, an octafluoropentyl group (e.g., HCF2CF2CF2CH2-), and a tridecafluorohexyl group.

[0040] In this specification, unless otherwise limited, examples of the "alkenyl group" include linear or branched C2-10 alkenyl groups such as vinyl, 1-propen-1-yl, 2-propen-1-yl, isopropenyl, 2-buten-1-yl, 4-penten-1-yl, and 5-hexen-1-yl.

[0041] In this specification, unless otherwise specified, examples of the "alkynyl group" include linear or branched C2-C10 alkynyl groups such as ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 4-pentyn-1-yl, 5-hexyn-1-yl, etc.

[0042] In this specification, unless otherwise specified, examples of the "cycloalkyl group" include C3-C7 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

[0043] In this specification, unless otherwise specified, examples of the "cycloalkenyl group" include C3-C7 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl.

[0044] In this specification, unless otherwise specified, examples of the "cycloalkadienyl group" include C4-C10 cycloalkadienyl groups such as cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, cyclononadienyl, and cyclodecadienyl.

[0045] In this specification, unless otherwise specified, the "aryl group" may be monocyclic, bicyclic, tricyclic, or tetracyclic. In this specification, unless otherwise specified, the "aryl group" can be a C6-C18 aryl group. In this specification, unless otherwise specified, examples of the "aryl group" include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl.

[0046] As used herein, a "fluoroaryl group" refers to a group in which at least one hydrogen atom is replaced with a fluorine atom. substituted aryl group.

[0047] In this specification, unless otherwise specified, examples of the "aralkyl group" include benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 2-biphenylylmethyl, 3-biphenylylmethyl, and 4-biphenylylmethyl.

[0048] In this specification, unless otherwise specified, the "non-aromatic heterocyclic group" can be monocyclic, bicyclic, tricyclic, or tetracyclic. In this specification, unless otherwise specified, the "non-aromatic heterocyclic group" may be, for example, a non-aromatic heterocyclic group containing, as ring-constituting atoms, in addition to carbon atoms, 1 to 4 heteroatoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom. In this specification, unless otherwise specified, the "non-aromatic heterocyclic group" may be saturated or unsaturated. In this specification, unless otherwise specified, examples of the "non-aromatic heterocyclic group" include tetrahydrofuryl, oxazolidinyl, imidazolinyl (e.g., 1-imidazolinyl, 2-imidazolinyl, 4-imidazolinyl), aziridinyl (e.g., 1-aziridinyl, 2-aziridinyl), azetidinyl (e.g., 1-azetidinyl, 2-azetidinyl), pyrrolidinyl (e.g., 1-pyrrolidinyl), and the like. nyl, 2-pyrrolidinyl, 3-pyrrolidinyl), piperidinyl (e.g. 1-piperidinyl, 2-piperidinyl, 3-piperidinyl), azepanyl (e.g. 1-azepanyl, 2-azepanyl, 3-azepanyl, 4-azepanyl), azocanyl (e.g. 1-azocanyl, 2-azocanyl, 3-azocanyl, 4-azocanyl), piperazinyl (e.g. 1,4-piperazine-1 -yl, 1,4-piperazin-2-yl), diazepinyl (e.g., 1,4-diazepin-1-yl, 1,4-diazepin-2-yl, 1,4-diazepin-5-yl, 1,4-diazepin-6-yl), diazocanyl (e.g., 1,4-diazocan-1-yl, 1,4-diazocan-2-yl, 1,4-diazocan-5-yl, 1,4-diazocan-6-yl, 1,5-diazocan-1-yl, 1,5-diazocan-2-yl, 1,5-diazocan-3-yl), tetrahydropyranyl (e.g., tetrahydropyran-4-yl), morpholinyl (e.g., 4-morpholinyl), thiomorpholinyl (e.g., 4-thiomorpholinyl), 2-oxazolidinyl, dihydrofuryl, dihydropyranyl, and dihydroquinolyl.

[0049] In this specification, unless otherwise specified, examples of the "heteroaryl group" include monocyclic aromatic heterocyclic groups (e.g., 5- or 6-membered monocyclic aromatic heterocyclic groups) and aromatic fused heterocyclic groups (e.g., 5- to 18-membered aromatic fused heterocyclic groups).

[0050] In this specification, unless otherwise specified, examples of the "5- or 6-membered monocyclic aromatic heterocyclic group" include pyrrolyl (e.g., 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (e.g., 2-furyl, 3-furyl), thienyl (e.g., 2-thienyl, 3-thienyl), pyrazolyl (e.g., 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (e.g., 1-imidazolyl, 2-imidazolyl, 4-imidazolyl), isoxazolyl (e.g., 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl), oxazolyl (e.g., 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (e.g., 3-isothiazolyl). , 4-isothiazolyl, 5-isothiazolyl), thiazolyl (e.g. 2-thiazolyl, 4-thiazolyl, 5-thiazolyl), triazolyl (e.g. 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxadiazolyl (e.g. 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl), thiadiazolyl (e.g. 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl), tetrazolyl, pyridyl (e.g. 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridazinyl (e.g. 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (e.g. 2-pyrimidinyl, pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), pyrazinyl, and the like.

[0051] In this specification, unless otherwise specified, examples of the "5- to 18-membered aromatic fused heterocyclic group" include isoindolyl (e.g., 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl), indolyl (e.g., 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), benzo[b]furanyl (e.g., 2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl, benzo[b]furanyl, 5-benzo[b]furanyl, 6-benzo[b]furanyl, 7-benzo[b]furanyl), benzo[c]furanyl (e.g., 1-benzo[c]furanyl, 4-benzo[c]furanyl, 5-benzo[c]furanyl), benzo[b]thienyl, (e.g., 2-benzo[b]thienyl, 3-benzo[b]thienyl, 4-benzo[b]thienyl, 5-benzo[b]thienyl, 6-benzo[b]thienyl, 7-benzo[b]thienyl), benzo[c]thienyl (e.g., 1-benzo[c]thienyl, 4-benzo[c]furanyl, 5-benzo[c]furanyl), [c]thienyl, 5-benzo[c]thienyl), indazolyl (e.g. 1-indazolyl, 2-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl), benzimidazolyl (e.g. 1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl), 1,2-benzisoxazolyl (e.g. 1,2-benzisoxazol-3-yl, 1,2-benzisoxazol-4-yl, 1,2-benzisoxazol-5-yl, 1,2-benzisoxazol-6-yl, 1,2-benzisoxazol-7-yl, 1,2-benzisoxazol-8-yl, 1,2-benzisoxazol-9-yl, 1,2-benzisoxazol-10-yl, 1,2-benzisoxazol-11-yl, 1,2-benzisoxazol-12-yl, 1,2-benzisoxazol-13-yl, 1,2-benzisoxazol-14-yl, 1,2-benzisoxazol-15-yl, 1,2-benzisoxazol-16-yl, 1,2-benzisoxazol-17-yl, 1,2-benzisoxazol-18-yl, 1,2-benzisoxazol-19-yl, 1,2-benzisoxazol-20-yl, 1,2-benzisoxazol-21-yl, 1,2-benzisoxazol-22-yl, 1,2-benzisoxazol-23 1,2-benzoisoxazol-5-yl, 1,2-benzoisoxazol-6-yl, 1,2-benzoisoxazol-7-yl), benzoxazolyl (e.g. 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl), 1,2-benzisothiazolyl (e.g. 1,2-benzisothiazol-3-yl, 1,2-benzisothiazol-4-yl, 1,2-benzisothiazol-5-yl, 1,2-benzisothiazol-6-yl, 1,2-benzisothiazol-7-yl), benzothiazolyl (e.g. 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), isoquinolyl (e.g. 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl), quinolyl (e.g. 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 8-quinolyl), cinnolinyl (e.g. : 3-cinnolinyl, 4-cinnolinyl, 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl), phthalazinyl (e.g. 1-phthalazinyl, 4-phthalazinyl, 5-phthalazinyl, 6-phthalazinyl, 7-phthalazinyl, 8-phthalazinyl), quinazolinyl (e.g. 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-quinazolinyl), Quinoxalinyl (e.g., 2-quinoxalinyl, 3-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 7-quinoxalinyl, 8-quinoxalinyl), pyrazolo[1,5-a]pyridyl (e.g., pyrazolo[1,5-a]pyridin-2-yl, pyrazolo[1,5-a]pyridin-3-yl, pyrazolo[1,5-a]pyridin-4-yl, pyrazolo[1,5-a]pyridin-5-yl, pyrazolo[1,5-a]pyridin-6-yl, pyrazolo[1,5-a]pyridin-8-yl, pyrazolo[1,5-a]pyridin-9-yl, pyrazolo[1,5-a]pyridin-10-yl, pyrazolo[1,5-a]pyridin-11-yl, pyrazolo[1,5-a]pyridin-12-yl, pyrazolo[1,5-a]pyridin-13-yl, pyrazolo[1,5-a]pyridin-14-yl, pyrazolo[1,5-a]pyridin-15-yl, pyrazolo[1,5-a]pyridin-16-yl, pyrazolo[1,5-a]pyridin-17-yl, pyrazolo[1,5-a]pyridin-18-yl, pyrazolo[1,5-a]pyridin-19-yl, pyrazolo[1,5-a]pyridin-20-yl, pyrazolo[1,5-a]pyridin-21-yl, pyrazolo[1,5-a]pyridin-22-yl, pyrazolo[1,5-a]pyridin-23-yl, pyrazolo[1,5-a]pyridin-24-yl, pyrazolo[1,5-a]pyridin-2 pyridin-6-yl, pyrazolo[1,5-a]pyridin-7-yl), imidazo[1,2-a]pyridyl (e.g., imidazo[1,2-a]pyridin-2-yl, imidazo[1,2-a]pyridin-3-yl, imidazo[1,2-a]pyridin-5-yl, imidazo[1,2-a]pyridin-6-yl, imidazo[1,2-a]pyridin-7-yl, imidazo[1,2-a]pyridin-8-yl), etc.

[0052] In this specification, unless otherwise specified, "a non-aromatic heterocyclic group optionally having one or more substituents", and "Heteroaryl group optionally having one or more substituents" Examples of the "substituents" in the above formula include a hydrocarbon group, which may have one or more substituents, a halo group, a nitro group, a cyano group, an oxo group, a thioxo group, a sulfo group, a sulfamoyl group, a sulfinamoyl group, and a sulfenamoyl group. The number of the substituents can be within the range from 1 to the maximum number of possible substitutions (eg, 1, 2, 3, 4, 5, 6).

[0053] As used herein, "poly(hydrocarbyl amine)" refers to a poly(hydrocarbyl amine), as understood by those skilled in the art. It means a polymer having the same chemical structure as a polymer formed by the hypothetical or actual polymerization of hydrocarbyl amines (e.g., allylamine, vinylamine, ethylamine). In other words, the name can represent the chemical structure without regard to its actual source. As will be understood, for example, poly(alkyleneimine) can be synonymous with poly(alkylamine).

[0054] As used herein, a "poly(hydrocarbyl amine)" can have a linear structure, a non-cyclic structure (eg, a branched structure), or a cyclic structure, or a structure that is a combination of one or more of these. In particular, a "poly(hydrocarbylamine)" having two or more cyclic structures may have a network structure.

[0055] As used herein, a "poly(hydrocarbyl amine)" preferably has one or more (more preferably two or more) cyclic structures (cyclic moieties).

[0056] Suitable examples of poly(hydrocarbylamines) include poly(C2-C4 alkyleneimines), poly(C2-C4 alkylamines), and particularly suitable examples thereof include poly(ethyleneimines), poly(allylamines), and poly(vinylamines). For clarity only, they may have linear structures (non-cyclic structures (e.g., branched structures)), or cyclic structures, or structures that are combinations of one or more of these, similar to those described for the poly(hydrocarbyl amines).

[0057] The present invention will be described in detail below.

[0058] 2. Liquid repellent The liquid repellent of the present invention is A poly(hydrocarbylamine) substituted with one or more substituents, at least one of which is substituted on an amine nitrogen of the poly(hydrocarbylamine), having the formula: -R ay : [In the formula, R ay has one or more substituents (at least one of which has one or more substituents and an alkyl group optionally having one or more -O- portions inserted therein, or an aryl group optionally having one or more substituents). A poly(hydrocarbylamine) derivative having a substituent represented by the formula: Contains:

[0059] The "poly(hydrocarbylamine) derivative" can have a network structure with one or more side chain moieties.

[0060] When the liquid repellent of the present invention is applied to the surface of an article, the network structure can be preferably attached to the surface of the article, and the side chains can be oriented perpendicular to the surface of the article.

[0061] The mechanism of the vertical alignment can be preferably based on the hydrophobicity of the side chain portion.

[0062] Although the present invention is not limited thereto, the function of the liquid repellent of the present invention can be based on the vertical alignment of the side chain portion.

[0063] In a preferred embodiment of the liquid repellent of the present invention, the "poly(hydrocarbylamine)" is polyethyleneimine.

[0064] In other words, the liquid repellent according to a preferred embodiment of the present invention is A polyethyleneimine substituted with one or more substituents, at least one of which is substituted on the amine nitrogen of the polyethyleneimine. Formula:-Ray [In the formula, R ay has one or more substituents (at least one of which has one or more substituents and an alkyl group optionally having one or more -O- portions inserted therein, or an aryl group optionally having one or more substituents). A polyethyleneimine derivative having a substituent represented by the formula: It is a liquid repellent agent containing

[0065] Polyethyleneimine Derivatives In other words, the polyethyleneimine derivative is At least one amine moiety is substituted with one or more substituents R ay is replaced by, and Any position may be substituted with one or more substituents. It can be a polyethyleneimine.

[0066] Suitable examples of the polyethyleneimine derivative include A polyethyleneimine substituted with one or more substituents, at least one of which is substituted on the amine nitrogen of the polyethyleneimine. Formula: -C2R4OH [In the formula, R, in each occurrence, is the same or different and represents a hydrogen atom or a substituent. However, at least one of the four R's is A fluoroalkyl group which may have one or more substituents and which may have one or more -O- portions inserted therein, or an alkyl group which may have one or more substituents and which may have one or more -O- portions inserted therein, A fluoroaryl group which may have one or more substituents. It is.] A polyethyleneimine derivative having a substituent represented by the formula: Includes:

[0067] The molecular weight of the polyethyleneimine derivative is Preferably 300 to 1,000,000, More preferably, 10,000 to 900,000, and More preferably, 20,000 to 800,000 The range may be:

[0068] As stated above, a polyethyleneimine derivative is a polyethyleneimine that is substituted with one or more substituents. The polyethyleneimine backbone of the polyethyleneimine derivative may have a branched or cyclic structure, or a combination thereof. For illustrative purposes, by way of example only, the structure may have a moiety having a branched or cyclic structure, or a combination thereof, as follows:

[0069] [ka]

[0070] Generally, polyethyleneimine having a branched or cyclic structure or a combination thereof may be referred to as a branched polyethyleneimine. In this specification, the term "branched polyethyleneimine" may also be used to mean a polyethyleneimine having such a structure.

[0071] The molecular weight of the polyethyleneimine can be similar to that of the polyethyleneimine derivative. Specifically, the molecular weight of the polyethyleneimine is Preferably 300 to 1,000,000, More preferably, 10,000 to 900,000, and More preferably, 20,000 to 800,000 The range may be:

[0072] The polyethyleneimine derivatives can also have a branched or cyclic structure, or a combination thereof. For illustrative purposes only, the structure may have a structure containing one or more branched moieties and one or more cyclic moieties, such as the following: ay is independently at each occurrence -CHCHR fa -OH or -CHCHR fa Represents -OH, etc.

[0073] [ka]

[0074] Examples of the "substituent" that the polyethyleneimine may have (i.e., the substituent in the polyethyleneimine derivative) are: Halo groups; Nitro group; Cyano group; oxo group; Thioxo group; Sulfo group; Sulfamoyl group; Sulfinamoyl group; Sulfenamoyl group; and organic group Includes:

[0075] The number of such substituents is one or more. The lower limit can be, for example, 5, 10, 15, or 20. The upper limit can be, for example, 5,000, 10,000, 30,000, or 50,000. The number of the substituents can be, for example, 0.1 to 10 times, 0.1 to 7 times, 0.1 to 5 times, or 0.1 to 3 times the number of ethyleneimines constituting the polyethyleneimine skeleton.

[0076] As described above, at least one of the substituents is substituted on the amine nitrogen of the polyethyleneimine, and is represented by the formula (S1): -R ay[The symbols in the formula are as defined above.] It is a substituent represented by the formula:

[0077] R ay In the "hydroxyethyl group which may have one or more substituents" represented by the formula: Examples of the substituents in the (Halo)alkyl groups which may have one or more ether functional groups (-O-), halo groups (e.g., fluoro groups), amino groups, nitro groups, cyano groups, hydroxy groups, oxo groups, formyl groups, hydroxycarbonyl groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, and sulfenamoyl groups. Includes:

[0078] The number of the substituents is 0 (unsubstituted), 1, 2, 3, or 4. At least one of the substituents is R fa The number can be one, two, three, or four.

[0079] As mentioned above, R fa is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents. R fa The alkyl group in the formula (I) is preferably a C1-C30 alkyl group, more preferably a C6-C20 alkyl group, and even more preferably a C12-C20 alkyl group.

[0080] R fa The alkyl group of the "alkyl group which may have one or more substituents" is Preferably, a C1-C30 alkyl group (among which, more preferably, a linear or branched C1-C30 alkyl group); More preferably, it is a C6-C30 alkyl group (among which, it is more preferably a linear or branched C6-C30 alkyl group). More preferably, a C6-C20 alkyl group (among which, a linear or branched C6-C20 alkyl group is preferred), and Even more preferably, it is a C12-C20 alkyl group (among which, it is more preferably a linear or branched C12-C20 alkyl group). It is. Examples of the substituent that the alkyl group may have are: (Halo)alkyl groups which may have one or more ether functional groups (-O-), halo groups ( Examples: fluoro group), amino group, nitro group, cyano group, hydroxy group, oxo group, formyl group, hydroxycarbonyl group, thioxo group, sulfo group, sulfamoyl group, sulfinamoyl group, and sulfenamoyl group. Includes:

[0081] R fa Preferred examples of the aryl group of the "aryl group which may have one or more substituents" include a phenyl group. Examples of the substituent that the aryl group may have are: (Halo)alkyl groups which may have one or more ether functional groups (-O-), halo groups (e.g., fluoro groups), amino groups, nitro groups, cyano groups, hydroxy groups, oxo groups, formyl groups, hydroxycarbonyl groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, and sulfenamoyl groups. Includes:

[0082] R fa teeth, Preferably, a fluoroalkyl group which may have one or more ether functional groups (—O—), More preferably, a linear C1-C30 fluoroalkyl group which may have one or more (preferably one) ether functional groups (-O-), and More preferred is a linear C6-C20 perfluoroalkyl group which may have one or more (preferably one) ether functional groups (-O-).

[0083] In the polyethyleneimine derivative, NR ay The molar ratio of parts / total ethyleneimine units is , Preferably, 0.01 to 2. More preferably, 0.01 to 1.5, and More preferably, it is 0.01 to 1 can be in the range of

[0084] In the polyethyleneimine derivative, R fa Department / NR ay The molar ratio of parts is Preferably 1 / 4 to 1, More preferably, 1 / 3 to 1, and More preferably, 1 / 2 to 1 can be in the range of

[0085] R ay is preferably one or more substituents, at least one of which is R f a is a 2-hydroxyethyl group which may have

[0086] The polyethyleneimine derivative is preferably Formula (U1): -CH2CH2-N(-R ay )- (U1) [The symbols in the formula are as defined above.] It is a polyethyleneimine derivative having one or more constitutional units represented by the following formula: In this specification, a polyethyleneimine derivative having one or more of the structural units (U1) may be referred to as a polyethyleneimine derivative (PU1).

[0087] The polyethyleneimine derivative is preferably ne end groups E, np building blocks G p , nqf building blocks G qf , and nr building blocks G r Includes.

[0088] Specific examples of the terminal group E include -NH2, -CH3, and -C2H5. The terminal group may have one or more of the above substituents. ne is, Preferably 0 to 50,000, More preferably, 0 to 40,000, and More preferably, 0 to 30,000 is within the range. Here, for the sake of explanation only, when ne is 0, as can be understood from common general technical knowledge, the polyethyleneimine derivative has a cyclic structure and has no branches other than the substituents of each structural unit described below.

[0089] Building block G p may be the same or different in each occurrence, Formula (Up1): -CH2CH2-NH- (Up1) It is a structural unit expressed as follows.

[0090] Building block G p The number of np is Preferably 0 to 50,000, More preferably, 0 to 40,000, and More preferably, 0 to 30,000 is within the range.

[0091] Building block G qf may be the same or different in each occurrence, Formula (Uq1): -CH2CH2-N(-R qfy )-(Uq1) [In the formula, R qfy represents a hydroxyethyl group optionally having one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents). It is a structural unit expressed as: Preferably, R qfyis a hydroxyethyl group optionally having one or more substituents (at least one of the substituents is a fluoroalkyl group which optionally has one or more substituents and which may have one or more -O- moieties inserted, or an alkyl group which optionally has one or more substituents and which may have one or more -O- moieties inserted, or a fluoroaryl group which optionally has one or more substituents). More preferably, R qfy is a hydroxyethyl group which may have one or more substituents (at least one of the substituents is a perfluoroalkyl group).

[0092] Building block G qf The number of nqf is Preferably 0 to 50,000, More preferably, 0 to 40,000, and More preferably, 0 to 30,000 is within the range.

[0093] Building block G r may be the same or different in each occurrence, Expression (Ur1): -CH2CH2-N(-R ot )-(Ur1) [In the formula, R ot is R qfy represents a substituent different from that shown. It is a structural unit expressed as: Building block G r The number of,nr,is Preferably 0 to 50,000, More preferably, 0 to 40,000, and More preferably, 0 to 30,000 is within the range.

[0094] The sum of np and nqf is Preferably 100 or more, More preferably, 100 to 100,000, and More preferably, 1,000 to 100,000 is within the range. The ratio of nqf / (np+nqf) is Preferably 0.02 to 100%, More preferably, 0.1 to 100%, and More preferably, 1 to 100% is within the range.

[0095] The structural unit G p , G qf , and G r each of the joins is of any type, and The structural unit G p , G qf , and G r may be linked to other structural units via a portion that does not constitute the main chain.] It is a polymer represented by the formula: Examples of such patterns include random, block, and alternating, as well as combinations thereof.

[0096] The liquid repellent agent of the present invention may contain, in addition to the polyethyleneimine derivative (PU1), an additive, and a solvent, etc., if desired.

[0097] As the additive, additives that are usually used in liquid repellents can be used.

[0098] Examples of such solvents are: water; alcohol solvents [e.g., methanol, ethanol]; non-aromatic hydrocarbon solvents [e.g., pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, n-decane, isododecane, tridecane]; Aromatic hydrocarbon solvents [e.g., benzene, toluene, xylene, tetralin, veratrole, diethylbenzene, methylnaphthalene, nitrobenzene, o-nitrotoluene, mesitylene, indene, diphenyl sulfide]; Ketone solvents [e.g., acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetophenone, propiophenone, diisobutyl ketone, isophorone]; Halogenated hydrocarbon solvents [e.g., dichloromethane, chloroform, chlorobenzene]; Ether solvents [e.g., diethyl ether, tetrahydrofuran (THF), diisopropyl ether, methyl-t-butyl ether (MTBE), dioxane, dimethoxyethane, diglyme, phenetole, 1,1-dimethoxycyclohexane, diisoamyl ether]; ester solvents [e.g., ethyl acetate, isopropyl acetate, diethyl malonate, 3-methoxy-3-methylbutyl acetate, gamma-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, alpha-acetyl-gamma-butyrolactone]; nitrile solvents [e.g., acetonitrile, benzonitrile]; Sulfoxide solvents [e.g., dimethyl sulfoxide, sulfolane]; and Amide solvents [e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacrylamide, N,N-dimethylacetoacetamide, N,N-diethylformamide, N,N-diethylacetamide] Includes: These solvents may be used alone or in combination of two or more.

[0099] 3. Manufacturing method of liquid repellent agent

[0100] The liquid repellent of the present invention is produced, for example, by mixing the poly(hydrocarbylamine) derivative with the optional additives and the optional solvent.

[0101] The poly(hydrocarbylamine) derivatives are commercially available or can be prepared by the method for preparing the polyethyleneimine derivatives of the present invention described below or a method similar thereto.

[0102] The liquid repellent of the present invention, in which the poly(hydrocarbylamine) derivative is the polyethyleneimine derivative (PU1), is produced, for example, by mixing the polyethyleneimine derivative (PU1) with the optional additives and the optional solvent.

[0103] The poly(hydrocarbylamine) derivatives are commercially available or can be prepared by the method for preparing the polyethyleneimine derivatives of the present invention described below or a method similar thereto. Specifically, for example, in the production of polyethyleneimine, ethyleneimine may be replaced with a cyclic hydrocarbon amine corresponding to the structure of the desired poly(hydrocarbylamine) [e.g., propyleneimine corresponding to the desired polypropyleneimine].

[0104] 4. Use of liquid repellent The liquid repellent of the present invention can be widely used for imparting liquid repellency to the surface of an article by applying (eg, coating) the surface of the article. In this specification, "imparting liquid repellency" can mean imparting antifouling properties. In this specification, "imparting liquid repellency to the surface of an article" can mean improving the liquid repellency of the surface of the article.

[0105] The details of the "use of the liquid repellent agent" can be understood by referring to the other parts of the present invention and common general technical knowledge.

[0106] The liquid repellent of the present invention is applied to the surface of an article to impart liquid repellency thereto. As described above, the material of the article surface is not particularly limited, and examples include glass, metal, and resin.

[0107] The liquid repellent of the present invention has the following properties on the surface of an article: The amount of polyethyleneimine derivative is 1 cm 2 Hit, Preferably 1 to 1000 mg, More preferably, 10 to 1000 mg, and More preferably, 50 to 1000 mg is applied in an amount that is

[0108] 5.Liquid repellent film The present invention also provides a liquid-repellent film containing the liquid-repellent agent of the present invention. The present invention also provides a liquid-repellent film containing the poly(hydrocarbylamine) derivative. The present invention also provides a liquid-repellent film formed from the liquid-repellent agent of the present invention. The present invention also provides a liquid-repellent film formed from the poly(hydrocarbylamine) derivative. The liquid-repellent film of the present invention can be a solidified product of the liquid-repellent agent of the present invention. The thickness of the liquid-repellent film of the present invention is, for example, Preferably, 0.0001 to 5 μm. More preferably, 0.0001 to 4 μm, and More preferably, 0.0001 to 3 μm The range may be:

[0109] The liquid-repellent film of the present invention contains the poly(hydrocarbylamine) derivative, and preferably contains the polyethyleneimine derivative (PU1) of the formula. The liquid-repellent film of the present invention can be understood based on the above explanation of the liquid-repellent agent of the present invention. The liquid-repellent film of the present invention can preferably have high crystallinity.

[0110] 6. Method for producing liquid-repellent film (1) Liquid-repellent film manufacturing method 1 The liquid-repellent film of the present invention is, for example, 1) applying a liquid containing polyethyleneimine onto a surface of an article; and 2) In addition, one or more substituents (at least one of the substituents is R fa (hereinafter, this may be simply referred to as an oxirane compound) which may have a structure of the formula (I) and (II) and a liquid-repellent film is formed by reacting at least a part of the liquid-repellent film. A manufacturing method including It can be manufactured by

[0111] Process 1 The "liquid containing polyethyleneimine" can be a liquid containing polyethyleneimine and a solvent. Examples of such solvents are: water; alcohol solvents [e.g., methanol, ethanol]; non-aromatic hydrocarbon solvents [e.g., pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, n-decane, isododecane, tridecane]; Aromatic hydrocarbon solvents [e.g., benzene, toluene, xylene, tetralin, veratrole, diethylbenzene, methylnaphthalene, nitrobenzene, o-nitrotoluene, mesitylene, indene, diphenyl sulfide]; Ketone solvents [e.g., acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetophenone, propiophenone, diisobutyl ketone, isophorone]; Halogenated hydrocarbon solvents [e.g., dichloromethane, chloroform, chlorobenzene]; Ether solvents [e.g., diethyl ether, tetrahydrofuran (THF), diisopropyl ether, methyl-t-butyl ether (MTBE), dioxane, dimethoxyethane, diglyme, phenetole, 1,1-dimethoxycyclohexane, diisoamyl ether]; ester solvents [e.g., ethyl acetate, isopropyl acetate, diethyl malonate, 3-methoxy-3-methylbutyl acetate, gamma-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, alpha-acetyl-gamma-butyrolactone]; nitrile solvents [e.g., acetonitrile, benzonitrile]; Sulfoxide solvents [e.g., dimethyl sulfoxide, sulfolane]; and Amide solvents [e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacrylamide, N,N-dimethylacetoacetamide, N,N-diethylformamide, N,N-diethylacetamide] can be included. These solvents may be used alone or in combination of two or more. The liquid may contain substances other than polyethyleneimine and a solvent, if desired. Examples of such substances include aziridines which may have one or more substituents, oxazolines which may have one or more substituents, and alkyl halides. Suitable examples of the substituent include an alkyl group and an aryl group.

[0112] The polyethyleneimine has a mass average molecular weight of preferably 300 to 1,000,000, more preferably 300 to 900,000, and even more preferably 300 to 800,000.

[0113] The polyethyleneimine concentration in the liquid can be, for example, within the range of 1 to 50% by mass.

[0114] A suitable example of the oxirane compound is represented by the formula (A): [ka] [In the formula, R is the same or different in each occurrence and is a hydrogen atom or R fa At least one of the four R's is R fa It is.] The oxirane compound may be represented by the formula: More preferred examples of the oxirane compound include those represented by the formula (A f ) is included.

[0115] Polyethyleneimine is commercially available or can be prepared by known methods. Specifically, polyethyleneimine can be produced, for example, by ring-opening polymerization of ethyleneimine in an aqueous solvent (eg, water) in the presence of an acid catalyst such as hydrochloric acid or sulfuric acid.

[0116] In step 1, the method for applying a liquid containing polyethyleneimine to a surface to which liquid repellency is to be imparted (hereinafter may be referred to as the "application surface") is not particularly limited as long as the application is achieved, and examples include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett method, and gravure coating.

[0117] The material of the surface to which the liquid repellency is to be imparted is not particularly limited, and examples thereof include metals and resins.

[0118] The coating is applied to 1 cm 2 Polyethyleneimine is Preferably 1 to 1000 mg, More preferably, 10 to 1000 mg, and More preferably, 50 to 1000 mg The composition is applied in an amount of 0.1 to 100 μg / g.

[0119] The coating can be carried out, for example, at room temperature.

[0120] The coating comprises poly(hydrocarbylamine), and an oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents); At least a portion of the reactants reacts to form the liquid-repellent film of the present invention.

[0121] Process 2 The liquid containing the oxirane may be a liquid containing the oxirane and a solvent. Examples of such solvents are: water; alcohol solvents [e.g., methanol, ethanol]; non-aromatic hydrocarbon solvents [e.g., pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, n-decane, isododecane, tridecane]; Aromatic hydrocarbon solvents [e.g., benzene, toluene, xylene, tetralin, veratrole, diethylbenzene, methylnaphthalene, nitrobenzene, o-nitrotoluene, mesitylene, indene, diphenyl sulfide]; Ketone solvents [e.g., acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetophenone, propiophenone, diisobutyl ketone, isophorone]; Halogenated hydrocarbon solvents [e.g., dichloromethane, chloroform, chlorobenzene]; Ether solvents [e.g., diethyl ether, tetrahydrofuran (THF), diisopropyl ether, methyl-t-butyl ether (MTBE), dioxane, dimethoxyethane, diglyme, phenetole, 1,1-dimethoxycyclohexane, diisoamyl ether]; ester solvents [e.g., ethyl acetate, isopropyl acetate, diethyl malonate, 3-methoxy-3-methylbutyl acetate, gamma-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, alpha-acetyl-gamma-butyrolactone]; nitrile solvents [e.g., acetonitrile, benzonitrile]; Sulfoxide solvents [e.g., dimethyl sulfoxide, sulfolane]; and Amide solvents [e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacrylamide, N,N-dimethylacetoacetamide, N,N-diethylformamide, N,N-diethylacetamide] can be included. These solvents may be used alone or in combination of two or more. The liquid may contain substances other than the oxirane and the solvent, if desired.

[0122] Examples of such substances include aziridines which may have one or more substituents, oxazolines which may have one or more substituents, and alkyl halides. Suitable examples of the substituent include an alkyl group and an aryl group.

[0123] In step 2, the liquid containing the oxirane is applied onto the coating layer formed in step 1. The method of application is not particularly limited as long as the coating is achieved, and examples thereof include spin coating, wipe coating, spray coating, squeegee coating, and direct coating. These include top coating, die coating, ink jet, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure coating.

[0124] The coating is applied within 1 cm 2 The hit is oxirane, Preferably 1 to 1000 mg, More preferably, 10 to 1000 mg, and More preferably, 50 to 1000 mg The composition is applied in an amount of 0.1 to 100 μg / g.

[0125] The coating can be carried out, for example, at room temperature.

[0126] By this coating, Poly(hydrocarbylamines), and an oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents); At least a portion of the reactants reacts to form the liquid-repellent film of the present invention.

[0127] After the coating, a heat treatment can be preferably carried out. The heat treatment can achieve adhesion of the liquid-repellent film to the application surface and stabilization of the structure.

[0128] The temperature of the heat treatment is Preferably, the temperature is 20 to 200° C. More preferably, 20 to 80° C., and More preferably, the temperature is 20 to 150°C. The range may be: The heat treatment time is: Preferably, for 5 to 3000 minutes. More preferably, for 10 to 2000 minutes, and More preferably, 15 to 1000 minutes The range may be:

[0129] Any solvent that the liquid may contain may be removed, if desired, by means such as reduced pressure, and heating, and combinations thereof.

[0130] If desired, the liquid-repellent film thus formed can be washed with a solvent (eg, THF) and dried by a method such as drying under reduced pressure.

[0131] (2) Liquid-repellent film manufacturing method 2 Alternatively, the liquid-repellent membrane of the present invention may also be, for example, Polyethylenimine, and an oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents); A liquid containing and forming the liquid-repellent film by applying the composition to the surface to which the composition is applied and reacting at least a portion of the composition. It can be manufactured by

[0132] The polyethyleneimine and the oxirane can be the same as those explained in the liquid-repellent film manufacturing method 1. In step 2, the liquid containing the oxirane is applied onto the coating layer formed in step 1. The method of application is not particularly limited as long as the coating is achieved, and examples thereof include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.

[0133] The molar ratio of the polyethyleneimine and the oxirane contained in the liquid is Preferably 1:1 to 1:10, More preferably, 1:1 to 1:7, and More preferably, it is 1:1 to 1:5. The mass ratio of the above may be

[0134] The coating is applied to 1 cm 2 Polyethyleneimine is Preferably 1 to 1000 mg, More preferably, 10 to 1000 mg, and More preferably, 50 to 1000 mg The composition is applied in an amount of 0.1 to 100 μg / g.

[0135] The coating is applied to 1 cm 2 The hit is oxirane, Preferably 1 to 3000 mg, More preferably, 10 to 3000 mg, and More preferably, 50 to 3000 mg The composition is applied in an amount of 0.1 to 100 μg / g.

[0136] The coating can be carried out, for example, at room temperature.

[0137] By this coating, polyethyleneimine, and an oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents); At least a portion of the reactants reacts to form the liquid-repellent film of the present invention.

[0138] After the coating, a heat treatment can be preferably carried out. The heat treatment can achieve adhesion of the liquid-repellent film to the application surface and stabilization of the structure.

[0139] The temperature of the heat treatment is Preferably, the temperature is 20 to 200° C. More preferably, the temperature is 20 to 180° C., and More preferably, the temperature is 20 to 150°C. can be in the range of The heat treatment time is: Preferably, for 5 to 3000 minutes. More preferably, for 10 to 2000 minutes, and More preferably, 15 to 1000 minutes can be in the range of

[0140] The solvent that the liquid may contain may be optionally subjected to pressure reduction, heating, and combinations thereof, etc. It may be removed by any means.

[0141] If desired, the liquid-repellent film thus formed can be washed with a solvent (eg, THF) and dried by a method such as drying under reduced pressure.

[0142] 7.Goods The article of the present invention (liquid-repellent article) comprises the liquid-repellent film of the present invention. The article of the present invention may have the liquid-repellent coating of the present invention on one or more portions, or on the entire surface thereof. The liquid-repellent film of the present invention in the article and the preparation method thereof can be understood from the above explanation of the liquid-repellent film of the present invention. The article of the present invention and the manufacturing method thereof are understood based on these descriptions and common general technical knowledge. The liquid-repellent article has the inherent function of the article and is provided with liquid-repellency.

[0143] The thickness of the liquid-repellent film of the present invention provided on the application surface is, for example, 0.0001~5μm, 0.0001 to 4 μm, or 0.0001 to 3 μm, can be in the range of

[0144] 8. Polyethyleneimine derivatives Among the polyethyleneimine derivatives contained in the liquid repellent agent of the present invention, A polyethyleneimine substituted with one or more substituents, at least one of which is substituted on the amine nitrogen of the polyethyleneimine. Formula:-R fy [In the formula, R fy is one or more substituents At least one of the substituents is A fluoroalkyl group which may have one or more substituents and which may have one or more -O- portions inserted therein, or an alkyl group which may have one or more substituents and which may have one or more -O- portions inserted therein, is a fluoroaryl group which may have one or more substituents. represents a hydroxyethyl group which may have the following formula: A polyethyleneimine derivative having a substituent represented by the formula: is a novel compound. The present invention also provides the novel compound.

[0145] The polyethyleneimine derivative can be produced, for example, by reacting polyethyleneimine with an oxirane compound.

[0146] The oxirane compound is preferably represented by the formula (A f ): [ka] [In the formula, R, in each occurrence, is the same or different and represents a hydrogen atom or a substituent. However, at least one of the four R's may be a fluoroalkyl group. The oxirane compound may be represented by the formula:

[0147] Preferably, R, at each occurrence, is the same or different and Hydrogen atom, an alkyl group, which may bear one or more substituents and which may be interrupted by one or more -O- moieties; or It represents an aryl group which may have one or more substituents. However, at least one of the four R's is a fluoroalkyl group, optionally bearing one or more substituents and optionally containing one or more -O- moieties; or It is a fluoroaryl group which may have one or more substituents.

[0148] More preferably, R, at each occurrence, is the same or different and is Hydrogen atom, an alkyl group having 1 to 30 carbon atoms (preferably having 6 to 20 carbon atoms, and more preferably having 12 to 20 carbon atoms), or Aryl group with 6 to 14 carbon atoms Represents. However, at least one of the four R's is a fluoroalkyl group having 1 to 30 carbon atoms (preferably having 6 to 20 carbon atoms, and more preferably having 12 to 20 carbon atoms), which may have one or more substituents and into which one or more -O- moieties may be inserted; or A fluoroaryl group which may have one or more substituents. It is.

[0149] The reaction temperature of the reaction is Preferably, the temperature is 20 to 200° C. More preferably, the temperature is 20 to 180° C., and More preferably, the temperature is 20 to 150°C. can be in the range of The reaction time of the reaction is Preferably, for 5 to 3000 minutes. More preferably, for 10 to 2000 minutes, and More preferably, 15 to 1000 minutes can be in the range of

[0150] Each of the methods 1 and 2 for producing a liquid-repellent film can be one embodiment of the method for producing the polyethyleneimine derivative.

[0151] The polyethyleneimine derivative is Preferably, 1 to 100. More preferably, 1 to 80, and More preferably, 1 to 60 The hydroxyl value is within the range of

[0152] The polyethyleneimine derivative is Preferably 1 to 50, More preferably, 1 to 40, and More preferably, 1 to 30 The amine number is in the range of

[0153] The polyethyleneimine derivative is Preferably 0 to 80, More preferably, 0 to 70, and More preferably, 0 to 60 The fluorine content is in the range of

[0154] The polyethyleneimine derivative is Preferably 300 to 1,000,000, More preferably, 300 to 900,000, and More preferably, 300 to 800,000 The weight average molecular weight is in the range of

[0155] The polyethyleneimine derivative is Preferably 1 to 100, more preferably 1 to 80, and even more preferably 1 to 60 having a hydroxyl number in the range of Preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30 having an amine number in the range of Preferably 0 to 80, more preferably 0 to 70, and even more preferably 0 to 60 and Preferably 300 to 1,000,000, more preferably 300 to 900,000, and even more preferably 300 to 800,000 The weight average molecular weight is in the range of

[0156] One embodiment of the liquid repellent of the present invention may be a liquid repellent containing the polyethyleneimine derivative of the present invention.

[0157] 9. Liquid repellent kit The present invention also provides 1) Polyethylenimine; and 2) Contains an oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents). Also provided is a repellent kit comprising: The kit preferably comprises: The polyethyleneimine 1 and the oxirane 2 are contained in a form in which they are not in contact with each other. Examples of such a form include a form in which the polyethyleneimine 1 and the oxirane 2 are placed in separate containers.

[0158] The kit, its manufacturing method, and its use can be understood from the above explanation of the liquid repellent agent and liquid repellent film, as well as from common general technical knowledge in the technical field to which the present invention pertains. EXAMPLES

[0159] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[0160] The meanings of the symbols and abbreviations used in the examples are as follows. PEI: Polyethyleneimine

[0161] The epoxy derivative (Ex1) used in Production Examples 1-1 and 1-2 described below is [ka] It is. The epoxy derivative (Ex2) used in Production Examples 2-1 and 2-2 described below is [ka] It is.

[0162] Manufacturing Example 1-1 Preparation of PEI-Ex1 thin film 1 Number average molecular weight 0.75×10 6 A 0.1 ml portion of a 15 wt % aqueous solution of the branched polyethyleneimine was spin-coated (2500 rpm, 100 sec) onto a glass substrate to prepare a PEI thin film. 0.03 ml of a methanol solution of an epoxy derivative (Ex1) was dropped onto the PEI thin film, and a cover glass was placed on top of it. This was heated at 120° C. for 30 minutes. After being left at room temperature and cooled to room temperature, the cover glass was removed, the thin film was washed with THF, and dried under reduced pressure to obtain a PEI-Ex1 thin film (film thickness: 10 nm or less).

[0163] Manufacturing Example 1-2 Preparation of PEI-Ex1 thin film 2 Number average molecular weight 0.75×10 6 A 15 wt % aqueous solution of the branched polyethyleneimine and a methanol solution of an epoxy derivative (Ex1) were reacted at 80° C. for 12 hours. The solvent was removed using an evaporator, and the residue was dried under reduced pressure to obtain PEI-Ex1. The PEI-Ex1 was dissolved in methanol, and 0.1 ml of the solution (10 wt%) was spin-coated (2500 rpm, 100 sec) onto a glass substrate to prepare a PEI-Ex1 thin film. The thin film was washed with THF and dried under reduced pressure to obtain a PEI-Ex1 thin film (film thickness: 10 nm or less).

[0164] Example 2-1 Preparation of PEI-Ex2 thin film 1 Number average molecular weight 0.75×10 6 A 0.1 ml portion of a 15 wt % aqueous solution of the branched polyethyleneimine was spin-coated (2500 rpm, 100 sec) onto a glass substrate to prepare a PEI thin film. 0.03 ml of a methanol solution of an epoxy derivative (EX2) was dropped onto the PEI thin film, and a cover glass was placed on top of it. This was heated at 120° C. for 30 minutes. After being left at room temperature and cooled to room temperature, the cover glass was removed, the thin film was washed with THF, and dried under reduced pressure to obtain a PEI-Ex2 thin film (film thickness: 10 nm or less).

[0165] Example 2-2 Preparation of PEI-Ex2 thin film 2 Number average molecular weight 0.75×10 6 A 15 wt% aqueous solution of the branched polyethyleneimine and a methanol solution of an epoxy derivative (Ex) were reacted at 80°C for 12 hours. The solvent was removed using an evaporator, and the residue was dried under reduced pressure to obtain PEI-Ex2. The PEI-Ex2 was dissolved in methanol, and 0.1 ml of the solution (10 wt%) was spin-coated (2500 rpm, 100 sec) onto a glass substrate to form a thin film of PEI-Ex2. A membrane was prepared. The thin film was washed with THF and dried under reduced pressure to obtain a PEI-Ex2 thin film (film thickness: 10 nm or less).

[0166] Production Example 3 Each thin film was prepared using each compound shown in the "Reacted Ex" column of Table 1 below, by the method of Production Example 1-1 or 2-1 above.

[0167] Production Example 4 Each thin film was prepared using each compound shown in the "Reacted Ex" column of Table 2 below, by the method of Production Example 1-2 or 2-2 above.

[0168] Test Example 1 Liquid repellency test A liquid repellency test was carried out on each of the PEI-Ex2 thin films produced in the above manner. The results are shown in Tables 1 and 2. <Condition> Equipment: Contact angle meter (manufactured by Excimer Corporation) (Setting conditions) Temperature: 25℃ droplet Water: 1.6μl n-Octane: 1.6μl

[0169] [Table 1]

[0170] [Table 2]

[0171] Test Example 2: Glass transition temperature measurement The glass transition temperature of the PEI-Ex2 thin film prepared in Example 2-1 was measured by differential scanning calorimetry under the following conditions. The DSC thermograms are shown in Figure 1 (from the top, the first heating up, the temperature down, and the second heating up). This result demonstrated that the PEI-Ex2 thin film had high crystallinity. <Condition> Instrument: Mettler Toledo DSC1 Method: Heat flow method (Setting conditions) First heating rate: 10°C / min Cooling rate: 10℃ / min Second heating rate: 10°C / min

[0172] Test Example 3 Thin film analysis by FT-IR The PEI-Ex2 thin film prepared in Example 2-1 was analyzed by FT-IR under the following conditions. The IR spectrum is shown in FIG. The results indicated the presence of amino and hydroxy groups. <Condition> Equipment: SHIMADZU IRAffinity-1 Method: Film method (Setting conditions) 400~4000cm -1 Resolution: 4cm-1

[0173] Test Example 4 Thin film analysis by H-NMR The PEI-Ex2 thin film prepared in Example 2-1 was analyzed by FT-IR under the following conditions. The IR spectrum is shown in FIG. The results indicate the presence of H atoms in several different environments. <Condition> Equipment: Bruker AV400 (400MHz) Method: Deuterated methanol is used as the deuterated solvent.

Claims

1. A poly(hydrocarbylamine) substituted with one or more substituents, at least one of which is substituted on an amine nitrogen of the poly(hydrocarbylamine), having the formula: -R ａy : [In the formula, R ａy is one or more substituents (at least one of the substituents is one or more substituents and an alkyl group optionally having one or more -O- moieties inserted therein, or an aryl group optionally having one or more substituents.] A poly(hydrocarbylamine) derivative having a substituent represented by the formula: Contains Liquid repellent.

2. The poly(hydrocarbylamine) derivative is A polyethyleneimine substituted with one or more substituents, at least one of which is substituted on the amine nitrogen of the polyethyleneimine. Formula: -R ａy : [In the formula, R ａy is one or more substituents (at least one of the substituents is one or more substituents and an alkyl group optionally having one or more -O- moieties inserted therein, or an aryl group optionally having one or more substituents.] A polyethyleneimine derivative having a substituent represented by the formula: That is, The liquid repellent according to claim 1.

3. The liquid repellent according to claim 1 or 2, wherein the poly(hydrocarbylamine) derivative has a linear, branched, or cyclic structure, or a combination thereof.

4. R ａy is one or more substituents (at least one of which is R ｆａ It is. ｆ ａ is an alkyl group which may have one or more substituents and into which one or more -O- moieties may be inserted, or an aryl group which may have one or more substituents.

5. The poly(hydrocarbylamine) derivative is Formula (U1): -chain hydrocarbon -N(-R ａy ) - (U1) [The symbols in the formula are as defined above.] A poly(hydrocarbylamine) derivative having one or more structural units represented by the formula: The liquid repellent according to any one of claims 1 to 4.

6. The poly(hydrocarbylamine) derivative is ne end groups E, np building blocks G ｐ , nqf building blocks G ｑｆ , and nr building blocks G ｒ Including; Structural unit G ｐ may be the same or different in each occurrence, Formula (Up1): -CH ２ CH ２ -NH- (Up11) It is a structural unit represented by Structural unit G ｑｆ may be the same or different in each occurrence, Formula (Uq1): -CH ２ CH ２ -N(-R ｑｆｙ )- (Uq1) [In the formula, R ｑｆｙ represents a hydroxyethyl group which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents). It is a structural unit represented by Structural unit G ｒ may be the same or different in each occurrence, Formula (Ur1): -CH ２ CH ２ -N(-R ｏｔ )- (Ur1) [In the formula, R ｏｔ is R ｑｆｙ represents a substituent different from the substituents shown. A structural unit represented by the formula: ne is an integer in the range of 0 to 50,000; np is an integer in the range of 0 to 50,000; nqf is an integer in the range of 0 to 50,000; nr is an integer in the range of 0 to 50,000; The sum of np and nqf is an integer of 100 or more, The ratio of nqf / (np+nqf) is in the range of 0.02 to 100%, The structural unit G ｐ , G ｑｆ , and G ｒ each of the joins is of any type, and The structural unit G ｐ , G ｑｆ , and G ｒ may be linked to other structural units via a portion that does not constitute the main chain. A polymer represented by the formula: The liquid repellent according to any one of claims 1 to 5.

7. R ｑｆｙ is a hydroxyethyl group optionally having one or more substituents (at least one of the substituents is a fluoroalkyl group which may have one or more substituents and which may have one or more -O- moieties inserted, or an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted).

8. The liquid repellent according to any one of claims 1 to 7, which is for surface treatment.

9. The liquid repellent according to any one of claims 1 to 8, which is used for imparting liquid repellency to a surface of an article.

10. A liquid-repellent film comprising the liquid-repellent agent according to any one of claims 1 to 9.

11. A method for producing a liquid-repellent film according to claim 10, comprising the steps of: 1) a step of applying a liquid containing a poly(hydrocarbylamine) onto a surface of an article, and 2) a step of applying a liquid containing an oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents) onto the poly(hydrocarbylamine), and reacting at least a portion of the applied liquid to form the liquid-repellent film according to claim 10. A manufacturing method comprising:

12. A method for producing a liquid-repellent film according to claim 10, comprising the steps of: Poly(hydrocarbylamines), and An oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents). A liquid containing A method for producing the liquid-repellent film according to claim 10, comprising applying the composition to a surface of an article and allowing at least a portion of the composition to react, thereby forming the liquid-repellent film according to claim 10.

13. An article comprising the liquid-repellent film according to claim 10.

14. A method for producing an article provided with the liquid-repellent film according to claim 10, comprising the steps of: Poly(hydrocarbylamines), and An oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents). A liquid containing A method for producing the liquid-repellent film according to claim 10, comprising applying the composition to a surface of an article and allowing at least a portion of the composition to react, thereby forming the liquid-repellent film according to claim 10.

15. A polyethyleneimine substituted with one or more substituents, At least one of the substituents is substituted on the amine nitrogen of the polyethyleneimine. Formula: -C ２ R ４ OH [In the formula, R, in each occurrence, is the same or different and represents a hydrogen atom or a substituent. However, at least one of the four R's is A fluoroalkyl group which may have one or more substituents and may have one or more -O- portions inserted therein, or an alkyl group which may have one or more substituents and may have one or more -O- portions inserted therein, or It is a fluoroaryl group which may have one or more substituents. A substituent represented by A polyethyleneimine derivative.

16. A liquid repellent agent comprising the polyethyleneimine derivative according to claim 15.

17. 1) polyethyleneimine; and 2) Contains an oxirane which may have one or more substituents (at least one of the substituents is an alkyl group which may have one or more substituents and which may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents). Repellent kit including:

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