Liquid dispensing agent

Abstract

To provide a novel liquid repellent.SOLUTION: There is provided a liquid repellent containing a poly(hydrocarbylamine)derivative, which is poly(hydrocarbylamine) substituted by one or more substituent, in which at least one of the substituent is a substituent represented by the formula:-R, wherein -Rrepresents a hydroxyethyl group which may have one or more substituent (at least one of the substituent is an alkyl group which may have one or more substituent).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Conventionally, various fluorine-containing compounds having excellent oil repellency have been used. have been provided. However, since such fluorine-containing compounds have low solubility in general-purpose solvents (fluorine-free organic solvents), they need to be dissolved in expensive fluorine-containing organic solvents during coating. On the other hand, Patent Document 1 proposes an oil-repellent and / or water-repellent coating agent having high solubility in general-purpose solvents.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] It would be useful to provide a liquid repellent agent in which the use of expensive fluorine-containing solvents is suppressed, particularly one that can be dissolved in water and used for coating. Accordingly, 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 used for coating. 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 coating the surface of the article.

Means for Solving the Problems

[0005] As a result of intensive studies, the present inventors have found that a poly(hydrocarbylamine) substituted with one or more substituents, wherein at least one of the substituents is substituted on the amine nitrogen of the poly(hydrocarbylamine), Formula: -R ay : [In the formula, R ay represents a hydroxyethyl group which may have one or more substituents (at least one of the substituents may have one or more substituents and may have one or more -O- moieties inserted, or an aryl group which may have one or more substituents).] A poly(hydrocarbylamine) derivative which is a substituent represented by containing a liquid repellent has been found to solve the above problems and the present invention has been completed.

[0006] The present invention includes the following aspects. Item 1. A poly(hydrocarbylamine) substituted with one or more substituents, wherein at least one of the substituents is substituted on the amine nitrogen of the poly(hydrocarbylamine), Formula: -R ay : [In the formula, R ay represents a hydroxyethyl group which may have one or more substituents (at least one of the substituents may have one or more substituents and may have one or more -O- moieties inserted, or an aryl group which may have one or more substituents).] A poly(hydrocarbylamine) derivative which is a substituent represented by containing a liquid repellent. Item 2. The poly(hydrocarbylamine) derivative is a polyethyleneimine substituted with one or more substituents, wherein at least one of the substituents is substituted on the amine nitrogen of the polyethyleneimine, Formula: -R ay : [In the formula, R ayrepresents 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 may have one or more -O- moieties inserted therein, or an aryl group which may have one or more substituents). A polyethyleneimine derivative which is a substituent represented by is The liquid repellent agent according to Item 1. Item 3. The liquid repellent agent according to Item 1 or 2, wherein the poly(hydrocarbylamine) derivative has a branched-chain, cyclic, or a combination thereof structure. Item 4. R ay is one or more substituents (at least one of the substituents is R fa as defined herein. R fa 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).) is a 2-hydroxyethyl group which may have one or more substituents, and is the liquid repellent agent according to any one of Items 1 to 3. Item 5. The poly(hydrocarbylamine) derivative is Formula (U1): -chain hydrocarbon -N(-R ay )- (U1) [The symbols in the formula have the same meanings as described above.] is a poly(hydrocarbylamine) derivative having one or more structural units represented by The liquid repellent agent according to any one of Items 1 to 4. Item 6. The poly(hydrocarbylamine) derivative is ne terminal groups E, np structural units G p , nqf structural units G qf , and nr structural units G r and contains; The structural unit G p is the same or different at each occurrence, Formula (Up1): -CH2CH2-NH- (Up1) is a structural unit represented by structural unit G qf is the same or different in each occurrence, Formula (Uq1): -CH2CH2-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 may have one or more substituents and one or more -O- moieties may be inserted, or an aryl group which may have one or more substituents).] is a structural unit represented by structural unit G r is the same or different in each occurrence, Formula (Ur1): -CH2CH2-N(-R ot )- (Ur1) [In the formula, R ot represents a substituent different from R qfy .] is a structural unit 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 of 100 or more, The ratio of nqf / (np + nqf) is in the range of 0.02 to 100%, The said structural unit G p , G qf , and G r may be combined in any form, and the said structural unit G p , G qf , and G r may be linked to other structural units by a moiety that does not form the main chain.] a polymer represented by The liquid repellent agent according to any one of items 1 to 5. Item 7. R qfy is a hydroxyethyl group which may have one or more substituents (at least one of the substituents may have one or more substituents and may have one or more -O- moieties inserted therein) and is a fluoroalkyl group. The liquid repellent agent according to item 6. Item 8. The liquid repellent agent according to any one of items 1 to 7, which is for surface treatment. Item 9. The liquid repellent agent according to any one of items 1 to 8, which is for imparting liquid repellency to the surface of an article. Item 10. A liquid repellent film containing the liquid repellent agent according to any one of items 1 to 9. Item 11. A method for producing the liquid repellent film according to item 10, comprising: 1) a step of applying a liquid containing poly(hydrocarbylamine) onto the surface of an article, and 2) further applying a liquid containing an oxirane which may have one or more substituents (at least one of the substituents may have one or more substituents and may have one or more -O- moieties inserted therein, or is an aryl group which may have one or more substituents) thereon, and reacting at least a part of these to form the liquid repellent film according to item 10. A production method including the above steps. Item 12. A method for producing the liquid repellent film according to item 10, comprising: poly(hydrocarbylamine), and an oxirane which may have one or more substituents (at least one of the substituents may have one or more substituents and may have one or more -O- moieties inserted therein, or is an aryl group which may have one or more substituents) containing a liquid is applied onto the surface of an article, and reacting at least a part of these to form the liquid repellent film according to item 10. A production method including this. Item 13. An article comprising the liquid-repellent film according to Item 10. Item 14. A method for producing an article comprising the liquid-repellent film according to Item 10, poly(hydrocarbylamine), and oxirane which may have one or more substituents (at least one of the substituents being an alkyl group which may have one or more substituents) containing a liquid is applied onto the surface of the article and at least a part thereof is reacted to form the liquid-repellent film according to Item 10. Item 15. Polyethyleneimine substituted with one or more substituents, at least one of the substituents being substituted on the amine nitrogen of the polyethyleneimine, of the formula: -C2R4OH [wherein R, in each occurrence, is the same or different and represents a hydrogen atom or a substituent. Provided that at least one of the four Rs is (1) a fluoroalkyl group which may have one or more substituents and may have one or more -O- moieties inserted therein 、 (2) An alkyl group which may have one or more substituents and may have one or more -O- moieties inserted therein, or (3) a fluoroaryl group which may have one or more substituents.] A polyethyleneimine derivative which is a substituent represented by Item 16. A liquid-repellent agent containing the polyethyleneimine derivative according to Item 15. Item 17. 1) polyethyleneimine; and 2) oxirane which may have one or more substituents (at least one of the substituents being 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) A liquid-repellent agent kit containing

Advantages of the Invention

[0007] According to the present invention, a new liquid repellent is provided.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0009] 1. Terms Unless otherwise specified, the symbols and abbreviations in this specification can be understood in the meaning commonly used in the technical field to which the present invention belongs in accordance with the context of this specification.

[0010] In this specification, the phrase "containing" is used with the intention of including the phrases "consisting essentially of" and "consisting of".

[0011] Unless otherwise limited, the processes, treatments, or operations described in this specification can 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" (where n and m are numbers) represents 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 "liquid repellent" means an agent that can impart liquid repellency to the surface of an article by applying (e.g., coating) it to the surface of the article. In this specification, the term "liquid repellent" can mean water repellent, oil repellent, or both. As used herein, the term "liquid repellency" may mean water repellency, oil repellency, or both. As used herein, the term "article surface" may mean all or a part of the surface of an article.

[0015] As used herein, unless otherwise particularly limited, examples of "halo (group)" can include fluoro (group), chloro (group), bromo (group), and iodo (group). As used herein, unless otherwise particularly limited, examples of "halogen (atom)" can 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 one hydrogen atom from an organic compound).

[0017] As used herein, "organic group" may be, for example, a hydrocarbon group which may have one or more substituents [in the hydrocarbon group, -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)-(in these formulas, R o is independently a hydrogen atom or an organic group.) One or more moieties selected from the group consisting of may be inserted.].

[0018] As is commonly understood based on the common knowledge in the chemical field, examples of hydrocarbon groups into which heteroatoms are inserted in this way can include non-aromatic heterocyclic groups and heteroaryl groups.

[0019] In this specification, the number of carbon atoms in the "hydrocarbon group" 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" include an alkyl group which may have one or more substituents and in which one or more -O- moieties may be inserted, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a heteroaryl group which may have one or more substituents, a cyano group, an aldehyde group, 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 in which one or more -O- moieties may be inserted, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, A cycloalkenyl group which may have one or more substituents, A cycloalkadienyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, or A heteroaryl group which may have one or more substituents) can be included.

[0021] In the present specification, "A hydrocarbon group which may have one or more substituents", "An alkyl group which may have one or more substituents and in which one or more -O- moieties may be inserted", "An alkenyl group which may have one or more substituents", "An alkynyl group which may have one or more substituents", "A cycloalkyl group which may have one or more substituents", "A cycloalkenyl group which may have one or more substituents", "A cycloalkadienyl group which may have one or more substituents", "An aryl group which may have one or more substituents", and "An aralkyl group which may have one or more substituents" Examples of the "substituents" in each of these cases 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. The number of such substituents can be in the range from 1 to the maximum number that can be substituted (e.g., 1, 2, 3, 4, 5, 6).

[0022] In the present specification, the terms "hydrocarbon group" and "hydrocarbyl (group)" can be used interchangeably. As is commonly understood by those skilled in the art, the hydrocarbon group may have a structure that is a chain structure (acyclic structure), or a cyclic structure, or a combination of one or more of these. In this specification, examples of the "hydrocarbon group" can include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group, an aralkyl group, and a group that is a combination of these.

[0023] In this specification, unless otherwise particularly limited, examples of the "alkyl group" can include linear or branched 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 this specification, the "alkyl group" can be, for example, an alkyl 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.

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

[0026] In this specification, the "haloalkyl group" is an alkyl group in which at least one hydrogen atom is substituted by a halogen atom.

[0027] In this specification, the number of halogen atoms that the "haloalkyl group" has can be 1 or more (e.g., 1 to 3, 1 to 6, 1 to 12, 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 the "(halo)alkyl group" include the (fluoro)alkyl group. In this specification, unless otherwise specified, the "(fluoro)alkyl group" means an alkyl group or a fluoroalkyl group.

[0030] In this specification, the "fluoroalkyl group" is an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom.

[0031] In this specification, the number of fluorine atoms in the "fluoroalkyl group" can be 1 or more (e.g., 1 to 3, 1 to 6, 1 to 12, up 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] In this specification, the "fluoroalkyl group" is an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom. In this specification, the number of fluorine atoms in the "fluoroalkyl group" can be 1 or more (e.g., 1 to 3, 1 to 6, 1 to 12, up 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 is commonly understood by those skilled in the art, the suffix "perhalogeno" means that all hydrogen atoms are substituted by halo groups. As is commonly understood by those skilled in the art, the suffix "perfluoro" means that all hydrogen atoms are Fluoro substituted by a group.

[0036] The "fluoroalkyl group" includes perfluoroalkyl groups.

[0037] The "perfluoroalkyl group" is an alkyl group in which all hydrogen atoms are substituted by 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, the "fluoroalkyl group" can be a linear or branched fluoroalkyl group. In this specification, as the "fluoroalkyl group", specifically, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group (CF3-), 2,2,2-trifluoroethyl group, pentafluoroethyl group (C2F5-), tetrafluoropropyl group (e.g., HCF2CF2CH2-), hexafluoropropyl group (e.g., (CF3)2CH-), nonafluorobutyl group, octafluoropentyl group (e.g., HCF2CF2CF2CF2CH2-), and tridecafluorohexyl group, etc. can be mentioned.

[0040] In this specification, unless otherwise particularly limited, examples of the "alkenyl group" can 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, etc.

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

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

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

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

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

[0046] In this specification, a "fluoroaryl group" is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom.

[0047] In this specification, unless otherwise particularly limited, examples of an "aralkyl group" can 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 particularly limited, a "non-aromatic heterocyclic group" can be monocyclic, bicyclic, tricyclic, or tetracyclic. In this specification, unless otherwise particularly limited, a "non-aromatic heterocyclic group" can be, for example, a non-aromatic heterocyclic group containing 1 to 4 heteroatoms selected from oxygen atoms, sulfur atoms, and nitrogen atoms in addition to carbon atoms as ring-constituting atoms. In this specification, unless otherwise particularly limited, a "non-aromatic heterocyclic group" can be saturated or unsaturated. In this specification, unless otherwise particularly limited, 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, 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-piperazin-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, etc.

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

[0050] In this specification, unless otherwise specifically limited, 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, 4-pyrimidinyl, 5-pyrimidinyl), pyrazinyl, and the like.

[0051] In this specification, unless otherwise particularly limited, examples of the "5- to 18-membered aromatic condensed 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, 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]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), 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-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. can be included.,

[0052] In this specification, unless otherwise particularly limited, "non-aromatic heterocyclic group which may have one or more substituents", and "heteroaryl group which may have one or more substituents" Examples of each "substituent" in can include hydrocarbon groups which may have one or more substituents, halo groups, nitro groups, cyano groups, oxo groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, and sulfenamoyl groups., The number of the substituents can be within the range from 1 to the maximum number that can be substituted (e.g., 1, 2, 3, 4, 5, 6).

[0053] In the present specification, as understood by those skilled in the art, "poly(hydrocarbylamine)" means a polymer having the same chemical structure as a polymer formed by virtual or actual polymerization of a hydrocarbylamine (e.g., allylamine, vinylamine, ethylamine). In other words, this name can represent its chemical structure regardless of its actual raw materials. As can be understood therefrom, for example, poly(alkyleneimine) can be synonymous with poly(alkylamine).

[0054] In the present specification, "poly(hydrocarbylamine)" can have a chain structure [acyclic structure (e.g., branched chain structure)], or a cyclic structure or a combination of one or more thereof. In particular, "poly(hydrocarbylamine)" having two or more cyclic structures can have a network structure.

[0055] In the present specification, "poly(hydrocarbylamine)" preferably has one or more (more preferably two or more) cyclic structures (cyclic moieties).

[0056] Preferred examples of poly(hydrocarbylamine) include poly(C2-C4 alkyleneimine), poly(C2-C4 alkylamine), and particularly preferred examples thereof include poly(ethyleneimine), poly(allylamine), and poly(vinylamine). It should be noted only for the sake of completeness that these can have a chain structure [acyclic structure (e.g., branched chain structure)], or a cyclic structure or a combination of one or more thereof, in the same manner as described for poly(hydrocarbylamine).

[0057] The liquid repellent of 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, wherein at least one of the substituents is substituted on the amine nitrogen of the poly(hydrocarbylamine), of the formula: -R ay : [wherein, R ay represents a hydroxyethyl group which may have one or more substituents (at least one of the substituents 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).] A poly(hydrocarbylamine) derivative which is a substituent represented by is contained.

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

[0060] When the liquid repellent of the present invention is applied to the surface of an article, preferably, the network structure adheres to the surface of the article, and the side chain portions can be vertically oriented with respect to the surface of the article.

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

[0062] The present invention is not limited thereto, but the function of the liquid repellent of the present invention can be based on the vertical orientation of the side chain portions.

[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 of a preferred embodiment of the present invention is A polyethyleneimine substituted with one or more substituents, wherein at least one of the substituents is substituted on the amine nitrogen of the polyethyleneimine, of the formula: -Ray [In the formula, R ay represents a hydroxyethyl group which may have one or more substituents (at least one of the substituents may have one or more substituents and may have one or more -O- moieties inserted, or an aryl group which may have one or more substituents).] A polyethyleneimine derivative which is a substituent represented by is a liquid repellent containing the same.

[0065] Polyethyleneimine derivative In other words, the polyethyleneimine derivative has at least one amine moiety substituted with one or more substituents R ay and any further site may be substituted with one or more substituents and can be polyethyleneimine.

[0066] Preferred examples of the polyethyleneimine derivative are polyethyleneimine substituted with one or more substituents, at least one of the substituents being substituted on the amine nitrogen of the polyethyleneimine, of the 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 Rs is (1) a fluoroalkyl group which may have one or more substituents and may have one or more -O- moieties inserted 、 (2) an alkyl group which may have one or more substituents and may have one or more -O- moieties inserted 、 or (3) a fluoroaryl group which may have one or more substituents. ​A polyethyleneimine derivative which is a substituent represented by is included.

[0067] The molecular weight of the polyethyleneimine derivative is preferably from 300 to 1,000,000, more preferably from 10,000 to 900,000, and even more preferably from 20,000 to 800,000 and can be within the range.

[0068] As described above, the polyethyleneimine derivative is polyethyleneimine substituted with one or more substituents. The polyethyleneimine which is the backbone of the polyethyleneimine derivative can have a branched-chain, cyclic, or a combination of these structures. For the purpose of illustration only, the structure can have a partial structure having a branched-chain, cyclic, or a combination of these structures as follows.

[0069]

Chemical formula

[0070] Generally, polyethyleneimine having a branched-chain, cyclic, or a combination of these structures may be referred to as branched polyethyleneimine in some cases. In this specification too, the term "branched polyethyleneimine" can be used intending to mean polyethyleneimine having such a structure.

[0071] The molecular weight of the polyethyleneimine can be the same as that of the polyethyleneimine derivative. Specifically, the molecular weight of the polyethyleneimine is preferably from 300 to 1,000,000, more preferably from 10,000 to 900,000, and even more preferably from 20,000 to 800,000 It can be within the range of.

[0072] The polyethyleneimine derivative can also have a branched-chain, cyclic, or a combination of these structures. For illustrative purposes only, an example is shown. The structure can have a structure including one or more branched-chain portions and one or more cyclic portions as follows. In the structural formula, R ay is, independently at each occurrence, -CH2CHR fa -OH, or -CH2CHR fa -OH, etc.

[0073]

Chemical formula

[0074] Examples of the "substituents" that the polyethyleneimine may have (i.e., substituents in the polyethyleneimine derivative) are halo group; nitro group; cyano group; oxo group; thioxo group; sulfonic group; sulfamoyl group; sulfinamoyl group; sulfenamoyl group; and organic group are included.

[0075] The number of the substituents is one or more. The lower limit can be, for example, 5, 10, 15, or 20. The upper limit can be, for example, 5000, 10000, 30000, or 50000. 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 with respect to the number of ethyleneimines constituting the polyethyleneimine backbone.

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

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

[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 thereof can be 1, 2, 3, or 4.

[0079] As described above, R fa is an alkyl group which may have one or more substituents and in which one or more -O- moieties may be inserted, or an aryl group which may have one or more substituents. R fa The alkyl group in is preferably a C1-C30 alkyl group, more preferably a C6-C20 alkyl group, and still more preferably a C12-C20 alkyl group.

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

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

[0082] R fa is 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 even more preferably a linear C6-C20 perfluoroalkyl group which may have one or more (preferably one) ether functional groups (-O-).

[0083] In the polyethyleneimine derivative, N-R ayThe molar ratio of the ethyleneimine unit(s) is preferably from 0.01 to 2, more preferably from 0.01 to 1.5, and even more preferably from 0.01 to 1 within the range.

[0084] In the polyethyleneimine derivative, the molar ratio of the R fa portion to the N-R ay portion is preferably from 1 / 4 to 1, more preferably from 1 / 3 to 1, and even more preferably from 1 / 2 to 1 within the range.

[0085] R ay is preferably a 2-hydroxyethyl group which may have one or more substituents (at least one of the substituents is R fa ).

[0086] The polyethyleneimine derivative is preferably Formula (U1): -CH2CH2-N(-R ay )- (U1) [The symbols in the formula have the same meanings as described above.] and is a polyethyleneimine derivative having one or more structural units represented by the 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 preferably contains ne terminal groups E, np structural units G p , nqf structural units G qf , and nr structural units G r .

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

[0089] Structural unit G p is, in each occurrence, the same or different, Formula (Up1): -CH2CH2-NH- (Up1) and is a structural unit represented by.

[0090] Structural unit G p The number np, which is the number of is preferably from 0 to 50,000, more preferably from 0 to 40,000, and even more preferably from 0 to 30,000 within the range.

[0091] Structural unit G qf is, in each occurrence, the same or different, Formula (Uq1): -CH2CH2-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 one or more -O- moieties may be inserted, or an aryl group which may have one or more substituents).] and is a structural unit represented by. Preferably, R qfy has one or more substituents [ At least one of the substituents is (1) a fluoroalkyl group which may have one or more substituents and in which one or more -O- moieties may be inserted 、 (2) an alkyl group which may have one or more substituents and in which one or more -O- moieties may be inserted 、 or (3) a fluoroaryl group which may have one or more substituents 。] is 、 a hydroxyethyl group which may be possessed is. 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] The number nqf of the constitutional unit G qf is preferably 0 to 50000, more preferably 0 to 40000, and even more preferably 0 to 30000 is within the range.

[0093] The constitutional unit G r is, in each occurrence, the same or different and is a constitutional unit represented by the formula (Ur1): -CH2CH2-N(-R ot )- (Ur1) [wherein, R ot represents a substituent different from R qfy .] is a constitutional unit represented by. The number nr of the constitutional unit G r is preferably 0 to 50000, more preferably 0 to 40000, and even more preferably 0 to 30000 is within the range.

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

[0095] The bonding methods of the constitutional unit G p , G qf , and G r are each of any type, and the constitutional unit G p , G qf , and G r may be linked to other constitutional units by a portion that does not form the main chain.] is a polymer represented by. Examples of such types include random, block, and alternating, as well as combinations thereof.

[0096] The liquid repellent of the present invention may contain, in addition to the polyethyleneimine derivative (PU1), additives and, if desired, solvents, etc.

[0097] As the additives, additives commonly used in liquid repellents can be used.

[0098] Examples of the solvent 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 [Examples: benzene, toluene, xylene, tetralin, veratrole, diethylbenzene, methylnaphthalene, nitrobenzene, o-nitrotoluene, mesitylene, indene, diphenyl sulfide]; Ketone solvents [Examples: acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetophenone, propiophenone, diisobutyl ketone, isophorone]; Halogenated hydrocarbon solvents [Examples: dichloromethane, chloroform, chlorobenzene]; Ether solvents [Examples: diethyl ether, tetrahydrofuran (THF), diisopropyl ether, methyl-t-butyl ether (MTBE), dioxane, dimethoxyethane, diglyme, phenetole, 1,1-dimethoxycyclohexane, diisoamyl ether]; Ester solvents [Examples: ethyl acetate, isopropyl acetate, diethyl malonate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, α-acetyl-γ-butyrolactone]; Nitrile solvents [Examples: acetonitrile, benzonitrile]; Sulfoxide solvents [Examples: dimethyl sulfoxide, sulfolane]; and Amide solvents [Examples: 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] are included. These solvents can be used alone or in combination of two or more.

[0099] 3. Method for producing a liquid repellent

[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 solvents.

[0101] The poly(hydrocarbylamine) derivative is commercially available or can be produced by the method for producing the polyethyleneimine derivative of the present invention described below or a method similar thereto.

[0102] In the liquid repellent of the present invention, where the poly(hydrocarbylamine) derivative is the polyethyleneimine derivative (PU1), for example, the polyethyleneimine derivative (PU1) is mixed with the additive as desired and the solvent as desired to produce the liquid repellent.

[0103] The poly(hydrocarbylamine) derivative is commercially available or can be produced by the method for producing the polyethyleneimine derivative of the present invention described below or a method similar thereto. Specifically, for example, in the production of polyethyleneimine, instead of ethyleneimine, a cyclic hydrocarbon amine corresponding to the structure of the target poly(hydrocarbylamine) [e.g., propyleneimine corresponding to the target polypropyleneimine] may be used.

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

[0105] Details of the "use of the liquid repellent" can be understood with reference to the description in other parts of the present invention and common general knowledge.

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

[0107] The liquid repellent of the present invention, for example, with respect to the article surface The amount of the polyethyleneimine derivative is per 1 cm of the article surface 2 per preferably 1 to 1000 mg, more preferably 10 to 1000 mg, and even more preferably 50 to 1000 mg and is applied in an amount to achieve this.

[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 even more preferably 0.0001 to 3 μm and can be within the range.

[0109] The liquid-repellent film of the present invention contains the poly(hydrocarbylamine) derivative and preferably contains the polyethyleneimine derivative (PU1) of the above formula. The liquid-repellent film of the present invention is understood based on the description 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 a liquid repellent film (1) Manufacturing method 1 of a liquid repellent film The liquid-repellent film of the present invention is, for example, 1) a step of applying a liquid containing polyethyleneimine on the surface of the article, and 2) further thereon, one or more substituents (at least one of the substituents is Rfa Coating a liquid containing an oxirane (hereinafter sometimes simply referred to as an oxirane compound) which may have (), and reacting at least a part of these to form the liquid-repellent film Manufacturing method including It can be manufactured by

[0111] Step 1 The "liquid containing polyethyleneimine" can be a liquid containing polyethyleneimine and a solvent. Examples of the solvent 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, γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, α-acetyl-γ-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 can be used singly or in combination of two or more. The liquid may optionally contain polyethyleneimine and substances other than the solvent. Examples of such substances include aziridine which may have one or more substituents, oxazoline which may have one or more substituents, and alkyl halides. Preferable examples of the substituent include an alkyl group and an aryl group.

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

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

[0114] Preferable examples of the oxirane compound are of formula (A):

Chemical formula

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

[0116] In Step 1, the method of applying a liquid containing polyethyleneimine onto a surface imparting liquid repellency (hereinafter sometimes referred to as the "application surface") is not particularly limited as long as the application 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 method, and gravure coating.

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

[0118] The application is carried out such that the amount of polyethyleneimine is 2 per 1 cm of the application surface, preferably 1 to 1000 mg, more preferably 10 to 1000 mg, and even more preferably 50 to 1000 mg.

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

[0120] By the application, at least a part of poly(hydrocarbylamine) and oxirane having one or more substituents (at least one of the substituents may have one or more substituents and may have one or more -O- moieties inserted, or may be an aryl group that may have one or more substituents) reacts to form the liquid-repellent film of the present invention.

[0121] Step 2 ​ The liquid containing the oxirane can be a liquid containing the oxirane and a solvent. Examples of the solvent include 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, γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, α-acetyl-γ-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 can be used singly or in combination of two or more. The liquid may optionally contain substances other than the oxirane and the solvents.

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

[0123] In Step 2, a liquid containing the oxirane is applied onto the coating layer provided in Step 1. The method of the application is not particularly limited as long as the application is achieved, and examples thereof include a spin coating method, a wipe coating method, a spray coating method, a squeegee coating method, a dip coating method, a die coating method, an inkjet method, a flow coating method, a roll coating method, a casting method, a Langmuir-Blodgett method, and a gravure coating method.

[0124] The application is carried out such that, per 1 cm 2 of the surface to be applied, the oxirane is preferably applied in an amount of 1 to 1000 mg, more preferably 10 to 1000 mg, and even more preferably 50 to 1000 mg. The application is preferably carried out at room temperature.

[0125] By the application,

[0126] at least a part of the poly(hydrocarbylamine) and the oxirane having 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) react to form the liquid-repellent film of the present invention.

[0127] ​ After the coating, heat treatment can be preferably carried out. By the heat treatment, adhesion of the liquid repellent film to the application surface and stabilization of the structure can be achieved.

[0128] The temperature of the heat treatment is preferably 20 to 200 °C, more preferably 20 to 80 °C, and even more preferably 20 to 150 °C and can be within the range. The time of the heat treatment is preferably 5 to 3000 minutes, more preferably 10 to 2000 minutes, and even more preferably 15 to 1000 minutes and can be within the range.

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

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

[0131] (2) Manufacturing method 2 of a liquid repellent film As an alternative method, the liquid repellent film of the present invention can also be, for example, polyethyleneimine, and one or more substituents (at least one of the substituents may have one or more substituents and may have one or more -O- moieties inserted, an alkyl group, or an aryl group that may have one or more substituents) and may have an oxirane containing liquid is applied onto the application surface and at least a part of them is reacted to form the liquid repellent film, and a manufacturing method by which it can be manufactured.

[0132] The polyethyleneimine and the oxirane can be the same as those described in the method 1 for manufacturing the liquid repellent film. In step 2, a liquid containing the oxirane is applied onto the coating layer provided in step 1. The method of the application is not particularly limited as long as the application 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 even more preferably 1:1 to 1:5 and can be contained in a mass ratio of.

[0134] The application is carried out such that per 1 cm of the application surface, the polyethyleneimine is 2 preferably 1 to 1000 mg, more preferably 10 to 1000 mg, and even more preferably 50 to 1000 mg and is applied in an amount of.

[0135] The application is carried out such that per 1 cm of the application surface, the oxirane is 2 preferably 1 to 3000 mg, more preferably 10 to 3000 mg, and even more preferably 50 to 3000 mg and is applied in an amount of.

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

[0137] By the application, polyethyleneimine, and An oxirane which may have one or more substituents (at least one of the substituents may have one or more substituents and may have one or more -O- moieties inserted therein, or may have one or more substituents which may be an aryl group) At least a part of reacts to form the liquid-repellent film of the present invention.

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

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

[0140] The solvent that the liquid may contain may be removed, if desired, by means such as reduced pressure, heating, and combinations thereof.

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

[0142] 7. Article The article (liquid-repellent article) of the present invention comprises the liquid-repellent film of the present invention. The article of the present invention can have the liquid-repellent film of the present invention on one or more parts or the entire surface thereof. The liquid-repellent film of the present invention in the article and the methods for preparing them are understood from the description of the liquid-repellent film of the present invention. The article of the present invention and its manufacturing method are understood based on these descriptions and common technical knowledge. The liquid-repellent article has its original 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 to 5 μm, 0.0001 to 4 μm, or 0.0001 to 3 μm, and can be within the range of.

[0144] 8. Polyethyleneimine derivative Among the polyethyleneimine derivatives contained in the liquid-repellent agent of the present invention, a polyethyleneimine substituted with one or more substituents, wherein at least one of the substituents is substituted on the amine nitrogen of the polyethyleneimine, Formula: -R fy [In the formula, R fy represents one or more substituents (at least one of the substituents is (1) a fluoroalkyl group which may have one or more substituents and may have one or more -O- moieties inserted therein 、 (2) an alkyl group which may have one or more substituents and may have one or more -O- moieties inserted therein 、 or (3) a fluoroaryl group which may have one or more substituents).) represents a hydroxyethyl group which may have.] The polyethyleneimine derivative which is a substituent represented by 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 of formula (A f ):

Chemical formula

[0147] Preferably, R, in each occurrence, is the same or different and is a hydrogen atom, 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. However, at least one of the four Rs is a fluoroalkyl group which may have one or more substituents and may have one or more -O- moieties inserted therein, or a fluoroaryl group which may have one or more substituents.

[0148] More preferably, R, in each occurrence, is the same or different and is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms (preferably 6 to 20 carbon atoms, and more preferably 12 to 20 carbon atoms), or an aryl group having 6 to 14 carbon atoms and represents. However, at least one of the four Rs is a fluoroalkyl group having 1 to 30 carbon atoms (preferably 6 to 20 carbon atoms, and more preferably 12 to 20 carbon atoms) which may have one or more substituents and may have one or more -O- moieties inserted therein, or A fluoroaryl group which may have one or more substituents is.

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

[0150] The production methods 1 and 2 of the liquid-repellent film can each be an aspect of the production method of the polyethyleneimine derivative.

[0151] The polyethyleneimine derivative preferably has a hydroxyl value in the range of 1 to 100, more preferably 1 to 80, and even more preferably 1 to 60 has a hydroxyl value within the range of.

[0152] The polyethyleneimine derivative preferably has an amine value in the range of 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30 has an amine value within the range of.

[0153] The polyethyleneimine derivative preferably has a fluorine content in the range of 0 to 80, more preferably 0 to 70, and even more preferably 0 to 60 has a fluorine content within the range of.

[0154] The polyethyleneimine derivative preferably 300 to 1000000, 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) 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). 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 usage method are understood from the above-described liquid repellent and the description of the liquid repellent film, as well as the common general knowledge in the technical field to which the present invention pertains.

Example

[0159] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

[0160] The meanings of the symbols and abbreviations in the examples are shown below. PEI: Polyethyleneimine

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

Chemical formula

Chemical formula

[0162] Production Example 1-1 Preparation 1 of PEI-Ex1 thin film 0.1 ml of a 15 wt% aqueous solution of branched polyethyleneimine with a number average molecular weight of 0.75×10 6 was spin-coated (2500 rpm, 100 sec) on a glass substrate to prepare a PEI thin film. 0.03 ml of a methanol solution (Ex1) of the epoxy derivative was dropped onto the PEI thin film, and a cover glass was placed thereon. This was heated at 120 °C for 30 minutes. After leaving it at room temperature and cooling it to room temperature, the cover glass was removed, and 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] Production Example 1-2 Preparation 2 of PEI-Ex1 thin film 0.1 ml of a 15 wt% aqueous solution of branched polyethyleneimine with a number average molecular weight of 0.75×10 6A 15 wt% aqueous solution of branched polyethyleneimine and a methanol solution of an epoxy derivative (Ex1) were reacted at 80 °C for 12 hours. The solvent was distilled off using an evaporator and 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 on a glass substrate (2500 rpm, 100 sec) 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] Production Example 2-1 Preparation 1 of PEI-Ex2 thin film A number average molecular weight of 0.75×10 6 0.1 ml of a 15 wt% aqueous solution of branched polyethyleneimine was spin-coated on a glass substrate (2500 rpm, 100 sec) 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 thereon. This was heated at 120 °C for 30 minutes. After leaving it at room temperature and cooling it 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] Production Example 2-2 Preparation 2 of PEI-Ex2 thin film A number average molecular weight of 0.75×10 6 A 15 wt% aqueous solution of branched polyethyleneimine and a methanol solution of an epoxy derivative (Ex) were reacted at 80 °C for 12 hours. The solvent was distilled off using an evaporator and 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 on a glass substrate (2500 rpm, 100 sec) to prepare a PEI-Ex2 thin film. 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 Using the method of Production Example 1-1 or 2-1 above, each thin film was prepared using each compound described in the "Reacted Ex" column of Table 1 below.

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

[0168] Test Example 1 Liquid repellency test For each of the PEI-Ex2 thin films prepared in the above production, a liquid repellency test was carried out by the following method. The results are shown in Table 1 and Table 2. <Conditions> Apparatus: Contact angle meter (manufactured by EXIMA CORPORATION) (Set conditions) Temperature: 25 °C Droplet Water: 1.6 μl n-Octane: 1.6 μl

[0169]

Table 1

[0170]

Table 2

[0171] Test Example 2 Glass transition temperature measurement For the PEI-Ex2 thin film prepared in Example 2-1 above, the glass transition temperature was measured under the following conditions by differential scanning calorimetry. The DSC thermogram is shown in Figure 1 (from the top, the first heating, cooling, and the second heating). This result indicated that the PEI-Ex2 thin film has high crystallinity. <Conditions> Apparatus: METTLER TOLEDO DSC1 Method: Heat flow method (Set conditions) First heating rate: 10 °C / min Cooling rate: 10 °C / min Second heating rate: 10 °C / min

[0172] Test Example 3 Thin film analysis by FT-IR Regarding the PEI-Ex2 thin film prepared in Example 2-1 above, thin film analysis by FT-IR was performed under the following conditions. The IR spectrum is shown in Figure 2. As a result, the presence of amino groups and hydroxy groups was indicated. <Conditions> Apparatus: SHIMADZU IRAffinity-1 Method: Film method (Set conditions) 400~4000 cm -1 Resolution: 4 cm-1

[0173] Test Example 4 Thin film analysis by H-NMR Regarding the PEI-Ex2 thin film prepared in Example 2-1 above, thin film analysis by FT-IR was performed under the following conditions. The IR spectrum is shown in Figure 3. As a result, the presence of H atoms in several different environments was indicated. <Conditions> Apparatus: Bruker AV400 (400 MHz) Method: Use deuterated methanol as the deuterated solvent

Claims

1. A liquid repellent for dissolving in water and applying by coating, comprising poly(hydrocarbylamine) substituted with one or more substituents, wherein the poly(hydrocarbylamine) is polyethyleneimine, and at least one of the substituents is a substituent of the formula: -C ２ H ３ ROH [wherein, R is (1) a perfluoroalkyl group having 6 to 20 carbon atoms which may have one or more substituents and may have one or more -O- moieties inserted therein, or (2) an alkyl group having 12 to 20 carbon atoms which may have one or more -O- moieties inserted therein]. ] A liquid repellent represented by the substituent.

2. The liquid repellent according to claim 1, wherein the polyethyleneimine has a linear, branched, or cyclic structure, or a combination thereof.

3. In the formula: -C ２ H ３ The liquid repellent according to claim 1 or 2, wherein the substituent represented by ROH is a 2-hydroxyethyl group to which R is bonded.

4. The polyethyleneimine is Formula (U1): -hydrocarbon chain-N(-R ａy ) - (U1) [wherein R ａy represents the above -C ２ H ３ ROH. ] having one or more structural units represented by The liquid repellent according to any one of claims 1 to 3.

5. The polyethyleneimine is ne terminal groups E, np structural units G ｐ , nqf constitutional units G ｑｆ and nr constitutional units G ｒ and includes; The constitutional unit G ｐ is the same or different in each occurrence, Formula (Up1): -CH ２ CH ２ -NH- (Up1) is a constitutional unit represented by The constitutional unit G ｑｆ is the same or different in each occurrence, Formula (Uq1): -CH ２ CH ２ -N(-R ｑｆｙ ) - (Uq1) [In the formula, R ｑｆｙ represents a substituent represented by the formula: -C ２ H ３ ROH. ] is a constitutional unit represented by The constitutional unit G ｒ is the same or different in each occurrence, Formula (Ur1): -CH ２ CH ２ -N(-R ｏｔ ) - (Ur1) [In the formula, R ｏｔ represents a substituent different from R ｑｆｙ . ] is a constitutional unit 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 of 100 or more, The ratio of nqf / (np + nqf) is in the range of 0.02 to 100%, The constitutional unit G ｐ G ｑｆ and G ｒ The bonding methods of and G are each of any type, and the structural unit G ｐ , G ｑｆ and G ｒ may be linked to other structural units by a portion that does not form the main chain. ] is a polymer represented by the liquid repellent agent according to any one of claims 1 to 4.

6. The liquid repellent agent according to any one of claims 1 to 5, which is for surface treatment.

7. The liquid repellent agent according to any one of claims 1 to 6, which is for imparting liquid repellency to the surface of an article.

8. A liquid repellent film containing the liquid repellent agent according to any one of claims 1 to 7.

9. A method for producing the liquid repellent film according to claim 8, comprising: 1) a step of coating a liquid containing poly(hydrocarbylamine) on the surface of an article, and 2) further coating a liquid containing an oxirane represented by the following formula (A) thereon 【Chemical Formula 1】 [In the formula, Among the four Rs, three are hydrogen atoms and one is (1) a fluoroalkyl group in which one or more -O- moieties may be inserted, or (2) an alkyl group in which one or more -O- moieties may be inserted ] and reacting at least a part of these to form the liquid repellent film according to claim 8. The production method including the step.

10. A method for producing the liquid repellent film according to claim 8, comprising: poly(hydrocarbylamine), and the following formula (A) 【Chemical Formula 2】 [In the formula, Of the four Rs, three are hydrogen atoms and one is (1) a fluoroalkyl group in which one or more -O- moieties may be inserted, or (2) an alkyl group in which one or more -O- moieties may be inserted ] An oxirane represented by A method of manufacturing including applying a liquid containing the same onto the surface of an article and reacting at least a part of these to form the liquid-repellent film according to claim 8.

11. An article provided with the liquid-repellent film according to claim 8.

12. A method of manufacturing an article provided with the liquid-repellent film according to claim 8, polyethyleneimine, and the following formula (A) [Chemical Formula 3] [In the formula, Of the four Rs, three are hydrogen atoms and one is (1) a fluoroalkyl group in which one or more -O- moieties may be inserted, or (2) an alkyl group in which one or more -O- moieties may be inserted ] An oxirane represented by A method of manufacturing including applying a liquid containing the same onto the surface of an article and reacting at least a part of these to form the liquid-repellent film according to claim 8.

13. A liquid-repellent agent for dissolving in water and applying, containing a polyethyleneimine derivative, The polyethyleneimine derivative is 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, independently represents a hydrogen atom or a substituent, which may be the same or different in each occurrence. However, among the four Rs, three are hydrogen atoms and one is (1) a perfluoroalkyl group having 6 to 20 carbon atoms, which may have one or more substituents and may have one or more -O- moieties inserted therein, or (2) an alkyl group having 12 to 20 carbon atoms with one or more -O- moieties inserted therein. ] a substituent represented by is a liquid repellent.

14. A liquid repellent kit for dissolving in water and applying by coating, comprising: 1) polyethyleneimine; and 2) an oxirane represented by the following formula (A) [Chemical Formula 4] [In the formula, among the four Rs, three are hydrogen atoms and one is (1) a perfluoroalkyl group having 6 to 20 carbon atoms, which may have one or more -O- moieties inserted therein, or (2) an alkyl group having 12 to 20 carbon atoms with one or more -O- moieties inserted therein is] and containing an oxirane represented by A liquid repellent kit containing the same.

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