Random copolymer, composition, and article using same

Abstract

To provide a technique capable of improving high liquid repellent performance and its durability with a material having no fluorine in the material or excluding fluorine as much as possible.SOLUTION: A random copolymer comprising a constitutional unit represented by the formula (1) and a constitutional unit having a photocrosslinkable functional group, wherein an abundance ratio of the constitutional unit represented by the formula (1) is 0.95 to 0.3 in terms of molar ratio and an abundance ratio of the constitutional unit having a photocrosslinkable functional group is 0.05 to 0.7 in terms of molar ratio, with respect to constitutional units constituting the entire random copolymer. (In the formula, X1 is -O - or - NH -, R10 is alkylene or phenylene group having 2 to 12 carbons, Y1 is a functional group capable of double or more hydrogen bonds between two adjacent constitutional unit, R11 is a linear, branched, or cyclic hydrocarbyl group having 8 to 30 carbons, and in these hydrocarbyl groups, -O - or unsaturated bonds may be included, and hydrogens on carbons separated by two or more carbons from Y1 may be substituted with fluorines.). ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a random copolymer, a composition, and an article using the same that are suitable for use as a liquid-repellent coating material that does not contain or has reduced PFAS (Per and polyfluoroalkyl Substances). [Background technology]

[0002] PFAS, which have been used in many applications as water- and oil-repellent materials, are being increasingly restricted in various countries as substances harmful to the human body and the environment. Therefore, there is a growing demand for materials that exhibit the properties of such water- and oil-repellent materials without containing fluorine. For example, the polymer disclosed in Patent Document 1 has been reported as such a material. This prior document discloses that the packing (crystallinity) of long-chain alkyl groups contributes to liquid repellency. Furthermore, Non-Patent Document 1 and other publications have been published as examples of materials in which such long-chain alkyl groups pack (crystallize). Furthermore, the polymer disclosed in Patent Document 2 has been reported as a fluorine-containing surface treatment agent with a lower environmental impact.

[0003] Patent Documents 1 and 2 evaluate the liquid repellency of materials. However, to fully develop liquid repellency and prevent its deterioration, it is necessary to improve the material's solvent solubility and its coatability and adhesion to the substrate or other object to which the liquid repellency is to be imparted. Furthermore, it is necessary to improve the durability of the liquid repellency. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2022-159191 [Patent Document 2] Special Publication No. 2011-523432 [Non-patent literature]

[0005] [Non-Patent Document 1] "In-plane oriented highly ordered lamellar structure formation of poly(N-dodecylacrylamide) induced by humid annealing," RSC Advance, 2017, Vol. 7, p. 6631. Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention discloses a technique that can provide a material that does not contain fluorine or that has fluorine removed as much as possible, while at the same time providing high liquid repellency and improving durability. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have found that a random copolymer having structural units with a specific structure satisfies the above-mentioned desired properties, and have completed the present invention.

[0008] [1] A random copolymer containing a structural unit represented by formula (1) and a structural unit having a functional group crosslinkable by light, wherein the molar ratio of the structural unit represented by formula (1) to the structural units constituting the entire random copolymer is 0.95 to 0.5, and the molar ratio of the structural unit having a functional group crosslinkable by light to the structural units constituting the entire random copolymer is 0.05 to 0.5. TIFF2026005203000001.tif17122 (In the formula, X 1 is -O- or -NH-, and R 10 is an alkylene or phenylene having 2 to 12 carbon atoms, and Y 1 is a functional group capable of forming double or more hydrogen bonds between two adjacent structural units, and R 11is a linear hydrocarbon group having 8 to 30 carbon atoms, a branched hydrocarbon group having 8 to 30 carbon atoms, or a cyclic hydrocarbon group having 8 to 30 carbon atoms, and these hydrocarbon groups may contain -O- or an unsaturated bond. 1 Hydrogens on carbons two or more away from may be replaced by fluorine.)

[0009] [2] The random copolymer according to [1], wherein the structural unit having a functional group crosslinkable by light has a structure represented by formula (2): TIFF2026005203000002.tif20124 (In the formula, X 2 is -O- or -NH-, and R 20 represents an alkylene or phenylene having 1 to 12 carbon atoms, and at least one —CH2— in the alkylene may be replaced by —O—, —COO—, or —NHCOO—; Y 2 is a photo-crosslinkable functional group, and R 21 is hydrogen or methyl.)

[0010] [3] X in the structural unit represented by formula (1) in [1] 1 is -O- and Y 1 The random copolymer according to [1] or [2], wherein is -NHCONH-.

[0011] [4] Y in the structural unit represented by formula (2) described in [2] 2 is (meth)acryloyloxy or epoxy.

[0012] [5] A composition comprising the random copolymer according to any one of [1] to [4] and a solvent.

[0013] [6] The composition according to [5], further comprising a photoinitiator.

[0014] [7] The composition according to [5] or [6], which contains a precipitate of an aggregate of a random copolymer.

[0015] [8] An article in which the composition according to any one of [5] to [7] is applied to a substrate and the random copolymer is crosslinked. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a material that has a low environmental impact and does not contain fluorine or that minimizes fluorine content, and that not only has high liquid repellency but also has excellent durability of the liquid repellency. DETAILED DESCRIPTION OF THE INVENTION

[0017] Hereinafter, the embodiments of the present invention will be described in detail, but the following description is an example (typical example) of the embodiment of the present invention, and the present invention is not limited to these examples. Furthermore, the embodiments of the present invention can be combined as appropriate.

[0018] As used herein, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyloxy" means acryloyloxy or methacryloyloxy.

[0019] The random copolymer of the present invention is a random copolymer containing a constituent unit represented by formula (1) and a constituent unit having a functional group crosslinkable by light, and is characterized in that the molar ratio of the constituent unit represented by formula (1) to the constituent units constituting the entire random copolymer is 0.95 to 0.3, and the molar ratio of the constituent unit having a functional group crosslinkable by light is 0.05 to 0.7, relative to the constituent units constituting the entire random copolymer. TIFF2026005203000003.tif18127 (In the formula, X 1 is -O- or -NH-, and R 10 is an alkylene or phenylene having 2 to 12 carbon atoms, and Y 1 is a functional group capable of forming double or more hydrogen bonds between two adjacent structural units, and R 11is a linear hydrocarbon group having 8 to 30 carbon atoms, a branched hydrocarbon group having 8 to 30 carbon atoms, or a cyclic hydrocarbon group having 8 to 30 carbon atoms, and these hydrocarbon groups may contain -O- or an unsaturated bond. 1 Hydrogens on carbons two or more away from may be replaced by fluorine.)

[0020] The high liquid repellency of the present invention is achieved by the aggregation of the structural units represented by formula (1) within the random copolymer. To improve the aggregation ability, it is important that the structural units represented by formula (1) are repeatedly linked to each other within the random copolymer. Therefore, the structural units represented by formula (1) must be contained in the random copolymer at a molar ratio of 0.95 to 0.3 relative to the structural units constituting the entire random copolymer of the present invention, preferably at a molar ratio of 0.9 to 0.4, and more preferably at a molar ratio of 0.9 to 0.5.

[0021] In order to improve the above-mentioned assembly ability, the structure of the constitutional unit represented by formula (1) is also important. In the constitutional unit represented by formula (1), X 1 is -O- or -NH-, and R 10 is an alkylene or phenylene having 2 to 12 carbon atoms, and Y 1 is a functional group capable of forming double or more hydrogen bonds between two adjacent structural units, and R 11 is a linear hydrocarbon group having 8 to 30 carbon atoms, a branched hydrocarbon group having 8 to 30 carbon atoms, or a cyclic hydrocarbon group having 8 to 30 carbon atoms, and these hydrocarbon groups may contain -O- or an unsaturated bond. 1 Hydrogen on carbon two or more away from may be replaced by fluorine.

[0022] At this time, Y 1The type of Y can be used without any particular limitation as long as it is a functional group that can form double or more hydrogen bonds between two adjacent structural units. Examples of such functional groups include -CONH-, -OCONH-, and -CH2CHOHCHOCONH-. In this case, in order to improve the strength of the hydrogen bond, it is preferable that the positions of one or more heteroatoms relative to the two or more hydrogen atoms that form hydrogen bonds are in the same direction. 1 In terms of ease of synthesis, -NHCONH- is particularly preferred. The term "double or more hydrogen bonds" means that two or more adjacent hydrogen bonds are contained in the functional group.

[0023] To improve the aggregation ability, 11 The structure of R is also important. 11 As R, a hydrocarbon group having hydrophobic interaction or a group obtained by modifying the hydrocarbon group can be used. In order to increase the hydrophobic interaction, the chain length of the hydrocarbon group is preferably long. Specifically, R 11 Preferably, R contains a linear alkyl group having 10 or more carbon atoms, and more preferably contains a linear alkyl group having 12 or more carbon atoms. However, depending on the desired properties, R 11 The alkyl group in the formula (2) may have a chain length other than that specified above. When the hydrocarbon group contains -O-, taking into consideration the stability of the compound, CH3-O-CH2-O-, in which oxygen atoms are not adjacent to each other, is preferred over CH3-OO-CH2-, in which oxygen atoms are adjacent to each other, and CH3-O-CH2-CH2-O- is even more preferred because it provides a more stable bond. Regarding the stability of the compound, the substituent R in the structural unit represented by formula (2) 20 or X 2 and R 20 The same applies to the combination of

[0024] To obtain the desired liquid repellency, R 11 The hydrogen atoms on the carbon atoms of the hydrocarbon group may be replaced by fluorine atoms. 1 In this case, in order to reduce the environmental load by using as little fluorine as possible, which is the aim of the present invention, Y1 It is preferred that the hydrogen on the carbon atom more distant from Y be replaced. 1 It is most preferable that the hydrogen on the terminal carbon opposite to R is replaced. 11 It is preferred that the hydrogen on the carbon of the hydrocarbon group is not replaced with fluorine.

[0025] Suitable examples of the constitutional unit represented by formula (1) include structures represented by the following formulas (1-1) to (1-29). TIFF2026005203000004.tif187110

[0026] TIFF2026005203000005.tif184129

[0027] TIFF2026005203000006.tif162131

[0028] TIFF2026005203000007.tif161130

[0029] In order to obtain the desired liquid repellency, one or more types of constitutional units represented by formula (1) contained in the random copolymer of the present invention may be selected. In this case, in order to improve the liquid repellency and reduce the environmental load, R 11 With regard to the alkyl group, either one of alkyl groups containing no fluorine or alkyl groups containing fluorine may be selected.

[0030] In the present invention, high liquid repellency and excellent durability of the liquid repellency are achieved by forming a random copolymer containing a structural unit represented by formula (1) and a structural unit having a functional group crosslinkable by light. This is because the use of photocrosslinking allows reliable crosslinking even at low temperatures. In this case, a suitable example of the structural unit having a functional group crosslinkable by light is the structure represented by the following formula (2). TIFF2026005203000008.tif20121 (In the formula, X 2is -O- or -NH-, and R 20 represents an alkylene or phenylene having 1 to 12 carbon atoms, and at least one —CH2— in the alkylene may be replaced by —O—, —COO—, or —NHCOO—; Y 2 is a photo-crosslinkable functional group, and R 21 is hydrogen or methyl.)

[0031] In equation (2), Y 2 As the functional group, any known functional group that is crosslinkable by light can be selected. These functional groups may be crosslinkable by light themselves or may be functional groups having a polymerizable group that is crosslinkable via another linking group. Among these functional groups, (meth)acryloyloxy, epoxy, maleic acid ester residue, maleimide residue, and functional groups having a double bond as a polymerizable group are preferably selected because they are relatively easy to introduce into a random copolymer. Of these functional groups, (meth)acryloyloxy or epoxy are more preferred because of the wide variety of crosslinking reactions, and (meth)acryloyloxy is most preferred.

[0032] In equation (2), R 21 is hydrogen or methyl. The choice of either of these does not significantly affect the liquid repellency or durability. However, in order to improve the yield during random copolymer synthesis, R 21 is preferably hydrogen.

[0033] Suitable examples of the constitutional unit represented by formula (2) include structures represented by the following formulas (2-1) to (2-14).

[0034] TIFF2026005203000009.tif222101

[0035] TIFF2026005203000010.tif208103

[0036] To obtain the desired durability of liquid repellency, one or more types of constitutional units represented by the above formula (2) may be selected. The constitutional units represented by formula (2) must be contained in the random copolymer of the present invention at a molar ratio of 0.05 to 0.7 relative to the constitutional units constituting the entire random copolymer, preferably at a molar ratio of 0.1 to 0.4, and more preferably at a molar ratio of 0.2 to 0.3.

[0037] The random copolymer of the present invention may contain a third structural unit in order to improve the solubility of the random copolymer or adjust the material properties, in addition to the structural unit represented by formula (1) and the structural unit represented by formula (2) as a structural unit having a functional group that can be crosslinked by light.

[0038] As a monomer that forms such a third constitutional unit, for example, a known (meth)acrylic acid derivative can be used. Examples of such known compounds include alkyl (meth)acrylates having 1 to 8 carbon atoms, propargyl (meth)acrylate, allyl (meth)acrylate, cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, oxotetrahydrofuran-3-yl (meth)acrylate, ethylene glycol monoacetoacetate mono(meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, 3-(tris(trimethylsilyloxy)silyl)propyl (meth)acrylate, 3-(dimethoxy(methyl)silyl)propyl (meth)acrylate, 3-(diethoxy(methyl)silyl)propyl (meth)acrylate, 3-sulfopropyl potassium (meth)acrylate, 3-((2-((meth)acryloyloxy)ethyl)dimethylammonio)propane-1-sulfonic acid, (meth)acrylic acid, (meth)acrylamide, N-(hydroxymethyl)acrylamide, and the like.

[0039] Other known styrene derivatives can also be used as the monomer that forms the third structural unit. Examples of such known compounds include styrene, α-methylstyrene, styrene in which one to three hydrogen atoms on the benzene ring are replaced by methyl groups, 2- and 4-acetoxystyrene, 4-methoxystyrene, 4-carboxystyrene, trimethoxy(4-vinylphenyl)silane, and sodium 4-vinylbenzenesulfonate.

[0040] Furthermore, other known monomers that can be suitably used to form the third structural unit include acrylonitrile, vinylpyridine, N-vinylpyrrolidinone, and 1-vinylimidazole.

[0041] To maintain liquid repellency while improving coatability and adhesion to substrates and other objects, it is preferable to select the following monomers to form the third structural unit: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-(tris(trimethylsilyloxy)silyl)propyl (meth)acrylate, (meth)acrylic acid, (meth)acrylamide, N-(hydroxymethyl)acrylamide, N-(hydroxyethyl)acrylamide, styrene, and α-methylstyrene. These monomers may be used alone or in combination to obtain the desired properties.

[0042] In order to exhibit liquid repellency and maintain its durability, the third constitutional unit may be contained in the random copolymer of the present invention at a molar ratio of 0 to 0.65 relative to the constitutional units constituting the entire random copolymer, preferably 0 to 0.3, more preferably 0 to 0.2.

[0043] The random copolymer of the present invention can be produced by known methods. In this case, the structural unit represented by formula (1) can be derived using an acrylic monomer having -NCO or a protected -NCO as its precursor. Examples of such monomers include 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI), 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, and 2-(O-(1'-methylpropylideneamino)carboxyamino)ethyl acrylate. "Karenz" is a trade name manufactured by Resonac Corporation.

[0044] A method of polymerizing the above-mentioned acrylic monomer having -NCO or a protected -NCO to obtain a precursor of the random copolymer of the present invention, and then converting the precursor into the structure represented by formula (1), is preferred as a method for producing the random copolymer of the present invention because of its ease of production. In this case, it is preferable to use a protected acrylate as a raw material for the acrylic monomer having a protected -NCO to avoid gelation during polymerization. Among such protected acrylates, 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate is most preferred because it can suppress gelation while maintaining high polymerizability.

[0045] In the random copolymer of the present invention, other monomers forming the structural unit represented by formula (1) can also be used, such as acrylates that form the structural unit represented by formula (1) without converting the functional group. Known examples of such acrylates (hereinafter referred to as urea acrylates) include the reaction product of 2-isocyanatoethyl acrylate and a primary amine having an alkyl group. However, the use of such monomers can easily lead to problems such as a significant increase in the viscosity of the reaction solution during polymerization. From this perspective, it is preferable to use an acrylic monomer having a protected -NCO group as described above as a raw material. On the other hand, when a monomer having a highly reactive functional group, such as the structural unit represented by formula (2), is used as a comonomer to form a structural unit having a photocrosslinkable functional group and copolymerize it as is, it is preferable to use urea acrylate. This selection can prevent the highly reactive functional group from being destroyed during conversion to the structural unit represented by formula (1).

[0046] The polymerization initiator used in producing the random copolymer of the present invention may be a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, depending on the polymerization method of these monomers. Preferred thermal radical polymerization initiators include peroxide-based polymerization initiators such as benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butyl peroxypivalate, di-t-butyl peroxide (DTBPO), t-butyl peroxydiisobutyrate, and lauroyl peroxide, and azo-based polymerization initiators such as 2,2'-azobis(2-methylpropionate)dimethyl (MAIB), azobisisobutyronitrile (AIBN), and azobiscyclohexanecarbonitrile (ACN). Commercially available peroxide polymerization initiators include benzoyl peroxide, available from various companies, as well as products such as "Dicumyl Peroxide" manufactured by Tokyo Chemical Industry Co., Ltd. and "Percumyl D, Niper BMT, and Perhexa 25Z" manufactured by NOF Corporation. Azo polymerization initiators include AIBN, available from various companies, as well as products such as "V-40, V-50, V-59, V-65, V-70, V-501, and V-601" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Generally, azo polymerization initiators can be suitably used for both thermal radical polymerization and photoradical polymerization. The photoradical polymerization initiator is not particularly limited, and known initiators can be used, such as 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, and benzophenone / methyltriethanolamine mixture. Commercially available products include those manufactured by BASF Japan Ltd. under the trade names "Darocur Series 1173, 4265" and "Irgacure Series 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, 2959".

[0047] In order to obtain the desired properties, there are no particular limitations on the average molecular weight or its dispersion value of the random copolymer of the present invention. However, in order to improve liquid repellency and prevent its deterioration over time, the weight-average molecular weight (Mw) of the random copolymer of the present invention is preferably 1,000 or more, more preferably 5,000 or more. Furthermore, in order to prevent deterioration of the solvent solubility of the random copolymer, Mw is preferably 1,000,000 or less, more preferably 500,000 or less. The most preferred range is 10,000 to 100,000.

[0048] In the production of the random copolymer of the present invention, the conversion of a precursor random copolymer having a protected -NCO group into the structural unit represented by formula (1) can also be carried out according to known methods. Specifically, the random copolymer can be obtained by reacting a commercially available or known compound having -NH2 with a precursor of the random copolymer. Examples of commercially available or known compounds having -NH2 include alkylamines and alkyl- or alkoxy-substituted aniline derivatives. The amount of these -NH2-containing compounds added during the reaction is a molar ratio of 0.8 or more relative to the -NCO equivalents in the random copolymer. Because the -NH2-containing compound reacts quantitatively with the -NCO equivalents, this range is consistent with the technology of the present invention. Similarly, the upper limit of the amount of the -NH2-containing compound used is preferably 2.0 or less, more preferably 1.5 or less, and most preferably 1.2 or less, in order to facilitate purification of the random copolymer. In the above calculation, the molar ratio of the -NCO equivalents in the random copolymer can be calculated from the amount of random copolymer used, the abundance ratio of the -NCO equivalents in the random copolymer, and the molecular weight of the structural unit containing the -NCO equivalent. The abundance ratio of -NCO equivalents in the random copolymer is, as will be described later, 1 It can be determined by measurements such as H-NMR.

[0049] The reaction temperature for the conversion to the constitutional unit represented by the above formula (1) is 1 In the case of a random copolymer in which the group is -NHCONH-, a temperature of 80°C or higher is preferred to allow the reaction to proceed quickly. Also, a temperature of 120°C or lower is preferred to prevent decomposition of the random copolymer. 100°C is the most preferred reaction temperature. The higher the temperature, the shorter the conversion time. To achieve a sufficient conversion rate, the reaction time at 100°C is preferably 30 minutes or more, and to prevent decomposition of the random copolymer, 2 hours or less is preferred. One hour is the most preferred reaction time.

[0050] The solvent used in the conversion to the structural unit represented by formula (1) can be a solvent that is non-reactive or has low reactivity with the precursor of the random copolymer. A solvent that dissolves both the precursor and the random copolymer of the present invention is preferred. Examples of such solvents include hydrocarbon solvents such as toluene and xylene, ester solvents such as n-propyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and γ-butyrolactone, ether solvents such as tetrahydrofuran (THF), 1,4-dioxane, anisole, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and dipropylene glycol dimethyl ether, dimethylformamide, diethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, ethyl methyl carbonate, and diethyl carbonate.

[0051] In the random copolymer of the present invention, the introduction of the structural unit represented by formula (2) as a structural unit having a photocrosslinkable functional group can be carried out using a monomer that forms the structural unit represented by formula (2) or a precursor monomer (hereinafter referred to as precursor monomer 2) that forms the structural unit represented by formula (2) upon conversion. In this case, it is preferable to use precursor monomer 2 in view of stability during production of the random copolymer and during conversion from the precursor of the random copolymer described above to the structural unit represented by formula (2). As such precursor monomer 2, it is preferable to use a monomer having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-(hydroxymethyl)acrylamide, or N-(hydroxyethyl)acrylamide.

[0052] Other examples of precursor monomer 2 include 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI), 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, 2-(O-(1'methylpropylideneamino)carboxyamino)ethyl acrylate, 2-isocyanatoethyl methacrylate (Karenz (registered trademark) MOI), 2-((3,5-dimethylpyrazolyl]carbamoyl)ethyl methacrylate (Karenz (registered trademark) MOI-BP), and 2-(O-(1'methylpropylideneamino)carboxyamino)ethyl methacrylate (Karenz (registered trademark) MOI-BM). "Karenz" is a trade name manufactured by Resonac Corporation.

[0053] Furthermore, other monomers that can be suitably used to introduce the structural unit represented by formula (2) as a structural unit having a functional group that can be crosslinked by light include glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, and 3-(triethoxysilyl)propyl (meth)acrylate.

[0054] Conversion of a random copolymer precursor to a structural unit represented by formula (2) can be carried out by known methods. For example, when introducing (meth)acryloyloxy into a random copolymer precursor having a hydroxyl group, compounds such as (meth)acrylic anhydride, (meth)acrylic acid chloride, (meth)acrylic acid, (meth)acrylic acid with an activated carboxylic acid, and 2-isocyanatoethyl (meth)acrylate can be used. The random copolymer of the present invention can be obtained by reacting these (meth)acrylic acid derivatives with the random copolymer precursor in the presence of a base or catalyst. In this case, it is most preferable to select (meth)acrylic anhydride because it has high reactivity and little side reaction with other functional groups. The conversion of a random copolymer precursor to a structural unit represented by formula (2) will be described in detail in the following examples.

[0055] The composition of the present invention comprises the random copolymer of the present invention, a photoinitiator or catalyst, and a solvent. If necessary, a compound that reacts with the crosslinkable functional group in the structural unit represented by formula (2) or other additives may be added as a structural unit having a photocrosslinkable functional group in the random copolymer of the present invention. Hereinafter, the compound that reacts with the crosslinkable functional group in the structural unit represented by formula (2) is referred to as a reactive compound.

[0056] The solvent that can be used in the composition of the present invention is not limited and can be appropriately selected from known solvents. In this case, it is preferable to use a mixed solvent in order to maintain the solubility of the random copolymer of the present invention and improve the coatability to the substrate or other object to be coated. As such a solvent, in addition to the above-mentioned hydrocarbon solvents, ester solvents, and ether solvents, alcohol solvents can also be suitably used. In addition to the above-mentioned solvents, such solvents include ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, dipropylene glycol methyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, ethyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, dimethyl carbonate 1,3-dioxolane, diisopropyl ether, ethylene glycol dimethyl ether, and water.

[0057] The photoinitiator or catalyst that can be used in the composition of the present invention is added for the purpose of rapidly promoting the reaction between crosslinkable functional groups in the structural unit represented by formula (2) as a structural unit having a photocrosslinkable functional group, or between the crosslinkable functional group and a reactive compound. Such a reaction initiator or catalyst is not limited and can be appropriately selected from known initiators. For example, when the crosslinkable functional group is (meth)acryloyloxy, it can be selected from the above-mentioned photoradical polymerization initiators. Other reaction initiators or catalysts that can be selected include photoanionic initiators, photocationic initiators, acid catalysts, and metal catalysts.

[0058] In view of the high storage stability of the composition and the high polymerization rate, the photoinitiator or catalyst is preferably a photoradical polymerization initiator. As the photoradical polymerization initiator, alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and oxime ester-based photopolymerization initiators are preferred. In view of good humidity and heat durability, oxime ester-based photopolymerization initiators are particularly preferred.

[0059] Examples of alkylphenone photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one. Commercially available products such as Omnirad 184, Omnirad 127, Omnirad 907, Omnirad 369, and Omnirad 379 may also be used. Omnirad is a trademark of IGM Resins BV.

[0060] Examples of acylphosphine oxide photopolymerization initiators include bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and commercially available products such as Omnirad TPO and Omnirad 819 may be used. Omnirad is a trademark of IGM Resins BV.

[0061] Examples of oxime ester photopolymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and the like. Commercially available products such as IrgacureOXE01, IrgacureOXE02, IrgacureOXE03, IrgacureOXE04, Adeka Arcles N-1919, Adeka Arcles NCI-831, Adeka Arcles NCI-930, and Adeka Arcles NCI-730 may also be used. Here, Irgacure is a trademark of BASF Japan Ltd., and Adeka Arcles is a trademark of ADEKA Corporation.

[0062] In the composition of the present invention, there are no particular limitations on the contents of the random copolymer of the present invention, the photoreaction initiator or catalyst, and the solvent. However, in order to achieve sufficient liquid repellency and from the viewpoints of the solubility of the random copolymer and cost, the content of the random copolymer of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, per 100 parts by weight of the composition.

[0063] In the composition of the present invention, the content of the photoinitiator or catalyst is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, per 100 parts by weight of the random copolymer in the composition, in order to promote sufficient reaction between the crosslinking groups introduced into the random copolymer and to prevent deterioration of material properties due to residual photoinitiator or its reaction products.

[0064] The composition of the present invention may contain a reactive compound. The reactive compound is a compound that reacts with the crosslinkable functional group of the structural unit represented by formula (2) as a structural unit having a photocrosslinkable functional group in the random copolymer of the present invention. In order to crosslink the random copolymer of the present invention, the reactive compound preferably has multiple reactive functional groups. Furthermore, since no acid or basic impurities are generated after crosslinking, the reactive compound is more preferably one that can undergo a radical reaction with the crosslinkable functional group of the structural unit represented by formula (2). Furthermore, the reactive compound may be a low-molecular-weight compound or a polymer, as long as it maintains solubility in a solvent. The amount of these reactive compounds added to the composition is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight, per 100 parts by weight of the random copolymer of the present invention.

[0065] Furthermore, when the reactive compound is a polymer and meets the following condition 1, it is preferable to set the content of the reactive compound to 100 to 10,000 parts by weight per 100 parts by weight of the block copolymer of the present invention in order to further improve durability while maintaining the liquid repellency of the material. For the same purpose, it is more preferable to set the content of the reactive compound to 1,000 to 5,000 parts by weight. Condition 1: The surface energy value when the random copolymer of the present invention is formed into a film is less than the surface energy value when the reactive compound is formed into a film.

[0066] Suitable examples of the reactive compound include bifunctional (meth)acrylates such as alkylene diol di(meth)acrylates having 2 to 12 alkylene carbon atoms, ethylene glycol di(meth)acrylates, propylene glycol di(meth)acrylates, 4,4'-biphenol di(meth)acrylate, bisphenol A di(meth)acrylate, dioxane glycol di(meth)acrylate, glycerol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, bisphenol A ethoxylate di(meth)acrylate, bisphenol A polyethylene glycol diether di(meth)acrylate, and bisphenol A polypropylene glycol diether di(meth)acrylate.

[0067] Suitable examples of the reactive compound include tri- to hexafunctional (meth)acrylates such as glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0068] Another suitable example of a reactive compound is a thiol compound. Thiol compounds undergo an ene-thiol reaction with a compound having a double bond. The ene-thiol reaction is usually carried out by adding a dicarboxylic acid initiator or the like, but this can suppress oxygen inhibition in the air. Examples of such thiol compounds include esters of polyols such as ethylene glycol, tetramethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, polymethylene glycol, polyethylene glycol, and polypropylene glycol with thiol group (mercapto group)-containing carboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; mercaptoalkyl ethers of the above polyols; and polymercaptoalkanes.

[0069] Specific examples of the thiol compound include trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol bis(thioglycolate), tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptothiopropionate), dipentaerythritol poly(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropyl)ether, pentaerythritol tetrakis(3-mercaptopropyl)ether, ethylene glycol bis(2-mercaptoethyl)ether, tetraethylene glycol bis(2-mercaptoethyl)ether, 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, Multhiol Y-3, and Multhiol Y-4 (trade names, manufactured by SC Organic Chemical Co., Ltd.).

[0070] These thiol compounds may be used alone or in any combination of two or more in any ratio.

[0071] The composition of the present invention may contain additives such as surfactants, emulsifiers, coupling agents, antioxidants, radical stabilizers (polymerization inhibitors), antistatic agents, and hydrolysis stabilizers.

[0072] Surfactants are used to improve wettability, leveling, and coating properties on substrates. Examples of surfactants that can be used include silicone surfactants, acrylic surfactants, and fluorine surfactants. Specific examples include BYK-342, BYK-350, BYK-352, BYK-354, BYK-356, BYK-381, BYK-392, BYK-394, BYK-3441, BYK-3440, and BYK-3550 (all trade names manufactured by BYK Japan Co., Ltd.). As an example of a leveling agent, commercially available silicone surface conditioners can be used, such as BYK-UV3500, BYK-UV-3570 (both trade names: manufactured by BYK Japan Co., Ltd.), and TEGO Examples of suitable acrylic resins include Rad2100, 2200N, 2250, 2500, 2600, and 2700 (all trade names: manufactured by Evonik Degussa Japan Co., Ltd.), X-22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X-22-1602, X-22-1603, X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22-8201, X-22-2426, X-22-164A, and X-22-164C (all trade names: manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added to the composition is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the random copolymer of the present invention.

[0073] The composition of the present invention may contain a coupling agent to improve adhesion to substrates and other coating targets. Examples of silane coupling agents include vinyltrialkoxysilane, 3-isocyanatepropyltriethoxysilane, N-(2-aminoethyl)3-aminopropyltrialkoxysilane, N-(1,3-dimethylbutylidene)-3-(trialkoxysilyl)-1-propanamine, 3-glycidoxypropyltrialkoxysilane, 3-chlorotrialkoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-methacryloxypropyltrialkoxysilane. Dialkoxymethylsilanes, in which one of the three alkoxy groups in the above alkoxysilanes is replaced with methyl, can also be used as silane coupling agents. These silane coupling agents may be used alone or in combination. These silane coupling agents may also be commercially available. The amount of these coupling agents added to the composition is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 1 part by weight, per 100 parts by weight of the random copolymer.

[0074] There is no limit to the antioxidants that can be used in the present invention. Examples include nitroso compounds such as 3,5-di(t-butyl)-4-hydroxytoluene (BHT), hydroquinone, methylene blue, diphenylpicric hydrazide (DPPH), phenothiazine, N,N-dimethyl-4-nitrosoaniline, o-hydroxybenzophenone, and benzothiazine derivatives such as 2H-1,3-benzothiazine-2,4-(3H)dione. Other examples include Adeka Stab AO-20, AO-30, AO-40, AO-50, AO-60, and AO-80, available from ADEKA Corporation; Sumilizer BHT, Sumilizer BBM-S, and Sumilizer GA-80, available from Sumitomo Chemical Co., Ltd.; and Irganox 1076, Irganox 1010, Irganox 3114, and Irganox 245, available from BASF Japan Ltd. These antioxidants may be used alone or in combination of two or more, and may be commercially available products.

[0075] The composition of the present invention may contain an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant, etc. Examples of ultraviolet absorbers include TINUVIN PS, TINUVIN P, TINUVIN 99-2, TINUVIN 109, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 328, TINUVIN 329, TINUVIN 384-2, TINUVIN 571, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, TINUVIN 5236, ADK STAB LA-32, ADK STAB LA-34, ADK STAB LA-36, ADK STAB LA-31, ADK STAB 1413, and ADK STAB LA-51. "Tinuvin (registered trademark)" is a trade name manufactured by BASF Japan Ltd., and "Adekastab (registered trademark)" is a trade name manufactured by ADEKA Corporation. These ultraviolet absorbents may be used alone or in combination of two or more. Furthermore, these ultraviolet absorbents may be commercially available products.

[0076] Examples of light stabilizers include Tinuvin 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622, Tinuvin 770, Tinuvin 765, Tinuvin 780, Tinuvin 905, Tinuvin 5100, Tinuvin 5050, 5060, Tinuvin 5151, Kimassorb 119FL, Kimassorb 944FL, Kimassorb 944LD, and ADK STAB. Examples of such stabilizers include ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77, ADK STAB LA-82, ADK STAB LA-87, Cytec's trade name: Cyasorb UV-3346, and Goodrich's trade name: Goodlite UV-3034. "Chimasorb (registered trademark)" is a trade name manufactured by BASF Japan Ltd. These light stabilizers may be used alone or in combination of two or more. These light stabilizers may also be commercially available products.

[0077] The amount of each of these antioxidants, ultraviolet absorbers, and light stabilizers added to the composition is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 1 part by weight, per 100 parts by weight of the random copolymer of the present invention.

[0078] It is also suitable to add a hydrolysis stabilizer to the composition of the present invention in order to suppress hydrolysis of the polyacrylic acid ester and the like and to prevent deterioration over time or due to the environment. Examples of such hydrolysis stabilizers include Carbodilite (registered trademark) manufactured by Nisshinbo Chemical Inc., Carbodista (registered trademark) manufactured by Teijin Limited, and Stavaxol (registered trademark) manufactured by Lanxess K.K.

[0079] The performance of the liquid-repellent coating material obtained from the composition of the present invention can be further improved by creating controlled irregularities on the surface of the liquid-repellent coating material when it is formed into a film. One such method is to utilize the self-aggregates formed by the liquid-repellent coating material obtained from the composition of the present invention. That is, in the liquid-repellent coating material obtained from the composition of the present invention, the random copolymer forms spherical aggregates in an appropriate solution. By utilizing these spherical aggregates, controlled irregularities can be created. In the random copolymer of the present invention, Y in formula (1) 1 A random copolymer in which is —NHCONH— is preferred from the viewpoint of forming the association.

[0080] To form spherical aggregates, it is preferable to use a mixture of a low-polarity solvent such as toluene, which is a good solvent for the liquid-repellent coating material obtained from the composition of the present invention, and a high-polarity solvent such as alcohol, which is a poor solvent for the liquid-repellent coating material obtained from the composition of the present invention. The actual improvement of liquid repellency using such aggregates will be described in detail in the Examples.

[0081] The article of the present invention, having the composition of the present invention applied to the surface thereof, can be obtained by applying the composition to a substrate, removing the solvent, and then photocrosslinking the random copolymer. In this case, the solvent removal and crosslinking steps may be performed in the reverse order or simultaneously.

[0082] Examples of methods for applying the composition of the present invention include a coating method using a dispenser, a spin coating method, a roll coating method, a caten coating method, a flow coating method, a printing method, a microgravure coating method, a gravure coating method, a wire bar coating method, a dip coating method, a spray coating method, a meniscus coating method, and an inkjet method.

[0083] There are no particular limitations on the method for removing the solvent, but heat treatment is preferred as it produces a uniform coating in a short time. There are no particular limitations on the temperature conditions, but when applying to substrates with low heat resistance such as fibers or paper, sufficiently good liquid repellency can be achieved under mild conditions of around 120°C. Heat treatment can be carried out using equipment such as an oven or hot plate.

[0084] The random copolymer of the present invention can be crosslinked by light. Photocrosslinking can be achieved by irradiating the composition of the present invention with, for example, ultraviolet light. Irradiation with ultraviolet light can be achieved by conventional methods such as using a high-pressure mercury lamp, an ultraviolet light-emitting diode (LED), or a low-pressure mercury lamp. Crosslinking may also be achieved by a combination of heat and light. When crosslinking is achieved by a radical reaction, it is preferable to carry out the crosslinking in a nitrogen atmosphere in order to increase the reaction rate.

[0085] The random copolymer of the present invention is preferably crosslinked by light, since reliable crosslinking can be achieved at low temperatures. Photocrosslinking can also pattern crosslinked and non-crosslinked regions as needed. On the other hand, the random copolymer of the present invention can also be crosslinked by heat in combination.

[0086] The composition of the present invention exhibits little deterioration over time in terms of liquid repellency and has high durability against heat and other factors. On the other hand, if further improvement in the durability of liquid repellency is desired, it is also preferable to subject the substrate to a treatment in advance that promotes adhesion between the composition of the present invention and the substrate. Examples of such treatments include UV ashing using ozone and plasma treatment. Another preferable method is to apply an adhesive or crosslinking agent to the substrate.

[0087] For example, when a textile product is used as the substrate, the textile product can be treated by applying a crosslinking agent to the textile product and heating it. Examples of crosslinking agents include methylol melamine and compounds having one or more isocyanate groups or blocked isocyanate groups. The composition of the present invention is then applied to the textile product and dried by heating. In this case, it is preferable to use a composition of the present invention that contains functional groups capable of reacting with the above-mentioned crosslinking agent in order to improve durability.

[0088] Examples of compounds having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate; diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; and trimers and trimethylolpropane adducts of these isocyanurate rings. Examples of compounds having one or more blocked isocyanate groups include compounds in which the isocyanate groups of the above-mentioned compounds are protected with a blocking agent. Examples of blocking agents used in this case include organic blocking agents such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, and lactams, as well as bisulfites such as sodium bisulfite and potassium bisulfite. The above-mentioned crosslinking agents may be used alone or in combination.

[0089] Treatment of textile products with a crosslinking agent can be carried out, for example, by immersing the textile product in a treatment solution prepared by dissolving the crosslinking agent in an organic solvent or emulsifying and dispersing it in water. The crosslinking agent is then immobilized on the substrate by a heat treatment or other treatment. The immobilization of the crosslinking agent may be carried out before or simultaneously with the treatment of the substrate with the composition of the present invention. Considering process simplification, energy savings, and economic efficiency, it is preferable to immobilize the crosslinking agent simultaneously with the treatment with the composition of the present invention. When the crosslinking agent is immobilized by heating, it is preferably carried out at a temperature of 110 to 180°C for 1 to 5 minutes.

[0090] The substrate to which the composition of the present invention can impart liquid repellency is not particularly limited, and glass, metal, plastic, paper, fiber, etc. can be suitably used. For example, the material for textile products is not particularly limited, and examples thereof include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polylactic acid, polyamide resins such as nylon 6 and nylon 6,6, polyurethane resins, fluorine-based resins such as polyvinylidene fluoride and polytetrafluoroethylene, polysulfone, polyethersulfone, and cellulose-based materials such as cellulose and cellulose acetate. These may be used alone or in combination of two or more. [Example]

[0091] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0092] <Measurement of weight average molecular weight (Mw) and dispersion value (Mw / Mn) of random copolymer> Analysis was performed by GPC measurement. The equipment used was a high-performance liquid chromatograph system manufactured by Shimadzu Corporation. The columns used were two Agilent Technologies PLgel 5μm MIXED-D2 columns connected in series, and THF was used as the solvent. The standard reagent (standard polystyrene) for average molecular weight was STANDARD SM-105 manufactured by Resonaq Co., Ltd.

[0093] <Confirmation of random copolymer structure> Nuclear magnetic resonance spectrum (500MHz, manufactured by JASCO Corporation) 1 The measurement solvent was CDCl3, and tetramethylsilane was used as the standard substance.

[0094] <Exposure> Photocrosslinking of the random copolymer was carried out using an ultra-high pressure mercury lamp (Multilight USH-250BY; manufactured by Ushio Inc.). The exposure dose was measured by connecting a UIT-150-A (manufactured by Ushio Inc.) to a UVD-S365 and measuring the luminance at a wavelength of 365 nm.

[0095] <Film observation and film thickness measurement> The state of the prepared film was confirmed using a KLA Tencor P+16 step gauge (manufactured by KLA Tencor). The film thickness was measured by scraping off a portion of the film with a cutter and measuring the step using the above step gauge. The film thickness was calculated by averaging five measurements taken at different locations.

[0096] <Surface tension measurement> Measurements were made using a contact angle meter (PCA-1; manufactured by Kyowa Interface Science Co., Ltd.). Values ​​were taken as the average of five measurements taken at different locations. Measurements were made at room temperature.

[0097] <Scratch test> Measurements were performed using a nanoindenter measuring device (Nano Indenter G200; manufactured by KLA Corporation). The conditions were scratch length: 400 μm, minimum indentation pressure: 0 mN, maximum indentation pressure: 0.5 mN, and scratch speed: 10 μm / s. Evaluation was performed by observing the scratched area with the device's camera and by the indentation pressure at which the scratch occurred. If the scratch mark was not noticeable in the former and the latter value was 0.15 mN or higher, the scratch resistance was judged to be good.

[0098] <Monomers, polymerization initiators, alkylamines, other reagents, reactive compounds, and solvents> The following commercially available products were used: Monomers: 2-isocyanatoethyl acrylate, methyl acrylate, acrylonitrile, 4-hydroxybutyl acrylate (HBA), 2-hydroxyethyl acrylate (HEA) (all manufactured by Tokyo Chemical Industry Co., Ltd.) Thermal radical polymerization initiator: 2,2'-azobis(isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.) Alkylamine: n-dodecylamine, n-hexadecylamine, stearylamine (all manufactured by Tokyo Chemical Industry Co., Ltd.) Other reagents: acrylic anhydride, pyridine, n-hexadecane (all manufactured by Tokyo Chemical Industry Co., Ltd.) Photoradical polymerization initiator: ADEKA Arcles NCI-930 (ADEKA Corporation), Omnirad184 (IGM Resins BV) Reactive compounds: polyfunctional acrylates; 1,6-bis(acryloyloxy)hexane (manufactured by Tokyo Chemical Industry Co., Ltd.), 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione (manufactured by Tokyo Chemical Industry Co., Ltd.) Urethane acrylate: UN-3320HA (manufactured by Negami Chemical Industries Co., Ltd.) Solvent: toluene, THF, isopropanol (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0099] The monomer, 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, was synthesized from the above-mentioned 2-isocyanatoethyl acrylate according to Japanese Patent No. 4879557 (JP 2006-151967 A). The compound structure is 1 This was confirmed by H-NMR.

[0100] <Base material> A glass substrate, Eagle XG (registered trademark) (trade name, manufactured by Corning, 0.5 mm thick), was cut into a 40 mm square. The surface of this substrate was washed with acetone and ultrapure water, dried in an oven at 120°C for 1 hour, and cooled to room temperature.

[0101] [Example 1] Synthesis of Random Copolymer 1 (Random Copolymer Composed of Structural Unit of Formula (1-11), Structural Unit of Formula (2-8), and Third Structural Unit) Synthesis of random copolymer 1 precursor;

[0102] A three-necked flask (25 ml) was charged with 2.3802 g (10.03 mmol) of 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, 0.6198 g (4.299 mmol) of 4-hydroxybutyl acrylate, 30.0 mg (0.183 mmol) of AIBN, and 6.9 ml of toluene, and the mixture was heated and stirred in an oil bath at 80°C under a nitrogen atmosphere for 1 hour. The reaction mixture was cooled to room temperature and used directly in the next reaction.

[0103] To the reaction solution, 2.97 g (11.4 mmol) of stearylamine and 2 ml of toluene were added and reacted at 100°C for 2 hours. The reaction solution was reprecipitated in 100 ml of isopropanol. After stirring at room temperature for 1 hour, the mixture was left overnight. The resulting precipitate was filtered, stirred in 50 ml of isopropanol for 1 hour, and then filtered. The resulting random copolymer 1 precursor was vacuum dried at 50°C for 8 hours. The weight-average molecular weight of the random copolymer 1 precursor was 176,000.

[0104] Conversion to random copolymer 1; 30 ml of THF was added to 3.00 g of the above random copolymer 1 precursor and heated to 50°C. 0.63 ml (5.4 mmol) of acrylic anhydride and 0.45 ml (5.6 mmol) of pyridine were added thereto and stirred at 50°C for 24 hours. The reaction solution was reprecipitated in 100 ml of methanol. After stirring at room temperature for 1 hour, the mixture was left overnight. The resulting precipitate was filtered, stirred in 50 ml of methanol for 1 hour, and then filtered again. The resulting powder was vacuum dried at room temperature for 8 hours to obtain random copolymer 1. The weight-average molecular weight of random copolymer 1 was 145,000 and the polydispersity (Mw / Mn) was 4.52.

[0105] [Example 2] to [Example 9] In the same manner as in Example 1 above, the following random copolymers 2 to 9 were obtained by varying the raw materials and their amounts, as well as the reaction time for introducing crosslinkable functional groups. In Table 1, the numbers in brackets [ ] indicate the abundance ratio (molar ratio) of each structural unit relative to the structural units constituting the entire random copolymer. The numbers in the Example / Copolymer column indicate both the example number and the random copolymer number. The base monomer of the third structural unit indicates the monomer that forms the third structural unit. Table 1 also lists the random copolymer 1 synthesized in Example 1.

[0106] [Table 1] TIFF2026005203000011.tif109155

[0107] [Example 10] <Preparation of Composition 1> 0.25 g of the random copolymer 1 obtained in Example 1 was dispensed into a sample bottle and dissolved in 3.80 g of toluene and 0.96 g of isopropanol, and 5.0 mg of Adeka Arcles NCI-930 was added and dissolved therein to obtain Composition 1 having a solids concentration of approximately 5 wt %.

[0108] [Example 11] to [Example 19] <Preparation of Compositions 2 to 10> Using the random copolymers synthesized in the above examples, compositions 2 to 10 having the formulations shown in Table 2 were prepared in the same manner as in Example 10. Table 2 also lists composition 1 from Example 10.

[0109] [Table 2] TIFF2026005203000012.tif67156

[0110] [Example 20] <Production of measurement items and evaluation of physical properties> Composition 1 was spin-coated onto a glass substrate. The rotation speed of the glass substrate was 500 rpm. The glass substrate spin-coated with Composition 1 was heated on a hot plate at 80°C for 1 minute to remove the solvent in Composition 1. Composition 1 was applied to the surface of the glass substrate, and the resulting coating was exposed to light under a nitrogen atmosphere to crosslink the random copolymer 1. The exposure dose was 1.4 J / cm 2 The film sample, which was an article formed on a glass substrate, had a film thickness of 1.45 μm. The contact angle of the film sample with hexadecane was 42.6 degrees.

[0111] A scratch test was carried out on the film sample prepared in the same manner as above. As a result, the pressing pressure required to generate a scratch was 0.180 mN, and the scratch resistance was good, including observation with the equipment camera.

[0112] [Example 21] to [Example 27] Except for replacing composition 1 with the composition shown in Table 3 below, a film sample was prepared on a glass substrate in the same manner as in Example 20. The results of the physical property measurements are shown in Table 3 below. Table 3 also lists the results of Example 20.

[0113] [Comparative Example 1] In the same manner as in Example 6 of Japanese Patent Application No. 2023-149334, a block copolymer having no crosslinkable functional group (a structural unit of formula (1), X 1 -O-, R 10 is ethylene, Y 1 -NHCONH-, R 11 nC 18 H 37 The obtained block copolymer was an AB type block copolymer having a block of methyl acrylate and a block of polymethyl acrylate in a molar ratio of 2:8 in terms of the structural units.

[0114] Using this block copolymer, Comparative Composition 1 with a solids concentration of approximately 5 wt% was prepared in the same manner as in Example 10. Adeka Arcles NCI-930 was not added to Comparative Composition 1. This Comparative Composition 1 was applied to a glass substrate in the same manner as in Example 20, and the solvent was then removed to obtain a film. No exposure to light was performed on the film. The film thickness of the Comparative Example 1 sample was 1.41 μm, and the contact angle of hexadecane was 42.4 degrees. The pressing pressure at which the clutch occurred was 0.090 mN, and the scratch resistance, including observation with an equipment camera, was poor.

[0115] Comparative Example 2 Using the random copolymer 1 precursor synthesized in Example 1, the compound described in Example 19 of JP 2022-159191 A, 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione, was used as a crosslinking agent. The crosslinking agent was added in an amount of 1 / 3 molar equivalent relative to the hydroxyl groups of the random copolymer 1 precursor to obtain a mixture. Using this mixture, comparative composition 2 with a solids concentration of approximately 5 wt% was prepared in the same manner as in Example 10. At this time, Adeka Arcles NCI-930 was not added to composition 6. Comparative composition 2 was applied to a glass substrate in the same manner as in Example 20, and the solvent was removed to obtain a film. At this time, the film was not exposed to light. The film thickness of the comparative example 2 sample was 1.61 μm, and the contact angle of hexadecane was 42.6 degrees. Furthermore, when the sample of Comparative Example 2 was subjected to a scratch test, the pressing pressure at which a clutch occurred was 0.098 mN, and the scratch resistance was poor, including observation using an apparatus.

[0116] Comparative Example 3 A random copolymer was obtained in the same manner as in Example 1, except that the types and amounts of monomers used in the polymerization of the random copolymer in Example 1 were changed to 0.5322 g (2.243 mmol) of 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, 0.4851 g (3.365 mmol) of 4-hydroxybutyl acrylate, and 0.4828 g (5.608 mmol) of methyl acrylate. The weight-average molecular weight of this random copolymer was 131,000, and the polydispersity (Mw / Mn) was 5.68.

[0117] Using this block copolymer, Comparative Composition 3 was prepared with a solids concentration of approximately 5 wt % in the same manner as in Example 10. Comparative Composition 3 was applied to a glass substrate in the same manner as in Example 20, and the solvent was then removed to obtain a film. The film thickness of the Comparative Example 3 sample was 1.58 μm, and the contact angle of hexadecane was 33.1 degrees. Furthermore, when the Comparative Example 3 sample was subjected to a scratch test, the indentation pressure at which a clutch occurred was 0.183 mN, demonstrating good scratch resistance. The results of the physical property measurements for Comparative Examples 1 to 3 are also shown in Table 3.

[0118] [Table 3] TIFF2026005203000013.tif83157

[0119] As is clear from the comparison between the examples of the present invention and the comparative examples, it is found that the membrane prepared by using the random copolymer of the present invention and crosslinking the random copolymer has high liquid repellency properties as well as high durability.

[0120] [Example 28] <Preparation of Composition 11, Fabrication of Measurement Articles, and Evaluation of Physical Properties> 0.0750 g of the random copolymer 1 of the present invention and 1.500 g of the urethane acrylate polymer UN-3320HA were dissolved in 16,000 g of toluene and 4,000 g of isopropanol. 0.0150 g of Omnirad 184 was added and dissolved to prepare Composition 11. Composition 11 was spin-coated onto a glass substrate in the same manner as in Example 20 above, followed by exposure. The film thickness of the prepared film sample was 0.68 μm. The contact angle of the film sample with hexadecane was 42.8 degrees.

[0121] A scratch test was carried out on the film sample prepared in the same manner as above. The result showed that the indentation pressure required to generate a scratch was 0.392 mN, and the scratch resistance was good, including observations using the device. [Industrial Applicability]

[0122] Articles such as membranes made using materials composed of compositions containing the random copolymers of the present invention have high liquid repellency, even though the materials contain no fluorine or have fluorine removed to the greatest extent possible. They also have excellent durability. The technology of the present invention contributes to reducing the environmental impact when imparting liquid repellency to, for example, various filters, clothing, leather, furniture, and film materials, and is therefore extremely useful industrially.

Claims

1. A random copolymer containing a structural unit represented by formula (1) and a structural unit having a functional group crosslinkable by light, wherein the molar ratio of the structural unit represented by formula (1) to the structural units constituting the entire random copolymer is 0.95 to 0.3, and the molar ratio of the structural unit having a functional group crosslinkable by light to the structural units constituting the entire random copolymer is 0.05 to 0.

5. (In the formula, X １ is —O— or —NH—, and R １０ is an alkylene or phenylene having 2 to 12 carbon atoms, and Y １ is a functional group capable of forming double or more hydrogen bonds between two adjacent structural units, and R １１ is a linear hydrocarbon group having 8 to 30 carbon atoms, a branched hydrocarbon group having 8 to 30 carbon atoms, or a cyclic hydrocarbon group having 8 to 30 carbon atoms, and these hydrocarbon groups may contain —O— or an unsaturated bond. １ Hydrogen on a carbon atom two or more away from may be replaced with fluorine.)

2. 2. The random copolymer according to claim 1, wherein the structural unit having a photocrosslinkable functional group has a structure represented by formula (2). (In the formula, X ２ is —O— or —NH—, and R ２０ is an alkylene or phenylene having 1 to 12 carbon atoms, and at least one —CH ２ - may be replaced by -O-, -COO-, or -NHCOO-, and Y ２ is a functional group that can be crosslinked by light, and R ２１ is hydrogen or methyl.)

3. X in the structural unit represented by formula (1) １ is —O—, and Y １ The random copolymer according to claim 1, wherein is -NHCONH-.

4. X in the structural unit represented by formula (1) according to claim 1 １ is —O—, and Y １ The random copolymer according to claim 2, wherein is -NHCONH-.

5. Y in the structural unit represented by formula (2) according to claim 2 ２ The random copolymer according to claim 4, wherein is (meth)acryloyloxy or epoxy.

6. A composition comprising the random copolymer according to any one of claims 1 to 5 and a solvent.

7. The composition of claim 6 further comprising a photoinitiator.

8. The composition of claim 6 comprising a precipitate of random copolymer associations.

9. The composition of claim 7 comprising a precipitate of random copolymer associations.

10. An article comprising a substrate coated with the composition according to claim 6 and a random copolymer crosslinked thereon.

11. An article comprising a substrate coated with the composition according to claim 7 and a random copolymer crosslinked thereon.

12. An article comprising a substrate coated with the composition according to claim 8 and a random copolymer crosslinked thereto.

13. An article comprising a substrate coated with the composition according to claim 9 and a random copolymer crosslinked thereto.

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