Block copolymer, composition, and article using same

Abstract

Provided is a feature capable of improving coating properties and adhesion to objects to be coated such as base substrates while having high water repellency, using a material that either does not contain fluorine therein or has excluded as much fluorine as possible. The present invention is a block copolymer, one of the blocks comprising structural units containing a structural unit represented by formula (1), and the presence ratio of the structural units constituting this block is a molar ratio of 0.05 to 0.7 with respect to the structural units constituting the entire block copolymer. (In the formula, X1 is -O- or -NH-, R1 is an alkylene or phenylene with 2 to 12 carbon atoms, Y1 is -NHCOO- or -NHCONH-, R2 is a linear, branched, or cyclic hydrocarbon group with 6 to 30 carbon atoms, and the hydrocarbon group may include -O- or an unsaturated bond. The hydrogen on a carbon two or more positions away from Y1 may be replaced with fluorine in this hydrocarbon group. R3 is hydrogen or methyl.)

Description

Block copolymers, compositions and articles using the same

[0001] The present invention relates to a block 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).

[0002] PFAS, which has been used in many applications as a water- and oil-repellent material, is now subject to stricter regulations in various countries as a substance 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 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] The liquid repellency of materials is evaluated in Patent Documents 1 and 2. However, in order to fully develop liquid repellency and prevent its deterioration, it is necessary to improve the solvent solubility of the material and the coatability and adhesion to the target object, such as a substrate, to which the liquid repellency is to be imparted.

[0004] Japanese Patent Application Laid-Open No. 2022-159191 Special Publication No. 2011-523432

[0005] "In-plane oriented highly ordered lamellar structure formation of poly(N-dodecylacrylamide) induced by humid annealing," RSC Advance, 2017, Vol. 7, p. 6631.

[0006] The present invention discloses a technology 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 the coatability and adhesion to the object to be coated, such as a substrate.

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

[0008] [1] A block copolymer, one of the blocks being a block composed of structural units containing a structural unit represented by formula (1), and the abundance ratio of the structural units constituting this block is, in molar ratio, 0.05 to 0.7 relative to the structural units constituting the entire block copolymer. (In the formula, X １ is —O— or —NH—, and R １ is an alkylene or phenylene having 2 to 12 carbon atoms, and Y １ is -NHCOO- or -NHCONH-, and R ２ is a linear hydrocarbon group having 6 to 30 carbon atoms, a branched hydrocarbon group having 6 to 30 carbon atoms, or a cyclic hydrocarbon group having 6 to 30 carbon atoms, which may contain —O— or an unsaturated bond, and in this hydrocarbon group, Y １ Hydrogen on carbon atoms two or more away from R may be replaced with fluorine, ３ is hydrogen or methyl.)

[0009] [2] R ３

[0023] [1] The block copolymer according to [1], wherein

[0010] [3] Y １ [3] The block copolymer according to [1] or [2], wherein

[0011] [4] R ２ [4] The block copolymer according to any one of [1] to [3], wherein

[0012] [5] The block copolymer according to any one of [1] to [4], which contains a block made of a (meth)acrylic acid ester as another block.

[0013] [6] A composition comprising the block copolymer according to any one of [1] to [5] and a solvent.

[0014] [7] The composition according to [6], which contains a precipitate of an association product of the block copolymer.

[0015] [8] An article obtained by applying the composition according to [6] or [7] to a substrate and removing the solvent.

[0016] According to the present invention, it is possible to provide a material that has a low environmental impact by containing as little fluorine as possible in the material, and that has high liquid repellency as well as excellent coatability and adhesion to objects to be coated such as substrates.

[0017] Figure 1 is a photograph of a film formed on a glass substrate using composition 1 of Example 42. The width of the photograph is approximately 1 μm. Figure 2 is a photograph of a film formed on a glass substrate using a composition containing a homopolymer of Comparative Example 1. The width of the photograph is approximately 1 μm.

[0018] 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 details. In addition, the embodiments of the present invention can be combined as appropriate.

[0019] The block copolymer of the present invention is characterized in that one of the blocks is a block composed of structural units containing a structural unit represented by formula (1). In the block copolymer, the block composed of structural units containing a structural unit represented by formula (1) exhibits liquid-repellent properties. From the viewpoints of liquid-repellent properties, coatability, and adhesion, the molar ratio of the structural units constituting the block relative to the structural units constituting the entire block copolymer is, on average, 0.05 to 0.7, preferably 0.1 to 0.5, and more preferably 0.1 to 0.4.

[0020] (In the formula, X １ is —O— or —NH—, and R １ is an alkylene or phenylene having 2 to 12 carbon atoms, and Y １ is -NHCOO- or -NHCONH-, and R ２is a linear hydrocarbon group having 6 to 30 carbon atoms, a branched hydrocarbon group having 6 to 30 carbon atoms, or a cyclic hydrocarbon group having 6 to 30 carbon atoms, which may contain —O— or an unsaturated bond, and in this hydrocarbon group, Y １ Hydrogen on carbon atoms two or more away from R may be replaced with fluorine, ３ is hydrogen or methyl.)

[0021] In the constitutional unit represented by formula (1), R ３ is preferably hydrogen. For the same reason, Y １ is preferably —NHCONH—.

[0022] R ２ is a straight-chain hydrocarbon group having 6 to 30 carbon atoms, a branched hydrocarbon group having 6 to 30 carbon atoms, or a cyclic hydrocarbon group having 6 to 30 carbon atoms, and this hydrocarbon group may contain -O- or an unsaturated bond. In this case, in order to exhibit liquid-repellent properties, it is preferable that the hydrocarbon group contains a straight-chain alkyl group having 6 or more carbon atoms. In selecting the hydrocarbon group, when water or hydrocarbon compounds are to be repelled, R ２ It is preferable that the hydrocarbon group contains a linear alkyl group having 12 or more carbon atoms. When the hydrocarbon group contains —O—, it is preferable that the oxygen atoms are not adjacent to each other in CH ３ -O-O-CH ２ -, rather than oxygen and oxygen are not adjacent ３ -O-CH ２ --O-- is preferred.

[0023] In order to obtain the desired liquid repellency, R ２ The hydrogen on the carbon of the hydrocarbon group may be replaced by fluorine. 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, Y １ Preferably, the hydrogen on the carbon atom further away from Y is replaced. １ Most preferably, the hydrogen on the terminal carbon opposite to is replaced.

[0024] Suitable examples of the constitutional unit represented by formula (1) include structures represented by the following formulas (1-1) to (1-29).

[0025]

[0026]

[0027]

[0028] A block (hereinafter, sometimes referred to as block (A)) composed of a structural unit containing a structural unit represented by formula (1) may be composed of multiple types of structural units represented by formula (1) in order to obtain the desired liquid repellency. In this case, in order to improve the liquid repellency and reduce the environmental load, R ２ Either alkyl or alkyl containing no fluorine may be selected.

[0029] A block composed of structural units containing a structural unit represented by formula (1) may contain a small amount of structural units other than those represented by formula (1). In this case, the ratio of the number of structural units other than those represented by formula (1) to the total number of structural units of block (A) is preferably 0.2 or less on average. In order to maintain liquid repellency, this ratio is more preferably 0.15 or less, and even more preferably 0.1 or less. A preferred lower limit for the ratio of the number of structural units is 0.01, a more preferred lower limit is 0.001, and an even more preferred lower limit is 0. In addition, in order to facilitate production of the block copolymer of the present invention, the structural units other than those represented by formula (1) are preferably structural units derived from a precursor structure before the structural unit represented by formula (1) is obtained, and specifically, structural units having a structure represented by the following formula (1-p): (In the formula, X １ is —O— or —NH—, and R １ is alkylene or phenylene having 2 to 12 carbon atoms, and R ３ is hydrogen or methyl, and Y ｐ is —NCO or protected —NCO.

[0030] In the block copolymer of the present invention, there are no limitations on the structure of the blocks other than block (A). That is, there are no limitations on the structure of the blocks other than the block consisting of structural units containing the structural unit represented by formula (1) (hereinafter, sometimes referred to as block (B)). A block copolymer in which one block consists of structural units containing the structural unit represented by formula (1) may be an AB diblock copolymer consisting of block (A) and block (B), or an ABA triblock copolymer consisting of block (A), block (B), and block (A). In this case, an AB diblock copolymer is preferred in order to obtain the desired properties and to easily produce the block copolymer at the same time.

[0031] In the block copolymer of the present invention, there is no limitation on the selection of the block other than the block consisting of structural units containing the structural unit represented by formula (1), i.e., block (B). However, in order to exhibit liquid repellency in the block copolymer of the present invention, it is preferable to select a block (B) that satisfies the following relationship, where A' is a polymer consisting only of structural units represented by formula (1) that constitutes block (A), and B' is a polymer consisting only of structural units other than those represented by formula (1) that constitutes the other block (B): surface tension of A' > surface tension of B'

[0032] In the block copolymer of the present invention, the block (B) is involved in solvent solubility, coatability, and adhesion to a coating target such as a substrate. To impart these properties, it is preferable to select a structural unit represented by the following formula (2) as the structural unit constituting the block (B): (In formula (2), R ３ is hydrogen or methyl, and R １０ is a group selected from the structures represented by the following formulas (20) to (23), pyridyl, or —CN.

[0033] In formulas (20) to (23), X １１ is —O—, —NH—, or —NR １１ - and R １１is hydrogen, linear alkyl having 1 to 8 carbon atoms, branched alkyl having 3 to 8 carbon atoms, cyclic alkyl having 3 to 8 carbon atoms, or phenyl, and the alkyl is not adjacent to —CH ２ - is -O-, -NMe-, or -NMe ２ ＋ - may be replaced by alkyl -CH ２ - may be replaced by -CO-, and hydrogens on non-adjacent carbons of an alkyl may be replaced by -OH or -N(CH ３ ) ２ and alkyl may be replaced by —CH ３ Ha-CO ２ H, -CO ２ － , -SO ３ － , or -SO ３ may be replaced by K, and R １２ -H, -CH ３ , -OCH ３ , —OH, —CO ２ H, -OCOCH ３ , -N(CH ３ ) ２ , or -SO ３ Na, Me is methyl, and * represents the binding site.

[0034] In order to improve the solvent solubility and coating property of the block copolymer of the present invention, X in formula (20) １１ as —O— or —NR １１ -, R １１ For the same purpose, it is preferable to select a short-chain linear alkyl having about 1 to 4 carbon atoms as R in formula (20). １１ In order to improve the adhesion of the block copolymer of the present invention to a coating object such as a substrate, it is preferable to select hydrogen, methyl, or methoxy as X in formula (20). １１ As the R １１ as -CH ２ It is preferable to select an alkyl in which - is replaced by -CO- and an alkyl in which hydrogen on a non-adjacent carbon is replaced by -OH. For the same purpose, R １２ It is preferable to select —OH as the group.

[0035] In order to improve solvent solubility, coatability, and adhesion, the block copolymer of the present invention contains, as the structural units constituting the block (B), a structural unit represented by formula (2) and a structural unit represented by formula (3) １０ It is more preferable to select from a plurality of structural units selected from a combination of groups having a structure represented by formula (20).

[0036] The block copolymer of the present invention can be produced by a known method. In this case, the structural unit represented by formula (1) can be derived from a (meth)acrylic monomer having —NCO or a protected —NCO group as its precursor. Examples of such monomers 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. In the following, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyloxy" means acryloyloxy or methacryloyloxy.

[0037] A method of producing the block copolymer of the present invention is preferred because of its ease of production. A precursor is obtained by block copolymerization using the above-described (meth)acrylic monomer having —NCO or a protected —NCO, followed by conversion to the structure represented by formula (1). In this case, it is preferable to use a (meth)acrylic monomer having a protected —NCO as a raw material to avoid gelation during polymerization. For block copolymerization, known methods such as ATRP (atom transfer radical polymerization) polymerization, NMP (nitroxide-mediated radical polymerization) polymerization, and RAFT (reversible addition-fragmentation chain transfer) polymerization can be used. Examples of such known techniques include those described in "Precise Radical Polymerization Guidebook" (Merck), "Organic Chemistry Information," Vol. 56, 2016 (Fujifilm Wako Pure Chemical Industries, Ltd.), and "Radical Polymerization Handbook," NTS Publishing, 2010. The method of producing the block copolymer of the present invention is also described in detail in the following examples.

[0038] As the monomer that provides the block (B) in the block copolymer of the present invention, known (meth)acrylic acid derivatives 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] Known styrene derivatives can be used as the monomer that provides block (B) in the block copolymer of the present invention, including styrene, α-methylstyrene, styrenes 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] As the monomer that provides the block (B) in the block copolymer of the present invention, acrylonitrile, vinylpyridine, N-vinylpyrrolidinone, and 1-vinylimidazole can also be suitably used.

[0041] In order to improve coatability and adhesion to substrates and other objects to be coated while maintaining liquid repellency, it is preferable to select, as the monomer that provides block (B), methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, 3-(tris(trimethylsilyloxy)silyl)propyl (meth)acrylate, (meth)acrylic acid, (meth)acrylamide, N-(hydroxymethyl)acrylamide, styrene, or α-methylstyrene. In order to obtain the desired properties, these monomers may be used alone or in combination of two or more.

[0042] In block copolymerization using these monomers, there are no limitations on the polymerization initiator, radical stabilizer (polymerization inhibitor), solvent, etc., and the conditions for the above-mentioned known precision polymerization method can be used. The polymerization initiator may be a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, depending on the polymerization method for 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, which is commercially available from various companies, as well as products manufactured by Tokyo Chemical Industry Co., Ltd. under the trade name "Dicumyl Peroxide," and products manufactured by NOF Corporation under the trade names "Percumyl D, Niper BMT, and Perhexa 25Z." Examples of azo polymerization initiators include AIBN, which is commercially available from various companies, as well as products manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. under the trade names "V-40, V-50, V-59, V-65, V-70, V-501, and V-601." In general, 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".

[0043] There are no particular limitations on the average molecular weight or its dispersion of the block copolymer of the present invention in order to obtain the desired properties. However, in order to improve liquid repellency and prevent its deterioration over time, the weight-average molecular weight (Mw) of the block 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 block 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. The dispersion of the average molecular weight, for example, Mw / Mn, the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), generally approaches 1 when the above-mentioned precision polymerization is carried out. Polymerization under conditions that result in a value approaching 1 results in a well-defined block copolymer. However, the block copolymer of the present invention tends to have an increased Mw / Mn due to the strong interaction between polymer chains. Therefore, from the viewpoint of block copolymer quality, Mw / Mn is preferably 1 to 10, more preferably 1 to 5.

[0044] The block copolymer of the present invention may be produced, for example, by separately producing a homopolymer comprising the structural unit represented by formula (1) and another homopolymer and then linking them together. Examples of such a production method include those described in Radical Polymerization Handbook, NTS Publishing, 2010, etc.

[0045] The conversion of the precursor block copolymer into the structure represented by formula (1) can also be carried out according to a known method. １ In the case of a block copolymer in which -NHCONH-, -NH ２ It can be obtained by reacting a commercially available or known compound having the formula: ２Examples of commercially available or known compounds having the formula include alkylamines having 6 or more carbon atoms and aniline derivatives substituted with alkyl or alkoxy. ２ The amount of the compound having the formula (I) is 0.8 or more in terms of molar ratio to the —NCO equivalent in the block copolymer. ２ Since compounds having the formula (I) react quantitatively with the —NCO equivalent, this range is in accordance with the technology of the present invention. ２ In order to facilitate purification of the block copolymer, the upper limit of the amount of the compound having the above molar ratio is preferably 2.0 or less, more preferably 1.5 or less, and most preferably 1.2 or less. In the above calculation, the molar ratio of -NCO equivalents in the block copolymer can be calculated from the amount of block copolymer used, the ratio of blocks present in the block copolymer, and the molecular weight of the structural unit containing the -NCO equivalent. The ratio of blocks present in the block copolymer can be calculated from the amount of block copolymer used, the ratio of blocks present in the block copolymer, and the molecular weight of the structural unit containing the -NCO equivalent, as described below. １ It can be determined by measurements such as H-NMR.

[0046] Y in formula (1) １ In the case of a block copolymer in which -NHCOO- is used, it can be obtained by reacting a commercially available or known compound having -OH with a precursor block copolymer. The reactivity of a compound having -OH with an -NCO equivalent is as follows: ２Since the reactivity is low relative to compounds having an -OH group, the amount of these compounds having an -OH group added during the reaction is preferably 1.0 or more in molar ratio relative to the -NCO equivalent in the block copolymer. Similarly, the upper limit of the amount of compounds having an -OH group used is preferably 3.0 or less in molar ratio, and most preferably 2.0 or less, in order to facilitate purification of the block copolymer. To improve the reaction rate, it is preferable to add a urethanization catalyst to the reaction solution. Examples of urethanization catalysts include dibutyltin dilaurate. To improve reactivity, the amount of the urethanization catalyst added is preferably 0.1 wt % or more, and more preferably 0.5 wt % or more, relative to the weight of the block copolymer. Furthermore, to facilitate purification of the block copolymer, it is preferably 2 wt % or less, and more preferably 1 wt % or less, relative to the weight of the block copolymer.

[0047] The reaction temperature for the conversion to the structure represented by the above formula (1) is １ In the case of a block copolymer where Y 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 block 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 block copolymer, 2 hours or less is preferred. One hour is the most preferred reaction time. １ In the case of a block copolymer in which the group is -NHCOO-, a reaction temperature of 100°C or higher is preferred to rapidly proceed with the reaction. Also, a temperature of 140°C or lower is preferred to prevent decomposition of the block copolymer. 120°C is the most preferred reaction temperature. At 120°C, the reaction time is preferably 1 hour or more to ensure a sufficient conversion rate, and 8 hours or less to prevent decomposition of the block copolymer. 4 hours is the most preferred reaction time.

[0048] As the solvent for the conversion to the structure represented by formula (1), a solvent that has no or low reactivity with the precursor block copolymer can be used. In this case, a solvent that dissolves both the precursor block copolymer and the block 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.

[0049] The composition of the present invention containing the block copolymer of the present invention comprises the block copolymer of the present invention, a solvent, and additives added as needed. The solvent is not limited and can be appropriately selected from known solvents. In this case, a mixed solvent is also preferred to maintain the solubility of the block copolymer of the present invention and improve its coatability to substrates and other objects. In addition to the hydrocarbon solvents, ester solvents, and ether solvents described above, alcohol solvents can also be suitably used as such solvents. In addition to the above-mentioned solvents, examples of 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.

[0050] The composition of the present invention may contain additives such as crosslinkers, surfactants, emulsifiers, coupling agents, antioxidants, radical stabilizers (polymerization inhibitors), antistatic agents, and hydrolysis stabilizers.

[0051] Adding a crosslinking agent to the composition of the present invention can prevent mechanical deterioration and degradation over time of the coating film. Known low-molecular-weight or high-molecular-weight compounds can be used as such additives. In this case, it is preferable to select a material in which a structural unit represented by formula (1-p) is introduced into block (A) of the block copolymer of the present invention, and to use a compound having multiple functional groups such as amine, alcohol, and thiol as the crosslinking agent. Suitable examples of such crosslinking agents include various alkylene diamines, polyamines, diaminobenzenes, polyols, alkylenedithiols, and polythiol compounds. Among these crosslinking agents, various alkylene diamines, polyamines, and diaminobenzenes are more preferred because the crosslinking reaction proceeds rapidly. The amino groups of such amine compounds may be protected with a group that is cleaved by heat, such as t-butoxycarbonyl.

[0052] Other crosslinking agents include polyfunctional isocyanate compounds. Examples include toluene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate. In this case, the -NCO group of the polyfunctional isocyanate compound may be protected. In order to crosslink with these polyfunctional isocyanate compounds, it is preferable to use a polymer into which a functional group such as a phenol or alcohol has been introduced as the block copolymer of the present invention.

[0053] The amount of the crosslinking agent is preferably 30% by weight or less, more preferably 1 to 20% by weight, and most preferably 2 to 10% by weight, based on the weight of the block copolymer of the present invention, in order to suppress deterioration of liquid repellency and obtain the desired effect.

[0054] The surfactant is used to improve the wettability, leveling property, and coating property of the substrate. 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.). Examples of leveling agents that can be used include commercially available silicone surface conditioners such as BYK-UV3500 and BYK-UV-3570 (all trade names: manufactured by BYK Japan Co., Ltd.), and TEGO. Examples of such polyolefin copolymers 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% by weight, more preferably 0.05 to 1% by weight, based on the weight of the block copolymer of the present invention.

[0055] The composition of the present invention may contain a coupling agent to improve adhesion to substrates and other objects to be coated. 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 wt %, more preferably 0.5 to 1 wt %, based on the weight of the block copolymer of the present invention.

[0056] There is no limitation on the antioxidant that can be used in the present invention, and examples thereof include 3,5-di(t-butyl)-4-hydroxytoluene (BHT), hydroquinone, methylene blue, diphenylpicric hydrazide (DPPH), phenothiazine, nitroso compounds such as 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 sold by ADEKA Corporation, Sumilizer BHT, Sumilizer BBM-S, and Sumilizer GA-80 sold by Sumitomo Chemical Co., Ltd., and Irganox 1076, Irganox 1010, Irganox 3114, and Irganox 245 (all trade names) sold by BASF Japan Ltd. These antioxidants may be used alone or in combination of two or more. These antioxidants may also be commercially available products.

[0057] 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" is a trade name manufactured by BASF Japan Ltd., and "Adekastab" 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.

[0058] 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, trade name: Cyasorb UV-3346 manufactured by Cytec Corporation, and trade name: Goodlight UV-3034 manufactured by Goodrich Corporation. "Chimassorb" 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.

[0059] The amount of each of these antioxidants, ultraviolet absorbers, and light stabilizers added to the composition is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, based on the weight of the block copolymer of the present invention.

[0060] It is also suitable to add a hydrolysis stabilizer to the composition of the present invention for the purpose of suppressing hydrolysis of the polyacrylic acid ester, etc., and preventing 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.

[0061] 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 block copolymer forms spherical aggregates in an appropriate solution. By utilizing these spherical aggregates, controlled irregularities can be created. In the block copolymer of the present invention, Y in formula (1) １ A block copolymer in which is —NHCONH— is preferred from the viewpoint of forming the association.

[0062] 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.

[0063] The article of the present invention, the surface of which is coated with the composition of the present invention, can be obtained by applying the composition to a substrate and then removing the solvent. Examples of the coating method include a coating method using a dispenser, spin coating, roll coating, caten coating, flow coating, printing, microgravure coating, gravure coating, wire bar coating, dip coating, spray coating, meniscus coating, and inkjet coating.

[0064] The method for removing the solvent is not particularly limited, but heat treatment is preferred. There are no particular limitations on the temperature conditions, but when applying to a substrate with low heat resistance such as fiber or paper, sufficiently good liquid repellency can be achieved under mild conditions of about 130°C.

[0065] The composition of the present invention exhibits little deterioration over time in terms of liquid repellency and has high durability against heat, etc. On the other hand, if it is desired to further improve the durability of liquid repellency, it is also preferable to subject the substrate to a treatment in advance that will promote adhesion of the composition of the present invention. Such treatments include UV ashing using ozone and plasma treatment. Also preferred is a method in which an adhesive or crosslinking agent is applied to the substrate.

[0066] 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 then 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 a functional group capable of reacting with the above-mentioned crosslinking agent in order to improve durability.

[0067] 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 having isocyanate groups 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.

[0068] Treatment of a textile product 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.

[0069] 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.

[0070] 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.

[0071] <Measurement of polymer weight average molecular weight (Mw) and polydispersity (Mw / Mn)> Analysis was performed by GPC measurement. A high performance liquid chromatograph system manufactured by Shimadzu Corporation was used as the instrument. Two PLgel 5 μm MIXED-D2 columns manufactured by Agilent Technologies, Inc., connected in series, were used, and THF was used as the solvent. STANDARD SM-105 manufactured by Resonac Inc. was used as the standard reagent (standard polystyrene) for the average molecular weight.

[0072] <Confirmation of Block Ratio of Block Copolymer and Confirmation of Polymer Structure> Nuclear magnetic resonance spectrum (500 MHz) manufactured by JASCO Corporation １ The measurement solvent was CDCl ３ was used, and tetramethylsilane was used as the standard substance.

[0073] <Film Observation and Film Thickness Measurement> The state of the prepared film was visually observed and confirmed using a step gauge KLA Tencor P+16 (manufactured by KLA Tencor Corporation). The film thickness was measured by scraping a portion of the film with a cutter and measuring the step using the above-mentioned step gauge. The film thickness value was calculated by averaging five measurements taken at different locations.

[0074] <Surface tension measurement> Measurement was performed using a contact angle meter (PCA-1) manufactured by Kyowa Interface Science Co., Ltd. The value was taken as an average value of five measurement points. The measurement was performed at room temperature.

[0075] <Monomers, polymerization initiators, RAFT reagents, alkylamines, alcohols, crosslinking agents, other reagents, urethanization catalysts, and solvents> The following commercially available products were used. Monomers: 2-isocyanatoethyl acrylate, methyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, n-dodecyl acrylate (all manufactured by Tokyo Chemical Industry Co., Ltd.) Thermal radical polymerization initiator: 2,2'-azobis(2-methylpropionate)dimethyl (V-601, trade name of Fujifilm Wako Pure Chemical Industries, Ltd.) RAFT reagent: 4-cyano-4-[[(dodecylthio)carbonothioyl]thio]pentanoic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Alkylamine: n-octylamine, n-dodecylamine, n-hexadecylamine (all manufactured by Tokyo Chemical Industry Co., Ltd.) Alcohol: n-octanol, n-dodecanol, n-hexadecanol (all manufactured by Tokyo Chemical Industry Co., Ltd.) Crosslinking agent: 1,6-diaminohexane, hexamethylene diisocyanate (all manufactured by Tokyo Chemical Industry Co., Ltd.) Other reagents: n-hexadecane (manufactured by Tokyo Chemical Industry Co., Ltd.) Urethane catalyst: dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.), Orgatix (registered trademark) ZC-150 (trade name of Matsumoto Fine Chemical Co., Ltd.) Solvent: anisole, toluene, isopropanol (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0076] 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.

[0077] <Substrate> Glass substrate: Eagle XG (registered trademark) (trade name, manufactured by Corning Corporation, 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. Filter paper: Qualitative filter paper (No. 2, ADVANTEC (registered trademark)) (trade name, manufactured by Toyo Roshi Kaisha, Ltd.) was used as is. Nonwoven fabric: Spunbond Eltas (registered trademark) (trade name, manufactured by Asahi Kasei Corporation, basis weight 30 g) was purchased and used as is.

[0078] [Example 1] Block copolymer 1 (X of formula (1) １ Ga-O-, R １ is ethylene, Y １ -NHCONH-,R ２ is n-C ８ H １７ -, R ３ Synthesis of a block copolymer consisting of a block containing a structural unit where is hydrogen, and another block is polymethyl acrylate

[0079] Into a Schlenk flask were placed 1.2238 g (5.158 mmol) of 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, which is a monomer that provides a structural unit represented by formula (1-p), which is a structure derived from a precursor prior to obtaining the structural unit represented by formula (1), 5.9 mg (0.026 mmol) of V-601, 13.4 mg (0.0331 mmol) of 4-cyano-4-[[(dodecylthio)carbonothioyl]thio]pentanoic acid, and 3.1 g of anisole, and the mixture was subjected to freeze-degassing three times using a vacuum pump. ２ The reaction was initiated in an oil bath at 75°C under atmospheric pressure. After 45 minutes of reaction, a solution of methyl acrylate in anisole (methyl acrylate: 1.89 ml (20.63 mmol), anisole: 1.9 g), which had been frozen and degassed in the same manner as above, was added to the reaction solution using a syringe. The polymer sampled in the reaction solution at this time had an Mw of 9,500 and an Mw / Mn of 1.31. The temperature of the oil bath was then raised to 80°C, and the reaction was carried out for approximately 4 hours. The reaction solution was cooled to room temperature and used as is for the urea or urethane conversion reaction. １From H-NMR measurement, the block abundance ratio (r, molar ratio, see the formula below) of the structural unit represented by formula (1-p) in the sample was 0.2. The polymerization rate of methyl acrylate was 90%. １ The content was determined from the ratio of methyl acrylate monomer to polymer using H-NMR.

[0080] r = A / (A+B) A: derived from the structural unit represented by formula (1-p) １ Abundance ratio calculated from the integral value of H B: Polymethyl acrylate (block B) １ The above-mentioned block abundance ratio (r, molar ratio) corresponds to the abundance ratio (molar ratio) of the structural units constituting the block composed of structural units including the structural unit represented by formula (1) relative to the structural units constituting the entire block copolymer of the present invention.

[0081] 2 g of the reaction solution was weighed out, and 0.098 g (0.76 mmol) of n-octylamine was added thereto, followed by a reaction in anisole (10 ml) at 100°C for 2 hours. After the reaction solution was cooled to room temperature, it was reprecipitated in heptane and stirred for 1 hour. The resulting precipitate was filtered by suction, added to acetonitrile, stirred for 1 hour, and then filtered. The resulting polymer powder was vacuum dried at room temperature for 8 hours. １ From H-NMR measurement, the conversion rate of protected NCO moieties to urea (α, see the following formula) was approximately 1. The Mw of the synthesized block copolymer 1 was 53,600, and the Mw / Mn was 2.26.

[0082] α = BCP / (BCP + Pre) BCP; derived from the conversion site １ Pre: Abundance ratio determined from the integral value of H １ Abundance ratio calculated from the integral value of H

[0083] [Examples 2] to [Examples 8] Block copolymers 2 to 8 were produced in the same manner as in Example 1 above, except for changing the type and amount of alkylamine added. That is, instead of n-octylamine, n-dodecylamine was used in Examples 2, 4, 5, and 7, n-hexadecylamine in Examples 3 and 8, and n-octadecylamine in Example 6, and the amounts added were changed to match the chemical equivalents. The results are shown in Table 1. Note that Example 1 is also listed in Table 1. In Table 1, the numbers in the Example / Copolymer column represent both the example number and the block copolymer number.

[0084] [Table 1] X in formula (1) １ Ga-O-, R １ is ethylene, Y １ -NHCONH-,R ３ A block copolymer comprising a block of structural units containing a structural unit in which is hydrogen, and another block of which is polymethyl acrylate.

[0085] [Example 9] Block copolymer 9 (X of formula (1) １ Ga-O-, R １ is ethylene, Y １ -NHCONH-,R ２ is n-C ８ H １７ -, R ３ Synthesis of a block copolymer in which a block is composed of structural units containing a structural unit in which is hydrogen, and another block is composed of structural units of methyl acrylate and 2-hydroxyethyl acrylate

[0086] Block copolymer 9 was obtained in the same manner as in Example 1, except that a mixture of methyl acrylate and 2-hydroxyethyl acrylate (methyl acrylate; 1.32 ml (14.44 mmol) and 2-hydroxyethyl acrylate 0.65 ml (6.19 mmol)) was used instead of methyl acrylate. The synthesized block copolymer 9 had an Mw of 51,700, an Mw / Mn of 1.81, an r of 0.2, and an α of 1.

[0087] [Example 10] to [Example 12] Block copolymers 10 to 12 were produced in the same manner as in Example 9 above, except for changing the type and amount of alkylamine added. That is, instead of n-octylamine, n-dodecylamine was used in Example 10, n-hexadecylamine in Example 11, and n-octadecylamine in Example 12, and the amounts added were adjusted to match the chemical equivalents. The results are shown in Table 2. Note that Example 9 is also listed in Table 2. In Table 2, the numbers in the Example / Copolymer column represent both the example number and the block copolymer number.

[0088] [Table 2] X in formula (1) １ Ga-O-, R １ is ethylene, Y １ -NHCONH-,R ３ is hydrogen, and another block is a block consisting of structural units of methyl acrylate and 2-hydroxyethyl acrylate.

[0089] [Example 13] Block copolymer 13 (X of formula (1) １ Ga-O-, R １ is ethylene, Y １ -NHCONH-,R ２ is n-C １８ H ３７ -, R ３ Synthesis of a block copolymer in which a block is composed of structural units containing a structural unit in which is hydrogen, and another block is composed of structural units of methyl acrylate and 4-hydroxybutyl acrylate

[0090] Block copolymer 13 was obtained in the same manner as in Example 1, except that a mixture of methyl acrylate and 4-hydroxybutyl acrylate (methyl acrylate; 1.48 ml (16.50 mmol) and 4-hydroxybutyl acrylate 0.57 ml (4.13 mmol)) was used instead of methyl acrylate. The synthesized block copolymer 13 had an Mw of 79,600, an Mw / Mn of 2.21, an r of 0.2, and an α of 1.

[0091] [Example 14] Block copolymer 14 (X of formula (1) １ Ga-O-, R １ is ethylene, Y １ -NHCONH-,R ２ is n-C １８ H ３７ -, R ３ Synthesis of a block copolymer in which a block is composed of structural units containing a structural unit in which is hydrogen, and another block is composed of structural units of methyl acrylate and n-dodecyl acrylate

[0092] Block copolymer 14 was obtained in the same manner as in Example 1, except that a mixture of methyl acrylate and n-dodecyl acrylate (methyl acrylate; 1.32 ml (10.32 mmol) and n-dodecyl acrylate 2.82 ml (10.32 mmol)) was used instead of methyl acrylate. The synthesized block copolymer 14 had an Mw of 76,900, an Mw / Mn of 1.93, an r of 0.2, and an α of 1.

[0093] [Example 15] Block copolymer 15 (X of formula (1) １ Ga-O-, R １ is ethylene, Y １ -NHCONH-,R ２ is n-C ８ H １７ -, R ３ Synthesis of a block copolymer consisting of a structural unit containing a structural unit where is hydrogen, and another block is polymethyl methacrylate

[0094] Block copolymer 13 was obtained in the same manner as in Example 1, except that 2.20 ml (20.7 mmol) of methyl methacrylate was used instead of methyl acrylate. The synthesized block copolymer 15 had an Mw of 49,200, an Mw / Mn of 1.98, an r of 0.48, and an α of 1.

[0095] [Example 16] and [Example 17] Block copolymers 16 and 17 were produced in the same manner as in Example 15 above, except that the type and amount of alkylamine added were changed. That is, n-dodecylamine was used in Example 16 and n-hexadecylamine was used in Example 17 instead of n-octylamine, and the amounts added were adjusted to match the chemical equivalents. The results are shown in Table 3. Table 3 also lists Example 13. In Table 3, the numbers in the Example / Copolymer column represent both the example number and the block copolymer number.

[0096] [Table 3] X in formula (1) １ Ga-O-, R １ is ethylene, Y １ -NHCONH-,R ３ is hydrogen, and the other block is polymethyl methacrylate.

[0097] [Example 18] Block copolymer 18 (X of formula (1) １ Ga-O-, R １ is ethylene, Y １ -NHCOO-, R ２ is n-C ８ H １７ -, R ３ Synthesis of a block copolymer consisting of a block containing a structural unit where is hydrogen, and another block is polymethyl acrylate

[0098] This was obtained by functional group conversion using the precursor block copolymer synthesized according to Example 1. Specifically, 2 g of the precursor block copolymer reaction solution was weighed out, and 0.16 g (1.2 mmol) of n-octanol and 7.5 mg (0.012 mmol) of dibutyltin dilaurate were added, followed by a reaction in anisole (5 ml) at 120°C for 8 hours. After cooling the reaction solution to room temperature, it was reprecipitated in heptane and stirred for 1 hour. The resulting precipitate was filtered by suction, added to acetonitrile, stirred for 1 hour, and then filtered. The resulting polymer powder was vacuum dried at room temperature for 8 hours. １From H-NMR measurement, the conversion rate (α) of the protected NCO moieties to urethane was about 0.8. The Mw of the synthesized block copolymer 18 was 48,500, and the Mw / Mn was 1.85.

[0099] [Example 19] and [Example 20] Block copolymers 19 and 20 were produced in the same manner as in Example 18, except for changing the type and amount of alcohol added. That is, instead of n-octanol, n-dodecanol was used in Example 19, and n-hexadecanol was used in Example 20, and the amounts added were changed to match the chemical equivalents. The results are shown in Table 4. Table 4 also lists Example 18. In Table 4, the numbers in the Example / Copolymer column represent both the example number and the block copolymer number.

[0100] [Table 4] X in formula (1) １ Ga-O-, R １ is ethylene, Y １ -NHCOO-, R ３ A block copolymer comprising a block of structural units containing a structural unit in which is hydrogen, and another block of which is polymethyl acrylate.

[0101] Example 21 Block Copolymer 21 (X in Formula (1) １ Ga-O-, R １ is ethylene, Y １ -NHCONH-,R ２ is n-C １８ H ３７ -, R ３ Synthesis of a block copolymer consisting of a block containing a structural unit where r is hydrogen and the other block is polystyrene

[0102] Block copolymer 21 was obtained in the same manner as in Example 1, except that 2.36 ml (20.6 mmol) of styrene was used instead of methyl acrylate. The synthesized block copolymer 21 had an Mw of 46,700, an Mw / Mn of 2.37, an r of 0.7, and an α of 1.

[0103] [Example 22] Preparation of Composition 1 0.25 g of the block copolymer 1 obtained in Example 1 was dispensed into a sample bottle, and 1.50 g of toluene was added and heated to dissolve. 0.75 g of isopropanol was added to this solution to obtain Composition 1, a polymer solution with a concentration of 10 wt%.

[0104] [Example 23] to [Example 41] Preparation of Compositions 2 to 21 Using the block copolymers synthesized in the above examples, compositions 2 to 21, which were polymer solutions with a concentration of approximately 10 wt%, were prepared in the same manner as in Example 22 (Table 5). In this case, after preparing the polymer solution, each compound of the crosslinker and urethanization catalyst was added to the composition in the amount shown in Table 5. The addition was carried out at room temperature. Table 5 also lists Example 22.

[0105] Table 5. Prepared compositions

[0106] Example 42: Preparation of Measurement Article 1 and Contact Angle Measurement Composition 1 was spin-coated onto a glass substrate as a substrate. The rotation speed of the glass substrate was 1000 rpm. The glass substrate was heated on a hot plate at 120°C for 15 minutes to remove the solvent, yielding a film made of the block copolymer of the present invention. The film sample had no holes due to coating omissions, was in a clean state, and exhibited excellent coatability and adhesion to the glass substrate as a substrate. A photograph of the film formed on the glass substrate, observed with a step gauge, is shown in Figure 1. The film thickness of the sample was 1.61 μm. The contact angle of hexadecane for the sample was 38.5 degrees. In this way, an article of the present invention was prepared by applying a composition containing the block copolymer of the present invention and a solvent to a glass substrate as a substrate, and then removing the solvent. The contact angle was measured using this measurement article.

[0107] [Example 43] to [Example 61] Film samples were prepared on glass substrates in the same manner as in Example 42, except that composition 1 was replaced with the compositions shown in the table below. The results of the physical property measurements are shown in the table below. Table 5 relists the results of Example 42. As with Example 42, the film samples of Examples 43 to 61 were free of holes due to coating omissions, and were in a clean film state, with excellent coatability and adhesion to the glass substrate as a base material.

[0108] [Table 6] Fabricated articles and contact angle measurements

[0109] Comparative Example 1 In the same manner as in Synthesis Example 1 of JP-A-2022-159191, X in formula (1) １ O, R １ is ethylene, Y １ -NHCONH-,R ２ is n-C １２ H ２５ , R ３ A polymer (homopolymer) consisting only of hydrogen structural units was obtained. This polymer was prepared into a polymer solution (homopolymer composition) in the same manner as in Example 22. This composition was then applied to a glass substrate in the same manner as in Example 42, and the solvent was then removed to obtain a film. Observation of this film sample revealed the presence of holes approximately 100 μm in diameter that reached the glass substrate due to coating omissions, as well as smaller, shallower holes, indicating poor coatability and adhesion to the glass substrate. A photograph of the film formed on the glass substrate is shown in Figure 2. The film thickness of this sample was 1.81 μm. The contact angle of this sample with hexadecane was 43.4 degrees.

[0110] Comparative Example 2 A monomer mixture of 2-(3-n-dodecylureido)ethyl acrylate and methyl acrylate in a molar ratio of 2:8 was used instead of the monomer of 2-(3-n-dodecylureido)ethyl acrylate alone, and the compound X in formula (1) was prepared in the same manner as in Comparative Example 1. １ O, R １ is ethylene, Y １ NHCONH, R ２ is n-C １２ H ２５ , and R in formula (2) ３ H, R １０ is the formula (20), X １１ O, R １１ is CH ３A random copolymer (random copolymer) of the formula (I) was obtained. The polymer was prepared into a polymer solution (random copolymer composition) in the same manner as in Example 22. The composition was applied to a glass substrate in the same manner as in Example 42. Observation of this film sample revealed that, as in Figure 1 of Example 42, there were no holes due to coating omissions, and the film was in a clean state. The film thickness of the sample was 2.27 μm. On the other hand, the contact angle of hexadecane on this sample was 34.1 degrees, indicating poor liquid repellency.

[0111] [Example 62] Preparation of measurement article 2 and contact angle measurement When composition 6 obtained in Example 47 was left overnight at room temperature, precipitation of block copolymer associations occurred. The composition containing this precipitation was dropped onto a glass substrate as a substrate and left at room temperature for 1 hour, resulting in film sample 55 with an uneven surface. The contact angle of hexadecane of this sample was measured using the same method as in Example 42 and was found to be 87.7 degrees.

[0112] [Example 63] and [Example 64] Preparation of measurement article 3 and contact angle measurement Filter paper substrates were impregnated with composition 3 obtained in Example 44 or composition 6 obtained in Example 47, and each was heated in an oven at 120°C for 15 minutes to remove the solvent. The contact angles of hexadecane for filter paper sample 56 and sample 57 were measured in the same manner as in Example 42, and were found to be 64.7 and 62.2 degrees.

[0113] [Example 65] and [Example 66] Preparation of measurement article 4 and contact angle measurement Nonwoven fabric substrates were impregnated with composition 3 obtained in Example 44 or composition 6 obtained in Example 47, and each was heated in an oven at 100°C for 15 minutes to remove the solvent. The contact angles of hexadecane for nonwoven fabric samples 58 and 59 were measured in the same manner as in Example 42, and were found to be 60.1 and 66.5 degrees, respectively.

[0114] As is clear from the comparison between the examples of the present invention and the comparative examples, it is found that the films prepared using the block copolymers of the present invention have high liquid repellency and at the same time have high coatability and adhesion to the object to be coated.

[0115] Articles such as films made using materials made from compositions containing the block copolymers of the present invention have high liquid repellency despite the fact that the materials contain as little fluorine as possible. At the same time, they also have excellent coatability and adhesion to the object to be coated. The technology of the present invention contributes to reducing environmental impact and is extremely useful in industry.

Claims

1. A block copolymer, one of the blocks being a block composed of structural units containing a structural unit represented by formula (1), and the abundance ratio of the structural units constituting this block is, in terms of molar ratio, 0.05 to 0.7 relative to the structural units constituting the entire block copolymer. (In the formula, X １ is -O- or -NH-, R １ is an alkylene or phenylene having 2 to 12 carbon atoms; Y １ is -NHCOO- or -NHCONH-, R ２ is a linear, branched or cyclic hydrocarbon group having 6 to 30 carbon atoms, which may contain -O- or an unsaturated bond. In this hydrocarbon group, Y １ Hydrogen on carbon two or more away from R may be replaced with fluorine, ３ is hydrogen or methyl.) 2. R ３ The block copolymer of claim 1 , wherein is hydrogen.

3. Y １ The block copolymer according to claim 1 , wherein is —NHCONH—.

4. R ２ The block copolymer according to claim 1, wherein is a fluorine-free alkyl having 6 to 30 carbon atoms.

5. The block copolymer according to claim 1, which contains a block made of a (meth)acrylic acid ester as another block.

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

7. The composition of claim 6, comprising a precipitate of block copolymer aggregates.

8. An article comprising the composition of claim 6 applied to a substrate and the solvent removed.

9. An article comprising the composition of claim 7 applied to a substrate and the solvent removed.