Block copolymer, composition, and article using same

Abstract

Provided is a technique for improving coatability and adhesion to an object to be coated, such as a base material, while having high liquid repellency by using a material that does not contain fluorine or excludes fluorine as much as possible. Provided is a block copolymer in which one of the blocks contains a constituent unit that contains a constituent unit represented by formula (1), and the abundance ratio of the constituent units that constitute the block is 0.05-0.7 in terms of molar ratio with respect to the constituent units that constitute the entire block copolymer. (In the formula, X1 is-O-or-NH-, R1 is an alkylene group or phenylene group having 2-12 carbon atoms, Y1 is-NHCOO-or-NHCONH-, R2 is a linear, branched, or cyclic hydrocarbon group having 6-30 carbon atoms, the hydrocarbon group may contain-O-or an unsaturated bond, in the hydrocarbon group, hydrogen separated from two or more carbons of Y1 may be substituted by fluorine, and R3 is hydrogen or a methyl group. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a block copolymer, a composition and an article using the same, which is preferably used for a liquid-repellent coating material that does not contain or reduces perfluoroalkyl and polyfluoroalkyl substances (PFAS). Background Art

[0002] Regarding PFAS, which is used in many applications as a water- and oil-repellent material, as a substance that is harmful to the human body or the environment, all countries have strengthened their control. Therefore, the demand for materials that do not contain fluorine and show the characteristics of such water- and oil-repellent materials has increased. As such a material, for example, the polymer disclosed in Patent Document 1 has been reported. The existing document discloses that the stacking (crystallization) of long-chain alkyl groups contributes to liquid-repellent performance. In addition, as a material with such long-chain alkyl stacking (crystallization), Non-Patent Document 1 and the like are disclosed. Furthermore, among fluorine-containing surface treatment agents, the polymer disclosed in Patent Document 2 has also been reported as a material with less environmental load.

[0003] The liquid repellency of the material is evaluated in Patent Documents 1 and 2. However, in order to fully exhibit the liquid repellency and prevent its degradation, it is necessary to improve the coating properties and adhesion of the material to an object such as a substrate imparting solvent solubility or liquid repellency.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2022-159191

[0007] Patent Document 2: Japanese Patent Application No. 2011-523432

[0008] Non-patent literature

[0009] Non-patent document 1: “In-plane oriented highly ordered lamellar structure formation of poly(N-dodecylacrylamide) induced by humid annealing”, Royal Society of Chemistry Research Progress (RSC Advance), 2017, Vol. 7, p. 6631. Summary of the Invention

[0010] Problems to be solved by the invention

[0011] The present invention discloses a technology that can improve coating properties and adhesion to a coating object such as a substrate while having high liquid repellency by using a material that does not contain fluorine or has fluorine eliminated as much as possible.

[0012] Technical means to solve the problem

[0013] The present inventors have diligently studied and, as a result, have found that a block copolymer having structural units of a specific structure satisfies the desired properties, thereby completing the present invention.

[0014] [1] A block copolymer, wherein one of the blocks is a block comprising a structural unit containing a structural unit represented by formula (1), and the molar ratio of the structural units constituting the block is 0.05 to 0.7 relative to the molar ratio of the structural units constituting the entire block copolymer.

[0015]

[0016] (Where X 1 is -O- or -NH-, R 1 is an alkylene group or a phenylene group having 2 to 12 carbon atoms, Y 1 is -NHCOO- or -NHCONH-, 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, wherein the hydrocarbon group may contain -O- or an unsaturated bond, wherein Y 1 A hydrogen on more than two carbon atoms can be replaced by fluorine. 3 is hydrogen or methyl)

[0017] [2] The block copolymer according to [1], wherein R 3 For hydrogen.

[0018] [3] The block copolymer according to [1] or [2], wherein Y 1 It is -NHCONH-.

[0019] [4] The block copolymer according to any one of [1] to [3], wherein R 2 It is a fluorine-free alkyl group having 6 to 30 carbon atoms.

[0020] [5] The block copolymer according to any one of [1] to [4], comprising a block containing a (meth)acrylate as another block.

[0021] [6] A composition comprising the block copolymer according to any one of [1] to [5] and a solvent.

[0022] [7] The composition according to [6], comprising a precipitate of an association of block copolymers.

[0023] [8] An article obtained by coating the composition according to [6] or [7] on a substrate and removing the solvent.

[0024] Effects of the Invention

[0025] The present invention provides a material having a low environmental load and containing as little fluorine as possible, and having excellent coating properties and adhesion to a coating object such as a substrate in addition to high liquid repellency. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] [ Figure 1 ] is a photograph of a film produced on a glass substrate using Composition 1 of [Example 42]. The horizontal width of the photograph is about 1 μm.

[0027] [ Figure 2 ] is a photograph of a film produced on a glass substrate using a composition containing the homopolymer of [Comparative Example 1]. The horizontal width of the photograph is about 1 μm. DETAILED DESCRIPTION

[0028] Hereinafter, the embodiment of the present invention will be described in detail, but the following description is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to these contents. In addition, the embodiment of the present invention can also be combined as appropriate.

[0029] The block copolymer of the present invention is characterized in that it is a block copolymer in which one of the blocks is a block containing a structural unit containing a structural unit represented by formula (1). In the block copolymer, the block containing a structural unit containing a structural unit represented by formula (1) exhibits liquid repellency. From the perspective of exhibiting liquid repellency, coating properties and adhesion, the existence ratio of the structural units constituting the block is calculated as a molar ratio, with respect to the structural units constituting the entire block copolymer, on average 0.05 to 0.7, preferably 0.1 to 0.5, and more preferably 0.1 to 0.4.

[0030]

[0031] (Where X 1 is -O- or -NH-, R 1 is an alkylene group or a phenylene group having 2 to 12 carbon atoms, Y 1 is -NHCOO- or -NHCONH-, 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, wherein the hydrocarbon group may contain -O- or an unsaturated bond, wherein Y1 A hydrogen on more than two carbon atoms can be replaced by fluorine. 3 is hydrogen or methyl)

[0032] In the structural unit represented by formula (1), in order to exhibit liquid repellency, R 3 Preferably, it is hydrogen. In addition, for the same reason, Y 1 Preferred is -NHCONH-.

[0033] R 2 It 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. The hydrocarbon group may contain -O- or an unsaturated bond. In this case, in order to exhibit liquid repellency, it is preferred to contain a straight-chain alkyl group having 6 or more carbon atoms. In the selection of the hydrocarbon group, in the case of liquid repellency to water or hydrocarbon compounds, R 2 It preferably contains a straight-chain alkyl group having at least 12 carbon atoms. When -O- is contained in the hydrocarbon group, CH3-O-CH2-O-, in which oxygen is not adjacent to oxygen, is more preferable than CH3-OO-CH2-, in which oxygen is adjacent to oxygen, in consideration of the stability of the compound.

[0034] In order to obtain the desired liquid repellency, R 2 The hydrogen on the carbon of the hydrocarbon group may be substituted by fluorine. The substituted position is from Y 1 At this time, in order to reduce the environmental load by not using the fluorine that is the target of the present invention as much as possible, it is preferred to keep away from the hydrogen on two or more carbons. 1 The hydrogen on the carbon at a position further away from Y is replaced. 1 In contrast, the hydrogen on the terminal carbon in the opposite position is replaced.

[0035] Preferred examples of the structural unit represented by formula (1) include structures represented by the following formulae (1-1) to (1-29).

[0036]

[0037]

[0038]

[0039]

[0040] In order to obtain the desired liquid repellency, the block containing the structural unit containing the structural unit represented by formula (1) (hereinafter sometimes referred to as block (A)) may also contain a plurality of structural units represented by formula (1). In this case, in order to improve the liquid repellency and reduce the environmental load, it is also possible to 2Either one of the alkyl groups containing no fluorine and the alkyl group containing fluorine can be selected.

[0041] In the block comprising the constitutional unit containing the constitutional unit represented by formula (1), a small amount of constitutional units other than those represented by formula (1) may also be included. At this time, the constitutional units other than those represented by formula (1) are preferably 0.2 or less on average relative to the constitutional units of the entire block (A) in terms of the ratio of the number of constitutional units. At this time, in order to maintain liquid repellency, it is more preferably 0.15 or less, and further preferably 0.1 or less. The preferred lower limit of the ratio of the number of constitutional units is 0.01, the more preferred lower limit is 0.001, and the further preferred lower limit is 0. In addition, in terms of ease of manufacturing the block copolymer of the present invention, the constitutional units other than those represented by formula (1) are preferably constitutional units of a structure of a precursor origin before obtaining the constitutional units represented by formula (1), specifically, constitutional units of a structure represented by the following formula (1-p).

[0042]

[0043] (Where X 1 is -O- or -NH-, R 1 is an alkylene group or a phenylene group having 2 to 12 carbon atoms, R 3 is hydrogen or methyl, Y p is -NCO or protected -NCO)

[0044] In the block copolymer of the present invention, the composition of other blocks other than block (A) is not limited. That is, the composition of the block (hereinafter sometimes referred to as block (B)) other than the block of the constituent unit containing the constituent unit represented by formula (1) is not limited. One of the blocks is a block copolymer comprising a block of a constituent unit containing the constituent unit represented by formula (1) and can be an AB diblock copolymer comprising block (A) and block (B), or can be an ABA triblock copolymer comprising block (A), block (B) and block (A). At this time, in order to easily manufacture a block copolymer while obtaining desired characteristics, it is preferably an AB diblock copolymer.

[0045] In the block copolymer of the present invention, the selection of blocks other than the block containing the structural unit containing the structural unit represented by formula (1), i.e., block (B), is not limited. However, in order to exhibit the liquid repellency of the block copolymer of the present invention, it is preferred that the following relationship be satisfied when the polymer containing only the structural unit represented by formula (1) constituting block (A) is designated as A', and the polymer containing only the structural unit other than that represented by formula (1) constituting the other block (B) is designated as B'.

[0046] The surface tension of A' is greater than the surface tension of B'

[0047] In the block copolymer of the present invention, block (B) is involved in solvent solubility, coating properties, and adhesion to a coating object such as a substrate. To impart such properties, it is preferred to select a structural unit represented by the following formula (2) as a structural unit constituting block (B).

[0048]

[0049] (In formula (2), R 3 is hydrogen or methyl, R 10 is a group selected from the structures represented by the following formulae (20) to (23), a pyridyl group, or -CN)

[0050]

[0051] In formulas (20) to (23), X 11 -O-, -NH-, or -NR 11 -, R 11 is hydrogen, a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a cyclic alkyl group having 3 to 8 carbon atoms, or a phenyl group. The non-adjacent -CH2- of the alkyl group may be replaced by -O-, -NMe-, or -NMe2 + -substituted, -CH2- of alkyl can be substituted by -CO-, hydrogen on non-adjacent carbon of alkyl can be substituted by -OH or -N(CH3)2, -CH3 of alkyl can be substituted by -CO2H, -CO2 - 、-SO3 - , or -SO3K substituted, R 12 is -H, -CH3, -OCH3, -OH, -CO2H, -OCOCH3, -N(CH3)2, or -SO3Na, Me is methyl, and * indicates a bonding site)

[0052] In order to improve the solvent solubility and coating properties of the block copolymer of the present invention, it is preferred to select -O- or -NR 11 - as X in formula (20) 11 , select a short-chain linear alkyl group with about 1 to 4 carbon atoms as R 11 For the same purpose, it is preferred to select hydrogen, methyl, or methoxy as R 11 In addition, in order to improve the adhesion of the block copolymer of the present invention to the coating object such as the substrate, it is preferred to select -O- or -NH- as X in formula (20). 11 , select -CH2- alkyl substituted by -CO- and alkyl substituted by -OH on non-adjacent carbon as R of formula (20) 11 For the same purpose, it is preferred to select -OH as R 12 .

[0053] In order to improve solvent solubility, coating properties, and adhesion, in the block copolymer of the present invention, as the structural unit constituting block (B), it is more preferable to be a structural unit represented by formula (2) and a structural unit selected from the group consisting of 10 The present invention is selected from a plurality of constitutional units of a combination of groups of the structure represented by formula (20).

[0054] 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 using a (meth)acrylic monomer having -NCO or protected -NCO 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'-methylpropyleneamino)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'-methylpropyleneamino)carboxyamino)ethyl methacrylate (Karenz (registered trademark) MOI-BM). "Karenz" is a trade name manufactured by Resonac Co., Ltd.

[0055] Herein, “(meth)acrylic acid” refers to acrylic acid or methacrylic acid, “(meth)acrylate” refers to acrylate or methacrylate, and “(meth)acryloyloxy” refers to acryloyloxy or methacryloyloxy.

[0056] In terms of ease of manufacture, as a method for producing the block copolymer of the present invention, it is preferred to use the (meth) acrylic monomer having -NCO or protected -NCO, obtain a precursor by block copolymerization, and then convert it into a method of a structure represented by formula (1). At this time, in order to avoid gelation during polymerization, it is preferred to use a (meth) acrylic monomer having protected -NCO as a raw material. Block copolymerization can use known methods such as atom transfer radical polymerization (ATRP) polymerization, nitrogen oxide-mediated radical polymerization (NMP) polymerization, and reversible addition-fragmentation chain transfer (RAFT) polymerization. As such known techniques, methods described in Precision Radical Polymerization Guide (Merck), Organic Chemistry Information Journal, Vol. 56, 2016, (Fujifilm Wako Pure Chemical Industries, Ltd.), and Radical Polymerization Handbook, NTS Publishing, 2010, etc. can be cited. The method for producing the block copolymer of the present invention is also described in detail in the following examples.

[0057] As the monomer imparting block (B) in the block copolymer of the present invention, 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, oxytetrahydrofuran-3-yl (meth)acrylate, ethylene glycol monoacetoacetate mono(meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, and (meth)acrylic acid. 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(meth)silyl)propyl (meth)acrylate, 3-(diethoxy(meth)silyl)propyl (meth)acrylate, potassium 3-sulfopropyl (meth)acrylate, 3-((2-((meth)acryloyloxy)ethyl)dimethylammonio)propane-1-sulfonic acid, (meth)acrylic acid, (meth)acrylamide, N-(hydroxymethyl)acrylamide, and the like.

[0058] As the monomer for imparting block (B) in the block copolymer of the present invention, known styrene derivatives can be used. Examples of such known compounds include styrene, α-methylstyrene, styrene in which one to three methyl groups replace hydrogen atoms on the benzene ring, 2-acetoxystyrene, 4-acetoxystyrene, 4-methoxystyrene, 4-carboxystyrene, trimethoxy(4-vinylphenyl)silane, and sodium 4-vinylbenzenesulfonate.

[0059] As the monomer that imparts block (B) in the block copolymer of the present invention, acrylonitrile, vinylpyridine, N-vinylpyrrolidone, and 1-vinylimidazole can also be preferably used.

[0060] As the monomers imparting block (B), in order to improve coating properties and adhesion to a coating object such as a substrate while maintaining liquid repellency, preferably selected are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol monomethyl (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, and α-methylstyrene. In order to obtain desired properties, these monomers may be used alone or in combination of two or more.

[0061] In the block copolymerization using these monomers, the polymerization initiator, radical stabilizer (polymerization inhibitor), solvent, etc. are not limited, and the conditions of the above-mentioned known precision polymerization method can be used.

[0062] The polymerization initiator 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, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, di-tert-butyl peroxide (DTBPO), tert-butyl peroxydiisobutyrate, and lauroyl peroxide; and azo-based polymerization initiators such as dimethyl 2,2'-azobis(2-methylpropionate) (MAIB), azobisisobutyronitrile (AIBN), and azobiscyclohexanecarbonitrile (ACN).

[0063] Examples of commercially available peroxide-based polymerization initiators include benzoyl peroxide commercially available from various companies, "Dicumyl peroxide" manufactured by Tokyo Chemical Industry Co., Ltd., and "Percumyl D, Nyper BMT, and Perhexa 25Z" manufactured by NOF Corporation. Examples of azo-based polymerization initiators include AIBN commercially available from various companies, and "V-40, V-50, V-59, V-65, V-70, V-501, and V-601" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. In general, azo-based polymerization initiators are preferably used for both thermal radical polymerization and photoradical polymerization.

[0064] The photoradical polymerization initiator is not particularly limited, and known photoradical polymerization initiators can be used, including 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxyphenyl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzophenazine, a benzophenone / Michler's ketone mixture, a hexaarylbiimidazole / mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, a 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, and a benzophenone / methyltriethanolamine mixture. Examples of commercially available products include "Darocur series 1173, 4265" and "Irgacure series 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, 2959," all manufactured by BASF Japan Co., Ltd.

[0065] In order to obtain the desired properties, the average molecular weight or dispersion value of the block copolymer of the present invention is not particularly limited. However, in order to improve the liquid repellency and prevent it from deteriorating over time, the weight average molecular weight (Mw) of the block copolymer of the present invention is preferably 1000 or more, more preferably 5000 or more. In addition, in order to prevent the deterioration of the solvent solubility of the block copolymer, Mw is preferably 1000000 or less, more preferably 500000 or less. The most preferred range is 10000 to 100000. The dispersion value of the average molecular weight, for example, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), i.e., Mw / Mn, is generally close to 1 when the precision polymerization is implemented. If polymerization is carried out under conditions representing a value close to 1, a neat block copolymer is formed. However, the block copolymer of the present invention has a tendency to increase Mw / Mn due to the large interaction between polymer chains. Therefore, from the perspective of the quality of the block copolymer, Mw / Mn is preferably 1 to 10, more preferably 1 to 5.

[0066] The block copolymer of the present invention can also be produced, for example, by separately producing a homopolymer containing the structural unit represented by formula (1) and another homopolymer and linking them. Examples of such production methods include those described in the Handbook of Radical Polymerization, NTS Publishing, 2010.

[0067] The conversion of the block copolymer of the precursor to the structure represented by formula (1) can also be carried out according to known methods. 1 In the case of a block copolymer of -NHCONH-, a commercially available or known compound having -NH2 can be reacted with a block copolymer of a precursor to obtain the block copolymer. As commercially available or known compounds having -NH2, aniline derivatives substituted with alkylamines or alkyl or alkoxy groups having more than 6 carbon atoms can be cited. The amount of these compounds having -NH2 added during the reaction is 0.8 or more in terms of a molar ratio relative to the -NCO equivalent in the block copolymer. The compound having -NH2 reacts quantitatively with the -NCO equivalent, so if it is within the range, it is consistent with the technology of the present invention. Similarly, in order to easily purify the block copolymer, the upper limit of the amount of the compound having -NH2 used is preferably 2.0 or less, further preferably 1.5 or less, and most preferably 1.2 or less in terms of the molar ratio. In the calculation, the molar ratio of the -NCO equivalent in the block copolymer can be calculated based on the amount of the block copolymer used, the ratio of the blocks in the block copolymer, and the molecular weight of the constituent unit containing the -NCO equivalent. The ratio of the blocks in the block copolymer is determined as described below. 1 H-NMR ( 1 H-NuclearMagnetic Resonance, 1It can be determined by measurements such as H-NMR).

[0068] In formula (1), Y 1 In the case of a block copolymer of -NHCOO-, a commercially available or known compound with -OH can be reacted with a block copolymer of a precursor to obtain it. The reactivity of the compound with -OH and the -NCO equivalent is low relative to the compound with -NH2, so the addition amount of these compounds with -OH during the reaction is preferably more than 1.0 relative to the -NCO equivalent in the block copolymer in terms of a molar ratio. Similarly, in order to easily carry out the purification of the block copolymer, the upper limit of the usage amount of the compound with -OH is preferably less than 3.0 in terms of the molar ratio, and most preferably less than 2.0. In order to improve the reaction rate, it is preferred to add a carbamate catalyst to the reaction solution. As a carbamate catalyst, dibutyltin dilaurate etc. can be listed. In order to improve reactivity, the addition amount of the carbamate catalyst is preferably more than 0.1 weight % relative to the weight of the block copolymer, and more preferably more than 0.5 weight %. In addition, in order to easily carry out the purification of the block copolymer, it is preferably less than 2 weight % relative to the weight of the block copolymer, and more preferably less than 1 weight %.

[0069] In Y 1 In the case of a block copolymer of -NHCONH-, in order to rapidly react, the reaction temperature when converting to the structure represented by the formula (1) is preferably 80°C or higher. In addition, in order to prevent the decomposition of the block copolymer, it is preferably 120°C or lower. 100°C is the most preferred reaction temperature. In addition, the higher the temperature, the shorter the conversion time. In order to form a sufficient conversion rate, the reaction time is preferably 30 minutes or more at 100°C, and in order to prevent the decomposition of the block copolymer, it is preferably 2 hours or less. 1 hour is the most preferred reaction time. In Y 1 In the case of a block copolymer of -NHCOO-, a reaction temperature of 100°C or higher is preferred for rapid reaction. Furthermore, to prevent decomposition of the block copolymer, the reaction temperature is preferably 140°C or lower. 120°C is the most preferred reaction temperature. To achieve a sufficient conversion rate at 120°C, the reaction time is preferably 1 hour or longer. To prevent decomposition of the block copolymer, the reaction time is preferably 8 hours or less. 4 hours is the most preferred reaction time.

[0070] The solvent during the structural conversion represented by formula (1) can use a solvent that is unreactive or has low reactivity with the block copolymer of the precursor. At this time, it is preferably a solvent that the block copolymer of the precursor and the block copolymer of the present invention dissolve both. As such a solvent, it can be enumerated as follows: hydrocarbon solvents such as toluene or xylene, n-propyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone and other ester solvents, tetrahydrofuran (tetrahydrofuran, THF), 1,4- dioxane, anisole, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether and other ether solvents, dimethylformamide, diethylformamide, dimethylacetamide, N- methyl-2- pyrrolidone, dimethyl sulfoxide, ethyl methyl carbonate, diethyl carbonate etc.

[0071] The composition of the present invention comprising the block copolymer of the present invention comprises the block copolymer of the present invention, a solvent, and optionally added additives. There is no limitation on the solvent, and it can be appropriately selected from known solvents. At this time, in order to maintain the solubility of the block copolymer of the present invention and improve the coating properties on the coating object such as the substrate, it is also preferably set as a mixed solvent. As such a solvent, in addition to the hydrocarbon solvent, ester solvent, and ether solvent, an alcohol solvent can also be preferably used. As such a solvent, in addition to the solvent,

[0072] Other examples include:

[0073] Ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,

[0074] 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,

[0075] Acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol,

[0076] Ethyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, dimethyl carbonate,

[0077] 1,3-dioxolane,

[0078] Diisopropyl ether, ethylene glycol dimethyl ether,

[0079] And water, etc.

[0080] The composition of the present invention may contain additives, such as crosslinking agents, surfactants, emulsifiers, coupling agents, antioxidants, free radical stabilizers (polymerization inhibitors), antistatic agents, and hydrolysis stabilizers.

[0081] If a cross-linking agent is added to the composition of the present invention, mechanical degradation or time-dependent degradation of the coating film can be prevented. As such additives, known low-molecular compounds or polymers can be used. At this time, as the block copolymer of the present invention, it is preferred to select a material in which a constituent unit of the structure represented by formula (1-p) is introduced into block (A), and a compound having a plurality of functional groups such as amines, alcohols, and thiols is used as a cross-linking agent. As preferred examples of such cross-linking agents, there can be cited: various alkylene diamines, polyamines, diaminobenzenes, polyols, alkylene dithiols, and polythiol compounds. In terms of the rapid progress of the cross-linking reaction, various alkylene diamines, polyamines, and diaminobenzenes are more preferred among these cross-linking agents. The amino group of such an amine compound can be protected by a group that is separated by heat, such as a tert-butoxycarbonyl group.

[0082] 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 perform a crosslinking reaction with these polyfunctional isocyanate compounds, it is preferred to use a polymer into which a functional group such as a phenol or alcohol is introduced as the block copolymer of the present invention.

[0083] In order to suppress deterioration of liquid repellency and obtain the desired effect, 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, relative to the weight of the block copolymer of the present invention.

[0084] Surfactants are used to improve wettability, leveling, and coating properties on a substrate. As surfactants, silicone surfactants, acrylic surfactants, fluorochemical surfactants, etc. can be used. Specifically, BYK-342, BYK-350, BYK-352, BYK-354, BYK-356, BYK-381, BYK-392, BYK-394, BYK-3441, BYK-3440, BYK-3550 (all trade names: BYK-Chemie Japan (stock) manufactured) can be mentioned.

[0085] In addition, as examples of leveling agents, commercially available silicone surface conditioners can be used, such as BYK-UV3500, BYK-UV-3570 (both trade names: manufactured by BYK-Chemie Japan Co., Ltd.), TEGORad 2100, 2200N, 2250, 2500, 2600, and 2700 (all trade names: manufactured by Evonik Degussa, Japan). 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, relative to the weight of the block copolymer of the present invention.

[0086] In order to improve the adhesion to the coating object such as the substrate, the composition of the present invention may also contain a coupling agent. Examples of silane coupling agents include vinyltrialkoxysilane, 3-isocyanatepropyltriethoxysilane, N-(2-aminoethyl)3-aminopropyltrialkoxysilane, N-(1,3-dimethylbutylene)-3-(trialkoxysilyl)-1-propaneamine, 3-glycidoxypropyltrialkoxysilane, 3-chlorotrialkoxysilane, 3-acryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropyltrialkoxysilane. In addition, among the alkoxysilanes, dialkoxymethylsilanes formed by replacing one of the three alkoxy groups with a methyl group may also be used as a silane coupling agent. These silane coupling agents may be used alone or in combination of two or more. In addition, these silane coupling agents may also be commercially available. The amount of these couplers added to the composition is preferably 0.1 to 5% by weight, more preferably 0.5 to 1% by weight, based on the weight of the block copolymer of the present invention.

[0087] The antioxidants that can be used in the present invention are not limited. Examples include 3,5-di(t-butyl)-4-hydroxytoluene (BHT), hydroquinone, methylene blue, diphenylpicryl hydrazide (DPPH), phenothiazine, nitroso compounds such as N,N-dimethyl-4-nitrosoaniline, o-hydroxybenzophenone, and benzothiazine derivatives of 2H-1,3-benzothiazine-2,4-(3H)dione. In addition, also can be listed: Adekastab AO-20, AO-30, AO-40, AO-50, AO-60 and AO-80 sold by ADEKA (stock), Sumilizer BHT, Sumilizer BBM-S and Sumilizer GA-80 sold by Sumitomo Chemical (stock) and Irganox 1076, Irganox 1010, Irganox 3114 and Irganox 245 (all are trade names) sold by BASF Japan (stock) etc. These antioxidants can be used alone or in combination of two or more. In addition, these antioxidants can also be commercially available products.

[0088] The composition of the present invention may also contain an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant, and the like. 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, Adekastab LA-32, Adekastab LA-34, Adekastab LA-36, Adekastab LA-31, Adekastab 1413, and Adekastab LA-51. "Tinuvin" is a trade name manufactured by BASF Japan, and "Adekastab" is a trade name manufactured by ADEKA Co., Ltd. These UV absorbers can be used alone or in combination of two or more. In addition, these ultraviolet absorbers may also be commercially available items.

[0089] Examples of the light stabilizer 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, Tinuvin 5060, Tinuvin 5151, Chimassorb 119FL, Chimassorb 944FL, and Chimassorb 944FL. b) 944LD, Adekastab LA-52, Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63P, Adekastab LA-68LD, Adekastab LA-77, Adekastab LA-82, Adekastab LA-87, Cyasorb UV-3346 (a trade name manufactured by Cytec), and Goodrite UV-3034 (a trade name manufactured by Goodrich). "Chimassorb" is a trade name manufactured by BASF Japan Co., Ltd. These light stabilizers may be used alone or in combination of two or more. These light stabilizers may also be commercially available products.

[0090] The amount of these antioxidants, ultraviolet absorbers, or 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.

[0091] In the composition of the present invention, a hydrolysis stabilizer is preferably added to inhibit hydrolysis of polyacrylates and prevent degradation over time or due to the environment. Examples of such hydrolysis stabilizers include Carbodilite (registered trademark) manufactured by Nisshinbo Chemical Co., Ltd., Carbosista (registered trademark) manufactured by Teijin Limited, and Stabaxol (registered trademark) manufactured by Lanxess Co., Ltd.

[0092] The performance of the liquid-repellent coating material obtained from the composition of the present invention can be further improved by making controlled concavities and convexities on its surface when the liquid-repellent coating material is made into a film. As one of such methods, the self-association formed by the liquid-repellent coating material obtained from the composition of the present invention can be utilized. That is, with respect to the liquid-repellent coating material obtained from the composition of the present invention, the block copolymer forms a spherical associate in an appropriate solution. By utilizing the spherical associate, controlled concavities and convexities can be produced. In the block copolymer of the present invention, from the viewpoint of forming the associate, it is preferred that Y in formula (1) 1 It is a block copolymer of -NHCONH-.

[0093] To form spherical aggregates, it is preferred to mix 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, with 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 improvement in liquid-repellency performance achieved by using such aggregates is described in detail in the Examples.

[0094] The article of the present invention, which is formed by coating the composition of the present invention on a surface, can be obtained by coating the composition on a substrate and removing the solvent. Examples of coating methods include coating methods using a dispenser, spin coating, roll coating, curtain coating, flow coating, printing, micro-gravure coating, gravure coating, wire rod coating, dip coating, spray coating, meniscus coating, and inkjet coating.

[0095] The method for removing the solvent is not particularly limited, but heat treatment is preferred. The temperature conditions are not particularly limited, but when coating on a substrate with low heat resistance such as fiber or paper, sufficiently good liquid repellency can be achieved at mild conditions of around 130°C.

[0096] The composition of the present invention exhibits minimal degradation over time related to its liquid repellency and exhibits high durability against heat and other factors. Furthermore, to further enhance the durability of its liquid repellency, it is also preferable to pre-treat the substrate to facilitate adhesion of the composition of the present invention. Examples of such treatments include ultraviolet (UV) ashing using ozone or plasma treatment. Furthermore, coating the substrate with an adhesive or crosslinking agent is also preferred.

[0097] For example, when using a fiber product as a substrate, a crosslinking agent can be attached to the fiber product and then heated to perform the treatment. 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 fiber product and heat-dried. In this case, to improve durability, it is preferable to use a composition of the present invention that contains functional groups that react with the crosslinking agent.

[0098] Examples of compounds having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenyl isocyanate, toluene isocyanate, and naphthalene isocyanate; diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; and their isocyanurate rings, i.e., trimers; and trimethylolpropane adducts. Furthermore, examples of compounds having one or more blocked isocyanate groups include compounds in which the isocyanate groups of the compounds having isocyanate groups are protected by blocking agents. 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; and bisulfites such as sodium bisulfite and potassium bisulfite. The crosslinking agents may be used alone or in combination.

[0099] The treatment of fiber products with a crosslinking agent can be carried out, for example, by immersing the fiber products in a treatment solution in which the crosslinking agent is dissolved in an organic solvent as a solvent or emulsified and dispersed in water. The crosslinking agent is then fixed to the substrate by heat treatment or the like. In this case, the crosslinking agent can be fixed before or simultaneously with the treatment of the substrate with the composition of the present invention. In this case, considering the simplification of the process, or energy reduction and economy, it is preferred to fix the crosslinking agent while treating the composition of the present invention. When the crosslinking agent is fixed by heating, it is preferably carried out at a temperature of 110°C to 180°C for 1 minute to 5 minutes.

[0100] The substrate to which the composition of the present invention can impart liquid repellency is not particularly limited, and glass, metal, plastic, paper, and fiber are preferably used. For example, the raw materials for fiber products are not particularly limited, and examples thereof include polyolefin resins such as polyethylene or polypropylene, polyester resins such as polyethylene terephthalate or polylactic acid, polyamide resins such as nylon 6 or nylon 6,6, polyurethane resins, fluororesins such as polyvinylidene fluoride or polytetrafluoroethylene, polysulfone, polyethersulfone, and cellulosic materials such as cellulose or cellulose acetate. These materials may be used alone or in combination of two or more.

[0101] Example

[0102] Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.

[0103] <Measurement of polymer weight average molecular weight (Mw) and dispersion value (Mw / Mn)>

[0104] Analysis was performed by gel permeation chromatography (GPC). A high-speed liquid chromatography system manufactured by Shimadzu Corporation was used. Two PLgel 5μm MIXED-D2 columns manufactured by Agilent Technologies were connected in series, and THF was used as the solvent. A standard reagent (standard polystyrene) for average molecular weight determination was Standard SM-105 manufactured by Resonac Co., Ltd.

[0105] <Confirmation of the block abundance ratio of block copolymers and confirmation of polymer structure>

[0106] The nuclear magnetic resonance spectrometer (500 MHz) was used. 1 CDCl3 was used as the solvent and tetramethylsilane was used as the reference substance.

[0107] <Film Observation and Film Thickness Measurement>

[0108] The condition of the produced film was visually observed and confirmed using a KLA Tencor P+16 step-difference meter (manufactured by KLA Tencor). The film thickness was also confirmed by cutting a portion of the film with a cutter and measuring the step using the step-difference meter. The film thickness value was the average of five points measured at different locations.

[0109] Surface tension measurement

[0110] The measurement was performed using a contact angle meter (PCA-1) manufactured by Kyowa Interface Science Co., Ltd. The value was the average value of five points at different measurement locations. The measurement was performed at room temperature.

[0111] <Monomers, polymerization initiators, RAFT agents, alkylamines, alcohols, crosslinking agents, other reagents, urethanization catalysts, and solvents>

[0112] The following commercially available products were used.

[0113] Monomers: 2-isocyanatoethyl acrylate, methyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, n-dodecyl acrylate (all manufactured by Tokyo Chemical Industry Co., Ltd.)

[0114] Thermal radical polymerization initiator; 2,2'-azobis(2-methylpropionic acid)dimethyl ester (V-601, a trade name manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0115] RAFT agent; 4-cyano-4-[[(dodecylthio)carbonylthio]thio]pentanoic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0116] Alkylamines; n-octylamine, n-dodecylamine, n-hexadecylamine (all manufactured by Tokyo Chemical Industry Co., Ltd.)

[0117] Alcohols; n-octanol, n-dodecanol, n-hexadecanol (all manufactured by Tokyo Chemical Industry Co., Ltd.)

[0118] Crosslinking agents: 1,6-diaminohexane, hexamethylene diisocyanate (all manufactured by Tokyo Chemical Industry Co., Ltd.)

[0119] Other reagents: n-hexadecane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0120] Urethane catalyst; dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.), ORGATIX (registered trademark) ZC-150 (trade name of Matsumoto Fine Chemicals Co., Ltd.)

[0121] Solvent: Anisole, toluene, isopropyl alcohol (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0122] The monomer 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate was synthesized using the aforementioned 2-isocyanatoethyl acrylate as a raw material according to Japanese Patent No. 4879557 (Japanese Patent Laid-Open No. 2006-151967). The compound structure is shown in FIG. 1 Confirmed by H-NMR.

[0123] <Base material>

[0124] Glass substrate: Eagle XG (registered trademark) (trade name manufactured by Corning, 0.5 mm thick) was cut into 40 mm squares. The surface of the substrate was cleaned with acetone and ultrapure water, dried in an oven at 120°C for 1 hour, and cooled to room temperature.

[0125] Filter paper: Qualitative filter paper (No. 2, ADVANTEC (registered trademark)) (trade name manufactured by Toyo Roshi Co., Ltd.) was used as it was.

[0126] Nonwoven fabric: Spunbond Eltas (Eltas) (registered trademark) (trade name manufactured by Asahi Kasei Corporation, weight per unit area 30 g) was purchased and used directly.

[0127] [Example 1] Block copolymer 1 (containing X containing formula (1) 1 -O-, R 1 For ethylene, Y 1 -NHCONH-, R 2 n-C8H 17 -、R 3 Synthesis of a block copolymer in which a block of a structural unit of which hydrogen is a structural unit and the other block is polymethyl acrylate

[0128] A Schlenk tube was charged with 1.2238 g (5.158 mmol) of 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, a monomer for imparting a structure of the structural unit represented by formula (1-p), 5.9 mg (0.026 mmol) of V-601, 13.4 mg (0.0331 mmol) of 4-cyano-4-[[(dodecylthio)carbonylthio]thio]pentanoic acid, and 3.1 g of anisole, which served as a precursor source prior to obtaining the structural unit represented by formula (1). Freeze-degassed the mixture three times using a vacuum pump. Then, the reaction was initiated in an oil bath at 75°C under a N2 atmosphere. After 45 minutes of reaction, a similarly freeze-degassed solution of methyl acrylate in anisole (methyl acrylate; 1.89 ml (20.63 mmol), anisole; 1.9 g) was added to the reaction solution using a syringe. The polymer in the reaction solution sampled at this time had an Mw of 9500 and an Mw / Mn of 1.31. Then, the temperature of the oil bath was raised to 80°C and the reaction was allowed to proceed for about 4 hours. The reaction solution was cooled to room temperature and directly used for urea or carbamate conversion reaction. 1 H-NMR measurement showed that the block ratio (r, molar ratio, refer to the following formula) of the constituent units represented by formula (1-p) of the sample was 0.2. In addition, the polymerization rate of methyl acrylate was 90%. In addition, the polymerization rate of methyl acrylate was calculated using 1 H-NMR was determined based on the abundance ratio of the monomer and polymer of methyl acrylate.

[0129] r=A / (A+B)

[0130] A; According to the constituent unit represented by formula (1-p) 1 The existence ratio obtained by the integral value of H

[0131] B; Based on the source of polymethyl acrylate (block B) 1 The existence ratio obtained by the integral value of H

[0132] The block abundance ratio (r, molar ratio) corresponds to the abundance ratio (molar ratio) of the constitutional units constituting the block containing the constitutional unit containing the constitutional unit represented by formula (1) relative to the constitutional units constituting the entire block copolymer of the present invention.

[0133] 2 g of the reaction solution was measured, 0.098 g (0.76 mmol) of n-octylamine was added, and the mixture was reacted at 100°C in anisole (10 ml) for 2 hours. After the reaction solution was cooled to room temperature, it was precipitated again 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 obtained polymer powder was vacuum dried at room temperature for 8 hours. 1 H-NMR measurement showed that the conversion rate of the protected NCO site to urea (α, see the following formula) was almost 1. The synthesized block copolymer 1 had an Mw of 53,600 and an Mw / Mn of 2.26.

[0134] α=BCP / (BCP+Pre)

[0135] BCP; according to the source of the conversion site 1 The existence ratio obtained by the integral value of H

[0136] Pre; Based on the protection of NCO sources 1 The existence ratio obtained by the integral value of H

[0137] [Example 2] to [Example 8]

[0138] Block copolymers 2 to 8 were produced in the same manner as in Example 1 except that the type and amount of alkylamine added were changed. Specifically, n-dodecylamine was used in place of n-octylamine in Examples 2, 4, 5, and 7, n-hexadecylamine was used in Examples 3 and 8, and n-octadecylamine was used in Example 6, with the amounts added being adjusted to match the chemical equivalents. The results are shown in Table 1. Example 1 is also reproduced in Table 1. In Table 1, the numbers in the Example / Copolymer column represent both the example number and the block copolymer number.

[0139] [Table 1] contains X containing formula (1) 1 -O-, R 1 For ethylene, Y 1 -NHCONH-, R 3 A block copolymer comprising a block of a constituent unit of which hydrogen is a constituent unit and the other block is polymethyl acrylate

[0140]

[0141] [Example 9] Block copolymer 9 (containing X containing formula (1)1 -O-, R 1 For ethylene, Y 1 -NHCONH-, R 2 n-C8H 17 -、R 3 Synthesis of a block copolymer in which the blocks are composed of constituent units of hydrogen and the other blocks are blocks of constituent units of methyl acrylate and 2-hydroxyethyl acrylate)

[0142] Block copolymer 9 was obtained in the same manner as in Example 1, except that methyl acrylate was replaced with 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)). 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.

[0143] [Example 10] to [Example 12]

[0144] Block copolymers 10 to 12 were produced in the same manner as in Example 9, except that the type and amount of alkylamine added were changed. Specifically, n-dodecylamine was used in Example 10, n-hexadecylamine was used in Example 11, and n-octadecylamine was used in Example 12 instead of n-octylamine, with the amounts added being adjusted to match the chemical equivalents. The results are shown in Table 2. Example 9 is also reproduced in Table 2. In Table 2, the numbers in the Example / Copolymer column represent both the example number and the block copolymer number.

[0145] [Table 2] contains X containing formula (1) 1 -O-, R 1 For ethylene, Y 1 -NHCONH-, R 3 A block copolymer comprising a block of a constituent unit containing a constituent unit of hydrogen and a block of a constituent unit containing methyl acrylate and 2-hydroxyethyl acrylate as the other blocks

[0146]

[0147] [Example 13] Block copolymer 13 (containing X containing formula (1) 1 -O-, R 1 For ethylene, Y 1 -NHCONH-, R 2 nC 18 H 37 -、R 3Synthesis of a block copolymer in which the blocks are composed of constituent units of hydrogen and the other blocks are blocks of constituent units of methyl acrylate and 4-hydroxybutyl acrylate)

[0148] Block copolymer 13 was obtained in the same manner as in Example 1, except that methyl acrylate was replaced with 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)). 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.

[0149] [Example 14] Block copolymer 14 (containing X containing formula (1) 1 -O-, R 1 For ethylene, Y 1 -NHCONH-, R 2 nC 18 H 37 -、R 3 Synthesis of a block copolymer comprising a block of a constituent unit containing a constituent unit of hydrogen and a block of a constituent unit containing methyl acrylate and n-dodecyl acrylate as the other blocks

[0150] Block copolymer 14 was obtained in the same manner as in Example 1, except that methyl acrylate was replaced with 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)). 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.

[0151] [Example 15] Block copolymer 15 (containing X containing formula (1) 1 -O-, R 1 For ethylene, Y 1 -NHCONH-, R 2 n-C8H 17 -、R 3 Synthesis of a block copolymer in which one block is a structural unit of hydrogen and the other block is polymethyl methacrylate

[0152] Block copolymer 13 was obtained by the same operation as in Example 1 except that methyl methacrylate was changed to 2.20 ml (20.7 mmol). The synthesized block copolymer 15 had Mw of 49,200, Mw / Mn of 1.98, r of 0.48, and α of 1.

[0153] [Example 16] and [Example 17]

[0154] Block copolymers 16 and 17 were produced in the same manner as in Example 15, except that the type and amount of alkylamine added were changed. Specifically, 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. Example 13 is also reproduced in Table 3. In Table 3, the numbers in the Example / Copolymer column represent both the example number and the block copolymer number.

[0155] [Table 3] contains X containing formula (1) 1 -O-, R 1 For ethylene, Y 1 -NHCONH-, R 3 A block copolymer comprising a block of a structural unit of a structural unit of hydrogen and a block of a structural unit of polymethyl methacrylate

[0156]

[0157] [Example 18] Block copolymer 18 (containing X containing formula (1) 1 -O-, R 1 For ethylene, Y 1 -NHCOO-, R 2 n-C8H 17 -、R 3 Synthesis of a block copolymer in which a block of a structural unit of which hydrogen is a structural unit and the other block is polymethyl acrylate

[0158] It is obtained by converting the functional groups of the block copolymer of the precursor synthesized according to Example 1. That is, 2 g of the reaction solution of the block copolymer of the precursor is measured, 0.16 g (1.2 mmol) of n-octanol and 7.5 mg (0.012 mmol) of dibutyltin dilaurate are added, and the mixture is reacted at 120°C in anisole (5 ml) for 8 hours. After the reaction solution is cooled to room temperature, it is precipitated again in heptane and stirred for 1 hour. The resulting precipitate is filtered by suction, added to acetonitrile, stirred for 1 hour, and then filtered. The powder of the obtained polymer is vacuum dried at room temperature for 8 hours. According to 1 H-NMR measurement showed that the conversion rate (α) of the protected NCO site to carbamate was about 0.8. The synthesized block copolymer 18 had an Mw of 48,500 and an Mw / Mn of 1.85.

[0159] [Example 19] and [Example 20]

[0160] Block copolymers 19 and 20 were produced in the same manner as in Example 18, except that the type and amount of alcohol added were changed. That is, instead of n-octanol, n-dodecanol was used for Example 19, and n-hexadecanol was used for Example 20, and the amounts added were changed to match the chemical equivalents. The results are shown in Table 4. In addition, Example 18 is also shown again in Table 4. In Table 4, the numbers in the Example / Copolymer column represent both the number of the example and the number of the block copolymer.

[0161] [Table 4] contains X containing formula (1) 1 -O-, R 1 For ethylene, Y 1 -NHCOO-, R 3 A block copolymer comprising a block of a constituent unit of which hydrogen is a constituent unit and the other block is polymethyl acrylate

[0162]

[0163] [Example 21]

[0164] Block copolymer 21 (containing X containing formula (1) 1 -O-, R 1 For ethylene, Y 1 -NHCONH-, R 2 nC 18 H 37 -、R 3 Synthesis of a block copolymer in which one block is a structural unit of hydrogen and the other block is polystyrene

[0165] 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 Mw of 46,700, Mw / Mn of 2.37, r of 0.7, and α of 1.

[0166] [Example 22] Preparation of Composition 1

[0167] 0.25 g of the block copolymer 1 obtained in Example 1 was aliquoted into a sample bottle, 1.50 g of toluene was added, and the mixture was heated to dissolve. 0.75 g of isopropyl alcohol was added to the solution to obtain Composition 1, which was a polymer solution having a concentration of 10 wt%.

[0168] [Example 23] to [Example 41] Preparation of Compositions 2 to 21

[0169] Using the block copolymers synthesized in the aforementioned examples, polymer solutions having a concentration of approximately 10% by weight, namely Compositions 2 to 21 (Table 5), were prepared in the same manner as in Example 22. In this case, the crosslinking agent and urethanization catalyst compounds were added to the compositions in the amounts listed in Table 5 after the polymer solutions were prepared. Addition was performed at room temperature. Example 22 is also reproduced in Table 5.

[0170] [Table 5] Prepared composition

[0171]

[0172] [Example 42] Preparation of Measurement Article 1 and Contact Angle Measurement

[0173] The composition 1 was spin-coated on a glass substrate as a substrate. At this time, the rotation speed of the glass substrate was 1000 rpm. The glass substrate was heated at 120°C for 15 minutes on a hot plate, and the solvent was removed to obtain a film containing the block copolymer of the present invention. The film sample had no holes caused by coating leakage, and in the state of a clean film, it had excellent coating and adhesion properties relative to the glass substrate as a substrate. A photograph of the film produced on the glass substrate observed using a step difference meter is shown in FIG. Figure 1 The film thickness of the sample was 1.61 μm. In addition, the contact angle of hexadecane of the sample was 38.5 degrees. The article of the present invention was prepared by applying a composition comprising the block copolymer of the present invention and a solvent onto a glass substrate as a base material in the manner described above and removing the solvent. The contact angle was measured using the measurement article.

[0174] [Example 43] to [Example 61]

[0175] 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 physical property measurements are shown in the table below. The results of Example 42 are repeated in Table 5. Similarly to Example 42, the film samples of Examples 43 to 61 exhibited excellent coating properties and adhesion to the glass substrate, with no holes or the like caused by coating gaps, even in a clean film state.

[0176] [Table 6] Fabricated articles and contact angle measurements

[0177] Example Composition Contact angle of hexadecane / degree Membrane status Film thickness / μm 42 1 41.6 good 1.61 43 2 38.5 good 1.38 44 3 44.6 good 1.33 45 4 42.3 good 1.58 46 5 41.1 good 1.58 47 6 44.8 good 1.43 48 7 42.0 good 1.55 49 8 45.1 good 1.38 50 9 39.1 good 1.36 51 10 41.0 good 1.55 52 11 45.3 good 1.48 53 12 44.2 good 1.67 54 13 43.6 good 1.45 55 14 46.7 good 1.38 56 16 41.8 good 1.32 57 17 43.5 good 1.56 58 18 32.4 good 1.32 59 19 35.5 good 1.28 60 20 35.8 good 1.27 61 21 46.2 good 1.75

[0178] [Comparative Example 1]

[0179] In the same manner as in Synthesis Example 1 of Japanese Patent Laid-Open No. 2022-159191, a compound X containing only the formula (1) was obtained. 1 O, R 1is ethylene, Y1 is -NHCONH-, R 2 nC 12 H 25 、R 3 A polymer (homopolymer) having a constituent unit of hydrogen. The polymer was prepared into a polymer solution (homopolymer 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, and the solvent was removed to obtain a film. The result of observing the film sample was that there were holes with a diameter of about 100 μm reaching the depth of the glass substrate and shallow holes with a small diameter caused by non-coating, and the coating and adhesion were poor relative to the glass substrate as the base material. The photograph of the film produced on the glass substrate is shown in Figure 2 The film thickness of the sample was 1.81 μm. The contact angle of the sample with hexadecane was 43.4 degrees.

[0180] [Comparative Example 2]

[0181] X of formula (1) was obtained in the same manner as in Comparative Example 1 except that a monomer mixture of 2-(3-n-dodecylureide)ethyl acrylate and methyl acrylate at a molar ratio of 2:8 was used instead of the monomer of 2-(3-n-dodecylureide)ethyl acrylate alone. 1 O, R 1 For ethylene, Y 1 NHCONH, R 2 nC 12 H 25 , and R in formula (2) 3 H, R 10 is formula (20), X 11 O, R 11 A random copolymer of CH3 (random copolymer). 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. The results of observing the film sample were as follows: Figure 1 Similarly, the film was clean without holes caused by coating failure, and the film thickness of the sample was 2.27 μm. On the other hand, the contact angle of the sample with hexadecane was 34.1 degrees, indicating poor liquid repellency.

[0182] [Example 62] Preparation of Measurement Article 2 and Contact Angle Measurement

[0183] Composition 6 obtained in Example 47 was left at room temperature overnight, resulting in precipitation of a block copolymer association complex. The precipitated composition was added dropwise to a glass substrate and left at room temperature for 1 hour, yielding a film sample 55 having an uneven surface. The hexadecane contact angle of this sample was measured using the same method as in Example 42, resulting in a value of 87.7 degrees.

[0184] [Example 63] and [Example 64] Preparation of Measurement Articles 3 and Contact Angle Measurement

[0185] Composition 3 obtained in Example 44 or Composition 6 obtained in Example 47 was impregnated into filter paper as a substrate and heated in an oven at 120°C for 15 minutes to remove the solvent. The hexadecane contact angles of these filter paper samples 56 and 57 were measured using the same method as in Example 42, and the results were 64.7 degrees and 62.2 degrees.

[0186] [Example 65] and [Example 66] Preparation of Measurement Articles and Contact Angle Measurement

[0187] Composition 3 obtained in Example 44 or Composition 6 obtained in Example 47 was impregnated into a nonwoven fabric substrate and heated in an oven at 100°C for 15 minutes, followed by removal of the solvent. The hexadecane contact angles of these nonwoven fabric samples 58 and 59 were measured using the same method as in Example 42, yielding values ​​of 60.1° and 66.5°, respectively.

[0188] As is clear from the comparison between the examples of the present invention and the comparative examples, it is found that the film produced using the block copolymer of the present invention has high liquid repellency and high coating properties and adhesion to the coating object.

[0189] Industrial applicability

[0190] Articles such as films made from materials containing compositions comprising the block copolymers of the present invention exhibit high liquid repellency despite being fluorine-free. Furthermore, they exhibit excellent coating properties and adhesion to the coated object. The technology of the present invention contributes to reducing environmental impact and is very useful industrially.

Claims

1. A block copolymer, wherein one of the blocks is a block comprising a structural unit comprising a structural unit represented by formula (1), and the molar ratio of the structural units constituting the block is 0.05 to 0.7 relative to the structural units constituting the entire block copolymer. (Where X 1 is -O- or -NH-, R 1 is an alkylene group or a phenylene group having 2 to 12 carbon atoms, Y 1 is -NHCOO- or -NHCONH-, 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, wherein the hydrocarbon group may contain -O- or an unsaturated bond, wherein Y 1 A hydrogen on more than two carbon atoms can be replaced by fluorine. 3 is hydrogen or methyl).

2. The block copolymer according to claim 1, wherein R 3 For hydrogen.

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

4. The block copolymer according to claim 1, wherein R 2 It is a fluorine-free alkyl group having 6 to 30 carbon atoms. The block copolymer according to claim 1 , comprising a block containing (meth)acrylate as another block. 6 . A composition comprising the block copolymer according to claim 1 and a solvent.

7. The composition according to claim 6, comprising a precipitate of an association of block copolymers.

8. An article, which is formed by coating the composition according to claim 6 on a substrate and removing the solvent.

9. An article, which is formed by coating the composition according to claim 7 on a substrate and removing the solvent.

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