Block copolymer, composition, and article using the same

Abstract

To provide technology that achieves high liquid repellency while allowing enhancement of its durability, using a material free of fluorine or substantially eliminating fluorine.SOLUTION: A block copolymer comprises a block consisting of structural units represented by formula (1) and a block consisting of structural units having a functional group crosslinkable by light. (In the formula X1 is -O- or -NH-, R10 is an alkylene or phenylene group having 2 to 12 carbon atoms, Y1 is a functional group capable of forming double or more hydrogen bonds between two adjacent structural units, and R11 is a linear hydrocarbon group having 10-30 carbon atoms, a branched hydrocarbon group having 10-30 carbon atoms, or a cyclic hydrocarbon group having 10-30 carbon atoms, the hydrocarbon groups may each contain -O- or an unsaturated bond, and in the hydrocarbon groups, a hydrogen atom on a carbon positioned two or more atoms away from Y1 may be replaced with fluorine).SELECTED DRAWING: None

Description

[Technical Field]

[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). [Background technology]

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

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

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

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

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

[0007] As a result of extensive research, the present inventors have found that a 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 comprising a block of a structural unit represented by formula (1) and a block of a structural unit having a functional group that can be crosslinked by light. TIFF2025172714000001.tif20136 (In the formula, X 1 is -O- or -NH-, and R 10 is an alkylene or phenylene having 2 to 12 carbon atoms, and Y 1 is a functional group capable of forming double or more hydrogen bonds between two adjacent structural units, and R 11 is a linear hydrocarbon group having 10 to 30 carbon atoms, a branched hydrocarbon group having 10 to 30 carbon atoms, or a cyclic hydrocarbon group having 10 to 30 carbon atoms, and these hydrocarbon groups may contain -O- or an unsaturated bond. 1 Hydrogens on carbons two or more away from may be replaced by fluorine.)

[0009] [2] The block copolymer according to [1], wherein the structural unit having a functional group crosslinkable by light has a structure represented by formula (2): TIFF2025172714000002.tif22140 (In the formula, X 2 is -O- or -NH-, and R 20 represents an alkylene or phenylene having 1 to 12 carbon atoms, and at least one —CH2— in the alkylene may be replaced by —O—, —COO—, or —NHCOO—; Y 2 is a photo-crosslinkable functional group, and R 21 is hydrogen or methyl.)

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

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

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

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

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

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

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

[0017] The following describes in detail the embodiments of the present invention, but the following description is merely an example (typical example) of the embodiments of the present invention, and the present invention is not limited to these examples. In addition, the embodiments of the present invention can be combined as appropriate.

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

[0019] The block copolymer of the present invention is characterized by being composed of a block consisting of a structural unit represented by formula (1) and a block consisting of a structural unit having a functional group that can be crosslinked by light. TIFF2025172714000003.tif19132 (In the formula, X 1 is -O- or -NH-, and R 10 is an alkylene or phenylene having 2 to 12 carbon atoms, and Y 1 is a functional group capable of forming double or more hydrogen bonds between two adjacent structural units, and R 11 is a linear hydrocarbon group having 10 to 30 carbon atoms, a branched hydrocarbon group having 10 to 30 carbon atoms, or a cyclic hydrocarbon group having 10 to 30 carbon atoms, and these hydrocarbon groups may contain -O- or an unsaturated bond. 1 Hydrogens on carbons two or more away from may be replaced by fluorine.)

[0020] The high liquid repellency of the present invention is achieved by the aggregation of the structural units represented by formula (1) between block copolymers. To improve the aggregation ability, it is important that the structural units represented by formula (1) are repeatedly linked to each other within the block. Therefore, the number of linked structural units represented by formula (1) is preferably 20 or more, more preferably 30 or more. From the viewpoint of the solvent solubility of the block copolymer, the number of linked structural units represented by formula (1) is preferably 1000 or less, more preferably 500 or less. However, depending on the desired properties, the upper and lower limits of the number of linked structural units can be selected from ranges other than those mentioned above.

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

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

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

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

[0025] Suitable examples of the constitutional unit represented by formula (1) include structures represented by the following formulas (1-1) to (1-29). TIFF2025172714000004.tif180105

[0026] TIFF2025172714000005.tif172120

[0027] TIFF2025172714000006.tif154124

[0028] TIFF2025172714000007.tif151122

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

[0030] In the block copolymer of the present invention, the content ratio of the structural unit represented by formula (1) relative to the total of the structural units of the block copolymer is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, in order to exhibit high liquid repellency. Furthermore, in order to improve the solvent solubility and liquid repellency durability of the block copolymer and to reduce production costs, the content ratio of the structural unit represented by formula (1) relative to the total of the structural units of the block copolymer is preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.2 or less.

[0031] In the present invention, high liquid repellency and excellent durability of the liquid repellency are achieved by introducing a block consisting of a structural unit represented by formula (1) and a block consisting of a structural unit having a functional group that can be crosslinked by light into a block copolymer. This is because photocrosslinking allows reliable crosslinking even at low temperatures. In this case, a suitable example of the structural unit having a functional group that can be crosslinked by light is the structure represented by formula (2) below. TIFF2025172714000008.tif21133 (In the formula, X 2 is -O- or -NH-, and R 20 represents an alkylene or phenylene having 1 to 12 carbon atoms, and at least one —CH2— in the alkylene may be replaced by —O—, —COO—, or —NHCOO—; Y 2 is a photo-crosslinkable functional group, and R 21 is hydrogen or methyl.)

[0032] In equation (2), Y 2 As the functional group, any known functional group that is crosslinkable by light can be selected. These functional groups may be crosslinkable by light themselves or may be functional groups having a polymerizable group that is crosslinkable via another linking group. Among these functional groups, (meth)acryloyloxy, epoxy, maleic acid ester residue, maleimide residue, and functional groups having a double bond as a polymerizable group are preferably selected because they can be introduced relatively easily into a block copolymer. Of these functional groups, (meth)acryloyloxy or epoxy are more preferred because of the wide variety of crosslinking reactions that can be performed, and (meth)acryloyloxy is most preferred.

[0033] In equation (2), R 21 is hydrogen or methyl. The choice of either of these does not significantly affect the liquid repellency or durability. However, in order to improve the yield during block copolymer synthesis, R 21 is preferably hydrogen.

[0034] Suitable examples of the constitutional unit represented by formula (2) include structures represented by the following formulas (2-1) to (2-14).

[0035] TIFF2025172714000009.tif222102

[0036] TIFF2025172714000010.tif207103

[0037] To obtain the desired durability of liquid repellency, one or more types of constitutional units represented by the above formula (2) may be selected. The constitutional units represented by formula (2) are preferably contained in an amount of 5 mol % to 50 mol %, more preferably 10 mol % to 50 mol %, of the total number of constitutional units of the block copolymer of the present invention.

[0038] In the block copolymer of the present invention, the content ratio of the structural unit represented by formula (2) relative to the total of the structural units of the block copolymer is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, in order to achieve high liquid repellency and durability. Furthermore, in order to reduce the production cost of the block copolymer, the content ratio of the structural unit represented by formula (2) relative to the total of the structural units of the block copolymer is preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.3 or less.

[0039] In addition to the constitutional unit represented by formula (1) and the constitutional unit represented by formula (2) as a constitutional unit having a functional group crosslinkable by light, the block copolymer of the present invention preferably also contains a third constitutional unit in order to improve the solubility of the block copolymer or adjust the material properties.

[0040] As the monomer that forms such a third constitutional unit, for example, a known (meth)acrylic acid derivative can be used. Examples of such known compounds include alkyl (meth)acrylates having 1 to 8 carbon atoms, propargyl (meth)acrylate, allyl (meth)acrylate, cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, oxotetrahydrofuran-3-yl (meth)acrylate, ethylene glycol monoacetoacetate mono(meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, 3-(tris(trimethylsilyloxy)silyl)propyl (meth)acrylate, 3-(dimethoxy(methyl)silyl)propyl (meth)acrylate, 3-(diethoxy(methyl)silyl)propyl (meth)acrylate, 3-sulfopropyl potassium (meth)acrylate, 3-((2-((meth)acryloyloxy)ethyl)dimethylammonio)propane-1-sulfonic acid, (meth)acrylic acid, (meth)acrylamide, N-(hydroxymethyl)acrylamide, and the like.

[0041] Other known styrene derivatives can also be used as the monomer that forms the third structural unit, including styrene, α-methylstyrene, styrene in which one to three hydrogen atoms on the benzene ring are replaced by methyl groups, 2- and 4-acetoxystyrene, 4-methoxystyrene, 4-carboxystyrene, trimethoxy(4-vinylphenyl)silane, and sodium 4-vinylbenzenesulfonate.

[0042] Furthermore, other known monomers that can be suitably used to form the third structural unit include acrylonitrile, vinylpyridine, N-vinylpyrrolidinone, and 1-vinylimidazole.

[0043] To maintain liquid repellency while improving coatability and adhesion to substrates and other objects, it is preferable to select the following monomers to form the third structural unit: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-(tris(trimethylsilyloxy)silyl)propyl (meth)acrylate, (meth)acrylic acid, (meth)acrylamide, N-(hydroxymethyl)acrylamide, N-(hydroxyethyl)acrylamide, styrene, and α-methylstyrene. These monomers may be used alone or in combination to obtain the desired properties.

[0044] The block copolymer of the present invention can be produced by a known method. In this case, the constituent unit represented by formula (1) can be derived using an acrylic monomer having -NCO or a protected -NCO as its precursor. Examples of such monomers include 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI), 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, and 2-(O-(1'-methylpropylideneamino)carboxyamino)ethyl acrylate. "Karenz" is a trade name manufactured by Resonac Corporation.

[0045] A method for producing the block copolymer of the present invention is preferred because it is easy to produce. The method involves block copolymerizing the above-mentioned acrylic monomer having -NCO or a protected -NCO to obtain a precursor, which is then converted to the structure represented by formula (1). In this case, to avoid gelation during polymerization, it is preferable to use a protected acrylate as a raw material for the acrylic monomer having a protected -NCO. Among these protected acrylates, 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate is most preferred because it can suppress gelation while maintaining high polymerizability.

[0046] In the block copolymer of the present invention, other monomers forming the structural unit represented by formula (1) can also be used, such as acrylates that form the structural unit represented by formula (1) without converting the functional group. Known examples of such acrylates (hereinafter referred to as urea acrylates) include the reaction product of 2-isocyanatoethyl acrylate and a primary amine having an alkyl group. However, the use of such monomers can easily lead to problems such as a significant increase in the viscosity of the reaction solution during polymerization. From this perspective, it is preferable to use an acrylic monomer having a protected -NCO group as described above as a raw material. On the other hand, when a monomer having a highly reactive functional group, such as the structural unit represented by formula (2), is used as a comonomer to form a structural unit having a photocrosslinkable functional group and then block copolymerized, it is preferable to use urea acrylate. This selection can prevent the highly reactive functional group from being destroyed during conversion to the structural unit represented by formula (1).

[0047] The polymerization initiator used in producing the block copolymer of the present invention may be a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, depending on the polymerization method of these monomers. Preferred thermal radical polymerization initiators include peroxide-based polymerization initiators such as benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butyl peroxypivalate, di-t-butyl peroxide (DTBPO), t-butyl peroxydiisobutyrate, and lauroyl peroxide, and azo-based polymerization initiators such as 2,2'-azobis(2-methylpropionate)dimethyl (MAIB), azobisisobutyronitrile (AIBN), and azobiscyclohexanecarbonitrile (ACN). Commercially available peroxide polymerization initiators include benzoyl peroxide, available from various companies, as well as products such as "Dicumyl Peroxide" manufactured by Tokyo Chemical Industry Co., Ltd. and "Percumyl D, Niper BMT, and Perhexa 25Z" manufactured by NOF Corporation. Azo polymerization initiators include AIBN, available from various companies, as well as products such as "V-40, V-50, V-59, V-65, V-70, V-501, and V-601" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Generally, azo polymerization initiators can be suitably used for both thermal radical polymerization and photoradical polymerization. The photoradical polymerization initiator is not particularly limited, and known initiators can be used, such as 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, and benzophenone / methyltriethanolamine mixture. Commercially available products include those manufactured by BASF Japan Ltd. under the trade names "Darocur Series 1173, 4265" and "Irgacure Series 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, 2959".

[0048] In order to obtain the desired properties, there are no particular limitations on the average molecular weight or its dispersion value of the block copolymer of the present invention. However, in order to improve liquid repellency and prevent its deterioration over time, the weight-average molecular weight (Mw) of the 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.

[0049] As long as the block copolymer of the present invention is characterized by being composed of a block consisting of a structural unit represented by formula (1) (hereinafter sometimes referred to as block A) and a block consisting of a structural unit having a functional group crosslinkable by light (hereinafter sometimes referred to as block B), it may contain blocks other than block A and block B. There are no restrictions on the structure of the block other than block A and block B (hereinafter sometimes referred to as block C). Preferred structural units constituting block A are the structural units represented by formulas (1-1) to (1-29) described above as structural units represented by formula (1). Preferred structural units constituting block B are the structural units represented by formula (2) as structural units having a functional group crosslinkable by light, particularly the structural units represented by formulas (2-1) to (2-14) described above. Preferred monomers forming the structural units constituting block C are the monomers forming the third structural unit described above. Blocks A, B, and C constituting the block copolymer of the present invention may be homopolymers, random copolymers, or block copolymers of the various structural units constituting these blocks, respectively. Furthermore, in block B, the structural unit having a functional group crosslinkable by light may be a random copolymer of a structural unit represented by formula (2), particularly a structural unit represented by any of formulas (2-1) to (2-14) above, and the third structural unit described above.

[0050] When the block copolymer of the present invention is used, it may be an AB diblock copolymer consisting of block A and block B, an ACB triblock copolymer consisting of block A, block C and block B, an ABC triblock copolymer consisting of block A, block B and block C, or an ACBC tetrablock copolymer consisting of block A, block C, block B and block C. In this case, an AB diblock copolymer is preferred in order to obtain desired properties and to easily produce the block copolymer at the same time.

[0051] For block copolymerization, known precision polymerization methods such as ATRP (atom transfer radical polymerization), NMP (nitroxide-mediated radical 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 for producing the block copolymer of the present invention will also be described in detail in the following examples.

[0052] When using the block copolymer of the present invention, for example, a homopolymer comprising the structural unit represented by formula (1) and another homopolymer other than the structural unit may be separately produced and then linked together. Examples of such a production method include those described in Radical Polymerization Handbook, NTS Publishing, 2010, etc.

[0053] When using the block copolymer of the present invention, the preferred molecular weight of the block copolymer is the same as the range described above. Furthermore, the dispersion value of the average molecular weight, for example, Mw / Mn, which is the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), generally approaches 1 when the above-described precision polymerization method is carried out. Polymerization under conditions that yield 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 the quality of the block copolymer, Mw / Mn is preferably 1 to 10, more preferably 1 to 5.

[0054] When a block copolymer is used as the polymer of the present invention, there are no limitations on the polymerization initiator, radical stabilizer (polymerization inhibitor), solvent, etc. used in block copolymerization, and the conditions for the above-mentioned known precision polymerization method can be used.

[0055] In the production of the block copolymer of the present invention, the conversion of a precursor block copolymer having a protected -NCO group to the structure represented by formula (1) can also be carried out according to known methods. Specifically, the block copolymer can be obtained by reacting a commercially available or known compound having -NH2 with the precursor block copolymer. Examples of commercially available or known compounds having -NH2 include alkylamines and alkyl- or alkoxy-substituted aniline derivatives. The amount of these -NH2-containing compounds added during the reaction is a molar ratio of 0.8 or more relative to the -NCO equivalents in the block copolymer. Because the -NH2-containing compound reacts quantitatively with the -NCO equivalents, this range is consistent with the technology of the present invention. Similarly, the upper limit of the amount of the -NH2-containing compound used is preferably 2.0 or less, more preferably 1.5 or less, and most preferably 1.2 or less, in order to facilitate purification of the block copolymer. In the above calculation, the molar ratio of the -NCO equivalents in the block copolymer can be calculated from the amount of block copolymer used, the abundance ratio of the -NCO equivalents in the block copolymer, and the molecular weight of the structural unit containing the -NCO equivalent. The ratio of -NCO equivalents in the block copolymer is, as will be described later, 1 It can be determined by measurements such as H-NMR.

[0056] The reaction temperature for the conversion to the structure represented by the above formula (1) is 1 In the case of a block copolymer in which the group is -NHCONH-, a temperature of 80°C or higher is preferred to allow the reaction to proceed quickly. Also, a temperature of 120°C or lower is preferred to prevent decomposition of the 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, a reaction time of 30 minutes or more at 100°C is preferred, and 2 hours or less is preferred to prevent decomposition of the block copolymer. One hour is the most preferred reaction time.

[0057] The solvent used in the conversion to the structure represented by formula (1) can be a solvent that is non-reactive or has low reactivity with the precursor block copolymer. A solvent that dissolves both the precursor 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.

[0058] In the block copolymer of the present invention, the introduction of the structural unit represented by formula (2) as a structural unit having a photocrosslinkable functional group can be carried out using a monomer containing the structural unit represented by formula (2) or a precursor monomer (hereinafter referred to as precursor monomer 2) that forms the structural unit represented by formula (2) upon conversion. In this case, it is preferable to use precursor monomer 2 in view of stability during production of the block copolymer and during conversion of the precursor block copolymer to the structure represented by formula (1). As such precursor monomer 2, it is preferable to use a monomer having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-(hydroxymethyl)acrylamide, or N-(hydroxyethyl)acrylamide.

[0059] Other examples of precursor monomer 2 include 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI), 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, 2-(O-(1'methylpropylideneamino)carboxyamino)ethyl acrylate, 2-isocyanatoethyl methacrylate (Karenz (registered trademark) MOI), 2-((3,5-dimethylpyrazolyl]carbamoyl)ethyl methacrylate (Karenz (registered trademark) MOI-BP), and 2-(O-(1'methylpropylideneamino)carboxyamino)ethyl methacrylate (Karenz (registered trademark) MOI-BM). "Karenz" is a trade name manufactured by Resonac Corporation.

[0060] Furthermore, other monomers that can be suitably used to introduce the structural unit represented by formula (2) as a structural unit having a functional group that can be crosslinked by light include glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, and 3-(triethoxysilyl)propyl (meth)acrylate.

[0061] Conversion of the precursor block copolymer into the structural unit represented by formula (2) can be carried out by known methods. For example, when introducing (meth)acryloyloxy into a precursor block copolymer having a hydroxyl group, compounds such as (meth)acrylic anhydride, (meth)acrylic acid chloride, (meth)acrylic acid, (meth)acrylic acid with an activated carboxylic acid, and 2-isocyanatoethyl (meth)acrylate can be used. The block copolymer of the present invention can be obtained by reacting these (meth)acrylic acid derivatives with the precursor block copolymer in the presence of a base or catalyst. In this case, it is most preferable to select (meth)acrylic anhydride because of its high reactivity and minimal side reactions with other functional groups. The conversion of the precursor block copolymer into the structural unit represented by formula (2) will be described in detail in the following examples.

[0062] The composition of the present invention comprises the block copolymer of the present invention, a photoinitiator or catalyst, and a solvent. If necessary, a compound that reacts with the crosslinkable functional group in the structural unit represented by formula (2) or other additives may be added as a structural unit having a photocrosslinkable functional group in the block copolymer of the present invention. Hereinafter, the compound that reacts with the crosslinkable functional group in the structural unit represented by formula (2) is referred to as a reactive compound.

[0063] The solvent that can be used in the composition of the present invention is not limited and can be appropriately selected from known solvents. In this case, it is preferable to use a mixed solvent in order to maintain the solubility of the block copolymer of the present invention and improve its coatability to the substrate or other object to be coated. As such a solvent, in addition to the above-mentioned hydrocarbon solvents, ester solvents, and ether solvents, alcohol solvents can also be suitably used. In addition to the above-mentioned solvents, such solvents include ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, dipropylene glycol methyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, ethyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, dimethyl carbonate 1,3-dioxolane, diisopropyl ether, ethylene glycol dimethyl ether, and water.

[0064] The photoinitiator or catalyst that can be used in the composition of the present invention is added for the purpose of rapidly promoting the reaction between crosslinkable functional groups in the structural unit represented by formula (2) as a structural unit having a photocrosslinkable functional group, or between the crosslinkable functional group and a reactive compound. There are no limitations on such a reaction initiator or catalyst, and it can be appropriately selected from known initiators. For example, when the crosslinkable functional group is (meth)acryloyloxy, it can be selected from the above-mentioned photoradical polymerization initiators. Other reaction initiators or catalysts that can be selected include photoanionic initiators, photocationic initiators, acid catalysts, and metal catalysts.

[0065] In view of the high storage stability of the composition and the high polymerization rate, the polymerization initiator is preferably a photoradical polymerization initiator. As the photoradical polymerization initiator, alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and oxime ester-based photopolymerization initiators are preferred. In view of good wet heat durability, oxime ester-based photopolymerization initiators are particularly preferred.

[0066] Examples of alkylphenone photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one. Commercially available products such as Omnirad 184, Omnirad 127, Omnirad 907, Omnirad 369, and Omnirad 379 may also be used. Omnirad is a trademark of IGM Resins BV.

[0067] Examples of acylphosphine oxide photopolymerization initiators include bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and commercially available products such as Omnirad TPO and Omnirad 819 may be used. Omnirad is a trademark of IGM Resins BV.

[0068] Examples of oxime ester photopolymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and the like. Commercially available products such as IrgacureOXE01, IrgacureOXE02, IrgacureOXE03, IrgacureOXE04, Adeka Arcles N-1919, Adeka Arcles NCI-831, Adeka Arcles NCI-930, and Adeka Arcles NCI-730 may also be used. Here, Irgacure is a trademark of BASF Japan Ltd., and Adeka Arcles is a trademark of ADEKA Corporation.

[0069] In the composition of the present invention, there are no particular limitations on the contents of the block copolymer of the present invention, the photoreaction initiator or catalyst, and the solvent. However, in order to achieve sufficient liquid repellency and from the viewpoints of the solubility of the block copolymer and cost, the content of the block copolymer of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, per 100 parts by weight of the composition.

[0070] In the composition of the present invention, the content of the photoinitiator or catalyst is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, relative to 100 parts by weight of the block copolymer in the composition, in order to promote a sufficient reaction between the crosslinking groups introduced into the block copolymer and to prevent deterioration of the material properties due to residual photoinitiator or its reaction product.

[0071] The composition of the present invention may contain a reactive compound. The reactive compound is a compound that reacts with the crosslinkable functional group of the structural unit represented by formula (2) as a structural unit having a functional group crosslinkable by light in the block copolymer of the present invention. In order to crosslink the block copolymer of the present invention, the reactive compound preferably has multiple reactive functional groups. Furthermore, since no acid or basic impurities are generated after crosslinking, the reactive compound is more preferably one that can undergo a radical reaction with the crosslinkable functional group of the structural unit represented by formula (2). Furthermore, the reactive compound may be a low-molecular-weight compound or a polymer, as long as it maintains solubility in a solvent.

[0072] The amount of these reactive compounds added to the composition is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight, per 100 parts by weight of the block copolymer of the present invention. Furthermore, when the reactive compound is a polymer and meets the following condition 1, the content of the reactive compound is preferably 100 to 10,000 parts by weight per 100 parts by weight of the block copolymer of the present invention in order to further improve durability while maintaining the liquid repellency of the material. For the same purpose, the content of the reactive compound is more preferably 1,000 to 5,000 parts by weight. Condition 1: Surface energy value when the block copolymer of the present invention is made into a film < Surface energy value when the reactive compound is made into a film

[0073] Suitable examples of the reactive compound include bifunctional (meth)acrylates such as alkylene diol di(meth)acrylates having 2 to 12 alkylene carbon atoms, ethylene glycol-based di(meth)acrylates, propylene glycol-based di(meth)acrylates, 4,4'-biphenol di(meth)acrylate, bisphenol A di(meth)acrylate, dioxane glycol di(meth)acrylate, glycerol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, bisphenol A ethoxylate di(meth)acrylate, bisphenol A polyethylene glycol diether di(meth)acrylate, and bisphenol A polypropylene glycol diether di(meth)acrylate.

[0074] Suitable examples of the reactive compound include tri- to hexafunctional (meth)acrylates such as glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0075] Another suitable example of a reactive compound is a thiol compound. Thiol compounds undergo an ene-thiol reaction with a compound having a double bond. The ene-thiol reaction is usually carried out by adding a dicarboxylic acid initiator or the like, but this can suppress oxygen inhibition in the air. Examples of such thiol compounds include esters of polyols such as ethylene glycol, tetramethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, polymethylene glycol, polyethylene glycol, and polypropylene glycol with thiol group (mercapto group)-containing carboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; mercaptoalkyl ethers of the above polyols; and polymercaptoalkanes.

[0076] Specific examples of the thiol compound include trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol bis(thioglycolate), tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptothiopropionate), dipentaerythritol poly(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropyl)ether, pentaerythritol tetrakis(3-mercaptopropyl)ether, ethylene glycol bis(2-mercaptoethyl)ether, tetraethylene glycol bis(2-mercaptoethyl)ether, 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, Multhiol Y-3, and Multhiol Y-4 (trade names, manufactured by SC Organic Chemical Co., Ltd.).

[0077] These thiol compounds may be used alone or in any combination of two or more in any ratio.

[0078] The composition of the present invention may contain additives such as surfactants, emulsifiers, coupling agents, antioxidants, radical stabilizers (polymerization inhibitors), antistatic agents, and hydrolysis stabilizers.

[0079] Surfactants are used to improve wettability, leveling, and coating properties on substrates. Examples of surfactants that can be used include silicone surfactants, acrylic surfactants, and fluorine surfactants. Specific examples include BYK-342, BYK-350, BYK-352, BYK-354, BYK-356, BYK-381, BYK-392, BYK-394, BYK-3441, BYK-3440, and BYK-3550 (all trade names manufactured by BYK Japan Co., Ltd.). As an example of a leveling agent, commercially available silicone surface conditioners can be used, such as BYK-UV3500, BYK-UV-3570 (both trade names: manufactured by BYK Japan Co., Ltd.), and TEGO Examples of suitable acrylic resins include Rad2100, 2200N, 2250, 2500, 2600, and 2700 (all trade names: manufactured by Evonik Degussa Japan Co., Ltd.), X-22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X-22-1602, X-22-1603, X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22-8201, X-22-2426, X-22-164A, and X-22-164C (all trade names: manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added to the composition is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, based on the weight of the block copolymer of the present invention.

[0080] The composition of the present invention may contain a coupling agent to improve adhesion to a substrate or other object 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.

[0081] There is no limit to the antioxidants that can be used in the present invention. Examples include nitroso compounds such as 3,5-di(t-butyl)-4-hydroxytoluene (BHT), hydroquinone, methylene blue, diphenylpicric hydrazide (DPPH), phenothiazine, N,N-dimethyl-4-nitrosoaniline, o-hydroxybenzophenone, and benzothiazine derivatives such as 2H-1,3-benzothiazine-2,4-(3H)dione. Other examples include Adeka Stab AO-20, AO-30, AO-40, AO-50, AO-60, and AO-80, available from ADEKA Corporation; Sumilizer BHT, Sumilizer BBM-S, and Sumilizer GA-80, available from Sumitomo Chemical Co., Ltd.; and Irganox 1076, Irganox 1010, Irganox 3114, and Irganox 245, available from BASF Japan Ltd. These antioxidants may be used alone or in combination of two or more, and may be commercially available products.

[0082] The composition of the present invention may contain an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant, etc. Examples of ultraviolet absorbers include TINUVIN PS, TINUVIN P, TINUVIN 99-2, TINUVIN 109, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 328, TINUVIN 329, TINUVIN 384-2, TINUVIN 571, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, TINUVIN 5236, ADK STAB LA-32, ADK STAB LA-34, ADK STAB LA-36, ADK STAB LA-31, ADK STAB 1413, and ADK STAB LA-51. "Tinuvin (registered trademark)" is a trade name manufactured by BASF Japan Ltd., and "Adekastab (registered trademark)" is a trade name manufactured by ADEKA Corporation. These ultraviolet absorbents may be used alone or in combination of two or more. Furthermore, these ultraviolet absorbents may be commercially available products.

[0083] Examples of light stabilizers include Tinuvin 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622, Tinuvin 770, Tinuvin 765, Tinuvin 780, Tinuvin 905, Tinuvin 5100, Tinuvin 5050, 5060, Tinuvin 5151, Kimassorb 119FL, Kimassorb 944FL, Kimassorb 944LD, and ADK STAB. Examples of such stabilizers include ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77, ADK STAB LA-82, ADK STAB LA-87, Cytec's trade name: Cyasorb UV-3346, and Goodrich's trade name: Goodlite UV-3034. "Chimasorb (registered trademark)" is a trade name manufactured by BASF Japan Ltd. These light stabilizers may be used alone or in combination of two or more. These light stabilizers may also be commercially available products.

[0084] 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.

[0085] It is also suitable to add a hydrolysis stabilizer to the composition of the present invention in order to suppress hydrolysis of the polyacrylic acid ester and the like and to prevent deterioration over time or due to the environment. Examples of such hydrolysis stabilizers include Carbodilite (registered trademark) manufactured by Nisshinbo Chemical Inc., Carbodista (registered trademark) manufactured by Teijin Limited, and Stavaxol (registered trademark) manufactured by Lanxess K.K.

[0086] 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.

[0087] 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.

[0088] The article of the present invention, having the composition of the present invention applied to the surface thereof, can be obtained by applying the composition to a substrate, removing the solvent, and then photocrosslinking the block copolymer. In this case, the solvent removal and crosslinking steps may be performed in the reverse order or simultaneously.

[0089] Examples of methods for applying the composition of the present invention include a coating method using a dispenser, a spin coating method, a roll coating method, a caten coating method, a flow coating method, a printing method, a microgravure coating method, a gravure coating method, a wire bar coating method, a dip coating method, a spray coating method, a meniscus coating method, and an inkjet method.

[0090] There are no particular limitations on the method for removing the solvent, but heat treatment is preferred as it allows for a uniform coating to be formed in a short time. There are no particular limitations on the temperature conditions, but when applying to substrates with low heat resistance such as fibers or paper, mild conditions of around 120°C can be used to achieve sufficiently good liquid repellency. Heat treatment can be performed using equipment such as an oven or hot plate.

[0091] The block copolymer of the present invention can be crosslinked by light. Photocrosslinking can be achieved by irradiating the composition of the present invention with, for example, ultraviolet light. Irradiation with ultraviolet light can be achieved by conventional methods such as using a high-pressure mercury lamp, an ultraviolet light-emitting diode (LED), or a low-pressure mercury lamp. Crosslinking may also be achieved by a combination of heat and light. When crosslinking is achieved by a radical reaction, it is preferable to carry out the crosslinking in a nitrogen atmosphere in order to increase the reaction rate.

[0092] The crosslinking of the block copolymer of the present invention is preferably carried out by light, since reliable crosslinking can be achieved at low temperatures. Photocrosslinking can also pattern crosslinked and non-crosslinked regions as needed. On the other hand, the crosslinking of the block copolymer of the present invention can also be carried out by combining photocrosslinking with heat.

[0093] The composition of the present invention exhibits little deterioration over time in terms of liquid repellency and has high durability against heat and other factors. On the other hand, if further improvement in the durability of liquid repellency is desired, it is also preferable to subject the substrate to a treatment in advance that promotes adhesion between the composition of the present invention and the substrate. Examples of such treatments include UV ashing using ozone and plasma treatment. Another preferable method is to apply an adhesive or crosslinking agent to the substrate.

[0094] 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 functional groups capable of reacting with the above-mentioned crosslinking agent in order to improve durability.

[0095] Examples of compounds having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate; diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; and trimers and trimethylolpropane adducts of these isocyanurate rings. Examples of compounds having one or more blocked isocyanate groups include compounds in which the isocyanate groups of the above-mentioned compounds are protected with a blocking agent. Examples of blocking agents used in this case include organic blocking agents such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, and lactams, as well as bisulfites such as sodium bisulfite and potassium bisulfite. The above-mentioned crosslinking agents may be used alone or in combination.

[0096] Treatment of textile products with a crosslinking agent can be carried out, for example, by immersing the textile product in a treatment solution prepared by dissolving the crosslinking agent in an organic solvent or emulsifying and dispersing it in water. The crosslinking agent is then immobilized on the substrate by a heat treatment or other treatment. The immobilization of the crosslinking agent may be carried out before or simultaneously with the treatment of the substrate with the composition of the present invention. Considering process simplification, energy savings, and economic efficiency, it is preferable to immobilize the crosslinking agent simultaneously with the treatment with the composition of the present invention. When the crosslinking agent is immobilized by heating, it is preferably carried out at a temperature of 110 to 180°C for 1 to 5 minutes.

[0097] The substrate to which the composition of the present invention can impart liquid repellency is not particularly limited, and glass, metal, plastic, paper, fiber, etc. can be suitably used. For example, the material for textile products is not particularly limited, and examples thereof include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polylactic acid, polyamide resins such as nylon 6 and nylon 6,6, polyurethane resins, fluorine-based resins such as polyvinylidene fluoride and polytetrafluoroethylene, polysulfone, polyethersulfone, and cellulose-based materials such as cellulose and cellulose acetate. These may be used alone or in combination of two or more. [Example]

[0098] 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.

[0099] <Measurement of polymer weight average molecular weight (Mw) and dispersion value (Mw / Mn)> Analysis was performed by GPC measurement. The equipment used was a high-performance liquid chromatograph system manufactured by Shimadzu Corporation. The columns used were two Agilent Technologies PLgel 5μm MIXED-D2 columns connected in series, and THF was used as the solvent. The standard reagent (standard polystyrene) for average molecular weight was STANDARD SM-105 manufactured by Resonaq Co., Ltd.

[0100] <Confirmation of block copolymer structure> Nuclear magnetic resonance spectrum (500MHz, manufactured by JASCO Corporation) 1 The measurement solvent was CDCl3, and tetramethylsilane was used as the standard substance.

[0101] <Exposure> Photocrosslinking of the block copolymer was carried out using an ultra-high pressure mercury lamp (Multilight USH-250BY; manufactured by Ushio Inc.). The exposure dose was measured by connecting a UIT-150-A (manufactured by Ushio Inc.) to a UVD-S365 and measuring the luminance at a wavelength of 365 nm.

[0102] <Film observation and film thickness measurement> The state of the prepared film was confirmed using a KLA Tencor P+16 step gauge (manufactured by KLA Tencor). The film thickness was measured by scraping off a portion of the film with a cutter and measuring the step using the above step gauge. The film thickness was calculated by averaging five measurements taken at different locations.

[0103] <Surface tension measurement> Measurements were made using a contact angle meter (PCA-1; manufactured by Kyowa Interface Science Co., Ltd.). Values ​​were taken as the average of five measurements taken at different locations. Measurements were made at room temperature.

[0104] <Scratch test> Measurements were performed using a nanoindenter measuring device (Nano Indenter G200; manufactured by KLA Corporation). The conditions were scratch length: 400 μm, minimum indentation pressure: 0 mN, maximum indentation pressure: 0.5 mN, and scratch speed: 10 μm / s. Evaluation was performed by observing the scratched area with the device and by the indentation pressure at which a scratch was created. If the scratch mark was not noticeable in the former case and the latter value was 0.15 mN or higher, the scratch resistance was judged to be good.

[0105] <Monomers, polymerization initiators, RAFT reagents, alkylamines, other reagents, reactive compounds, and solvents> The following commercially available products were used: Monomers: 2-isocyanatoethyl acrylate, methyl acrylate, 2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate (HBA) (all manufactured by Tokyo Chemical Industry Co., Ltd.) Thermal radical polymerization initiator: 2,2'-azobis(isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.) RAFT reagent: 4-cyano-4-[[(dodecylthio)carbonothioyl]thio]pentanoic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) Alkylamine: n-dodecylamine, n-hexadecylamine, stearylamine (all manufactured by Tokyo Chemical Industry Co., Ltd.) Other reagents: acrylic anhydride, pyridine, n-hexadecane (all manufactured by Tokyo Chemical Industry Co., Ltd.) Photoradical polymerization initiator: ADEKA Arcles NCI-930 (manufactured by ADEKA Corporation) Reactive compounds: multifunctional acrylate; 1,6-bis(acryloyloxy)hexane (Tokyo Chemical Industry Co., Ltd.); multifunctional thiol; Multhiol Y-3 (SC Organic Chemical Co., Ltd.); 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione (Tokyo Chemical Industry Co., Ltd.) Urethane acrylate: UN-3320HA (manufactured by Negami Chemical Industries Co., Ltd.) Solvent: toluene, THF, isopropanol (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0106] 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.

[0107] <Base material> A glass substrate, Eagle XG (registered trademark) (trade name, manufactured by Corning, 0.5 mm thick), was cut into a 40 mm square. The surface of this substrate was washed with acetone and ultrapure water, dried in an oven at 120°C for 1 hour, and cooled to room temperature.

[0108] [Example 1] Synthesis of Block Copolymer 1 (AB-type block copolymer consisting of structural units of formula (1-11) (block A) and structural units derived from formula (2-1) and methyl acrylate (block B))

[0109] <Synthesis of Block Copolymer 1 Precursor> A Schlenk flask was charged with 1.1637 g (4.905 mmol) of 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, 7.0 mg (0.043 mmol) of AIBN, 15.9 mg (0.0394 mmol) of 4-cyano-4-[[(dodecylthio)carbonothioyl]thio]pentanoic acid, and 3.4 mL of toluene. The mixture was freeze-degassed three times using a vacuum pump. After 50 minutes of reaction in an 80 °C oil bath under a nitrogen atmosphere, a solution of 0.51 mL of HEA and 1.32 mL of methyl acrylate (freeze-degassed as above) in 1.2 mL of toluene was added. The reaction mixture was heated and stirred in an 80 °C oil bath for 4 hours. The reaction mixture was cooled to room temperature and used directly in the next reaction.

[0110] To the reaction solution, 1.45 g (5.38 mmol) of stearylamine and 1 ml of toluene were added and reacted at 100°C for 2 hours. The reaction solution was reprecipitated in 100 ml of isopropanol. After stirring at room temperature for 1 hour, the mixture was left overnight. The resulting precipitate was filtered, stirred in 50 ml of isopropanol for 1 hour, and then filtered. The resulting block copolymer 1 precursor was vacuum dried at 50°C for 8 hours. The weight-average molecular weight of the block copolymer 1 precursor was 93,000.

[0111] Block copolymer 1 precursor 1 From H-NMR measurement, the molar ratio of the structural units of formula (1-11) / HEA-derived / methyl acrylate-derived was 2 / 1.8 / 6.

[0112] <Conversion to block copolymer 1> 30 ml of THF was added to 3.00 g of the above block copolymer 1 precursor and heated to 50°C. 0.90 ml (7.7 mmol) of acrylic anhydride and 0.61 ml (7.6 mmol) of pyridine were added thereto and stirred at 50°C for 24 hours. The reaction solution was reprecipitated in 100 ml of methanol. After stirring at room temperature for 1 hour, the mixture was left overnight. The resulting precipitate was filtered, stirred in 50 ml of methanol for 1 hour, and then filtered again. The resulting powder was vacuum dried at room temperature for 8 hours to obtain block copolymer 1.

[0113] The weight average molecular weight of block copolymer 1 was 92,000. 1 H-NMR analysis revealed that the incorporation rate of acrylic acid into the block copolymer was approximately 75 mol%. Therefore, the molar ratio of the constituent units of block copolymer 1, i.e., formula (1-11) / formula (2-1) / 2-HEA-derived / methyl acrylate-derived, was 2 / 1.17 / 0.63 / 6.

[0114] [Example 2] to [Example 7] In the same manner as in Example 1 above, the raw materials and their amounts, as well as the reaction time for introducing crosslinkable functional groups, were varied to obtain the following block copolymers 2 to 7. These are all AB-type block copolymers. In Table 1, the numbers in brackets indicate the abundance ratio (molar ratio) of the constituent units. The numbers in the Example / Copolymer column indicate both the example number and the block copolymer number. Block copolymer 1 synthesized in Example 1 is also listed in the table.

[0115] [Table 1] TIFF2025172714000011.tif93162

[0116] [Example 8] <Preparation of Composition 1> 0.25 g of the block copolymer 1 obtained in Example 1 was dispensed into a sample bottle and dissolved in 3.80 g of toluene and 0.96 g of isopropanol. 5.0 mg of Adeka Arcles NCI-930 was added and dissolved therein to obtain Composition 1 with a solids concentration of approximately 5 wt %.

[0117] [Example 9] to [Example 13] <Preparation of Compositions 2 to 6> Using the block copolymers synthesized in the above examples, compositions 2 to 6 having the formulations shown in Table 2 were prepared in the same manner as in Example 8. Table 2 also lists Example 8.

[0118] [Table 2] TIFF2025172714000012.tif47158

[0119] [Example 14] <Production of measurement items and evaluation of physical properties> Composition 1 was spin-coated onto a glass substrate. The rotation speed of the glass substrate was 500 rpm. The glass substrate was heated on a hot plate at 80°C for 1 minute to remove the solvent. The substrate was exposed to light in a nitrogen atmosphere to crosslink the block copolymer. The exposure dose was 1.4 J / cm 2 The film thickness of the prepared film sample was 1.47 μm, and the contact angle of the film sample with hexadecane was 43.9 degrees.

[0120] A scratch test was carried out on the film sample prepared in the same manner as above. The result showed that the indentation pressure required to generate a scratch was 0.293 mN, and the scratch resistance was good, including observations using the device.

[0121] In this manner, a composition containing the block copolymer of the present invention and a solvent was applied to a glass substrate as a base material, and an article of the present invention was prepared in which the block copolymer was crosslinked. The contact angle and scratch resistance were measured using this measurement article.

[0122] [Example 15] to [Example 19] Film samples were prepared on glass substrates in the same manner as in Example 14, 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 3 shows the results of Example 14 again.

[0123] [Table 3] TIFF2025172714000013.tif62156

[0124] [Comparative Example 1] In the same manner as in Example 6 of Japanese Patent Application No. 2023-149334, a block copolymer having no crosslinkable functional group (a structural unit of formula (1), X 1 -O-, R 10 is ethylene, Y 1 -NHCONH-, R 11 nC 18 H 37 The obtained copolymer had a molar ratio of 2:8 of the constituent units of the AB block copolymer.

[0125] Using this block copolymer, Composition 7 with a solids concentration of approximately 5 wt% was prepared in the same manner as in Example 8. Adeka Arcles NCI-930 was not added to Composition 7. Composition 7 was applied to a glass substrate in the same manner as in Example 14, and the solvent was then removed to obtain a film. The film was not exposed to light. The film thickness of the sample in Comparative Example 1 was 1.31 μm, and the contact angle of hexadecane was 44.4 degrees. The pressing pressure at which the clutch occurred was 0.083 mN, and the scratch resistance, including observation using an instrument, was poor.

[0126] Comparative Example 2 Using the block copolymer 1 precursor synthesized in Example 1, a mixture was obtained by adding 1 / 3 molar equivalent of the crosslinking agent, 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione, a compound described in Example 19 of JP 2022-159191 A, relative to the hydroxyl groups of the block copolymer 1 precursor. Using this mixture, Composition 8 with a solids concentration of approximately 5 wt. % was prepared in the same manner as in Example 8. Adeka Arcles NCI-930 was not added to Composition 8. Composition 8 was applied to a glass substrate in the same manner as in Example 14 of the present application, and the solvent was removed to obtain a film. The film was not exposed to light. The film thickness of the sample in Comparative Example 2 was 1.49 μm, and the contact angle of hexadecane was 42.4 degrees. A scratch test was also attempted on the sample in Comparative Example 2, but the film had significant unevenness, making it impossible to measure.

[0127] Comparative Example 3 Using the block copolymer 5 precursor synthesized in Example 5, a compound described in Example 19 of JP 2022-159191 A (1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione) was used as a crosslinking agent. The crosslinking agent was added in an amount of 1 / 3 molar equivalent relative to the hydroxyl groups of the block copolymer 5 precursor to obtain a mixture. Using this mixture, a film of Composition 9 with a solids concentration of approximately 5 wt. % was prepared in the same manner as in Comparative Example 2. The film thickness of the Comparative Example 3 sample was 1.46 μm, and the contact angle of hexadecane was 43.4°. A scratch test was also attempted on the Comparative Example 3 sample, but the indentation pressure at which a clutch occurred was 0.114 mN, and the scratch resistance, including observations using the device, was poor. The results of the physical property measurements of Comparative Examples 1 to 3 are also summarized in Table 3 above.

[0128] [Example 20] <Preparation of Composition 7, Fabrication of Measurement Articles, and Evaluation of Physical Properties> 0.0750 g of the random copolymer 1 of the present invention and 1.425 g of the urethane acrylate polymer UN-3320HA were dissolved in a mixed solution of 16,000 g of toluene and 4,000 g of isopropanol. 0.0150 g of Omnirad 184 was added and dissolved to obtain Composition 7. Composition 7 was spin-coated onto a glass substrate in the same manner as in Example 14 above, and then exposed to light. The film thickness of the prepared film sample was 0.73 μm. The contact angle of the film sample with hexadecane was 42.0 degrees.

[0129] A scratch test was carried out on the film sample prepared in the same manner as above. As a result, the indentation pressure at which scratches were generated was 0.385 mN, and the scratch resistance was good, including observation by the instrument.

[0130] As is clear from the comparison between the examples of the present invention and the comparative examples, it is found that the film prepared by using the block copolymer of the present invention and crosslinking the block copolymer has high liquid repellency and at the same time high durability. [Industrial Applicability]

[0131] Articles such as membranes made using materials composed of compositions containing the block copolymers of the present invention have high liquid repellency, even though the materials contain no fluorine or have fluorine removed to the greatest extent possible. They also have excellent durability. The technology of the present invention contributes to reducing the environmental impact when imparting liquid repellency to, for example, various filters, clothing, leather, furniture, and film materials, and is therefore extremely useful industrially.

Claims

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

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

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

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

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

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 further comprising a photoinitiator.

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

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

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

11. An article comprising a substrate to which the composition according to claim 7 is applied, and the block copolymer is crosslinked.

12. An article comprising the composition according to claim 8 applied to a substrate and the block copolymer crosslinked.

13. An article comprising the composition according to claim 9 applied to a substrate and the block copolymer crosslinked.

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