ABA triblock polymer, composition, surface treatment agent, article, and method for producing article

Abstract

Provided are: an ABA triblock polymer having an A block and a B block, the A block being a random polymer containing structural units derived from a polymerizable monomer containing a reactive group and structural units derived from a polymerizable monomer containing a hydrophobic group, and the B block containing a divalent organopolysiloxane residue in the main chain; and the use of the ABA triblock polymer.

Description

ABA triblock polymer, composition, surface treatment agent, article, and method for manufacturing article

[0001] The present disclosure relates to ABA triblock polymers, compositions, surface treatments, articles, and methods of making articles.

[0002] In recent years, there has been a demand for technologies that make surfaces of articles less susceptible to fingerprints and that make them easier to remove stains, in order to improve performance such as appearance and visibility. As a specific method, a method of performing a surface treatment on the surface of an article using a surface treatment agent is known.

[0003] For example, Patent Document 1 describes a curable composition containing a specific organosilicon compound and / or its partial hydrolysis condensate, water in an amount theoretically sufficient for 100% hydrolysis condensation, a vinyl group-containing alkoxysilane, a vinyl group-containing polysiloxane, a methacrylic acid ester and / or an acrylic acid ester having a hydroxyl group, and a silicone-modified acrylic copolymer obtained by copolymerizing the methacrylic acid ester and / or the acrylic acid ester. Patent Document 2 describes a surfactant containing a block copolymer having a segment consisting of a molecular chain containing a unit derived from a monomer having a perfluoroalkyl group having 1 to 6 carbon atoms and a segment consisting of another molecular chain. Patent Document 3 describes a water repellent containing a silicon-containing polymer whose essential components are a repeating unit derived from a (meth)acrylate having a linear or branched hydrocarbon group having 8 to 30 carbon atoms and a repeating unit derived from a silicone macromer having a radically polymerizable group.

[0004] Japanese Patent Laid-Open No. 9-111185 Japanese Patent Laid-Open No. 2007-186671 Japanese Patent Laid-Open No. 2018-95879

[0005] On the other hand, compositions used as surface treatment agents and the like are required to be further improved in terms of antifouling properties.

[0006] The present disclosure has been made in consideration of these circumstances, and a problem to be solved by one embodiment of the present invention is to provide an ABA triblock polymer and a composition useful as a surface treatment agent capable of forming a surface treatment layer having excellent antifouling properties on a substrate. Another problem to be solved by one embodiment of the present invention is to provide a surface treatment agent capable of forming a surface treatment layer having excellent antifouling properties on a substrate. Another problem to be solved by one embodiment of the present invention is to provide an article having a surface treatment layer having excellent antifouling properties, and a method for producing the article.

[0007] The present disclosure includes the following aspects. <1> An ABA triblock polymer having an A block and a B block, wherein the A block is a random polymer including a structural unit derived from a polymerizable monomer having a reactive group and a structural unit derived from a polymerizable monomer having a hydrophobic group, and the B block includes a divalent organopolysiloxane residue in the main chain. <2> The ABA triblock polymer according to <1>, wherein the hydrophobic group is at least one group selected from the group consisting of a linear alkyl group having 12 to 30 carbon atoms and a divalent organopolysiloxane residue. <3> The ABA triblock polymer according to <1> or <2>, wherein the reactive group is at least one group selected from the group consisting of a reactive silyl group, an isocyanato group, a phosphate ester group, a carboxy group, a carbodiimide group, an oxazoline group, and an epoxy group. <4> The ABA triblock polymer according to any one of <1> to <3>, wherein the reactive group is a reactive silyl group. <5> The ABA triblock polymer according to any one of <1> to <4>, wherein the B block has a structure represented by the following formula (B1): In formula (B1), R １１ are each independently a divalent linking group, and R １２ are each independently a hydrocarbon group, and X １are each independently an electron-withdrawing group, m is an integer of 1 or greater, and * represents a linking site with the A block. <6> The ABA triblock polymer according to any one of <1> to <5>, wherein the mass ratio of the content of the A block to the content of the B block is 0.4 to 9. <7> The ABA triblock polymer according to any one of <1> to <6>, wherein the mass ratio of the content of the structural units derived from a polymerizable monomer containing a hydrophobic group to the content of the structural units derived from a polymerizable monomer containing a reactive group in the A block is 5 to 20. <8> A composition comprising the ABA triblock polymer according to any one of <1> to <7> and a liquid medium. <9> A surface treatment agent comprising the ABA triblock polymer according to any one of <1> to <7>. <10> The surface treatment agent according to <9>, further comprising a liquid medium. <11> A method for producing an article, comprising surface-treating a substrate with the surface treatment agent according to <9> or <10>, to produce an article having a surface-treated layer formed on the substrate. <12> An article comprising a substrate and a surface treatment layer disposed on the substrate and surface-treated with the surface treatment agent according to <9> or <10>. <13> The article according to <12>, which is an optical member. <14> The article according to <12>, which is a display or a touch panel. <15> The article according to <12>, wherein the substrate is a fabric or a nonwoven fabric.

[0008] According to one embodiment of the present invention, an ABA triblock polymer and composition useful as a surface treatment agent capable of forming a surface treatment layer having excellent antifouling properties on a substrate are provided. According to one embodiment of the present invention, a surface treatment agent capable of forming a surface treatment layer having excellent antifouling properties on a substrate is provided. According to one embodiment of the present invention, an article having a surface treatment layer having excellent antifouling properties and a method for producing an article are provided.

[0009] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit value of that numerical range may be replaced with a value shown in the Examples. In the present disclosure, "surface treatment layer" refers to a layer formed on the surface of a substrate by surface treatment. In the present disclosure, "polymerizable monomer" refers to a monomer having a polymerizable group. In the present disclosure, "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate. Furthermore, "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic.

[0010] [ABA Triblock Polymer] The ABA triblock polymer of the present disclosure is an ABA triblock polymer having an A block and a B block, in which the A block is a random polymer containing a constitutional unit derived from a polymerizable monomer containing a reactive group and a constitutional unit derived from a polymerizable monomer containing a hydrophobic group, and the B block contains a divalent organopolysiloxane residue in the main chain.

[0011] When the ABA triblock polymer of the present disclosure is used as a surface treatment agent, a surface treatment layer with excellent antifouling properties can be formed. The reason for this is unclear, but is presumed to be as follows. In the ABA triblock polymer of the present disclosure, the A block contains a structural unit derived from a polymerizable monomer containing a hydrophobic group, resulting in a hydrophobic side chain. In addition, the divalent organopolysiloxane residue contained in the main chain of the B block is also hydrophobic. Since the entire polymer is hydrophobic and both the hydrophobic functions of the side chain and the hydrophobic functions of the main chain are achieved, it is believed that a surface treatment layer with excellent antifouling properties can be obtained. In addition, since the A block contains a structural unit derived from a polymerizable monomer containing a reactive group, it is believed that the reactive group reacts with the substrate surface, contributing to improved adhesion to the substrate.

[0012] The polymers described in Patent Documents 1 and 3 are random polymers, and there is no description of an ABA triblock polymer. The polymer described in Patent Document 2 is a block polymer, but does not contain a structural unit derived from a polymerizable monomer containing a reactive group. Furthermore, Patent Document 2 does not focus on antifouling properties.

[0013] The ABA triblock polymer (hereinafter also simply referred to as "block polymer") of the present disclosure will be described in detail below.

[0014] The block polymer of the present disclosure is an ABA triblock polymer having an A block and a B block. In the block polymer of the present disclosure, the A block is bonded to both ends of the B block. That is, in the block polymer of the present disclosure, the A block and the B block are linked in the order A block-B block-A block.

[0015] The A block is a random polymer containing a constitutional unit derived from a polymerizable monomer containing a reactive group and a constitutional unit derived from a polymerizable monomer containing a hydrophobic group.

[0016] (Structural Unit Derived from Polymerizable Monomer Having a Reactive Group) The structural unit derived from a polymerizable monomer having a reactive group contained in the A block may be of only one type, or may be of two or more types. The structural unit derived from a polymerizable monomer having a reactive group may have only one reactive group, or may have two or more reactive groups.

[0017] The polymerizable group contained in the polymerizable monomer containing a reactive group may be a cationically polymerizable group or a radically polymerizable group. From the viewpoint of excellent curability, the polymerizable group is preferably a radically polymerizable group. Furthermore, from the viewpoint of excellent curability, the radically polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloyl group.

[0018] In the structural unit derived from a polymerizable monomer containing a reactive group, the reactive group is preferably a functional group capable of forming a covalent bond with a hydroxyl group, in view of excellent adhesion between the substrate and the surface treatment layer.

[0019] Among these, from the viewpoint of forming a surface treatment layer having excellent antifouling properties, the reactive group is more preferably at least one selected from the group consisting of a reactive silyl group, an isocyanato group, a phosphate ester group, a carboxy group, a carbodiimide group, an oxazoline group, and an epoxy group, and is even more preferably a reactive silyl group.

[0020] The reactive silyl group refers to a group in which a reactive group is bonded to a silicon atom (Si atom). The reactive group is preferably a hydrolyzable group or a hydroxyl group.

[0021] A hydrolyzable group is a group that becomes a hydroxyl group upon hydrolysis. That is, a hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH upon hydrolysis. The silanol groups further react with each other to form Si-O-Si bonds. Furthermore, the silanol groups can undergo a dehydration condensation reaction with silanol groups derived from oxides present on the surface of the substrate to form Si-O-Si bonds. Examples of hydrolyzable groups include alkoxy groups, aryloxy groups, halogen atoms, acyl groups, acyloxy groups, and isocyanato groups (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. However, the aryl group of the aryloxy group includes a heteroaryl group. The halogen atom is preferably a chlorine atom. The acyl group is preferably an acyl group having 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.

[0022] From the viewpoints of facilitating the production of a uniform film and providing excellent durability, the reactive silyl group is preferably an alkoxysilyl group. Among these, the alkoxysilyl group is preferably a dialkoxysilyl group or a trialkoxysilyl group, and more preferably a trialkoxysilyl group.

[0023] The reactive silyl group is preferably a group represented by the following formula A:

[0024] -Si(R １ ) ｎ L ３－ｎ … (A) R １are each independently a hydrocarbon group; each L is independently a hydrolyzable group or a hydroxyl group; and n is an integer of 0 to 2.

[0025] When there are multiple reactive silyl groups in one molecule, the multiple reactive silyl groups may be the same or different from each other. From the viewpoints of availability of raw materials and ease of production of the compound, it is preferable that the multiple reactive silyl groups are the same.

[0026] R １ are each independently a hydrocarbon group, preferably a saturated hydrocarbon group. １ The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0027] As the hydrolyzable group, those mentioned above are preferred.

[0028] Among these, from the viewpoint of ease of production of the compound, L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom. L is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group or a methoxy group, from the viewpoint of less outgassing during coating and better storage stability of the compound.

[0029] n is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. The presence of a plurality of Ls strengthens the adhesion of the surface treatment layer to the substrate. When n is 1 or less, the plurality of Ls present in one molecule may be the same or different from each other. From the viewpoint of the ease of obtaining raw materials and the ease of manufacturing the compound, it is preferable that the plurality of Ls are the same. When n is 2, the plurality of Rs present in one molecule may be the same or different from each other. １ may be the same or different from each other. From the viewpoint of availability of raw materials and ease of production of the compound, it is preferable to use a plurality of R １ are preferably the same.

[0030] Examples of polymerizable monomers having a reactive silyl group include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 4-methacryloxybutyltrimethoxysilane, 4-methacryloxybutyltriethoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 4-acryloxybutyltrimethoxysilane, and 4-acryloxybutyltriethoxysilane. Among these, from the viewpoint of excellent curability, the polymerizable monomer having a reactive silyl group is preferably 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, or 3-acryloxypropyltrimethoxysilane, and more preferably 3-methacryloxypropyltrimethoxysilane.

[0031] Examples of polymerizable monomers having an isocyanato group include 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate.

[0032] The polymerizable monomer having an isocyanato group may be blocked with a blocking agent, such as a pyrazole such as 3,5-dimethylpyrazole, an oxime such as 2-butanone oxime, or a lactam such as ε-caprolactam.

[0033] An example of the polymerizable monomer having a phosphate group is 2-(meth)acroyloxyethyl acid phosphate.

[0034] Examples of polymerizable monomers having a carboxy group include (meth)acrylic acid, itaconic acid, 2-(meth)acryloyloxyethyl succinic acid, and 2-(meth)acryloyloxyhexahydrophthalic acid.

[0035] The polymerizable monomer having a carboxy group may be an anhydride, such as (meth)acrylic anhydride or itaconic anhydride.

[0036] An example of the polymerizable monomer having a carbodiimide group is 1-ethyl-3-propyl(meth)acroylcarbodiimide.

[0037] An example of a polymerizable monomer having an oxazoline group is 2-vinyl-oxazoline.

[0038] An example of the polymerizable monomer having an epoxy group is glycidyl (meth)acrylate.

[0039] The content of the structural unit derived from the polymerizable monomer containing a reactive group is preferably from 1 to 20% by mass, and more preferably from 3 to 15% by mass, based on the total amount of the A block.

[0040] (Constituent Unit Derived from Polymerizable Monomer Containing Hydrophobic Group) The constituent unit derived from a polymerizable monomer containing a hydrophobic group contained in the A block may be of only one type, or may be of two or more types.

[0041] The number of polymerizable groups contained in the hydrophobic group-containing polymerizable monomer may be only one, or may be two or more.

[0042] The polymerizable group contained in the hydrophobic group-containing polymerizable monomer may be a cationically polymerizable group or a radically polymerizable group. From the viewpoint of excellent curability, the polymerizable group is preferably a radically polymerizable group. Furthermore, from the viewpoint of excellent curability, the radically polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloyl group.

[0043] In this disclosure, a hydrophobic group means a group that is not capable of hydrogen bonding with water.

[0044] The number of hydrophobic groups contained in the hydrophobic group-containing polymerizable monomer may be only one, or may be two or more.

[0045] In the structural unit derived from a polymerizable monomer containing a hydrophobic group, the hydrophobic group may be, for example, at least one group selected from the group consisting of a hydrocarbon group and an organopolysiloxane residue.

[0046] The hydrocarbon group may be a monovalent hydrocarbon group or a divalent hydrocarbon group. The monovalent hydrocarbon group may be an aliphatic hydrocarbon group (alkyl group), an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. The alkyl group may be a linear alkyl group or a branched alkyl group.

[0047] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a decyl group, a lauryl group, a tetradecyl group, a hexadecyl group, a stearyl group, an eicosyl group, and a behenyl group.

[0048] Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decahydronaphthyl group, an adamantyl group, and a norbornyl group.

[0049] Examples of aromatic hydrocarbon groups include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group.

[0050] Examples of combinations of an alkyl group and an aromatic hydrocarbon group include a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

[0051] Examples of the combination of an alkyl group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, and an isobornyl group.

[0052] The divalent hydrocarbon group may be a divalent aliphatic hydrocarbon group (alkylene group), a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination thereof. The alkylene group may be a linear alkylene group or a branched alkylene group.

[0053] Examples of the divalent hydrocarbon group include groups in which one hydrogen atom has been removed from the above-mentioned monovalent hydrocarbon groups.

[0054] Examples of organopolysiloxane residues include groups represented by the following formulae P1 to P3. Formulae P1 to P3 may be contained alone or in combination of two or more.

[0055]

[0056] In formulas P1 to P3, R ３ are each independently a hydrocarbon group. In formula P1, s1 is an integer of 1 or more. In formula P2, s2 and s3 are each independently an integer of 1 or more. In formula P3, s4 is an integer of 1 to 3.

[0057] Examples of the organopolysiloxane residue include the groups shown below. ａ are each independently a hydrocarbon group. * indicates a linking site.

[0058]

[0059] R ３ or R ａ Examples of the hydrocarbon group represented by the formula (I) include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among these, the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. The alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferred, and a methyl group, an ethyl group, an n-propyl group, or an n-butyl group is more preferred, and a methyl group is even more preferred.

[0060] s1 is an integer of 1 or more, preferably 5 to 250, and more preferably 10 to 200.

[0061] s2 is an integer of 1 or more, preferably 2 to 5, and more preferably 2 to 3.

[0062] s3 is an integer of 1 or more, preferably 5 to 250, and more preferably 10 to 200.

[0063] s4 is an integer of 1 to 3, preferably 1 or 2.

[0064] Examples of polymerizable monomers containing a hydrophobic group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, and isobornyl (meth)acrylate. (meth)acrylates such as methyl acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dodecyl (meth)acrylate [also known as lauryl (meth)acrylate], tetradecyl (meth)acrylate [also known as myristyl (meth)acrylate], hexadecyl (meth)acrylate, octadecyl (meth)acrylate [also known as stearyl (meth)acrylate], eicosyl (meth)acrylate, and docosyl (meth)acrylate [also known as behenyl (meth)acrylate]; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, pentyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, and cyclohexyl vinyl ether; vinyls such as vinyl pivalate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl palmitate, and vinyl stearate; olefins such as ethylene, propylene, isoprene, butene, 1,4-butadiene, 1,3-butadiene, pentene, 1-hexene, cyclohexyl-1-pentene, 1-dodecene, 1-tetradecene, 2-methylpentene, 2,2-dimethylpentene, and 2-methoxypropylene; styrenes such as styrene, α-methylstyrene, p-methylstyrene, hexylstyrene, octylstyrene, and nonylstyrene; vinyl chloride, vinylidene chloride, and Examples include polydimethylsiloxane having a (meth)acryloyl group at one or both ends.

[0065] From the viewpoint of forming a surface treatment layer having excellent antifouling properties, in the structural unit derived from a polymerizable monomer containing a hydrophobic group, the hydrophobic group is preferably at least one group selected from the group consisting of a linear alkyl group having 12 to 30 carbon atoms and a divalent organopolysiloxane residue.

[0066] In the structural unit derived from a polymerizable monomer having a linear alkyl group having 12 to 30 carbon atoms, from the viewpoint of forming a surface treatment layer that has excellent antifouling properties, the linear alkyl group more preferably has 14 to 28 carbon atoms, and even more preferably has 16 to 26 carbon atoms.

[0067] Examples of polymerizable monomers having a linear alkyl group having 12 to 30 carbon atoms include dodecyl (meth)acrylate (also known as lauryl (meth)acrylate), tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), hexadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as stearyl (meth)acrylate), eicosyl (meth)acrylate, and docosyl (meth)acrylate (also known as behenyl (meth)acrylate).

[0068] In the structural units derived from polymerizable monomers having an organopolysiloxane residue, from the viewpoint of forming a surface treatment layer having excellent antifouling properties, the organopolysiloxane residue is preferably a divalent organopolysiloxane residue, and more preferably a group represented by the above formula P1.

[0069] Examples of polymerizable monomers having a divalent organopolysiloxane residue include polydimethylsiloxane having a methacryloyl group at one end (product name "X-22-174BX", manufactured by Shin-Etsu Chemical Co., Ltd., number of repeating units: 29.1) and polydimethylsiloxane having methacryloyl groups at both ends (product names "Silaplane FM-7711", "Silaplane FM-7721", and "Silaplane FM-7725", manufactured by JNC Corporation).

[0070] The content of the structural unit derived from a polymerizable monomer containing a hydrophobic group is preferably 80 to 99% by mass, and more preferably 85 to 97% by mass, based on the total amount of the A block.

[0071] From the viewpoint of forming a surface treatment layer having excellent antifouling properties, the mass ratio of the content of structural units derived from polymerizable monomers having a hydrophobic group to the content of structural units derived from polymerizable monomers having a reactive group in the A block is preferably 5 to 20, and more preferably 7 to 18.

[0072] <Block B> The block B contains a divalent organopolysiloxane residue in the main chain.

[0073] In the present disclosure, the main chain refers to the longest chain in the molecular structure of a polymer.

[0074] Examples of the divalent organopolysiloxane residue include the same ones as the divalent organopolysiloxane residues that can be contained in the above-mentioned block A. Among them, the divalent organopolysiloxane residue is preferably a group represented by the above-mentioned formula P1.

[0075] From the viewpoint of ease of production, the B block is preferably represented by the following formula (B1).

[0076]

[0077] In formula (B1), R １１ are each independently a divalent linking group, and R １２ are each independently a hydrocarbon group, and X １ are each independently an electron-withdrawing group, m is an integer of 1 or more, and * represents a linking site to the A block.

[0078] In formula (B1), R １１ Examples of the group include -CH ２ CH ２ CONHCH ２ CH ２ CH ２ - (wherein the propyl group is bonded to Si). １２ A preferred embodiment of the present invention is that R in the formula P1 ３This is the same as the preferred embodiment of the above.

[0079] X １ Examples of X include a cyano group, an amidine group, an amide group, an imidazoline group, an ester group, and an acetoxy group. １ is preferably a cyano group.

[0080] m is preferably 20 to 500, and more preferably 80 to 250.

[0081] In the polymer of the present disclosure, the content of the A blocks is preferably 30 to 90 mass %, and more preferably 40 to 85 mass %, based on the total amount of the polymer of the present disclosure. The content of the A blocks here means the total content of two A blocks bonded to a B block.

[0082] In the polymer of the present disclosure, the content of the B block is preferably 10 to 70 mass %, and more preferably 15 to 60 mass %, based on the total amount of the polymer of the present disclosure.

[0083] In the polymer of the present disclosure, from the viewpoint of forming a surface treatment layer having excellent antifouling properties, the mass ratio of the content of the A blocks to the content of the B blocks is preferably 0.4 to 9, and more preferably 0.6 to 6. The content of the A blocks herein means the total content of the two A blocks bonded to the B block.

[0084] The polymer of the present disclosure can be produced, for example, by carrying out a polymerization reaction using a polymerization initiator capable of forming a B block and a monomer solution for forming an A block, which contains a polymerizable monomer having a reactive group and a polymerizable monomer not having a reactive group.

[0085] [Composition] The composition of the present disclosure may contain the polymer of the present disclosure, and may also contain other components in addition to the polymer of the present disclosure.

[0086] The composition of the present disclosure preferably further contains a liquid medium. When the composition of the present disclosure contains a liquid medium, the composition may be in a liquid state, and may be a solution or a dispersion.

[0087] The content of the polymer of the present disclosure contained in the composition of the present disclosure is preferably 0.01 to 60 mass%, more preferably 0.1 to 40 mass%, and even more preferably 1 to 20 mass%, relative to the total amount of the composition of the present disclosure.

[0088] Examples of the liquid medium include water and organic solvents, and among these, organic solvents are preferred as the liquid medium.

[0089] When the liquid medium is water, the polymer of the present disclosure is preferably dispersed in a surfactant. The surfactant is preferably a surfactant that does not contain a fluorine atom. Specifically, the surfactant is preferably an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant that does not contain a fluorine atom.

[0090] Examples of organic solvents include compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms. Specific examples include hydrocarbon organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, glycol organic solvents, and alcohol organic solvents.

[0091] Specific examples of hydrocarbon organic solvents include hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene. Specific examples of ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Specific examples of ether organic solvents include diethyl ether and tetrahydrofuran. Specific examples of ester organic solvents include ethyl acetate and butyl acetate. Specific examples of glycol organic solvents include ethylene glycol, ethylene glycol dimethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, diethylene glycol, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether pentane, dipropylene glycol, dipropylene glycol monomethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and tripropylene glycol. Specific examples of the alcohol-based organic solvent include methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, diacetone alcohol, and 3-methoxy-3-methyl-1-butanol.

[0092] Examples of organic solvents include halogenated organic solvents, nitrogen-containing compounds, and sulfur-containing compounds. Specific examples of halogenated organic solvents include dichloromethane, chloroform, carbon tetrachloride, and dichloroethane. Specific examples of nitrogen-containing compounds include nitrobenzene, acetonitrile, benzonitrile, dimethylformamide, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. Specific examples of sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.

[0093] The content of the liquid medium is preferably 40 to 99.99 mass %, more preferably 60 to 99.9 mass %, and even more preferably 80 to 99 mass %, based on the total amount of the composition of the present disclosure.

[0094] The composition of the present disclosure may contain other components in addition to the above components, as long as the effects of the present disclosure are not impaired. Examples of other components include known additives such as an acid catalyst that promotes hydrolysis and condensation reaction of reactive silyl groups, a basic catalyst, a non-fluorinated polymer, a crosslinking agent, a penetrating agent, an antifoaming agent, a film-forming aid, an insect repellent, an antifungal agent, an antiseptic, a flame retardant, an antistatic agent, an anti-wrinkle agent, a softener, and a pH adjuster.

[0095] Other components also include metal compounds having a hydrolyzable group (hereinafter, metal compounds having a hydrolyzable group are also referred to as "specific metal compounds"). When the composition of the present disclosure contains a specific metal compound, the slip properties and antifouling properties of the surface treatment layer can be further improved. Examples of the specific metal compounds include those represented by the following formulas (M1) to (M3).

[0096] M (X ｂ１ ) ｍ１ (X ｂ２ ) ｍ２ (X ｂ３ ) ｍ３ ... (M1) Si (X ｂ４ ) (X ｂ５ ) ３ ... (M2) (X ｂ６ ) ３ Si-(Y ｂ１ )-Si(X ｂ７ ) ３ …(M3)

[0097] In formula (M1), M represents a trivalent or tetravalent metal atom. ｂ１ Each of X independently represents a hydrolyzable group. ｂ２ Each of X independently represents a siloxane skeleton-containing group. ｂ３ each independently represents a hydrocarbon chain-containing group, m1 is an integer of 2 to 4, m2 and m3 are each independently an integer of 0 to 2, when M is a trivalent metal atom, m1 + m2 + m3 is 3, and when M is a tetravalent metal atom, m1 + m2 + m3 is 4.

[0098] In formula (M2), X ｂ４ represents a hydrolyzable silane oligomer residue. ｂ５ each independently represents a hydrolyzable group or an alkyl group having 1 to 4 carbon atoms.

[0099] In formula (M3), X ｂ６ and X ｂ７ each independently represents a hydrolyzable group or a hydroxyl group. ｂ１ represents a divalent organic group.

[0100] In formula (M1), the metal represented by M also includes semimetals such as Si and Ge. M is preferably a trivalent metal or a tetravalent metal, more preferably Al, Fe, In, Hf, Si, Ti, Sn, or Zr, still more preferably Al, Si, Ti, or Zr, and particularly preferably Si.

[0101] In formula (M1), X ｂ１ The hydrolyzable group represented by the formula (I) is the reactive silyl group represented by the formula (I). １ ) ｎ L ３－ｎ Examples of the hydrolyzable group include the same as the hydrolyzable group represented by L in the formula (1).

[0102] X ｂ２The siloxane skeleton-containing group represented by the formula (I) has a siloxane unit (—Si—O—) and may be linear or branched. Examples of the siloxane unit include a dialkylsilyloxy group, such as a dimethylsilyloxy group or a diethylsilyloxy group. The number of repeating siloxane units in the siloxane skeleton-containing group is 1 or more, preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3. The siloxane skeleton-containing group may contain a divalent hydrocarbon group as part of the siloxane skeleton. Specifically, some oxygen atoms in the siloxane skeleton may be replaced with a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include alkylene groups such as methylene, ethylene, propylene, and butylene. A hydrolyzable group, a hydrocarbon group (preferably an alkyl group), or the like may be bonded to the terminal silicon atom of the siloxane skeleton-containing group. The number of elements in the siloxane skeleton-containing group is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less. The number of elements is preferably 10 or more. Examples of the siloxane skeleton-containing group include: ＊ -(O-Si(CH ３ ) ２ ) ｎ CH ３ In this case, n is an integer of 1 to 5, and * represents a bonding site with an adjacent atom.

[0103] X ｂ３ The hydrocarbon chain-containing group represented by the formula (I) may be a group consisting of only a hydrocarbon chain, or may be a group having an etheric oxygen atom between carbon atoms in the hydrocarbon chain. The hydrocarbon chain may be a straight chain or a branched chain, with a straight chain being preferred. The hydrocarbon chain may be a saturated hydrocarbon chain or an unsaturated hydrocarbon chain, with a saturated hydrocarbon chain being preferred. The number of carbon atoms in the hydrocarbon chain-containing group is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. The hydrocarbon chain-containing group is preferably an alkyl group, and more preferably a methyl group, an ethyl group, or a propyl group.

[0104] Preferably, m1 is 3 or 4.

[0105] The compound represented by formula (M1) is preferably a compound represented by the following formulas (M1-1) to (M1-5) in which M is Si, and more preferably a compound represented by formula (M1-1). Preferred compounds represented by formula (M1-1) are tetraethoxysilane, tetramethoxysilane, and triethoxymethylsilane.

[0106] Si(X ｂ１ ) ４ ... (M1-1) CH ３ -Si(X ｂ１ ) ３ 　 …(M1-2) C ２ H ５ -Si(X ｂ１ ) ３ ...(M1-3) n-C ３ H ７ -Si(X ｂ１ ) ３ ...(M1-4) (CH ３ ) ２ CH—Si(X ｂ１ ) ３ …(M1-5)

[0107] In formula (M2), X ｂ４ The number of silicon atoms contained in the hydrolyzable silane oligomer residue represented by the formula (I) is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more. The number of silicon atoms is preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less. The hydrolyzable silane oligomer residue may have an alkoxy group bonded to a silicon atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, with a methoxy group and an ethoxy group being preferred. The hydrolyzable silane oligomer residue may have one or more of these alkoxy groups, and preferably has one type. Examples of the hydrolyzable silane oligomer residue include (C ２ H ５ O) ３ Si-(OSi(OC) ２ H ５ ) ２ ) ４ O- ＊Here, * represents a bonding site with an adjacent atom.

[0108] In formula (M2), X ｂ５ The hydrolyzable group represented by the formula (I) is the reactive silyl group represented by the formula (I). １ ) ｎ L ３－ｎ Examples of the hydrolyzable group include the same as the hydrolyzable group represented by L in the formula (1), a cyano group, a hydrogen atom, and an allyl group, and an alkoxy group or an isocyanato group is preferred. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. X ｂ５ As the group, a hydrolyzable group is preferred.

[0109] The compound represented by formula (M2) includes (H ５ C ２ O) ３ -Si-(OSi(OC) ２ H ５ ) ２ ) ４ O.C. ２ H ５ etc.

[0110] The compound represented by formula (M3) is a compound having reactive silyl groups at both ends of a divalent organic group, i.e., a bissilane. ｂ６ and X ｂ７ Examples of the hydrolyzable group represented by formula (M3) include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanato group, and a halogen atom, and an alkoxy group and an isocyanato group are preferred. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred, and a methoxy group and an ethoxy group are more preferred. In formula (M3), X ｂ６ and X ｂ７ may be the same group or different groups. ｂ６ and X ｂ７ are preferably the same group.

[0111] In formula (M3), Y ｂ１ is a divalent organic group that connects the reactive silyl groups at both ends. ｂ１ The number of carbon atoms in Y is preferably 1 to 8, and more preferably 1 to 3.ｂ１ Examples of the alkylene group include an alkylene group, a phenylene group, and an alkylene group having an etheric oxygen atom between carbon atoms. ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ -, -CH ２ C(CH ３ ) ２ CH ２ -, -C(CH ３ ) ２ CH ２ CH ２ C(CH ３ ) ２ -, -CH ２ CH ２ OCH ２ CH ２ -, -CH ２ CH ２ CH ２ OCH ２ CH ２ CH ２ -, -CH(CH ３ ) CH ２ OCH ２ CH (CH ３ ) -, -C ６ H ４ - are listed.

[0112] The compound represented by formula (M3) includes (CH ３ O) ３ Si(CH ２ ) ２ Si(OCH ３ ) ３ , (C ２ H ５ O) ３ Si(CH２ ) ２ Si(OC ２ H ５ ) ３ , (OCN) ３ Si(CH ２ ) ２ Si(NCO) ３ , Cl ３ Si(CH ２ ) ２ SiCl ３ , (CH ３ O) ３ Si(CH ２ ) ６ Si(OCH ３ ) ３ , (C ２ H ５ O) ３ Si(CH ２ ) ６ Si(OC ２ H ５ ) ３ Examples include:

[0113] The content of other components that may be included in the composition of the present disclosure is preferably 10% by mass or less, and more preferably 1% by mass or less, relative to the total amount of the composition of the present disclosure. When the composition of the present disclosure contains a specific metal compound, the content of the specific metal compound is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.03 to 1% by mass, relative to the total amount of the composition of the present disclosure.

[0114] The solids concentration of the composition of the present disclosure is preferably 0.01 to 60 mass%, more preferably 0.1 to 40 mass%, and even more preferably 1 to 20 mass%, based on the total amount of the composition of the present disclosure. The solids concentration of the composition of the present disclosure is a value calculated from the mass of the composition before heating and the mass after heating in a convection dryer at 120°C for 4 hours.

[0115] The composition of the present disclosure contains a liquid medium, and is therefore useful for coating applications and can be used as a coating liquid.

[0116] [Surface Treatment Agent] In one embodiment, the surface treatment agent of the present disclosure includes the polymer of the present disclosure. The surface treatment agent of the present disclosure may include the polymer of the present disclosure and a liquid medium. Preferred embodiments of the liquid medium contained in the surface treatment agent are the same as preferred embodiments of the liquid medium contained in the composition of the present disclosure.

[0117] By using a surface treatment agent containing the polymer of the present disclosure, a surface treatment layer with excellent antifouling properties can be formed.

[0118] [Article] In one embodiment, the article of the present disclosure includes a substrate and a surface treatment layer disposed on the substrate and surface-treated with the surface treatment agent.

[0119] The surface treatment layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface of the substrate. The surface treatment layer may be spread in the form of a film on the surface of the substrate, or may be scattered in the form of dots. In the surface treatment layer, the polymer of the present disclosure is contained in a state in which hydrolysis of some or all of the reactive silyl groups has progressed and dehydration condensation reaction of the silanol groups has progressed.

[0120] The thickness of the surface treatment layer is preferably 1 to 100 nm, more preferably 1 to 50 nm. If the thickness of the surface treatment layer is 1 nm or more, the effect of the surface treatment is likely to be sufficient. If the thickness of the surface treatment layer is 100 nm or less, the utilization efficiency is high. The thickness of the surface treatment layer can be calculated from the oscillation period of the interference pattern obtained by X-ray reflectivity using a thin film analysis X-ray diffractometer (product name "ATX-G", manufactured by RIGAKU Corporation). The thickness of the surface treatment layer can also be calculated by observation with a transmission electron microscope or the like.

[0121] The type of substrate is not particularly limited, and examples thereof include substrates that are required to be water-repellent. Examples of substrates include substrates that may be used by contacting other articles (e.g., stylus) or human fingers; substrates that may be held by human fingers during operation; and substrates that may be placed on other articles (e.g., a mounting table). Examples of substrate materials include metal, resin, glass, sapphire, ceramic, stone, fiber, fabric, nonwoven fabric, paper, wood, natural leather, artificial leather, and composite materials thereof. Glass may be chemically strengthened.

[0122] Examples of the substrate include building materials, decorative building materials, interior goods, transportation equipment (e.g., automobiles), signs and bulletin boards, drinking vessels and tableware, aquariums, ornamental equipment (e.g., frames, boxes), laboratory equipment, furniture, textile products, and packaging containers; glass or resin used in art, sports, games, etc.; and glass or resin used in the exterior parts (excluding display parts) of devices such as mobile phones (e.g., smartphones), personal digital assistants, game consoles, and remote controls. The shape of the substrate may be sheet-like, plate-like, or film-like. The texture of the substrate may be solid or porous.

[0123] Suitable substrates include substrates for touch panels, substrates for displays, eyeglass lenses, substrates for protective clothing such as medical gowns, and substrates for filters for dust prevention and antifouling, with substrates for touch panels, substrates for protective clothing such as medical gowns, and substrates for filters for dust prevention and antifouling being particularly suitable. Glass or transparent resin is preferred as a material for the touch panel substrate. Nonwoven fabric is preferred as a substrate for protective clothing such as medical gowns, and polypropylene is a preferred material. Nonwoven fabric is preferred as a substrate for filters for dust prevention and antifouling, and glass, polyolefin (polypropylene, polyethylene, etc.), polyvinyl chloride, nylon, polyester, or polystyrene are preferred as materials for this.

[0124] The substrate may be a substrate whose one or both surfaces have been subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment. A surface-treated substrate has better adhesion to the surface treatment layer and further improved abrasion resistance of the surface treatment layer. Therefore, it is preferable to perform the surface treatment on the surface of the substrate that comes into contact with the surface treatment layer. Furthermore, when a base layer described below is provided on the surface-treated substrate, it has better adhesion to the base layer and further improved abrasion resistance of the surface treatment layer. Therefore, when a base layer is provided, it is preferable to perform the surface treatment on the surface of the substrate that comes into contact with the base layer.

[0125] The surface treatment layer may be provided directly on the surface of the substrate, or a primer layer may be provided between the substrate and the surface treatment layer. From the viewpoint of further improving the water repellency and abrasion resistance of the surface treatment layer, the article of the present disclosure preferably includes a substrate, a primer layer disposed on the substrate, and a surface treatment layer surface-treated with the surface treatment agent of the present disclosure, disposed on the primer layer.

[0126] The underlayer is preferably a layer containing an oxide containing silicon and at least one specific element selected from the group consisting of Group 1 elements, Group 2 elements, Group 4 elements, Group 5 elements, Group 13 elements, and Group 15 elements of the periodic table.

[0127] Group 1 elements of the periodic table (hereinafter also referred to as "Group 1 elements") refer to lithium, sodium, potassium, rubidium, and cesium. As the Group 1 elements, lithium, sodium, and potassium are preferred, and sodium and potassium are more preferred, from the viewpoint of enabling a water- and oil-repellent layer to be formed more uniformly on the underlayer without defects, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples. The underlayer may contain two or more types of Group 1 elements.

[0128] Group 2 elements of the periodic table (hereinafter also referred to as "Group 2 elements") refer to beryllium, magnesium, calcium, strontium, and barium. As the Group 2 elements, magnesium, calcium, and barium are preferred, and magnesium and calcium are more preferred, from the viewpoint of enabling a water- and oil-repellent layer to be formed more uniformly on the underlayer without defects, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples. The underlayer may contain two or more types of Group 2 elements.

[0129] The Group 4 elements of the periodic table (hereinafter also referred to as "Group 4 elements") refer to titanium, zirconium, and hafnium. As the Group 4 elements, titanium and zirconium are preferred, and titanium is more preferred, from the viewpoint of being able to form a water- and oil-repellent layer on the underlayer more uniformly and without defects, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples. The underlayer may contain two or more types of Group 4 elements.

[0130] The Group 5 elements of the periodic table (hereinafter also referred to as "Group 5 elements") refer to vanadium, niobium, and tantalum. As the Group 5 element, vanadium is particularly preferred from the viewpoint of providing the water- and oil-repellent layer with better abrasion resistance. The underlayer may contain two or more Group 5 elements.

[0131] Group 13 elements of the periodic table (hereinafter also referred to as "Group 13 elements") refer to boron, aluminum, gallium, and indium. As the Group 13 elements, boron, aluminum, and gallium are preferred, and boron and aluminum are more preferred, from the viewpoint of enabling a water- and oil-repellent layer to be formed more uniformly on the underlayer without defects, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples. The underlayer may contain two or more Group 13 elements.

[0132] The Group 15 elements of the periodic table (hereinafter also referred to as "Group 15 elements") refer to nitrogen, phosphorus, arsenic, antimony, and bismuth. As the Group 15 elements, phosphorus, antimony, and bismuth are preferred, and phosphorus and bismuth are more preferred, from the viewpoint of enabling a water- and oil-repellent layer to be formed more uniformly and without defects on the underlayer, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples. The underlayer may contain two or more Group 15 elements.

[0133] As the specific element contained in the underlayer, Group 1 elements, Group 2 elements, and Group 13 elements are preferred because they provide the water- and oil-repellent layer with better abrasion resistance, and Group 1 elements and Group 2 elements are more preferred, with Group 1 elements being even more preferred. The specific element may contain only one type of element or two or more types of elements.

[0134] The oxide contained in the underlayer may be a mixture of oxides of the above elements (silicon and the specific element) alone (for example, a mixture of silicon oxide and an oxide of the specific element), a composite oxide containing two or more of the above elements, or a mixture of an oxide of the above elements alone and a composite oxide.

[0135] From the viewpoint of achieving superior abrasion resistance of the water- and oil-repellent layer, the ratio of the total molar concentration of the specific elements in the underlayer to the molar concentration of silicon in the underlayer (specific element / silicon) is preferably 0.02 to 2.90, more preferably 0.10 to 2.00, and even more preferably 0.20 to 1.80. The molar concentrations (mol %) of each element in the underlayer can be measured, for example, by depth profile analysis using X-ray photoelectron spectroscopy (XPS) using ion sputtering.

[0136] The underlayer may be a single layer or multiple layers. The underlayer may have an uneven surface. The thickness of the underlayer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and even more preferably 2 to 20 nm. When the thickness of the underlayer is equal to or greater than the above lower limit, the adhesion of the underlayer to the surface treatment layer is further improved, and the surface treatment layer has better abrasion resistance. When the thickness of the underlayer is equal to or less than the above upper limit, the underlayer itself has excellent abrasion resistance. The thickness of the underlayer is measured by observing the cross section of the underlayer using a transmission electron microscope (TEM).

[0137] The underlayer can be formed by, for example, a vapor deposition method using a vapor deposition material or a wet coating method.

[0138] The deposition material used in the deposition method preferably contains an oxide containing silicon and a specific element. Specific examples of the form of the deposition material include powder, melt, sintered body, granules, and crushed body, with melt, sintered body, and granules being preferred from the viewpoint of ease of handling. Here, the melt refers to a solid obtained by melting the powder of the deposition material at a high temperature and then cooling and solidifying it. The sintered body refers to a solid obtained by firing the powder of the deposition material. If necessary, a molded body obtained by pressing the powder may be used instead of the powder of the deposition material. The granule refers to a solid obtained by kneading the powder of the deposition material with a liquid medium (e.g., water, organic solvent) to obtain particles, and then drying the particles.

[0139] The vapor deposition material can be produced by, for example, the following methods: A method of mixing silicon oxide powder with a powder of an oxide of a specific element to obtain a vapor deposition material powder. A method of kneading the vapor deposition material powder with water to obtain particles, and then drying the particles to obtain granules of the vapor deposition material. A method of mixing a powder containing silicon (e.g., silicon oxide powder, silica sand, silica gel), a powder containing a specific element (e.g., oxide powder, carbonate, sulfate, nitrate, oxalate, hydroxide of the specific element), and water, drying the mixture, and then firing the dried mixture or a compact obtained by pressing the dried mixture to obtain a sintered body. A method of melting a powder containing silicon (e.g., silicon oxide powder, silica sand, silica gel) and a powder containing a specific element (e.g., oxide powder, carbonate, sulfate, nitrate, oxalate, hydroxide of the specific element) at a high temperature, and then cooling and solidifying the melt to obtain a melt.

[0140] A specific example of a vapor deposition method using a vapor deposition material is a vacuum vapor deposition method. The vacuum vapor deposition method is a method in which a vapor deposition material is evaporated in a vacuum chamber and attached to the surface of a substrate. The temperature during vapor deposition (for example, the temperature of the boat in which the vapor deposition material is placed when a vacuum vapor deposition apparatus is used) is preferably 100 to 3,000°C, and more preferably 500 to 3,000°C. The pressure during vapor deposition (for example, the pressure in the chamber in which the vapor deposition material is placed when a vacuum vapor deposition apparatus is used) is preferably 1 Pa or less, and more preferably 0.1 Pa or less. When forming an underlayer using a vapor deposition material, one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used.

[0141] Specific examples of evaporation methods for the deposition material include a resistance heating method, in which the deposition material is melted and evaporated on a resistance heating boat made of a high-melting-point metal, and an electron gun method, in which the deposition material is irradiated with an electron beam to directly heat the deposition material, melting and evaporating the surface. The electron gun method is preferred as an evaporation method for the deposition material because it can evaporate high-melting-point substances due to its ability to locally heat the material, and because areas not irradiated by the electron beam are at low temperatures, eliminating the risk of reaction with the container or the inclusion of impurities. The evaporation method for the deposition material may use multiple boats, or all of the deposition materials may be placed in a single boat. The deposition method may be co-evaporation or alternating deposition. Specific examples include mixing silica and a specific source in the same boat, co-evaporating silica and a specific element source in separate boats, or similarly placing them in separate boats and alternately depositing them. The deposition conditions, order, etc., are appropriately selected depending on the composition of the underlayer.

[0142] In the wet coating method, it is preferable to form an undercoat layer on a substrate by a wet coating method using a coating liquid containing a silicon-containing compound, a compound containing a specific element, and a liquid medium.

[0143] Specific examples of the silicon compound include silicon oxide, silicic acid, partial condensates of silicic acid, alkoxysilanes, and partial hydrolysis condensates of alkoxysilanes.

[0144] Specific examples of compounds containing a specific element include oxides of the specific element, alkoxides of the specific element, carbonates of the specific element, sulfates of the specific element, nitrates of the specific element, oxalates of the specific element, and hydroxides of the specific element.

[0145] Examples of the liquid medium include the same liquid medium as that contained in the composition of the present disclosure.

[0146] The content of the liquid medium is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the coating liquid used to form the underlayer.

[0147] Specific examples of wet coating methods for forming the underlayer include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.

[0148] After wet-coating the coating liquid, it is preferable to dry the coating film. The drying temperature for the coating film is preferably 20 to 200°C, more preferably 80 to 160°C.

[0149] The article of the present disclosure may be an optical component, protective clothing such as a medical gown, or a dust-proof or stain-proof filter used in semiconductor manufacturing equipment, etc., and is preferably an optical component. Examples of optical components include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, displays (e.g., liquid crystal displays, organic electroluminescence displays, plasma displays, touch panel displays), touch panels, protective films, and anti-reflection films. In particular, the article is preferably a display or a touch panel.

[0150] [Method for manufacturing an article] The method for manufacturing an article according to the present disclosure is, for example, a method for manufacturing an article in which a surface treatment layer is formed on a substrate by performing a surface treatment on the substrate using the surface treatment agent according to the present disclosure. Examples of the surface treatment include a wet coating method. When the molecular weight of the polymer according to the present disclosure is small, a dry coating method can also be used.

[0151] Examples of dry coating methods include vacuum deposition, CVD, and sputtering. Vacuum deposition is preferred as a dry coating method from the viewpoints of suppressing decomposition of the compound and simplicity of the equipment. For vacuum deposition, a pellet-shaped substance obtained by impregnating a metal porous body such as iron or steel with the compound of the present disclosure may be used. A composition containing the compound of the present disclosure and a liquid medium may be impregnated into a metal porous body such as iron or steel, and the liquid medium may be dried to obtain a pellet-shaped substance impregnated with the compound of the present disclosure.

[0152] Examples of wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.

[0153] In order to improve the antifouling properties of the surface-treated layer, an operation for promoting the reaction between the polymer of the present disclosure and the substrate may be carried out as necessary. Examples of such an operation include heating, humidification, and light irradiation. For example, the substrate on which the surface-treated layer is formed can be heated in a moist atmosphere to promote reactions such as the hydrolysis reaction of hydrolyzable groups, the reaction between hydroxyl groups and silanol groups on the surface of the substrate, and the formation of siloxane bonds through the condensation reaction of silanol groups.

[0154] After the surface treatment, compounds in the surface treatment layer that are not chemically bonded to other compounds or the substrate may be removed as needed. Examples of methods for removing the compounds include pouring a solvent over the surface treatment layer and wiping the compounds with a cloth soaked in the solvent.

[0155] The present invention will be explained in more detail below using examples, but the present invention is not limited to these examples.

[0156] <Polymerizable Monomer for A Block> Polymerizable monomers for forming the A block are shown below.

[0157] - Polymerizable monomers containing reactive groups - (in Tables 1 and 2, "reactive group-containing monomers") 3-methacryloxypropyltrimethoxysilane (product name "KBM-503", manufactured by Shin-Etsu Chemical Co., Ltd.) 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl methacrylate (product name "Karenz MOI-BP", manufactured by Showa Denko K.K.)

[0158] -Polymerizable monomers containing hydrophobic groups ("hydrophobic group-containing monomers" in Tables 1 and 2)- StA: stearyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) BeA: behenyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) Polydimethylsiloxane containing a methacryloyl group at one end (product name "X-22-174BX", manufactured by Shin-Etsu Chemical Co., Ltd., number of repeating units: 29.1)

[0159] <Polymerization initiator for B block> The polymerization initiator for forming the B block is shown below: Polymerization initiator containing a dimethylpolysiloxane residue in the main chain (product name "VPS-1001N", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., silicone unit molecular weight: approximately 10,000)

[0160] Example 1: To a 500 mL three-neck flask were added 119 g of 1-methoxy-2-propanol as a polymerization solvent, 21 g of diacetone alcohol, 45 g of StA and 3 g of KBM-503 as A block polymerizable monomers, and 12 g of VPS-1001N as a B block polymerization initiator. The resulting mixture was stirred at 80°C under a nitrogen atmosphere for 16 hours to obtain a solution containing an ABA triblock polymer. The yield was 200 g, and the solids concentration was 30% by mass. Analysis by GPC revealed a 100% yield. In the ABA triblock polymer, the A block was a random polymer containing structural units derived from StA and structural units derived from KBM-503, and the B block contained a dimethylpolysiloxane residue in its main chain.

[0161] [Examples 2 to 16] In Examples 2 to 16, solutions containing an ABA triblock polymer were obtained in the same manner as in Example 1, except that the types and contents of the polymerizable monomer for the A block and the polymerization initiator for the B block were changed to those shown in Tables 1 and 2. In Examples 10 to 14, azoisobutyronitrile (AIBN) was used as another polymerization initiator.

[0162] The solutions obtained in Examples 1 to 14 were each diluted with 1-methoxy-2-propanol so that the concentration of the ABA triblock polymer was 1% by mass, thereby obtaining a surface treatment agent. In Examples 1 to 3 and 7 to 14, a glass substrate was surface-treated by a spray coating method using the surface treatment agent, and the substrate was left at 25°C for 15 minutes, and then heated at 120°C for 1 hour. This resulted in an article having a surface-treated layer on the surface of the glass substrate. In Examples 4 to 6, an article having a surface-treated layer on the surface of cotton (cotton fabric) was obtained in the same manner as in Example 1, except that cotton (cotton fabric) was used as the treated substrate instead of the glass substrate. In Example 15, a polypropylene (PP) nonwoven fabric (basis weight: 63 g / m) was used as the treated substrate instead of cotton (cotton fabric). ２ In Example 16, an article having a surface-treated layer on the surface of a polypropylene (PP) nonwoven fabric was obtained in the same manner as in Example 4, except that a glass fiber nonwoven fabric was used instead of cotton (cotton fabric) as the treated substrate.

[0163] In Table 1, the values ​​for the polymerizable monomer for the A block and the polymerization initiator for the B block are contents based on mass. Also, "-" indicates that the corresponding component is not included.

[0164] The resulting articles were evaluated for their ability to wipe off dirt, using the following evaluation methods.

[0165] <Stain wiping ability> 1 mL of coffee at 25°C was dropped onto an article, which was then covered with plastic wrap (product name "Saran Wrap (registered trademark)", manufactured by Asahi Kasei Corporation), a 1 kg weight was placed on top, and the article was left to stand for 10 minutes. After 10 minutes, the weight and plastic wrap were removed, and the area where the coffee had been dropped was wiped three times with a paper wiper (product name "Kimtowel (registered trademark)", manufactured by Nippon Paper Crecia Co., Ltd.). After wiping, the amount of coffee remaining on the article was visually observed. The stain wiping ability was evaluated based on the amount of coffee remaining. The evaluation criteria are as follows: AA: No coffee remains. A: Some coffee remains. B: Some coffee has been removed, but much remains and has spread over the surface of the article. C: Almost no coffee has been removed.

[0166] The evaluation results are shown in Tables 1 and 2.

[0167] Examples 1 to 9, 15 and 16 are working examples, and Examples 10 to 14 are comparative examples.

[0168]

[0169] As shown in Table 1, in Examples 1 to 9, 15, and 16, the A block was a random polymer containing a structural unit derived from a polymerizable monomer containing a reactive group and a structural unit derived from a polymerizable monomer containing a hydrophobic group, and the B block contained a divalent organopolysiloxane residue in the main chain, and therefore a surface treatment layer with excellent antifouling properties could be formed.

[0170] On the other hand, as shown in Table 2, in Examples 10 to 14, the surface treatment layer had poor antifouling properties because the main chain contained no B block containing a divalent organopolysiloxane residue.

[0171] The ABA triblock polymer of the present disclosure is useful as a surface treatment agent. The surface treatment agent can be used, for example, for substrates used in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automotive parts, nanoimprint technology, and the like. The surface treatment agent can also be used for the bodies, window glass (windshields, side glass, rear glass), mirrors, bumpers, and the like of transportation equipment such as trains, automobiles, ships, and aircraft. The surface treatment agent can also be used for outdoor items such as building exterior walls, tents, solar power generation modules, soundproofing panels, and concrete; fishing nets, insect nets, and aquariums. The surface treatment agent can also be used for various indoor facilities such as kitchens, bathrooms, sinks, mirrors, and toilet peripherals; ceramics such as chandeliers and tiles; artificial marble, and air conditioners. The surface treatment agent can also be used for antifouling treatment of jigs, interior walls, piping, and the like in factories. The surface treatment agent can also be used for goggles, eyeglasses, helmets, pachinko machines, fibers, fabrics, nonwoven fabrics, clothing, protective clothing, filters, bags, umbrellas, playground equipment, and soccer balls. The surface treatment agent can also be used as an anti-adhesion agent for various packaging materials such as food packaging materials, cosmetic packaging materials, the inside of pots, etc. The surface treatment agent can also be used for car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio equipment, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, medical devices such as gastroscopes, copiers, PCs, displays (e.g., liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, anti-reflection films, and other optical components.

[0172] The disclosure of Japanese Patent Application No. 2022-057656, filed on March 30, 2022, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. an ABA triblock polymer having an A block and a B block; the A block is a random polymer including a constitutional unit derived from a polymerizable monomer including a reactive group and a constitutional unit derived from a polymerizable monomer including a hydrophobic group, The B block is an ABA triblock polymer containing a divalent organopolysiloxane residue in the main chain.

2. The ABA triblock polymer according to claim 1, wherein the hydrophobic group is at least one group selected from the group consisting of a linear alkyl group having 12 to 30 carbon atoms and a divalent organopolysiloxane residue.

3. 2. The ABA triblock polymer according to claim 1, wherein the reactive group is at least one selected from the group consisting of a reactive silyl group, an isocyanato group, a phosphate ester group, a carboxy group, a carbodiimide group, an oxazoline group, and an epoxy group.

4. 2. The ABA triblock polymer of claim 1, wherein the reactive group is a reactive silyl group.

5. The ABA triblock polymer according to claim 1 , wherein the B block has a structure represented by the following formula (B1): 【Chemistry 1】 In formula (B1), R １１ are each independently a divalent linking group, R １２ are each independently a hydrocarbon group; １ are each independently an electron-withdrawing group, m is an integer of 1 or more, and * represents a linking site with the A block.

6. 2. The ABA triblock polymer according to claim 1, wherein the mass ratio of the content of the A block to the content of the B block is 0.4 to 9.

7. The ABA triblock polymer according to claim 1, wherein in the A block, a mass ratio of a content of the structural unit derived from the polymerizable monomer containing a hydrophobic group to a content of the structural unit derived from the polymerizable monomer containing a reactive group is 5 to 20.

8. A composition comprising the ABA triblock polymer according to any one of claims 1 to 7 and a liquid medium.

9. A surface treatment agent comprising the ABA triblock polymer according to any one of claims 1 to 7.

10. The surface treatment agent according to claim 9 , further comprising a liquid medium.

11. A method for producing an article, comprising: performing a surface treatment on a substrate using the surface treatment agent according to claim 9 to produce an article having a surface treatment layer formed on the substrate.

12. An article comprising a substrate and a surface treatment layer disposed on the substrate and surface-treated with the surface treatment agent according to claim 9.

13. The article of claim 12 which is an optical component.

14. The article according to claim 12, which is a display or a touch panel.

15. The article of claim 12, wherein the substrate is a fabric or nonwoven.

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