Surface treatment solution and hydrophilic treatment method

Abstract

To provide a hydrophilizing surface treatment liquid that suppresses a surface treatment effect from being lost over time even when a surface-treated article is exposed to a variety of chemicals; and a hydrophilizing treatment method that uses the hydrophilizing surface treatment liquid.SOLUTION: A hydrophilizing surface treatment liquid includes a polymerizable compound having an ethylenic unsaturated double bond (A), a polymerization initiator (B) and a solvent (S). The polymerizable compound (A) is a hydrophilic polymerizable compound (A1), an adhesive polymerizable compound (A2), an acidic polymerizable compound (A3a) and / or a basic polymerizable compound (A3b). An aqueous solution including the polymerizable compound (A) at a concentration of 10 mass% has a pH at 23°C of 6.5 or more and 7.5 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a surface treatment liquid and a hydrophilization treatment method using the surface treatment liquid. [Background technology]

[0002] Conventionally, surface treatments have been performed using various surface treatment liquids to modify the surface properties of various articles. Among surface modifications, there is a great demand for hydrophilizing the surface of an article, and many hydrophilizing agents and surface treatment liquids have been proposed. By treating the surface of an object using a hydrophilizing agent or surface treatment liquid, a coating is formed on the surface of the object, making the surface of the object hydrophilic.

[0003] As such hydrophilizing agents and surface treatment liquids, for example, a hydrophilic coating liquid containing a siloxane monomer having a nitrogen-containing heterocyclic structure and a betaine structure has been proposed (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2018 / 230514 Summary of the Invention [Problem to be solved by the invention]

[0005] For example, objects to be surface-treated, such as windows and mirrors, may be exposed to chemicals such as detergents used during cleaning. Windows and mirrors used around water are particularly susceptible to acidic detergents used to remove limescale and basic detergents used to remove mold. In addition, regardless of the pH of the detergent, various detergents, including soaps and shampoos, also contain various ionic surfactants such as sodium fatty acid, sodium dodecyl sulfate (SDS), and sodium linear alkyl ether sulfonate. Furthermore, detergents may contain organic acids or organic bases that can generate anions or cations having hydrophobic sites, such as oleic acid, behenic acid, dimethylstearylamine, and dimethylcoconutamine.

[0006] However, when an article that has been surface-treated with the conventional hydrophilic treatment agent described in Patent Document 1 is exposed to cleaning agents containing acids and alkalis, various ionic surfactants, or organic acids and organic bases that can generate anions or cations having hydrophobic sites, there is a problem that the hydrophilicity of the surface of the surface-treated article may gradually decrease over time.

[0007] The present invention has been made in consideration of the above problems, and aims to provide a hydrophilic surface treatment liquid in which the effect of the surface treatment is not likely to decrease over time even when the surface-treated article is exposed to various chemicals, and a hydrophilic treatment method using the hydrophilic surface treatment liquid. [Means for solving the problem]

[0008] The present inventors have found that the above problems can be solved by using a hydrophilic polymerizable compound (A1), an adhesive polymerizable compound (A2), and an acidic polymerizable compound (A3a) and / or a basic polymerizable compound (A3b) as the polymerizable compound (A) in a hydrophilic surface treatment liquid containing a polymerizable compound (A) having an ethylenically unsaturated double bond, a polymerization initiator (B), and a solvent (S), and by adjusting the pH of an aqueous solution of the polymerizable compound (A) having a concentration of 10% by mass at 23°C to 6.5 or more and 7.5 or less, thereby completing the present invention. More specifically, the present invention provides the following.

[0009] A first aspect of the present invention is a hydrophilic surface treatment liquid comprising a polymerizable compound (A), a polymerization initiator (B), and a solvent (S), The polymerizable compound (A) has an ethylenically unsaturated double bond, the polymerizable compound (A) contains a hydrophilic polymerizable compound (A1), an adhesive polymerizable compound (A2), and an acidic polymerizable compound (A3a) and / or a basic polymerizable compound (A3b); The hydrophilic surface treatment liquid is an aqueous solution containing the polymerizable compound (A) at a concentration of 10% by mass, and the pH at 23° C. is 6.5 or more and 7.5 or less.

[0010] A second aspect of the present invention includes a method for forming a coating film on a surface of a target object by applying the surface treatment liquid according to the first aspect; and heating the coating film to form a film on the surface of the object to be treated. Effect of the Invention

[0011] According to the present invention, it is possible to provide a hydrophilic surface treatment liquid in which the effect of the surface treatment is not likely to decrease over time even when the surface-treated article is exposed to various chemicals, and a hydrophilic treatment method using the hydrophilic surface treatment liquid. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] <Hydrophilic surface treatment liquid> The hydrophilic surface treatment liquid contains a polymerizable compound (A), a polymerization initiator (B), and a solvent (S). The hydrophilic surface treatment liquid can hydrophilize the surface of a treatment target, which is an object of the surface treatment. The optional components, essential components, etc. of the hydrophilic surface treatment solution will be described below.

[0013] <Polymerizable compound (A)> The polymerizable compound (A) is polymerized on the surface of the object to be treated by the action of the polymerization initiator (B) to form a resin coating that adheres well to the surface of the object to be treated. The polymerizable compound (A) has an ethylenically unsaturated double bond. Examples of the group having an ethylenically unsaturated double bond include alkenyl groups such as vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl, and 3-n-butenyl, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, and methacryloylamino. From the viewpoint of polymerizability and film-forming property, the polymerizable compound (A) preferably contains a compound having one or more polymerizable groups selected from vinyl and allyl groups as the group having an ethylenically unsaturated double bond.

[0014] The polymerizable compound (A) includes a hydrophilic polymerizable compound (A1), an adhesive polymerizable compound (A2), and an acidic polymerizable compound (A3a) and / or a basic polymerizable compound (A3b). In addition, the polymerizable compound (A) may contain a polyfunctional monomer (A4) or other monomers (A5) in addition to the above-mentioned hydrophilic polymerizable compound (A1), adhesive polymerizable compound (A2), acidic polymerizable compound (A3a) and / or basic polymerizable compound (A3b), as long as the object of the present invention is not impaired.

[0015] [Hydrophilic polymerizable compound (A1)] The hydrophilic polymerizable compound (A1) is a compound having a hydrophilic group and an ethylenically unsaturated double bond. By including the hydrophilic polymerizable compound (A) in the polymerizable compound (A), a hydrophilic coating can be formed on the surface of the treated object using the hydrophilization surface treatment liquid. The hydrophilic group is not particularly limited as long as it is a functional group that has been conventionally recognized as a hydrophilic group by those skilled in the art, and can be appropriately selected from among them. Specific examples of the hydrophilic group include polyoxyalkylene groups (e.g., polyoxyethylene groups, polyoxypropylene groups, polyoxyalkylene groups in which oxyethylene groups and oxypropylene groups are block- or randomly bonded, etc.), carboxy groups, primary amino groups, secondary amino groups, hydroxyl groups, phosphonic acid groups, phosphinic acid groups, and sulfonic acid groups, etc. Organic groups containing these groups are also preferred as hydrophilic groups.

[0016] In terms of excellent hydrophilic effect, the hydrophilic group is preferably a group represented by the following formula (ai): -NH-R 01 (ai) (In formula (ai), R 01 is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, a phosphonic acid group, and a hydroxyl group, or a hydrogen atom. A group represented by the following formula is preferred. R 01 Regarding the above, an amino group corresponds to a cationic group, a sulfonic acid group and a phosphonic acid group correspond to an anionic group, and among hydroxyl groups, a phenolic hydroxyl group corresponds to an anionic group.

[0017] Specific examples of the hydrophilic group represented by formula (ai) include an amino group and a group represented by the following formula: 01 is the above R 01 is the same as: [ka]

[0018] Among specific examples of the hydrophilic group represented by the above formula (ai), particularly preferred groups include the following groups. [ka]

[0019] In terms of polymerizability, ease of synthesis or availability, and the like, the hydrophilic polymerizable compound (A1) is preferably a (meth)acrylamide compound represented by the following formula (a1-a). CH2=CR 02 -CO-NH-R 01 (a1-a) (In formula (a1-a), R 01 is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, a phosphonic acid group, and a hydroxyl group, or a hydrogen atom; R02 is a hydrogen atom or a methyl group.

[0020] In formula (a1-a), R 01 As mentioned above,

[0021] (Polymerizable betaine compound) The polymerizable compound (A) preferably contains a polymerizable betaine compound having a betaine structure containing a cationic group and an anionic group and a group having an ethylenically unsaturated double bond as a hydrophilic polymerizable compound (A1). Both the cationic group and the anionic group act as a hydrophilic group. The surface of the treated object may come into contact with a cleaning solution containing a large amount of anions having hydrophobic groups or cations having hydrophobic groups. When the resin in the surface treatment solution has only anionic groups such as carboxyl groups, carboxylate groups, sulfonic acid groups, and sulfonate groups as hydrophilic groups, these hydrophilic groups may not function as hydrophilic groups due to interaction with cations having hydrophobic groups. When the resin in the surface treatment solution has only cationic groups such as quaternary ammonium groups as hydrophilic groups, the cationic groups may not function as hydrophilic groups due to interaction with anions having hydrophobic groups. However, since the polymer of the polymerizable compound (A) containing a polymerizable betaine compound has both cationic groups and anionic groups as hydrophilic groups, either one of the cationic groups or the anionic groups can maintain the function as a hydrophilic group even when the surface of the treated object comes into contact with a cleaning agent rich in cations having hydrophobic groups, or with a cleaning agent rich in anions having hydrophobic groups, so that the hydrophilicity of the surface of the treated object is unlikely to decrease.

[0022] The number of cationic groups and the number of anionic groups in the polymerizable betaine compound are not particularly limited. In the polymerizable betaine compound, it is preferred that the number of cationic groups is the same as the number of anionic groups. In view of ease of synthesis and availability of the polymerizable betaine compound, the number of cationic groups and the number of anionic groups in the polymerizable betaine compound are preferably each 1.

[0023] In the polymerizable betaine compound, for example, a group having an ethylenically unsaturated double bond, a cationic group, and an anionic group are preferably bonded in this order, optionally via a linking group.

[0024] Preferably, the cationic group is a cationic group which is a quaternary nitrogen cation. The anionic group is preferably a sulfonate anion group, a phosphonate anion group, or a carboxylate anion group.

[0025] In the polymerizable betaine compound, the group having an ethylenically unsaturated double bond may be an alkenyl group such as a vinyl group, a 1-propenyl group, a 2-n-propenyl group (allyl group), a 1-n-butenyl group, a 2-n-butenyl group, and a 3-n-butenyl group. Among these groups, the vinyl group and the 2-n-propenyl group (allyl group) are preferred. The number of ethylenically unsaturated double bonds in the polymerizable betaine compound is not limited, but one or two is preferred.

[0026] As the polymerizable betaine compound, for example, a compound represented by the following formula (a1-i) or formula (a1-ii) is preferable. The polymerizable betaine compound represented by the following formula (a1-i) or formula (a1-ii) is N + and an anionic group as R. Both the cationic group and the anionic group act as hydrophilic groups. [ka] (In formula (a1-i), R 1 is a hydrocarbon group containing an ethylenically unsaturated double bond, R 2 is a divalent hydrocarbon group having from 1 to 10 carbon atoms, R is an anionic group, Ring A is a heterocycle. [ka] (In formula (a1-ii), R 3 , R 4 , and R 5 each independently represents a hydrocarbon group having an ethylenically unsaturated double bond, or a hydrocarbon group having from 1 to 10 carbon atoms, R 3 , R 4 , and R 5 at least one of the groups is a hydrocarbon group having an ethylenically unsaturated double bond; R 6 is a divalent hydrocarbon group having from 1 to 10 carbon atoms, R is an anionic group.

[0027] In formula (a1-i), R 1 Examples of the hydrocarbon group containing an ethylenically unsaturated double bond as the aryl group include alkenyl groups such as a vinyl group, a 1-propenyl group, a 2-n-propenyl group (allyl group), a 1-n-butenyl group, a 2-n-butenyl group, and a 3-n-butenyl group.

[0028] In formula (a1-i), R 2 Examples of the divalent hydrocarbon group as include an alkylene group, an arylene group, and a combination of an alkylene group and an arylene group, with an alkylene group being preferred. R 2 Specific preferred examples of the alkylene group as the alkyl group include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, and a decane-1,10-diyl group.

[0029] In formula (a1-i), the heterocycle as ring A may be an aromatic heterocycle or an aliphatic heterocycle. Examples of the aromatic heterocycle include nitrogen-containing aromatic heterocycles such as an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, and a pyrazine ring, in which any one nitrogen atom in the nitrogen-containing aromatic heterocycle is quaternized. Examples of the aliphatic heterocycle include nitrogen-containing heterocycles such as a pyrrolidine ring, a piperidine ring, and a piperazine ring, in which any one of the nitrogen atoms in the nitrogen-containing heterocycle is quaternized.

[0030] In formula (a1-ii), R 3 ~R 5 Examples of the hydrocarbon group containing an ethylenically unsaturated double bond as the aryl group include alkenyl groups such as a vinyl group, a 1-propenyl group, a 2-n-propenyl group (allyl group), a 1-n-butenyl group, a 2-n-butenyl group, and a 3-n-butenyl group.

[0031] In formula (a1-ii), R 3 ~R 5 Examples of the hydrocarbon group as the alkyl group include an alkyl group, an aryl group, and an aralkyl group, and the alkyl group is preferred. R 3 ~R 5 The hydrocarbon group represented by R may have a substituent. 3 ~R 5 The substituent that the hydrocarbon group may have is not particularly limited as long as it does not impair the object of the present invention. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group having from 1 to 4 carbon atoms, an acyl group having from 2 to 4 carbon atoms, an acyloxy group having from 2 to 4 carbon atoms, an amino group, and an alkylamino group substituted with one or two alkyl groups having from 1 to 4 carbon atoms. R 3 ~R 5Specific preferred examples of the alkyl group as 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 sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group.

[0032] In formula (a1-ii), R 6 Examples of the divalent hydrocarbon group as include an alkylene group, an arylene group, and a combination of an alkylene group and an arylene group, with an alkylene group being preferred. R 6 Specific preferred examples of the alkylene group as the alkyl group include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, and a decane-1,10-diyl group.

[0033] As the polymerizable betaine compound in which the anionic group is a sulfonate anionic group, a monomer represented by the following formula (a1-iii) or formula (a1-iv) is preferred because of ease of synthesis and availability. [ka] (In formula (a1-iii), R 1 , R 2 and ring A is R in formula (a1-i). 1 , R 2 , and ring A.) [ka] (In formula (a1-iv), R 3 , R 4 , R 5 , and R 6 is R in formula (a1-ii) 3 , R 4 , R 5 , and R 6is equivalent to.)

[0034] Examples of the monomer represented by the above formula (a1-iii) or formula (a1-iv) include monomers represented by the following formula (a1-v), (a1-vi) or (a1-vii). [ka] (In formulas (a1-v), (a1-vi), and (a1-vii), R 2 is R in formula (a1-iii) 2 is the same as R 5 and R 6 is R in formula (a1-iv). 5 and R 6 is the same as R 11 and R 12 are each independently a hydrogen atom or a methyl group, R 13 and R 14 are each independently a single bond or an alkylene group having 1 to 4 carbon atoms.

[0035] In formulae (a1-v), (a1-vi), and (a1-vii), R 13 and R 14 Examples of the alkylene group having 1 to 4 carbon atoms as the alkylene group include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, and a butane-1,4-diyl group.

[0036] The polymerizable betaine compound in which the anionic group is a phosphonate anion group or a carboxylate anion group includes a monomer represented by the above formula (a1-iii) or formula (a1-iv), and a monomer represented by the above formula (a1-v), (a1-vi), or (a1-vii) in which the sulfonate anion group (-SO3 - ) is a phosphonate anion group (-(PO3) 2- ) and carboxylate anion groups (-COO - ) is a monomer in which

[0037] Specific examples of the polymerizable betaine compound represented by formula (a1-i) or formula (a1-ii) include the compounds of the following formulae and the compounds of the following formulae having a sulfonate anion group (-SO3 - ) is a phosphonate anion group (-(PO3) 2- ) and carboxylate anion groups (-COO - ) is a monomer in which [ka]

[0038] The polymerizable betaine compound represented by formula (a1-i) or formula (a1-ii) can be synthesized by a known reaction. For example, it can be obtained by reacting a compound having a group having an ethylenically unsaturated double bond and a group that becomes a cationic group with a compound having an anionic group. As a specific example, the compound represented by formula (a1-iii) can be obtained by reacting the following compound with sultone in a solvent. Examples of the sultone include sultones having 4 to 10 membered rings, and 1,3-propane sultone and 1,4-butane sultone are preferred. [ka] (In the formula, R 1 is R in (a1-i) above 1 and ring A is a heterocycle.

[0039] The compound represented by the following formula (a1-viii) is also preferred as the polymerizable betaine compound. The polymerizable betaine compound represented by the following formula (a1-viii) is N + and a cationic group comprising R 20 and an anionic group as a hydrophilic group. Both the cationic group and the anionic group act as hydrophilic groups. CH2=CR 15 -CO-NH-R 16 -N + (R 17 )(R 18 )-R 19 -R 20 (a1-viii) (In formula (a1-viii), R 15 is a hydrogen atom or a methyl group, R 16 and R 19 are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms; R 17 and R 18 each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent; R 20 is a sulfonate anion group (-SO3 - ), phosphonate anion group (-(PO3) 2- ), or a carboxylate anion group (-COO - )

[0040] In formula (a1-viii), R 16 and R 19 Examples of the divalent hydrocarbon group as include an alkylene group, an arylene group, and a combination of an alkylene group and an arylene group, with an alkylene group being preferred. R 16 and R 19 Specific preferred examples of the alkylene group as the alkyl group include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, and a decane-1,10-diyl group.

[0041] In formula (a1-viii), R 17 and R 18 Examples of the hydrocarbon group as the alkyl group include an alkyl group, an aryl group, and an aralkyl group, and the alkyl group is preferred. R 17 and R 18 The hydrocarbon group represented by R may have a substituent. 17 and R 18The substituent that the hydrocarbon group may have is not particularly limited as long as it does not impair the object of the present invention. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group having from 1 to 4 carbon atoms, an acyl group having from 2 to 4 carbon atoms, an acyloxy group having from 2 to 4 carbon atoms, an amino group, and an alkylamino group substituted with one or two alkyl groups having from 1 to 4 carbon atoms. R 17 and R 18 Specific preferred examples of the alkyl group as 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 sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group.

[0042] In formula (a1-viii), R 20 is a sulfonate anion group (-SO3 - ), phosphonate anion group (-PO3 2- ), or carboxylate anion group (-COO - ) and the sulfonate anion group (-SO3 - ) is preferred.

[0043] Suitable examples of the N-substituted (meth)acrylamide represented by formula (a1-viii) include compounds of the following formula: 15 is a hydrogen atom or a methyl group.

[0044] [ka]

[0045] The content of the hydrophilic polymerizable compound (A1) in the polymerizable compound (A) is not particularly limited within the range that does not impair the object of the present invention. From the viewpoint of achieving both a good hydrophilization effect and good adhesion of the formed resin coating to the surface of the treated object, the ratio of the number of moles of the hydrophilic polymerizable compound (A1) to the number of moles of the polymerizable compound (A) is preferably 50 mol% or more and 99 mol% or less, more preferably 60 mol% or more and 99 mol% or less, and even more preferably 70 mol% or more and 99 mol% or less.

[0046] [Adhesive polymerizable compound (A2)] The polymerizable compound (A) includes an adhesive polymerizable compound (A2) in addition to the hydrophilic polymerizable compound (A1). The adhesive polymerizable compound (A2) has an ethylenically unsaturated double bond and an adhesive group. The adhesive group is a functional group that can be chemically bonded to the surface of the object to be treated by forming a covalent bond, or can be bonded to the surface of the object to be treated by the action of electrostatic force based on polarity, etc. The adhesive group is preferably at least one group selected from a hydrolyzable silyl group, an amino group (-NH2), a carboxy group, a mercapto group, a cyano group, and a hydroxyl group. The hydrolyzable silyl group reacts with the surface of the object to be treated to form a covalent bond, thereby firmly binding the coating formed by using the hydrophilic surface treatment liquid to the surface of the object to be treated. Also, the amino group (-NH2), carboxy group, mercapto group, cyano group, and hydroxyl group are polar groups, and based on their polarity, firmly bind the coating formed by using the hydrophilic surface treatment liquid to the surface of the object to be treated.

[0047] Preferred examples of the adhesive polymerizable compound (A2) include an unsaturated group-containing silicon compound (A2-1) having an ethylenically unsaturated double bond and a hydrolyzable silyl group, and a polar polymerizable compound (A2-2) having an ethylenically unsaturated double bond and at least one selected from an amino group (-NH2), a carboxy group, a mercapto group, a cyano group, and a hydroxyl group.

[0048] (Unsaturated group-containing silicon compound (A2-1)) The unsaturated group-containing silicon compound (A2-1) has a group having an ethylenically unsaturated double bond and a hydrolyzable silyl group.

[0049] The group having an ethylenically unsaturated double bond is not particularly limited, so long as the unsaturated group-containing silicon compound (A2-1) is copolymerizable with the polymerizable betaine compound (A1). Specific preferred examples of the group having an ethylenically unsaturated double bond include alkenyl groups such as vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl, and 3-n-butenyl; monoalkenylamino groups such as N-vinylamino, N-1-propenylamino, N-allylamino, N-1-n-butenylamino, N-2-n-butenylamino, and N-3-n-butenylamino; dialkenylamino groups such as N,N-divinylamino, N,N-di(1-propenyl)amino, N,N-diallylamino, N,N-di(1-n-butenyl)amino, N,N-di(2-n-butenyl)amino, and N,N-di(3-n-butenyl)amino; allyloxy, 2-n-butenyloxy, 3- alkenyloxy groups such as an n-butenyloxy group; alkenylaminocarbonyl groups such as a vinylaminocarbonyl group, a 1-propenylaminocarbonyl group, an allylaminocarbonyl group, a 1-n-butenylaminocarbonyl group, a 2-n-butenylaminocarbonyl group, and a 3-n-butenylaminocarbonyl group; alkenyloxycarbonyl groups such as a vinyloxycarbonyl group, a 1-propenyloxycarbonyl group, an allyloxycarbonyl group, a 1-n-butenyloxycarbonyl group, a 2-n-butenyloxycarbonyl group, and a 3-n-butenyloxycarbonyl group; and (meth)acryloyl group-containing groups such as an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, and a methacryloylamino group. Of these groups, alkenyl groups and (meth)acryloyl group-containing groups are preferred. The number of carbon atoms in the alkenyl group is preferably, for example, 2 to 6, and more preferably 2 or 3.

[0050] The hydrolyzable silyl group is a silyl group that can generate a silanol group by hydrolysis. Suitable examples of the hydrolyzable silyl group include -SiR 11 a R 12 3-a In this case, R 11 is a group capable of generating a silanol group by hydrolysis of an alkoxy group, a halogen atom, or the like. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms or less, such as a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, and an n-butyloxy group, is preferred. As the halogen atom, a chlorine atom and a bromine atom are preferred, and a chlorine atom is more preferred. R 12 may be various organic groups that do not fall under the group that can generate a silanol group by hydrolysis, so long as the object of the present invention is not hindered. As such an organic group, a hydrocarbon group having 1 to 10 carbon atoms is preferable. The hydrocarbon group may be an aliphatic group or an aromatic group. The structure of the hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Specific examples of suitable hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, phenyl, naphthalene-1-yl, naphthalene-2-yl, benzyl, and phenethyl groups. Among these, methyl and ethyl groups are preferable. The above-described hydrocarbon groups may have a substituent such as an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a cyano group. The value of a is preferably 2 or 3, and more preferably 3. When a is 2 or 3, the -SiR 11 a R 12 3-aAs a result, a network of siloxane bonds is formed in the coating film formed using the hydrophilic surface treatment liquid, which spreads along the surface of the treated object, and this makes it easy to bond the polymer of the polymerizable compound (A) particularly strongly to the surface of the treated object.

[0051] -SiR 11 a R 12 3-a Preferred specific examples of the hydrolyzable silyl group represented by the formula (I) include a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group, an ethyldimethoxysilyl group, a methyldiethoxysilyl group, and an ethyldiethoxysilyl group.

[0052] As the unsaturated group-containing silicon compound (A2-1), for example, a compound represented by the following formula (a2-1) is preferable. R 13 -(-CO-R 14 -) b -R 15 -SiR 11 a R 12 3-a (a2-1)

[0053] In formula (a2-1), R 11 , R 12 and a are as described above for the hydrolyzable silyl group. 13 R is an alkenyl group having 2 to 6 carbon atoms. 14 is -O- or -NH-. 15 represents a single bond, an alkylene group having from 1 to 10 carbon atoms, an aromatic hydrocarbon group, or a nitrogen-containing heterocyclic group. b is 0 or 1.

[0054] R 13 is an alkenyl group having 2 to 6 carbon atoms. Suitable examples of the alkenyl group include a vinyl group, a 1-methylvinyl group, an allyl group, a 3-butenyl group, a 4-pentenyl group, and a 5-hexenyl group. When b is 1, R 13is preferably a vinyl group or a 1-methylvinyl group. That is, when b is 1, R 13 -CO-R 14 The group represented by - is preferably an acryloyloxy group, an acryloylamino group, a methacryloyloxy group, or a methacryloylamino group.

[0055] R 15 Examples of the alkylene group as the alkyl group include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, and a decan-1,10-yl group. R 15 Examples of the aromatic hydrocarbon group as the aromatic ring include a p-phenylene group, an m-phenylene group, an o-phenylene group, a naphthalene-2,6-diyl group, a naphthalene-2,7-diyl group, a biphenyl-4,4'-diyl group, a biphenyl-3.4'-diyl group, and a biphenyl-3,3'-diyl group.

[0056] R 15Specific examples of the nitrogen-containing heterocycle include groups in which two hydrogen atoms have been removed from the following nitrogen-containing heterocycles. Examples of the nitrogen-containing heterocycle include nitrogen-containing five-membered rings such as a pyrrolidine ring, a pyrazolidine ring, an imidazolidine ring, a triazolidine ring, a tetrazolidine ring, a pyrroline ring, a pyrazoline ring, an imidazoline ring, a triazoline ring, a tetrizoline ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring; nitrogen-containing six-membered rings such as a piperidine ring, a piperidine ring, a piperidine ring, a piperidine ring, a triazinane ring, a tetrazinane ring, a pentazinane ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a tetrazine ring, and a pentazine ring. rings; nitrogen-containing seven-membered rings such as an azepane ring, a diazepane ring, a triazepane ring, a tetrazepane ring, an azepine ring, a diazepine ring, and a triazepine ring; and nitrogen-containing condensed polycyclic rings such as an indole ring, an indolenine ring, an indoline ring, an isoindole ring, an isoindolenine ring, an isoindoline ring, a benzimidazole ring, an indolizine ring, a purine ring, an indolizidine ring, a benzodiazepine ring, a quinoline ring, an isoquinoline ring, a quinolizidine ring, a quinoxaline ring, a cinnoline ring, a quinazoline ring, a phthalazine ring, a naphthyridine ring, and a pteridine ring.

[0057] Specific preferred examples of the silane compound represented by formula (a2-1) include unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane; and (meth)acryloxy group-containing silanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane.

[0058] (Polar polymerizable compound (A2-2)) The polar polymerizable compound (A2-2) has a group having an ethylenically unsaturated double bond, and a polar group selected from an amino group, a carboxy group, a mercapto group, a cyano group, and a hydroxyl group.

[0059] The polar polymerizable compound (A2-2) is preferably a compound represented by the following formula (a2-2). CH2=CR A1 -(R A2 ) c -CO-R A3 (a2-2) (In formula (a2-2), R A1 is a hydrogen atom or a methyl group, R A2 is a divalent hydrocarbon group, c is 0 or 1, R A3 -OH, -OR A4 or -NH-R A4 and R A4 is a hydrocarbon group substituted with one or more polar groups selected from the group consisting of an amino group, a carboxy group, a mercapto group, a cyano group, and a hydroxyl group.

[0060] In the above formula (a2-2), R A2 is a divalent hydrocarbon group. The number of carbon atoms in the divalent hydrocarbon group is not particularly limited as long as it does not impair the object of the present invention. Since the compound represented by formula (a2-2) is easily available and can be easily prepared, R A2 The divalent hydrocarbon group as the alkyl group preferably has 1 or more and 20 or less carbon atoms, more preferably has 1 or more and 12 or less carbon atoms, particularly preferably has 1 or more and 10 or less carbon atoms, and most preferably has 1 or more and 6 or less carbon atoms.

[0061] R A2 The divalent hydrocarbon group as may be an aliphatic group, an aromatic group, or a hydrocarbon group containing an aliphatic portion and an aromatic portion. When the divalent hydrocarbon group is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. The structure of the aliphatic group may be linear, branched, cyclic, or a combination of these structures.

[0062] R A2Preferred specific examples of the alkyl group include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, a n-butane-1,4-diyl group, a n-pentane-1,5-diyl group, a n-hexane-1,6-diyl group, a n-heptane-1,7-diyl group, a n-octane-1,8-diyl group, a n-nonane-1,9-diyl group, a n-decane-1,10-diyl group, an o-phenylene group, a m-phenylene group, a p-phenylene group, a naphthalene-2,6-diyl group, a naphthalene-2,7-diyl group, a naphthalene-1,4-diyl group, and a biphenyl-4,4'-diyl group.

[0063] R A3 -OH, -OR A4 or -NH-R A4 R A4 is a hydrocarbon group substituted with one or more polar groups selected from the group consisting of an amino group, a carboxy group, a mercapto group, a cyano group, and a hydroxyl group. R A4 The hydrocarbon group constituting the main skeleton of the group may be a linear, branched or cyclic aliphatic group, or an aromatic hydrocarbon group. The linear, branched or cyclic aliphatic group preferably has 1 or more and 20 or less carbon atoms, and more preferably has 1 or more and 12 or less carbon atoms. Suitable examples of the linear or branched aliphatic group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Suitable examples of the cyclic aliphatic group include cyclooctyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; groups in which one hydrogen atom has been removed from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and groups in which one hydrogen atom has been removed from C1-C4 alkyl substituted versions of these polycycloalkanes. Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, and a biphenylyl group, etc. The aromatic hydrocarbon group may be substituted with a C1-C4 alkyl group such as a methyl group or an ethyl group.

[0064] Preferable specific examples of the compound represented by formula (a2-2) include the following compounds. [ka]

[0065] The polar polymerizable compound (A2-2) is also preferably a compound represented by the following formula (a2-3). (R 3a -R 2a ) n -XR 1a (a2-3) (In formula (a2-3), R 1a is an organic group having one or more ethylenically unsaturated double bonds, and R 2a is a single bond or an alkylene group having 1 to 10 carbon atoms; R 3a is a hydrogen atom or a polar group selected from an amino group, a carboxy group, a mercapto group, a cyano group, and a hydroxyl group, n is 1 or 2, X is a nitrogen-containing heterocyclic group having a valence of n+1, and when n is 1, R a3 is the polar group as defined above, and when n is 2, at least one of R 3a is the polar group.)

[0066] In formula (a2-3), R a1is an organic group having one or more ethylenically unsaturated double bonds. Suitable examples of the organic group having one or more ethylenically unsaturated double bonds include groups represented by the following formulae (a2-3i) to (a2-3vii). In the following formulae (a3-2i) to (a2-3vii), R a01 is an alkenyl group having 1 to 10 carbon atoms, R a02 is a hydrocarbon group having from 1 to 10 carbon atoms. -R a01 (a2-3i) -NH-R a01 (a2-3ii) -N(R a01 )(R a02 )···(a2-3iii) -N(R a01 )2···(a2-3iv) -OR a01 (a2-3v) -CO-NH-R a01 (a2-3vi) -CO-OR a01 (a2-3vii)

[0067] R a01 The number of carbon atoms in the alkenyl group represented by R is preferably 1 or more and 6 or less, and more preferably 1 or more and 4 or less. a01 The alkenyl group as may be a straight-chain alkenyl group or a branched-chain alkenyl group. R a02 The hydrocarbon group as R may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. a02 The number of carbon atoms in the hydrocarbon group as the alkyl group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and even more preferably 1 or more and 3 or less.

[0068] R a1Specific preferred examples of the organic group having one or more ethylenically unsaturated double bonds as the ethylenically unsaturated double bond include alkenyl groups such as vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl, and 3-n-butenyl groups; N-vinylamino, N-1-propenylamino, N-allylamino, N-1-n-butenylamino, N-2-n-butenyl, Monoalkenylamino groups such as an amino group and an N-3-n-butenylamino group; dialkenylamino groups such as an N,N-divinylamino group, an N,N-di(1-propenyl)amino group, an N,N-diallylamino group, an N,N-di(1-n-butenyl)amino group, an N,N-di(2-n-butenyl)amino group, and an N,N-di(3-n-butenyl)amino group; an allyloxy group, a 2-n-butenyloxy group, alkenyloxy groups such as a vinylaminocarbonyl group, a 1-propenylaminocarbonyl group, an allylaminocarbonyl group, a 1-n-butenylaminocarbonyl group, a 2-n-butenylaminocarbonyl group, and a 3-n-butenylaminocarbonyl group; alkenyloxycarbonyl groups such as a vinyloxycarbonyl group, a 1-propenyloxycarbonyl group, an allyloxycarbonyl group, a 1-n-butenyloxycarbonyl group, a 2-n-butenyloxycarbonyl group, and a 3-n-butenyloxycarbonyl group; and (meth)acryloyl group-containing groups such as an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, and a methacryloylamino group. Among these groups, vinyl group, allyl group, N,N-diallylamino group, allyloxy group, acryloyl group, methacryloyl group, acryloyloxy group, and methacryloyloxy group are preferred, and N,N-diallylamino group is more preferred.

[0069] In formula (a2-3), R 2ais a single bond or an alkylene group having 1 to 10 carbon atoms. The number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. Specific examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, a n-butane-1,4-diyl group, a n-pentane-1,5-diyl group, a n-hexane-1,6-diyl group, a n-heptane-1,7-diyl group, a n-octane-1,8-diyl group, a n-nonane-1,9-diyl group, and a n-decane-1,10-diyl group. Among these alkylene groups, a methylene group, an ethane-1,2-diyl group, and a propane-1,3-diyl group are preferred, and a methylene group and an ethane-1,2-diyl group are more preferred.

[0070] In formula (a2-3), R 2a X is a nitrogen-containing heterocyclic group having a valence of (n+1), where n is 1 or 2. The nitrogen-containing heterocyclic group may be an aromatic group or an aliphatic group. The nitrogen-containing heterocycle may be a monocycle or a condensed polycycle in which a monocyclic nitrogen-containing heterocycle is condensed with one or more monocycles selected from a monocyclic aromatic hydrocarbon ring and a monocyclic nitrogen-containing heterocycle. The nitrogen-containing heterocycle may be a ring in which two or more rings selected from a monocyclic nitrogen-containing heterocycle and a condensed polycyclic nitrogen-containing heterocycle are bonded via a single bond.

[0071] In formula (a2-3), R a1 and R 3a -R 2a The group represented by - may be bonded to a carbon atom which is a ring-constituting atom of the nitrogen-containing heterocyclic group represented by X, or may be bonded to a nitrogen atom which is a ring-constituting atom.

[0072] Specific examples of nitrogen-containing heterocycles that provide X include nitrogen-containing 5-membered rings such as a pyrrolidine ring, a pyrazolidine ring, an imidazolidine ring, a triazolidine ring, a tetrazolidine ring, a pyrroline ring, a pyrazoline ring, an imidazoline ring, a triazoline ring, a tetrizoline ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring; nitrogen-containing 6-membered rings such as a piperidine ring, a piperideine ring, a piperazine ring, a triazinane ring, a tetrazinane ring, a pentazinane ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a tetrazine ring, and a pentazine ring; an azepane ring, a diazepane ring. nitrogen-containing seven-membered rings such as a triazepane ring, a tetrazepane ring, an azepine ring, a diazepine ring, and a triazepine ring; nitrogen-containing condensed polycyclic rings such as an indole ring, an indolenine ring, an indoline ring, an isoindole ring, an isoindolenine ring, an isoindoline ring, a benzimidazole ring, an indolizine ring, a purine ring, an indolizidine ring, a benzodiazepine ring, a quinoline ring, an isoquinoline ring, a quinolizidine ring, a quinoxaline ring, a cinnoline ring, a quinazoline ring, a phthalazine ring, a naphthyridine ring, and a pteridine ring; and polycyclic rings in which two or more rings selected from these nitrogen-containing heterocyclic rings are bonded via a single bond. As X derived from these nitrogen-containing heterocycles, from the viewpoint of good adhesion of the polymer of the polymerizable compound (A) to the surface of the target object, etc., a divalent or trivalent group containing a nitrogen-containing six-membered ring is preferable, a divalent or trivalent group containing a triazine ring is more preferable, and a 1,3,5-triazine-2,4-diyl group and a 1,3,5-triazine-2,4,6-triyl group are even more preferable.

[0073] Specific examples of suitable divalent or trivalent nitrogen-containing heterocyclic groups as X include the following groups. [ka]

[0074] Preferable specific examples of the compound represented by formula (a2-3) include the following compounds. [ka]

[0075] [ka]

[0076] Among the above compounds, the following compounds are preferred. [ka]

[0077] Furthermore, it is also preferable to use, as the polar polymerizable compound (A2-2), a polyfunctional compound having a hydroxyl group, such as N,N'-di(meth)acryloyl-1,2-dihydroxyethylenediamine, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, and phthalic acid diglycidyl ester di(meth)acrylate.

[0078] Such a polyfunctional polar polymerizable compound (A2-2) can improve the adhesion of the resin coating formed by polymerization of the polymerizable compound (A) to the surface of the substrate, not only by the action of the hydroxyl groups but also by crosslinking of the molecular chains. The ratio of the number of moles of the adhesive polymerizable compound (A2) to the number of moles of the polymerizable compound (A) is not particularly limited within the range that does not impair the object of the present invention. In terms of achieving both a good hydrophilization effect and good adhesion of the resin coating film formed to the surface of the treated object, the ratio of the number of moles of the adhesive polymerizable compound (A2) to the number of moles of the polymerizable compound (A) is preferably 0.1 mol% or more and 30 mol% or less, more preferably 0.1 mol% or more and 20 mol% or less, and even more preferably 0.1 mol% or more and 10 mol% or less, in terms of achieving both the adhesion of the resin (A) to the surface of the treated object and the excellent hydrophilization effect.

[0079] [Acidic polymerizable compound (A3a) and basic polymerizable compound (A3b)] Regarding the hydrophilic surface treatment liquid, the pH of an aqueous solution of the polymerizable compound (A) with a concentration of 10% by mass at 23°C is 6.5 to 7.5. By adjusting the pH of the aqueous solution of the polymerizable compound (A) in this manner, the resin coating formed on the surface of the treated object using the hydrophilic surface treatment liquid approaches electrostatic neutrality. As a result, even if the surface of the treated object after the surface treatment is exposed to various chemical solutions such as anionic chemical solutions and cationic chemical solutions, the anionic and cationic components of the chemical solutions are unlikely to bind to the coating, and the effect of the surface treatment is unlikely to decrease over time.

[0080] The method for adjusting the pH of an aqueous solution of the polymerizable compound (A) having a concentration of 10% by mass is not particularly limited. The polymerizable compound (A) contains an acidic polymerizable compound (A3a) and / or a basic polymerizable compound (A3b). The pH of an aqueous solution of the polymerizable compound (A) having a concentration of 10% by mass at 23°C is preferably adjusted by adjusting the content of the acidic polymerizable compound (A3a) and / or the basic polymerizable compound (A3b) in the polymerizable compound (A).

[0081] (Acidic polymerizable compound (A3a)) The acidic polymerizable compound (A3a) has an ethylenically unsaturated double bond and an acidic group, preferably a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a phosphonic acid group.

[0082] The structure of the portion of the acidic polymerizable compound (A3a) other than the ethylenically unsaturated double bond and the acidic group is not particularly limited as long as an aqueous solution of the acidic polymerizable compound (A3a) exhibits acidity. Preferred examples of the acidic polymerizable compound (A3a) include alkenyl sulfonic acids having from 2 to 10 carbon atoms, (meth)acryloyloxyalkyl sulfonic acids having from 3 to 10 carbon atoms, alkenyl-substituted arenesulfonic acids having from 8 to 20 carbon atoms, unsaturated aliphatic carboxylic acids having from 3 to 10 carbon atoms, (meth)acryloyloxyalkanoic acids having from 4 to 10 carbon atoms, alkenyl-substituted arene carboxylic acids having from 9 to 20 carbon atoms, alkenyl phosphates having from 2 to 10 carbon atoms, (meth)acryloyloxyalkyl phosphates having from 3 to 10 carbon atoms, alkenyl-substituted aryl phosphates having from 8 to 20 carbon atoms, alkenyl phosphonic acids having from 2 to 10 carbon atoms, (meth)acryloyloxyalkyl phosphonic acids having from 3 to 10 carbon atoms, and alkenyl-substituted arene phosphonic acids having from 8 to 20 carbon atoms.

[0083] Specific examples of suitable acidic polymerizable compounds (A3a) include vinyl sulfonic acid, allyl sulfonic acid, 3-butene-1-sulfonic acid, 4-pentene-1-sulfonic acid, 5-hexene-1-sulfonic acid, 2-(meth)acryloyloxyethane-1-sulfonic acid, 3-(meth)acryloyloxypropane-1-sulfonic acid, 4-(meth)acryloyloxybutane-1-sulfonic acid, 4-vinylbenzenesulfonic acid, 3-vinylbenzenesulfonic acid, 2-vinylbenzenesulfonic acid, acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, (meth)acryloyloxyacetic acid, 3-(meth)acryloyloxyethyl acetate ... Examples of the acryloyloxypropyl phosphate include cypropionic acid, 4-(meth)acryloyloxybutanoic acid, 4-vinylbenzoic acid, 3-vinylbenzoic acid, 2-vinylbenzoic acid, vinyl phosphate, allyl phosphate, isopropenyl phosphate, 3-butenyl phosphate, 4-pentenyl phosphate, (meth)acryloyloxymethyl phosphate, 2-(meth)acryloyloxyethyl phosphate, 3-(meth)acryloyloxypropyl phosphate, 4-(meth)acryloyloxybutyl phosphate, 4-vinylphenyl phosphate, 3-vinylphenyl phosphate, 2-vinylphenyl phosphate, vinylphosphonic acid, allylphosphonic acid, 3-butenylphosphonic acid, and 4-pentenylphosphonic acid.

[0084] (Basic polymerizable compound (A3b)) The basic polymerizable compound (A3b) has an ethylenically unsaturated double bond and a basic group, such as a primary amino group, a secondary amino group, a tertiary amino group, or a basic aromatic heterocyclic group. The structure of the portion other than the ethylenically unsaturated double bond and the basic group in the basic polymerizable compound (A3b) is not particularly limited as long as an aqueous solution of the basic polymerizable compound (A3b) exhibits acidity. Specific preferred examples of the basic polymerizable compound (A3b) include vinylamine, allylamine, 3-butenylamine, 4-pentenylamine, divinylamine, diallylamine, di(3-butenyl)amine, di(4-pentenyl)amine, triallylamine, 4-vinylaniline, 3-vinylaniline, 2-vinylaniline, 4-vinylpyridine, 3-vinylpyridine, 2-vinylpyridine, 2-vinyl-1H-imidazole, and 2-allyl-1H-imidazole.

[0085] The amounts of the acidic polymerizable compound (A3a) and the basic polymerizable compound (A3b) used are not particularly limited as long as the pH of an aqueous solution having a concentration of 10% by mass of the polymerizable compound (A) at 23° C. is 6.5 or more and 7.5 or less. The amount of the acidic polymerizable compound (A3a) and the basic polymerizable compound (A3b) used, as the total amount of both, is preferably 0.1 mol % or more and 30 mol % or less, more preferably 0.1 mol % or more and 20 mol % or less, and even more preferably 0.1 mol % or more and 10 mol % or less, based on the number of moles of the polymerizable compound (A). The polymerizable compound (A) may contain only an acidic polymerizable compound (A3a) or a basic polymerizable compound (A3b), or may contain a combination of an acidic polymerizable compound (A3a) and a basic polymerizable compound (A3b).

[0086] [Polyfunctional Monomer (A4)] The polymerizable compound (A) may contain a polyfunctional monomer (A4) other than the hydrophilic polymerizable compound (A1), the adhesive polymerizable compound (A2), the acidic polymerizable compound (A3a), and the basic polymerizable compound (A3b). The polyfunctional monomer (A4) is a compound having two or more ethylenically unsaturated double bonds and not corresponding to the hydrophilic polymerizable compound (A1), the adhesive polymerizable compound (A2), the acidic polymerizable compound (A3a), or the basic polymerizable compound (A3b). The polyfunctional monomer (A4) crosslinks molecular chains in the resin coating formed by polymerization of the polymerizable compound (A), improving the adhesion of the resin coating to the surface of the substrate.

[0087] Specific examples of the polyfunctional monomer (A4) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, pentapropylene glycol di(meth)acrylate, di(meth)acrylate, hexapropylene glycol di(meth)acrylate, heptapropylene glycol di(meth)acrylate, octapropylene glycol di(meth)acrylate, nonapropylene glycol di(meth)acrylate, decapropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, and 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane.

[0088] The ratio of the number of moles of the polyfunctional monomer (A4) to the number of moles of the polymerizable compound (A) is not particularly limited as long as it does not impair the object of the present invention. In order to appropriately crosslink the polymer of the polymerizable compound (A), the ratio of the number of moles of the polyfunctional monomer (A4) to the number of moles of the polymerizable compound (A) is preferably 0.5 mol% or more and 20 mol% or less, more preferably 1 mol% or more and 15 mol% or less, and more preferably 1 mol% or more and 10 mol% or less.

[0089] [Other monomers (A5)] The polymerizable compound (A) may contain a monomer (A5) other than the hydrophilic polymerizable compound (A1), the adhesive polymerizable compound (A2), the acidic polymerizable compound (A3a), the acidic polymerizable compound (A3a), the basic polymerizable compound (A3b), and the polyfunctional monomer (A4), as long as the object of the present invention is not impaired. The other monomer (A5) is a compound which has an ethylenically unsaturated double bond and does not fall under the hydrophilic polymerizable compound (A1), the adhesive polymerizable compound (A2), the acidic polymerizable compound (A3a), the acidic polymerizable compound (A3a), the basic polymerizable compound (A3b), or the polyfunctional monomer (A4).

[0090] Examples of the other monomers (A5) include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, phenyl (meth)acrylate, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nn-butyl(meth)acrylamide, Nn Examples of such methyl styrene copolymers include 1,2-pentyl(meth)acrylamide, N-isopentyl(meth)acrylamide, N-phenyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N,N-di-n-butyl(meth)acrylamide, N,N-di-n-pentyl(meth)acrylamide, styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, chlorostyrene, methyldiallylamine, ethyldiallylamine, and triallylamine.

[0091] The ratio of the number of moles of the other monomer (A5) to the number of moles of the polymerizable compound (A) is not particularly limited, as long as the polymerizable compound (A) contains the hydrophilic polymerizable compound (A1), the adhesive polymerizable compound (A2), the acidic polymerizable compound (A3a), and the basic polymerizable compound (A3b) in desired amounts.

[0092] The ratio of the mass of the polymerizable compound (A) to the mass of the hydrophilization surface treatment liquid is not particularly limited, but is preferably 1% by mass to 40% by mass or less, more preferably 2% by mass to 20% by mass or less, and even more preferably 2% by mass to 15% by mass or less.

[0093] <Polymerization initiator (B)> The hydrophilic surface treatment liquid contains a polymerization initiator (B) as a component for polymerizing the polymerizable compound (A). The polymerization initiator (B) is not particularly limited as long as it is a compound capable of polymerizing the polymerizable compound (A) having an ethylenically unsaturated double bond.

[0094] Suitable examples of the polymerization initiator (B) include an azo polymerization initiator (B1) and a peroxide (B2).

[0095] Specific examples of the azo polymerization initiator (B1) include 2,2'-azobis(2-methylpropionamidine) dihydrochloride (dihydrochloride), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide, 2,2'-azobis[2-(phenylamidino)propane]dihydrochloride, 2,2'-azobis{2-[N-(4-chlorophenyl)amidino]propane}dihydrochloride, 2 ,2'-Azobis{2-[N-(4-hydroxyphenyl)amidino]propane}dihydrochloride, 2,2'-Azobis[2-(N-benzylamidino)propane]dihydrochloride, 2,2'-Azobis[2-(N-allylamidino)propane]dihydrochloride, 2,2'-Azobis(2-amidinopropane)dihydrochloride, 2,2'-Azobis{2-[N-(2-hydroxyethyl)amidino ]propane}dihydrochloride, 2,2-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane]dihydrochloride, 2,2-azobis[2-(3,4,5,6-tetrahydro- Examples of the azo polymerization initiator (B1) include 2,2-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride, and 2,2-azobis[2-(2-imidazolin-2-yl)propane]. These azo polymerization initiators (B1) may be used alone or in combination of two or more.

[0096] Specific examples of the peroxide (B2) include alkyl peroxides such as isobutyl peroxide and decanoyl peroxide; peroxycarboxylic anhydrides such as acetyl peroxide; aromatic peroxycarboxylic anhydrides such as benzoyl peroxide; peroxyanhydrides of polycarboxylic acids such as succinic acid peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diallyl peroxydicarbonate; peroxyesters such as tert-butyl peroxyisobutyrate, tert-butyl peroxyneodecanate, and cumene peroxyneodecanate; peroxyanhydrides of carboxylic acids and sulfonic acids such as acetylcyclohexylsulfonyl peroxide; and inorganic peroxides such as ammonium persulfate, potassium persulfate, potassium chlorate, potassium bromate, and potassium perphosphate. These peroxides (B2) may be used alone or in combination of two or more kinds.

[0097] The amount of the polymerization initiator (B) is not particularly limited as long as the polymerization reaction can be carried out satisfactorily. The amount of the polymerization initiator (B) is preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.1 mol% or more and 15 mol% or less, based on the total number of moles of the polymerizable compound (A).

[0098] From the viewpoint of the stability of the surface treatment liquid over time, the surface treatment liquid may be a two-liquid type surface treatment liquid consisting of a first liquid containing a polymerizable compound (A) and a solvent (S) and a second liquid containing a polymerization initiator (B) and a solvent (S). Such a two-liquid type surface treatment liquid is mixed and used immediately before the surface treatment.

[0099] [Solvent (S)] The surface treatment liquid contains a solvent (S). The solvent (S) may be water, an organic solvent, or an aqueous solution of an organic solvent. As the solvent (S), water is preferred in terms of the solubility of the polymerizable compound (A), the safety of the hydrophilization treatment operation, and low cost. A suitable example of the organic solvent used as the solvent (S) is alcohol. The alcohol may be an aliphatic alcohol, and is preferably an alcohol having 1 to 3 carbon atoms. Specific examples include methanol, ethanol, n-propyl alcohol, and isopropyl alcohol (IPA), and methanol, ethanol, and isopropyl alcohol are preferred. The alcohol may be used alone or in combination of two or more.

[0100] The water content in the solvent (S) is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 100% by mass.

[0101] [Other ingredients] The hydrophilic surface treatment liquid may contain various additives within the range that does not impair the object of the present invention. Examples of such additives include antioxidants, ultraviolet absorbers, colorants, antifoaming agents, and viscosity modifiers. The content of these additives is appropriately determined taking into account the amounts of these additives that are usually used.

[0102] <Hydrophilic treatment method> The hydrophilic treatment method is applying the hydrophilic surface treatment liquid to the surface of the object to be treated to form a coating film; Heating the coating film to form a coating on the surface of the object to be treated; Includes. However, so long as the surface of the treatment target object is rendered hydrophilic to a desired degree, it is not necessary to apply the surface treatment liquid uniformly over the entire surface of the treatment target object to be rendered hydrophilic. The hydrophilic treatment method preferably further includes rinsing the surface of the treatment target with a rinsing liquid after heating the coating. In particular, by rinsing with water or an aqueous solution of an organic solvent, low molecular weight polymers with a low degree of polymerization or crosslinking can be easily removed from the coating.

[0103] Hereinafter, applying a surface treatment liquid to form a coating film on the surface of the workpiece will also be referred to as a "coating step." Heating the coating film to form a coating on the surface of the workpiece will also be referred to as a "heating step." Rinsing the surface of the workpiece with a rinse liquid after heating the coating will also be referred to as a "rinsing step." The coating step, the heating step, and the rinsing step will be described in detail below.

[0104] <Coating process> In the coating step, the above-mentioned surface treatment liquid is applied to the surface of the treatment target to form a coating film. The coating method is not particularly limited. Specific examples of the coating method include spin coating, spraying, roller coating, immersion, etc. When the object to be treated is a substrate, spin coating is preferred as the coating method because it is easy to form a coating of a uniform thickness evenly on the surface of the substrate.

[0105] The material of the surface of the object to be treated onto which the surface treatment liquid is applied is not particularly limited, and may be either an organic material or an inorganic material. Examples of organic materials include various resin materials such as polyester resins such as PET resin and PBT resin, various nylons, polyimide resins, polyamide-imide resins, polyolefins such as polyethylene and polypropylene, polystyrene, (meth)acrylic resins, cycloolefin polymers (COP), cycloolefin copolymers (COC), and silicone resins (e.g., polyorganosiloxanes such as polydimethylsiloxane (PDMS)). Additionally, photosensitive resin components contained in various resist materials and alkali-soluble resin components are also preferred as organic materials. Inorganic materials include glass, silicon, and various metals such as copper, aluminum, iron, tungsten, etc. The metals may be alloys.

[0106] The shape of the object to be processed is not particularly limited. The object to be processed may be flat or may have a three-dimensional shape such as a sphere or a columnar shape.

[0107] The treated object may be exposed to chemicals such as cleaning agents, and there is concern that the exposure to chemicals may reduce the hydrophilicity of the coating formed on the treated object. However, by using the above-mentioned surface treatment liquid, it is possible to suppress the reduction in hydrophilicity when the surface-treated surface comes into contact with various chemicals. Therefore, by using a treated object that is often exposed to chemicals such as cleaning liquids, such as glass members provided in windows, mirrors, furniture, and optical devices (e.g., devices having lenses) and translucent resin members, as the treated object, the effect of chemical resistance regarding hydrophilicity can be particularly exhibited.

[0108] After the surface treatment liquid is applied to the surface of the treatment target, at least a part of the solvent (S) may be removed from the coating film of the surface treatment liquid by a known drying method, if necessary.

[0109] The thickness of the coating film formed in the coating step is not particularly limited. For example, the thickness of the coating film formed in the coating step is preferably 1 μm or less, more preferably 300 nm or less, and even more preferably 100 nm or less.

[0110] The thickness of the coating film formed by the coating step can be adjusted by adjusting the solids concentration of the surface treatment liquid, coating conditions, and the like.

[0111] <Heating process> In the heating step, the coating film formed in the coating step is heated. By heating, the polymerizable compound (A) contained in the coating film is polymerized by the action of the polymerization initiator (B), and a resin coating film that is firmly bonded to the surface of the substrate is formed.

[0112] The heating conditions are not particularly limited as long as the polymerizable compound (A) is polymerized to a desired degree and the treated object is not deteriorated or deformed. The heating temperature is, for example, preferably 30°C or more and 300°C or less, more preferably 40°C or more and 250°C or less. The heating time is, for example, preferably 1 minute or more and 6 hours or less, more preferably 3 minutes or more and 60 minutes or less, and even more preferably 5 minutes or more and 30 minutes or less.

[0113] <Rinse process> In the rinsing step, after the coating film is heated, the surface of the workpiece is rinsed with a rinsing liquid, which can reduce the thickness of the coating film formed on the surface of the workpiece. The rinse liquid is not particularly limited as long as it can form a coating of a desired thickness. As the rinse liquid, water, an organic solvent, or an aqueous solution of an organic solvent can be used. As the rinse liquid, water is preferred. The method for rinsing the coating is not particularly limited, but typically, rinsing is performed by contacting the coating with a rinsing liquid in the same manner as in the coating method described above.

[0114] The thickness of the coating obtained after rinsing is, for example, preferably 10 nm or less, more preferably 0.1 nm or more and 10 nm or less, even more preferably 0.1 nm or more and 8 nm or less, even more preferably 0.5 nm or more and 5 nm or less, and particularly preferably 0.5 nm or more and 3 nm or less.

[0115] The thickness of the coating can be adjusted by adjusting the solids concentration of the surface treatment liquid, the application conditions, the amount of rinse liquid used, the type of rinse liquid, the temperature of the rinse liquid, and the like.

[0116] After rinsing, the treated object may be dried as necessary, and then the treated object may be suitably used for various applications. EXAMPLES

[0117] The present invention will be described in more detail below by showing examples, but the scope of the present invention is not limited to these examples.

[0118] [Examples 1 to 4 and Comparative Examples 1 to 4] In the examples and comparative examples, the following A1-1 to A1-3 were used as the hydrophilic polymerizable compound (A1). [ka]

[0119] In the examples and comparative examples, 3-(trimethoxysilyl)propyl acrylate was used as the adhesive polymerizable compound (A2).

[0120] In the examples and comparative examples, the following A3-1 to A3-3 were used as the acidic polymerizable compound (A3a) and the basic polymerizable compound (A3b). A3-1: Vinyl sulfonic acid A3-2: 4-vinylpyridine A3-3: Diallylamine

[0121] In the examples and comparative examples, 2,2'-azobis(2-methylpropionamidine) dihydrochloride in the amount shown in Table 1 was used as the polymerization initiator (B).

[0122] The type and amount of polymerizable compound (A) shown in Table 1 was dissolved in water to a solid concentration of 10 mass %, and then the amount of polymerization initiator (B) shown in Table 1 was added to the obtained solution to obtain the surface treatment liquids of Examples 1 to 4 and Comparative Examples 1 to 4.

[0123] <pH of the aqueous solution of the polymerizable compound (A)> Each compound used as the polymerizable compound (A) was dissolved in water to give a molar ratio similar to that shown in Table 1 and a concentration of the polymerizable compound (A) of 10 mass %. The pH of the resulting aqueous solution was measured at 23° C. The pH measurement results are shown in Table 1.

[0124] <Water contact angle> The surface treatment solutions of each of the Examples and Comparative Examples were spin-coated onto a silicon wafer at 1000 rpm for 60 seconds, and then the wafer was heated for 10 minutes at 100° C. The wafer surface was then washed with water to form a coating made of a resin that was a copolymer of the above-mentioned polymerizable compound (A) on the wafer. Using a Dropmaster700 (manufactured by Kyowa Interface Science Co., Ltd.), a pure water droplet (2.0 μL) was dropped onto the surface-treated surface of the silicon wafer, and the contact angle of water was measured as the contact angle 10 seconds after the drop. The average value of the contact angle of water at three points on the silicon wafer is shown in Table 1. The contact angle of water on an untreated silicon wafer is 13.8°.

[0125] <Chemical resistance> The silicon wafer, which had been surface-treated in the same manner as in the measurement of the water contact angle, was immersed for 1 minute in an anionic chemical solution, a sodium laureth sulfate aqueous solution with a concentration of 1% by mass, or a cationic chemical solution, a 1% by mass aqueous solution of amine-modified polydimethylsiloxane. The surface of the silicon wafer was then shower-washed with pure water for 1 minute. The water contact angle of the surface-treated silicon wafer after washing was measured according to the above method. The measured water contact angles are shown in Table 1.

[0126] [Table 1]

[0127] According to the examples, in a hydrophilic surface treatment liquid containing a polymerizable compound (A) having an ethylenically unsaturated double bond, a polymerization initiator (B), and a solvent (S), a hydrophilic polymerizable compound (A1), an adhesive polymerizable compound (A2), and an acidic polymerizable compound (A3a) and / or a basic polymerizable compound (A3b) are used as the polymerizable compound (A), and the pH of an aqueous solution of the polymerizable compound (A) having a concentration of 10 mass % at 23°C is set to 6.5 or more and 7.5 or less, whereby it is possible to form a coating on the surface of a treated object whose hydrophilicity is not easily reduced even when the hydrophilic treatment liquid is used and the coating comes into contact with an anionic chemical solution or a cationic chemical solution. On the other hand, according to Comparative Examples 1 to 3, even if the hydrophilic treatment liquid contains a hydrophilic polymerizable compound (A1), an adhesive polymerizable compound (A2), and an acidic polymerizable compound (A3a) and / or a basic polymerizable compound (A3b) as the polymerizable compound (A), if the pH of an aqueous solution of the polymerizable compound (A) having a concentration of 10% by mass at 23°C is outside the range of 6.5 or more and 7.5 or less, it is found that a coating whose hydrophilicity is not easily reduced when contacted with an anionic chemical solution or a cationic chemical solution cannot be formed on the surface of the treated body using the hydrophilic treatment liquid. Furthermore, according to Comparative Example 4, even if the pH of an aqueous solution containing the polymerizable compound (A) at 23°C with a concentration of 10% by mass is within the range of 6.5 to 7.5, if the polymerizable compound (A) does not contain the hydrophilic polymerizable compound (A1), it is not possible to form a coating on the surface of the treated body using a hydrophilization treatment liquid, the hydrophilicity of which is not easily reduced when the hydrophilicity is contacted with an anionic chemical solution or a cationic chemical solution.

Claims

1. A hydrophilic surface treatment liquid comprising a polymerizable compound (A), a polymerization initiator (B), and a solvent (S), the polymerizable compound (A) contains a hydrophilic polymerizable compound (A1), an adhesive polymerizable compound (A2), and an acidic polymerizable compound (A3a) and / or a basic polymerizable compound (A3b); the hydrophilic polymerizable compound (A1) is a polymerizable betaine compound having a group having an ethylenically unsaturated double bond and a cationic group which is a quaternary nitrogen cation, the adhesive polymerizable compound (A2) is an unsaturated group-containing silicon compound (A2-1) having a group having an ethylenically unsaturated double bond and a hydrolyzable silyl group, the acidic polymerizable compound (A3a) and the basic polymerizable compound (A3b) each have an ethylenically unsaturated double bond, The hydrophilization surface treatment liquid, wherein an aqueous solution of the polymerizable compound (A) having a concentration of 10% by mass has a pH of 6.5 or more and 7.5 or less at 23° C.

2. 2. The hydrophilization surface treatment liquid according to claim 1, wherein the polymerizable compound (A) comprises a compound having one or more polymerizable groups selected from a vinyl group and an allyl group.

3. The hydrophilic surface treatment liquid according to claim 1 or 2, wherein a ratio of the number of moles of the adhesive polymerizable compound (A2) to the number of moles of the polymerizable compound (A) is 0.1 mol % or more and 10 mol % or less.

4. Coating the hydrophilic surface treatment liquid according to any one of claims 1 to 3 to form a coating film on the surface of a treatment target; and heating the coating film to form a coating on the surface of the object to be treated.

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