Coincidence composition and hydrophilic treatment method

Abstract

To provide a polymerizable composition which enables formation of a thick hydrophilic resin film having high hardness and excellent durability on a surface of a body to be treated that is a surface treatment object, and a hydrophilic treatment method using the polymerizable composition.SOLUTION: A polymerizable composition contains a polymerizable compound (A), a polymerization initiator (B) inorganic fine particles (C), and a solvent (S), wherein a polymerizable betaine compound (A1) having an ethylenically unsaturated double bond and a betaine structure and an adhesive polymerizable compound (A2) having an ethylenically unsaturated double bond and a specific kind of an adhesive group are used as the polymerizable compound (A), a water-soluble radical polymerization initiator (B1) is used as the polymerization initiator (B), and inorganic fine particles (C) having a functional group which can form a covalent bond to a polymer of the polymerizable compound (A) are used.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polymerizable composition and a hydrophilic treatment method using the polymerizable composition.

Background Art

[0002] Conventionally, in order to modify the surface properties of various articles, surface treatment has been performed using various surface treatment liquids. Among surface modifications, the demand for hydrophilization of the surface of articles is large, and many proposals have been made for hydrophilizing agents and surface treatment liquids. By subjecting an object to surface treatment using a hydrophilizing agent or a surface treatment liquid, a film is formed on the surface of the object, and the surface of the object is hydrophilized.

[0003] Examples of such hydrophilizing agents and surface treatment liquids include a hydrophilization treatment agent containing a copolymer using at least an acrylamide monomer and a mono(meth)acrylate monomer as components for expressing hydrophilicity (Patent Document 1), and a block copolymer of a polyvinyl alcohol resin block having a mercapto group and a polyanion resin block formed by polymerizing a polymerizable monomer having at least one carboxy group and / or sulfonic acid group in one molecule, and a hydrophilization treatment agent containing polyacrylic acid (Patent Document 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the resin, which is a hydrophilic component contained in the conventional hydrophilic treatment agents described in Patent Document 1, Patent Document 2, etc., does not always have sufficient adhesion to the surface of the object to be treated. As a result, with the conventional hydrophilic treatment agents described in Patent Document 1, Patent Document 2, etc., it may be difficult to obtain a sufficient hydrophilic effect, or only a resin film that is easily peeled off from the surface of the object to be treated and has low durability can be formed, resulting in a problem that the hydrophilic effect is easily impaired.

[0006] The present invention has been made in view of the above problems, and an object thereof is to provide a polymerizable composition capable of forming a hydrophilic resin film having high hardness and excellent durability on the surface of an object to be treated, which is a surface treatment target, and a hydrophilic treatment method using the polymerizable composition.

Means for Solving the Problems

[0007] The present inventors have found that in a polymerizable composition containing a polymerizable compound (A), a polymerization initiator (B), inorganic fine particles (C), and a solvent (S), as the polymerizable compound (A), a polymerizable betaine compound (A1) having an ethylenically unsaturated double bond and a betaine structure, and an adhesive polymerizable compound (A2) having an ethylenically unsaturated double bond and a specific type of adhesive group are used, and as the polymerization initiator (B), a water-soluble radical polymerization initiator (B1) is used, and by using inorganic fine particles (C) having a functional group capable of forming a covalent bond with the polymer of the polymerizable compound (A), the above problems can be solved, and the present invention has been completed. More specifically, the present invention provides the following.

[0008] A first aspect of the present invention includes a polymerizable compound (A), a polymerization initiator (B), inorganic fine particles (C), and a solvent (S), the polymerizable compound (A) includes a polymerizable betaine compound (A1) and an adhesive polymerizable compound (A2), the polymerizable betaine compound (A1) has an ethylenically unsaturated double bond and a betaine structure, The adhesion and polymerization compound (A2) has at least one adhesion group selected from the group consisting of an ethylenically unsaturated double bond and a hydrolyzable silyl group, an amino group, a carboxy group, a mercapto group, a cyano group, and a hydroxyl group. The polymerization initiator (B) contains a water-soluble radical polymerization initiator (B1). The inorganic particles (C) are a polymerizable composition having a functional group capable of forming a covalent bond with a polymer of the polymerizable compound (A).

[0009] A second aspect of the present invention is to apply the polymerizable composition according to the first aspect to form a coating film on the surface of an object to be treated, and heat the coating film to form a film on the surface of the object to be treated, which is a hydrophilization treatment method for hydrophilizing the surface of the object to be treated.

Advantages of the Invention

[0010] According to the present invention, it is possible to provide a polymerizable composition capable of forming a hydrophilic resin film having high thickness, high hardness, and excellent durability on the surface of an object to be surface-treated, and a hydrophilization treatment method using the polymerizable composition.

Modes for Carrying Out the Invention

[0011] ≪Polymerizable Composition≫ The polymerizable composition contains a polymerizable compound (A), a polymerization initiator (B), inorganic fine particles (C), and a solvent (S). Such a polymerizable composition can hydrophilize the surface of an object to be surface-treated. Hereinafter, regarding the polymerizable composition, optional components, essential components, etc. will be described.

[0012] <Polymerizable Compound (A)> The polymerizable compound (A) polymerizes on the surface of the object to be treated by the action of the polymerization initiator (B) to form a resin film that adheres well to the surface treatment of the object to be treated. The polymerizable compound (A) contains a polymerizable betaine compound (A1) and an adhesion polymerizable compound (A2). The amphoteric betaine compound (A1) has an ethylenically unsaturated double bond and a betaine structure. The adhesion polymerizable compound (A2) has an ethylenically unsaturated double bond and at least one adhesion group selected from the group consisting of a hydrolyzable silyl group, an amino group, a carboxy group, a mercapto group, a cyano group, and a hydroxyl group. In addition, the polymerizable compound (A) may contain a polyfunctional monomer (A3) and other monomers (A4) in addition to the above polymerizable betaine compound (A1) and adhesion polymerizable compound (A2) as long as the object of the present invention is not inhibited. By the polymerizable compound (A) containing the polymerizable betaine compound (A1) and the adhesion polymerizable compound (A2), these compounds are first firmly bonded to the surface of the object to be treated during surface treatment, and starting from these compounds bonded to the surface of the object to be treated, it is considered that the polymerization reaction of the polymerizable compound (A) proceeds in the vicinity of the surface of the object to be treated. And the polymerizable composition contains inorganic fine particles (C) having a functional group capable of forming a covalent bond with the polymer of the polymerizable compound (A). For this reason, while the polymerizable compound (A) binds to the surface of the inorganic fine particles (C), the polymerization of the polymerizable compound (A) proceeds. In this way, it is considered that a thick, high-hardness, hydrophilic film composed of the polymer of the polymerizable compound (A) firmly bonded to the surface of the object to be treated and the inorganic fine particles (C) is formed.

[0013] [Polymerizable Betaine Compound (A1)] The polymerizable compound (A) includes a polymerizable betaine compound (A1) having a betaine structure containing a cationic group and an anionic group, and a group having an ethylenically unsaturated double bond. Both the cationic group and the anionic group act as hydrophilic groups. The surface of the surface-treated object may come into contact with a cleaning liquid containing a large amount of anions having a hydrophobic group or cations having a hydrophobic group. When the resin in the surface treatment liquid has only anionic groups such as carboxy groups, carboxylate groups, sulfonic acid groups, and sulfonate groups as hydrophilic groups, these hydrophilic groups may cease to act as hydrophilic groups due to their interaction with cations having a hydrophobic group. Also, when the resin in the surface treatment liquid has only a cationic group such as a quaternary ammonium group as a hydrophilic group, the cationic group may cease to act as a hydrophilic group due to its interaction with anions having a hydrophobic group. However, since the polymer of the polymerizable compound (A) containing the polymerizable betaine compound (A1) has both a cationic group and an anionic group as hydrophilic groups, even when the surface of the surface-treated object comes into contact with a cleaning agent rich in cations having a hydrophobic group or with a cleaning agent rich in anions having a hydrophobic group, either the cationic group or the anionic group can maintain its function as a hydrophilic group, and it is difficult for the hydrophilicity of the surface of the object to be treated to decrease.

[0014] In the polymerizable betaine compound (A1), the number of cationic groups and the number of anionic groups are not particularly limited. In the polymerizable betaine compound (A1), it is preferable that the number of cationic groups and the number of anionic groups are the same. Since the synthesis and acquisition of the polymerizable betaine compound (A1) are easy, it is preferable that the number of cationic groups and the number of anionic groups in the polymerizable betaine compound (A1) are each 1.

[0015] In the polymerizable betaine compound (A1), for example, it is preferable that a group having an ethylenically unsaturated double bond, a cationic group, and an anionic group are bonded in this order via a linking group as necessary.

[0016] The cationic group is preferably a cationic group that is a quaternary nitrogen cation. The anionic group is preferably a sulfonic acid anion group, a phosphonic acid anion group or a carboxylic acid anion group.

[0017] Examples of the group having an ethylenically unsaturated double bond in the polymerizable betaine compound (A1) include alkenyl groups such as vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group. Among these groups, vinyl group and 2-n-propenyl group (allyl group) are preferred. The number of ethylenically unsaturated double bonds in the polymerizable betaine compound (A1) is not limited, but 1 or 2 is preferred.

[0018] As the polymerizable betaine compound (A1), for example, a compound represented by the following formula (a1-i) or formula (a1-ii) is preferred. The polymerizable betaine compound represented by the following formula (a1-i) or formula (a1-ii) contains , , 4 , , 5 , 3 , , , 1 , , , , , , 5 , 3 , , 4 , , 2 ,

[0018] , + , , , , , a cationic group containing N and an anionic group as R. Both the cationic group and the anionic group act as hydrophilic groups.

Chemical formula

Chemical formula

[0019] In formula (a1-i), examples of the hydrocarbon group containing an ethylenically unsaturated double bond as R 1 include alkenyl groups such as vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group.

[0020] In formula (a1-i), examples of the divalent hydrocarbon group as R 2 include alkylene groups, arylene groups, and groups combining an alkylene group and an arylene group, and alkylene groups are preferred. R 2 Preferred specific examples of the alkylene group as R

[0021] In formula (a1-i), the heterocyclic ring as ring A may be an aromatic heterocyclic ring or an aliphatic heterocyclic ring. Examples of the aromatic heterocyclic ring include rings in which any one nitrogen atom in a nitrogen-containing aromatic heterocyclic ring such as an imidazole ring, pyrazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, pyridine ring, pyrimidine ring, pyridazine ring, and pyrazine ring is quaternized. Examples of the aliphatic heterocyclic ring include rings in which any one nitrogen atom in a nitrogen-containing heterocyclic ring such as a pyrrolidine ring, piperidine ring, and piperazine ring is quaternized.

[0022] In formula (a1-ii), R 3 ~R 5 Examples of the hydrocarbon group containing an ethylenically unsaturated double bond as such include alkenyl groups such as vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, 3-n-butenyl group and the like.

[0023] In formula (a1-ii), R 3 ~R 5 Examples of the hydrocarbon group as such include alkyl group, aryl group, aralkyl group and the like, and an alkyl group is preferred. R 3 ~R 5 The hydrocarbon group as such may have a substituent. The substituent that the hydrocarbon group as R 3 ~R 5 may have is not particularly limited as long as it does not inhibit the object of the present invention. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an amino group, and an alkylamino group substituted with one or two alkyl groups having 1 to 4 carbon atoms. R 3 ~R 5 Preferable specific examples of the alkyl group as such include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.

[0024] In formula (a1-ii), R 6 Examples of the divalent hydrocarbon group as such include an alkylene group, an arylene group, and a group combining an alkylene group and an arylene group, and an alkylene group is preferred. R 6Preferable specific examples of the alkylene group as such 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.

[0025] As for the polymerizable betaine compound in which the anionic group is a sulfonic acid anion group, since synthesis and availability are easy, monomers represented by the following formula (a1-iii) or formula (a1-iv) are preferable.

Chemical formula

Chemical formula

[0026] 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).

Chemical formula

[0027] In formulas (a1-v), (a1-vi), and (a1-vii), R 13 and R 14 Examples of the alkylene group having 1 to 4 carbon atoms as R

[0028] Examples of the polymerizable betaine compound in which the anionic group is a phosphonic acid anion group or a carboxylic acid anion group include monomers represented by the above formula (a1-iii) or formula (a1-iv), and monomers represented by the above formula (a1-v), (a1-vi), or (a1-vii) in which a sulfonic acid anion group (-SO3 - ) is replaced with a phosphonic acid anion group (-(PO3) 2- ) or a carboxylic acid anion group (-COO - ).

[0029] Specific examples of the polymerizable betaine compound represented by formula (a1-i) or formula (a1-ii) include compounds of the following formula and monomers in which a sulfonic acid anion group (-SO3 - ) in the compound of the following formula is replaced with a phosphonic acid anion group (-(PO3) 2- ) or a carboxylic acid anion group (-COO - ).

Chemical formula

[0030] The polymerizable betaine compound represented by the formula (a1-i) or formula (a1-ii) can be synthesized by known reactions. For example, it can be obtained by reacting a compound having a group with an ethylenically unsaturated double bond and a cationic group with a compound having an anionic group. As a specific example, for instance, the compound represented by the formula (a1-iii) can be obtained by reacting the following compound with sultone in a solvent. Examples of sultone include sultones having a ring size of 4 to 10 members, and 1,3-propanesultone and 1,4-butanesultone are preferred.

Chemical formula

[0031] Also, the compound represented by the following formula (a1-viii) is also preferred as the polymerizable betaine compound (A1). The polymerizable betaine compound (A1) represented by the following formula (a1-viii) contains a cationic group containing N + and an anionic group as R 20 . 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 the 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 are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R 20 is a sulfonate anion group (-SO3 - ), a phosphonate anion group (-(PO3) 2-), or carboxylate anion group (-COO - )

[0032] 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 group formed by combining 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 alkylene 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] In formula (a1-viii), R 17 and R 18 Examples of the hydrocarbon group include an alkyl group, an aryl group, and an aralkyl group, with an alkyl group being preferred. R 17 and R 18 The hydrocarbon group represented by R may have a substituent. 17 and R 18 The substituents that the hydrocarbon group may have are not particularly limited as long as they do not impair the object of the present invention. Examples of the substituents 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 18Preferable specific examples of the alkyl group as such 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.

[0034] In formula (a1-viii), R 20 is a sulfonate anion group (-SO3 - ), a phosphonate anion group (-PO3 2- ), or a carboxylate anion group (-COO - ), and a sulfonate anion group (-SO3 - ) is preferred.

[0035] Preferable examples of the N-substituted (meth)acrylamide represented by formula (a1-viii) include compounds of the following formula. In the following formula, R 15 is a hydrogen atom or a methyl group.

[0036]

Chemical formula

[0037] The content of the polymerizable betaine compound (A1) in the polymerizable compound (A) is not particularly limited as long as it does not inhibit the object of the present invention. In terms of achieving both a good hydrophilic effect and good adhesion of the formed resin film to the surface of the object to be treated, the ratio of the mass of the polymerizable betaine compound (A1) to the mass of the polymerizable compound (A) is preferably 50% by mass or more and 99.9% by mass or less, more preferably 60% by mass or more and 99.9% by mass or less, still more preferably 70% by mass or more and 99.9% by mass or less, even more preferably 90% by mass or more and 99.9% by mass or less, and particularly preferably 95% by mass or more and 99.9% by mass or less.

[0038] 〔Adhesive polymerizable compound (A2)〕 The coincidence compound (A) includes an adhesion polymerizable compound (A2) together with the aforementioned polymerizable betaine compound (A1). The adhesion polymerizable compound (A2) has an ethylenically unsaturated double bond and at least one adhesion group selected from a hydrolyzable silyl group, an amino group (-NH2), a carboxy group, a mercapto group, a cyano group, and a hydroxy group. The hydrolyzable silyl group reacts with the surface of the object to be treated to form a covalent bond, thereby firmly bonding the film formed using the polymerizable composition to the surface of the object to be treated. Further, the amino group (-NH2), the carboxy group, the mercapto group, the cyano group, and the hydroxy group are polar groups, and based on their polarity, the film formed using the polymerizable composition is firmly bonded to the surface of the object to be treated.

[0039] Preferable examples of the adhesion polymerizable compound (A2) include an unsaturated group-containing silicon compound (A2-1) having an ethylenically unsaturated double bond and a hydrolyzable silyl group, and an ethylenically unsaturated double bond and at least one polar polymerizable compound (A2-2) selected from an amino group (-NH2), a carboxy group, a mercapto group, a cyano group, and a hydroxy group.

[0040] (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.

[0041] The group having an ethylenically unsaturated double bond is not particularly limited as long as the unsaturated group-containing silicon compound (A2-1) is copolymerizable with the polymerizable betaine compound (A1). Preferable specific examples of the group having an ethylenically unsaturated double bond include alkenyl groups such as vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; monoalkenylamino groups such as N-vinylamino group, N-1-propenylamino group, N-allylamino group, N-1-n-butenylamino group, N-2-n-butenylamino group, and N-3-n-butenylamino group; dialkenylamino groups such as N,N-divinylamino group, N,N-di(1-propenyl)amino group, N,N-diallylamino group, N,N-di(1-n-butenyl)amino group, N,N-di(2-n-butenyl)amino group, and N,N-di(3-n-butenyl)amino group; alkenyloxy groups such as allyloxy group, 2-n-butenyloxy group, and 3-n-butenyloxy group; alkenylaminocarbonyl groups such as vinylaminocarbonyl group, 1-propenylaminocarbonyl group, allylaminocarbonyl group, 1-n-butenylaminocarbonyl group, 2-n-butenylaminocarbonyl group, and 3-n-butenylaminocarbonyl group; alkenyloxycarbonyl groups such as vinyloxycarbonyl group, 1-propenyloxycarbonyl group, allyloxycarbonyl group, 1-n-butenyloxycarbonyl group, 2-n-butenyloxycarbonyl group, and 3-n-butenyloxycarbonyl group; and (meth)acryloyl group-containing groups such as acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, and methacryloylamino group. Among these groups, alkenyl groups and (meth)acryloyl group-containing groups are preferable. The number of carbon atoms of the alkenyl group is preferably, for example, 2 or more and 6 or less, more preferably 2 or 3.

[0042] The hydrolyzable silyl group is a silyl group capable of generating a silanol group by hydrolysis. Preferable examples of the hydrolyzable silyl group include a group represented by -SiR 01 a R 02 3-a Here, R 01is a group capable of generating a silanol group by hydrolysis such as an alkoxy group and a halogen atom. As the alkoxy group, an alkoxy group having 1 or more and 4 or less carbon atoms such as a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, and an n-butyloxy group is preferable. As the halogen atom, a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable. R 02 R may be various organic groups that do not fall under the group capable of generating a silanol group by hydrolysis as long as they do not inhibit the object of the present invention. As such an organic group, a hydrocarbon group having 1 or more and 10 or less 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. Preferable specific examples of the hydrocarbon group having 1 or more and 10 or less carbon atoms 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, an n-nonyl group, an n-decyl group, a phenyl group, a naphthalene-1-yl group, a naphthalene-2-yl group, a benzyl group, and a phenethyl group. Among these, a methyl group and an ethyl group are preferable. The hydrocarbon group described above may have substituents such as an alkoxy group having 1 or more and 6 or less carbon atoms, a halogen atom, a hydroxyl group, and a cyano group. a is preferably 2 or 3, and more preferably 3. Further, when a is 2 or 3, a condensation reaction is likely to occur between the groups represented by -SiR 01 a R 02 3-a As a result, a network of siloxane bonds extending along the surface of the object to be treated is formed in the film formed using the polymerizable composition, so that the polymer of the polymerizable compound (A) can be particularly strongly bonded to the surface of the object to be treated.

[0043] -SiR 01 a R 02 3-aPreferable specific examples of the hydrolyzable silyl group represented by include a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group, an ethyldimethoxysilyl group, a methyldiethoxysilyl group, and an ethyldiethoxysilyl group.

[0044] As the unsaturated group-containing silicon compound (A2-1), for example, a compound represented by the following formula (a2-1) is preferable. R 03 -(-CO-R 04 -) b -R 05 -SiR 01 a R 02 3-a ···(a2-1)

[0045] In formula (a2-1), R 01 、R 02 、and a are as described above for the hydrolyzable silyl group. R 03 is an alkenyl group having 2 to 6 carbon atoms. R 04 is -O- or -NH-. R 05 is a single bond, an alkylene group having 1 to 10 carbon atoms, an aromatic hydrocarbon group, or a nitrogen-containing heterocyclic group. b is 0 or 1.

[0046] R 03 is an alkenyl group having 2 to 6 carbon atoms. Preferable 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, R03 is preferably a vinyl group or a 1-methylvinyl group. That is, when b is 1, the group represented by R 03 -CO-R 04 -is preferably an acryloyloxy group, an acryloylamino group, a methacryloyloxy group, or a methacryloylamino group.

[0047] R 05Examples of the alkylene group as such 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 decane-1,10-yl group. R 05 Examples of the aromatic hydrocarbon group as such 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.

[0048] R 05 Specific examples of the nitrogen-containing heterocyclic ring include groups obtained by removing two hydrogen atoms from the following nitrogen-containing heterocyclic rings. Examples of the nitrogen-containing heterocyclic ring 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 tetrazoline 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 piperidine 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; nitrogen-containing 7-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 quinolidine ring, a quinoxaline ring, a cinnoline ring, a quinazoline ring, a phthalazine ring, a naphthyridine ring, and a pteridine ring.

[0049] Preferable specific examples of the silane compound represented by the formula (a2-1) include unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane; (meth)acryloxy group-containing silanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane.

[0050] (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 hydroxy group.

[0051] As the polar polymerizable compound (A2-2), a compound represented by the following formula (a2-2) is preferable. CH2=CR A1 -(R A2 ) c -CO-R A3 ···(a2-2) (In the 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 is -OH, -O-R 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 hydroxy group.)

[0052] In the above formula (a2-2), R A2 is a divalent hydrocarbon group. The number of carbon atoms of the divalent hydrocarbon group is not particularly limited as long as it does not inhibit the object of the present invention. Since the compound represented by the formula (a2-2) is easily available or preparable, R A2The number of carbon atoms of the divalent hydrocarbon group as is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, particularly preferably 1 or more and 10 or less, and most preferably 1 or more and 6 or less.

[0053] R A2 The divalent hydrocarbon group as may be an aliphatic group, an aromatic group, or a hydrocarbon group containing an aliphatic moiety and an aromatic moiety. When the divalent hydrocarbon group is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. Further, the structure of the aliphatic group may be linear, branched, cyclic, or a combination of these structures.

[0054] R A2 Suitable specific examples of 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, an n-butane-1,4-diyl group, an n-pentane-1,5-diyl group, an n-hexane-1,6-diyl group, an n-heptane-1,7-diyl group, an n-octane-1,8-diyl group, an n-nonane-1,9-diyl group, an n-decane-1,10-diyl group, an o-phenylene group, an 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, a biphenyl-4,4'-diyl group, and the like.

[0055] R A3 is -OH, -O-R A4 or -NH-R A4 is. 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 number of carbon atoms of the linear, branched, or cyclic aliphatic group is preferably 1 or more and 20 or less, and more preferably 1 or more and 12 or less. Preferable 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, an n-decyl group, and the like. Preferable examples of the cyclic aliphatic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group such as a cyclooctyl group, a group obtained by removing one hydrogen atom from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, and a group obtained by removing one hydrogen atom from a C1-C4 alkyl-substituted derivative of these polycycloalkanes. Preferable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, and a biphenylyl group, and the like. The aromatic hydrocarbon group may be substituted with a C1-C4 alkyl group such as a methyl group or an ethyl group.

[0056] Preferable specific examples of the compound represented by the formula (a2-2) include the following compounds. [Chemical formula]

[0057] As the polar polymerizable compound (A2-2), a compound represented by the following formula (a2-3) is also preferable. (R 3a -R 2a ) n -X-R 1a ···(a2-3) (In the formula (a2-3), R 1a is an organic group having one or more ethylenically unsaturated double bonds, R 2a is a single bond or an alkylene group having 1 to 10 carbon atoms, and R 3ais a hydrogen atom or a polar group selected from an amino group, a carboxy group, a mercapto group, a cyano group, and a hydroxy group, n is 1 or 2, X is an (n + 1)-valent nitrogen-containing heterocyclic group, and when n is 1, R a3 is the aforementioned polar group, and when n is 2, at least one of R 3a is the aforementioned polar group.)

[0058] In formula (a2-3), R a1 is an organic group having one or more ethylenically unsaturated double bonds. Preferable examples of the organic group having one or more ethylenically unsaturated double bonds include groups represented by the following formulas (a2-3i) to (a2-3vii). In the following formulas (a3-2i) to (a2-3vii), R a01 is an alkenyl group having 1 to 10 carbon atoms, and R a02 is a hydrocarbon group having 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) -O-R a01 ···(a2-3v) -CO-NH-R a01 ···(a2-3vi) -CO-O-R a01 ···(a2-3vii)

[0059] R a01 The number of carbon atoms of the alkenyl group as R a01 is preferably 1 to 6, more preferably 1 to 4. The alkenyl group as R R a02 The hydrocarbon group as may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. R a02The number of carbon atoms of the hydrocarbon group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and still more preferably 1 or more and 3 or less.

[0060] R a1 Preferable specific examples of the organic group having one or more ethylenically unsaturated double bonds include alkenyl groups such as vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; monoalkenylamino groups such as N-vinylamino group, N-1-propenylamino group, N-allylamino group, N-1-n-butenylamino group, N-2-n-butenylamino group, and N-3-n-butenylamino group; dialkenylamino groups such as N,N-divinylamino group, N,N-di(1-propenyl)amino group, N,N-diallylamino group, N,N-di(1-n-butenyl)amino group, N,N-di(2-n-butenyl)amino group, and N,N-di(3-n-butenyl)amino group; alkenyloxy groups such as allyloxy group, 2-n-butenyloxy group, and 3-n-butenyloxy group; alkenylaminocarbonyl groups such as vinylaminocarbonyl group, 1-propenylaminocarbonyl group, allylaminocarbonyl group, 1-n-butenylaminocarbonyl group, 2-n-butenylaminocarbonyl group, and 3-n-butenylaminocarbonyl group; alkenyloxycarbonyl groups such as vinyloxycarbonyl group, 1-propenyloxycarbonyl group, allyloxycarbonyl group, 1-n-butenyloxycarbonyl group, 2-n-butenyloxycarbonyl group, and 3-n-butenyloxycarbonyl group; and (meth)acryloyl group-containing groups such as acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, and 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 preferable, and N,N-diallylamino group is more preferable.

[0061] 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, an n-butane-1,4-diyl group, an n-pentane-1,5-diyl group, an n-hexane-1,6-diyl group, an n-heptane-1,7-diyl group, an n-octane-1,8-diyl group, an n-nonane-1,9-diyl group, and an 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.

[0062] In formula (a2-3), R 2a where X is an n+1-valent nitrogen-containing heterocyclic group. n is 1 or 2. The nitrogen-containing heterocycle may be an aromatic group or an aliphatic group. The nitrogen-containing heterocycle may be a monocyclic ring, or a condensed polycyclic ring in which a monocyclic nitrogen-containing heterocyclic ring is condensed with one or more monocyclic rings selected from a monocyclic aromatic hydrocarbon ring and a monocyclic nitrogen-containing heterocyclic ring. Also, the nitrogen-containing heterocycle may be a ring in which two or more rings selected from a monocyclic nitrogen-containing heterocyclic ring and a condensed polycyclic nitrogen-containing heterocyclic ring are bonded via a single bond.

[0063] In formula (a2-3), the group represented by R a1 and the group represented by R 3a -R 2a - may be bonded to a carbon atom as a ring-constituting atom of the nitrogen-containing heterocyclic group represented by X, or may be bonded to a nitrogen atom as a ring-constituting atom.

[0064] Specific examples of the nitrogen-containing heterocycle that gives X include nitrogen-containing 5-membered rings such as pyrrolidine ring, pyrazolidine ring, imidazolidine ring, triazolidine ring, tetrazolidine ring, pyrroline ring, pyrazoline ring, imidazoline ring, triazoline ring, tetrazoline ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, and tetrazole ring; nitrogen-containing 6-membered rings such as piperidine ring, piperidine ring, piperazine ring, triazinane ring, tetrazinane ring, pentazinane ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, tetrazine ring, and pentazine ring; nitrogen-containing 7-membered rings such as azepane ring, diazepane ring, triazepane ring, tetrazepane ring, azepine ring, diazepine ring, and triazepine ring; nitrogen-containing condensed polycycles such as indole ring, indolenine ring, indoline ring, isoindole ring, isoindolenine ring, isoindoline ring, benzimidazole ring, indolizine ring, purine ring, indolizidine ring, benzodiazepine ring, quinoline ring, isoquinoline ring, quinolidine ring, quinoxaline ring, cinnoline ring, quinazoline ring, phthalazine ring, naphthyridine ring, and pteridine ring; and polycycles in which two or more rings selected from these nitrogen-containing heterocycles are bonded via single bonds. As X derived from these nitrogen-containing heterocycles, a divalent or trivalent group containing a nitrogen-containing 6-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, in terms of good adhesion of the polymer of the polymerizable compound (A) to the surface of the object to be treated.

[0065] Preferable specific examples of the divalent or trivalent nitrogen-containing heterocycles as X include the following groups.

Chemical formula

[0066] Preferable specific examples of the compound represented by the formula (a2-3) include the following compounds.

Chemical formula

[0067]

Chem.

[0068] Among the above compounds, the following compounds are preferred.

Chem.

[0069] Furthermore, it is also preferable to use 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 as the polar polymerizable compound (A2-2). Such a polyfunctional polar polymerizable compound (A2-2) can improve the adhesion of the resin film formed by the polymerization of the polymerizable compound (A) to the surface of the object to be treated not only by the action of the hydroxyl group but also by the cross-linking of the molecular chain.

[0070] The ratio of the mass of the adhesion polymerizable compound (A2) to the mass of the polymerizable compound (A) is not particularly limited as long as it does not inhibit the object of the present invention. In terms of achieving both a good hydrophilic effect and good adhesion of the formed resin film to the surface of the object to be treated, the ratio of the mass of the adhesion polymerizable compound (A2) to the number of moles of the polymerizable compound (A) is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.1% by mass or more and 40% by mass or less, still more preferably 0.1% by mass or more and 30% by mass or less, even more preferably 0.1% by mass or more and 10% by mass or less, and particularly preferably 0.1% by mass or more and 5% by mass or less.

[0071] 〔Polyfunctional monomer (A3)〕 The polymerizable compound (A) may contain a polyfunctional monomer (A3) other than the polymerizable betaine compound (A1) and the adhesion-imparting polymerizable compound (A2). The polyfunctional monomer (A3) is a compound having two or more ethylenically unsaturated double bonds and not corresponding to the polymerizable betaine compound (A1) and the adhesion-imparting polymerizable compound (A2). In the resin film formed by the polymerization of the polymerizable compound (A), the polyfunctional monomer (A3) crosslinks the molecular chains. By crosslinking, the fastness such as the hardness of the resin film and the adhesion of the resin film to the surface of the object to be treated are improved.

[0072] Specific examples of the polyfunctional monomer (A3) 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, 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 - hexanediol 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, etc.

[0073] The ratio of the mass of the polyfunctional monomer (A3) to the mass of the polymerizable compound (A) is not particularly limited as long as it does not inhibit the object of the present invention. In terms of appropriately cross - linking the polymer of the polymerizable compound (A), the ratio of the polyfunctional monomer (A3) to the mass of the polymerizable compound (A) is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and still more preferably 1% by mass or more and 10% by mass or less.

[0074] 〔Other monomer (A4)〕 The polymerizable compound (A) may contain other monomers (A4) other than the polymerizable betaine compound (A1), the adhesion polymerizable compound (A2), and the polyfunctional monomer (A3) as long as the object of the present invention is not inhibited. The other monomer (A4) has two or more ethylenically unsaturated double bonds and is a compound that does not correspond to the polymerizable betaine compound (A1), the adhesion polymerizable compound (A2), and the polyfunctional monomer (A3).

[0075] Examples of the other monomer (A4) 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, N-n-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-n-butyl(meth)acrylamide, N-n-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.

[0076] The ratio of the mass of the other monomer (A4) to the number of moles of the polymerizable compound (A) is not particularly limited as long as the polymerizable compound (A) contains the polymerizable betaine compound (A1) and the adhesion polymerizable compound (A2) in desired amounts.

[0077] The ratio of the mass of the polymerizable compound (A) to the mass of the coincidence composition is not particularly limited, but is preferably 1% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 20% by mass or less, and even more preferably 2% by mass or more and 15% by mass or less.

[0078] <Polymerization initiator (B)> The polymerizable composition contains a polymerization initiator (B) as a component for polymerizing the polymerizable compound (A). The polymerization initiator (B) includes a water-soluble radical polymerization initiator (B1). 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. Further, the water-soluble radical polymerization initiator (B1) is not particularly limited as long as it is a compound that can promote the polymerization of the polymerizable compound (A) in an aqueous system by being partially or completely dissolved in water or a water-containing solvent.

[0079] Preferable examples of the water-soluble radical polymerization initiator include a water-soluble azo polymerization initiator (B1-1) and a water-soluble peroxide (B1-2). Among these, for the water-soluble peroxide (B1-2), the radicals generated by itself can cause self-induced decomposition that promotes the decomposition of the peroxide, whereas the water-soluble azo polymerization initiator (B1-1) is non-induced decomposable and does not cause such self-induced decomposition, and is preferable in terms of following the primary reaction and obtaining a stable reaction rate regardless of the solvent.

[0080] Specific examples of the water-soluble azo polymerization initiator (B1-1) include 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[2-(phenylamidinopropane] dihydrochloride, 2,2'-azobis{2-[N-(4-chlorophenyl)amidinopropane]} dihydrochloride, 2,2'-azobis{2-[N-(4-hydroxyphenyl)amidinopropane]} dihydrochloride, 2,2'-azobis[2-(N-benzylamidinopropane] dihydrochloride, 2,2'-azobis[2-(N-allylamidinopropane] dihydrochloride, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis{2-[N-(2-hydroxyethyl)amidinopropane]} 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-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 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, 2,2-azobis[2-(2-imidazolin-2-yl)propane]. These water-soluble azo polymerization initiators (B1-1) may be used alone or in combination of two or more.

[0081] Specific examples of the water-soluble peroxide (B1-2) include alkyl peroxides such as isobutyl peroxide and decanoyl peroxide; peroxycarboxylic anhydrides such as acetyl peroxide; aromatic peroxycarboxylic anhydrides such as benzoyl peroxide; peroxy anhydrides of polycarboxylic acids such as succinic peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diallyl peroxydicarbonate; peroxyesters such as tert-butyl peroxyisobutyrate, tert-butyl peroxyneodecanoate, and cumene peroxyneodecanoate; peroxide anhydrides 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 metaphosphate. These water-soluble peroxides (B1-2) may be used alone or in combination of two or more.

[0082] The ratio of the mass of the water-soluble radical polymerization initiator (B1) to the mass of the polymerization initiator (B) is not particularly limited as long as a film having a desired film thickness can be formed using the polymerizable composition. The ratio of the mass of the water-soluble radical polymerization initiator (B1) to the mass of the polymerization initiator (B) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and most preferably 100% by mass. When a water-insoluble radical polymerization initiator (B2) is used together with the water-soluble radical polymerization initiator (B1), the type of the water-insoluble radical polymerization initiator (B2) is not particularly limited. The water-insoluble radical polymerization initiator (B2) is a radical polymerization initiator that does not correspond to the water-soluble radical polymerization initiator (B1). The amount of the polymerization initiator (B) used is not particularly limited as long as the polymerization reaction can be carried out satisfactorily. The amount of the polymerization initiator (B) used is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 15% by mass or less, based on the mass of the polymerizable compound (A).

[0083] In terms of the stability of the polymerizable composition over time, the polymerizable composition may be a two-component composition comprising 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-component composition is mixed immediately before surface treatment and used. In this case, the inorganic fine particles (C) may be contained in either the first liquid or the second liquid, or may be contained in both the first liquid and the second liquid.

[0084] 〔Inorganic fine particles (C)〕 The polymerizable composition contains inorganic fine particles (C). The inorganic fine particles (C) have a functional group capable of forming a covalent bond with the polymer of the polymerizable compound (A). Therefore, when a coating film formed by applying the polymerizable composition is heated to form a film, the inorganic fine particles (C) are incorporated into the polymer of the polymerizable compound (A) by a covalent bond. As a result, a film having a thick film thickness, high hardness, and excellent durability can be formed on the surface of the object to be treated.

[0085] The inorganic fine particles (C) have a functional group capable of forming a covalent bond with the polymer of the polymerizable compound (A). As the inorganic fine particles (C), inorganic fine particles made of an inorganic material having the functional group can be used, or inorganic fine particles surface-modified with an organic compound having the functional group can also be used.

[0086] When the functional group of the polymer of the polymerizable compound (A) reacts with the functional group of the inorganic fine particles (C) to form a covalent bond, the combination of the functional group of the polymer of the polymerizable compound (A) and the functional group of the inorganic fine particles (C) is not particularly limited. For example, when the polymerizable compound (A) contains an unsaturated group-containing silicon compound (A2-1) as an adhesion polymerizable compound (A2), the polymer of the polymerizable compound (A) has a hydrolyzable silyl group. In this case, preferable examples of the functional group of the inorganic fine particles (C) include a hydroxyl group, a carboxy group, and an amino group. These groups form a covalent bond by hydrolytic condensation with the hydrolyzable silyl group. When the polymer of the polymerizable compound (A) has an amino group or a carboxy group, preferred examples of the functional group of the inorganic fine particles (C) include an epoxy group and a hydrolyzable silyl group. Furthermore, when the inorganic fine particles (C) have an ethylenically unsaturated double bond, the inorganic fine particles are copolymerizable with the polymerizable compound (A). The combination of the functional group of the polymer of the polymerizable compound (A) and the functional group of the inorganic fine particles (C) is not limited to the above combination at all.

[0087] As the inorganic fine particles (C), silica fine particles or metal oxide fine particles having a hydroxyl group such as a silanol group on the surface thereof can be preferably used. Also, silica fine particles or metal oxide fine particles surface-modified with an organic compound having a functional group capable of forming a covalent bond with the polymer of the polymerizable compound (A) are also preferable as the inorganic fine particles (C). Examples of the metal oxide fine particles include metal oxide fine particles composed of metal oxides such as titanium oxide (TiO2), zinc oxide (ZnO), yttrium oxide (Y2O3), hafnium oxide (HfO2), or zirconium oxide (ZrO2). As the inorganic fine particles (C), silica fine particles are preferable because fine particles of various particle diameters are easily available and a high-hardness film is easily formed using the polymerizable composition.

[0088] As the organic compound used for introducing into the inorganic fine particles (C) by surface modification of a functional group that reacts with the functional group of the polymer of the polymerizable compound (A) to form a covalent bond, aminosilanes such as 2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 4-aminobutyltrimethoxysilane, 2-aminoethyltriethoxysilane, 3-aminopropyltriethoxysilane, and 4-aminobutyltriethoxysilane; Epoxysilanes such as 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 4-glycidoxybutyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltriethoxysilane; Unsaturated group-containing silanes such as 2-(meth)acryloyloxyethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 4-(meth)acryloyloxybutyltrimethoxysilane, 2-(meth)acryloyloxyethyltriethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 4-(meth)acryloyloxybutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane may be mentioned.

[0089] The method for surface-modifying the inorganic fine particles (C) with the above organic compound is not particularly limited. The surface modification can be carried out by various well-known methods.

[0090] The particle size of the inorganic fine particles (C) is not particularly limited. The particle size of the inorganic fine particles (C) is appropriately determined in consideration of the film thickness of the film formed using the polymerizable composition. The average particle size of the inorganic fine particles (C) is preferably 5 nm or more and 5000 nm or less, more preferably 10 nm or more and 400 nm or less. The average particle size (nm) of the inorganic fine particles (C) is obtained from the specific surface area (m 2 / g) of the inorganic fine particles (C) determined by the BET method and the density (g / m 3 ) of the inorganic fine particles (C) based on the following formula. Average particle size (nm) = 6 / (specific surface area (m 2 / g) × density (g / m 3 )) × 10 -9

[0091] The content of the inorganic fine particles (C) in the polymerizable composition is not particularly limited as long as the desired effect is not inhibited. The content of the inorganic fine particles (C) is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, as the ratio of the mass of the inorganic fine particles (C) to the mass obtained by excluding the mass of the solvent (S) described later from the mass of the polymerizable composition, because it is easy to form a thick and high-hardness film using the polymerizable composition. Also, the ratio of the inorganic fine particles (C) to the mass of the polymerizable compound (A) is preferably 10% by mass or more and 200% by mass or less, more preferably 50% by mass or more and 150% by mass or less.

[0092] 〔Solvent (S)〕 The polymerizable composition contains a solvent (S). The solvent (S) may be water, an organic solvent, or an aqueous solution of an organic solvent. Water is preferred as the solvent (S) in terms of the solubility of the polymerizable compound (A), the safety of the hydrophilic treatment operation, and low cost. Preferable examples of the organic solvent used as the solvent (S) include alcohols. The alcohol includes aliphatic alcohols, and alcohols having 1 to 3 carbon atoms are preferred. Specifically, methanol, ethanol, n-propyl alcohol, and isopropyl alcohol (IPA) are included, and methanol, ethanol, and isopropyl alcohol are preferred. The alcohol may be used alone or in combination of two or more.

[0093] 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.

[0094] The amount of the solvent (S) used is not particularly limited. The solvent (S) is preferably used in such an amount that the solid content concentration of the polymerizable composition is 0.1% by mass or more and 20% by mass or less from the viewpoint of the coatability of the polymerizable composition.

[0095] 〔Other Components〕 The curability composition may contain various additives as long as the object of the present invention is not inhibited. Examples of such additives include antioxidants, ultraviolet absorbers, colorants, defoaming agents, and viscosity modifiers. The content of these additives is appropriately determined in consideration of the amounts usually used for these additives.

[0096] ≪Hydrophilic treatment method≫ The hydrophilic treatment method includes: applying the above-described curability composition to form a coating film on the surface of the object to be treated; heating the coating film to form a film on the surface of the object to be treated; and. However, as long as the surface of the object to be treated is hydrophilized to the desired degree, it is not necessary to uniformly apply the curability composition to the entire surface of the surface of the object to be treated that is to be hydrophilized. The hydrophilic treatment method preferably further includes rinsing the surface of the object to be treated with a rinsing solution after heating the film. In particular, by rinsing with water or an aqueous solution of an organic solvent, it is easy to remove a polymer having a low molecular weight and a low degree of polymerization or crosslinking from the film.

[0097] Hereinafter, applying the curability composition to form a coating film on the surface of the object to be treated is also referred to as a "coating step". Heating the coating film to form a film on the surface of the object to be treated is also referred to as a "heating step". Rinsing the surface of the object to be treated with a rinsing solution after heating the film is also referred to as a "rinsing step". Hereinafter, the coating step, the heating step, and the rinsing step will be described in detail.

[0098] <Coating step> In the coating step, the above-described curability composition is applied to the surface of the object to be treated to form a coating film. The coating method is not particularly limited. Specific examples of the coating method include a spin coating method, a spray method, a roller coating method, and a dipping method. When the object to be treated is a substrate, the spin coating method is preferable as the coating method because it is easy to form a coating film having a uniform film thickness without unevenness on the surface of the substrate.

[0099] The material of the surface on which the polymerizable composition of the object to be treated is applied is not particularly limited and may be an organic material or an inorganic material. Examples of the organic material include various resin materials such as polyester resins such as PET resin and PBT resin, various nylons, polyimide resin, polyamideimide resin, polyolefins such as polyethylene and polypropylene, polystyrene, (meth)acrylic resin, cycloolefin polymer (COP), cycloolefin copolymer (COC), and silicone resin (for example, polyorganosiloxane such as polydimethylsiloxane (PDMS), etc.). In addition, a photosensitive resin component and an alkali-soluble resin component contained in various resist materials are also preferable as the organic material. Examples of the inorganic material include glass, silicon, and various metals such as copper, aluminum, iron, and tungsten. The metal may be an alloy.

[0100] The shape of the object to be treated is not particularly limited. The object to be treated may be flat or may have a three-dimensional shape such as spherical or columnar.

[0101] The object to be treated may be exposed to chemicals such as cleaning agents, and there is a concern that the hydrophilicity of the film formed on the object to be treated may decrease due to the exposure to the chemicals. However, by using the above-mentioned polymerizable composition, it is possible to suppress the decrease in hydrophilicity when the surface-treated surface comes into contact with various chemicals. Therefore, by using an object to be treated that is often exposed to chemicals such as cleaning liquid, for example, a glass member provided in a window, a mirror, furniture, an optical device (for example, a device having a lens), or a translucent resin member as the object to be treated, the effect of chemical resistance with respect to hydrophilicity can be particularly exhibited.

[0102] After applying the polymerizable composition to the surface of the object to be treated, at least a part of the solvent (S) may be removed from the film made of the polymerizable composition as necessary by a well-known drying method.

[0103] The film thickness of the coating film formed in the coating step is not particularly limited as long as a film having a finally desired film thickness is formed.

[0104] The thickness of the coating film formed by the coating process can be adjusted by adjusting the solid content concentration of the surface treatment liquid, coating conditions, and the like.

[0105] <Heating process> In the heating process, the coating film formed in the coating process is heated. By heating, the polymerizable compound (A) contained in the coating film polymerizes by the action of the thermal polymerization initiator (B), and the formation of covalent bonds between the polymer of the polymerizable compound (A) and the inorganic fine particles (C) proceeds. As a result, a high-hardness resin film that firmly adheres to the surface of the object to be treated is formed.

[0106] The heating conditions are not particularly limited as long as the polymerizable compound (A) polymerizes to a desired degree and the object to be treated does not deteriorate or deform. As the heating temperature, for example, 30°C or higher and 300°C or lower is preferable, and 40°C or higher and 250°C or lower is more preferable. The heating time is, for example, preferably 1 minute or longer and 6 hours or shorter, more preferably 3 minutes or longer and 60 minutes or shorter, and even more preferably 5 minutes or longer and 30 minutes or shorter. Also, for the purpose of allowing radical polymerization to proceed well, heating is preferably performed in a low-oxygen atmosphere. Examples of the low-oxygen atmosphere include an inert gas atmosphere such as nitrogen, helium, or argon, and a vacuum condition.

[0107] <Rinsing process> In the rinsing process, after heating the film, the surface of the object to be treated is rinsed with a rinsing liquid. By rinsing, low-molecular-weight polymers with low degrees of polymerization and crosslinking can be removed from the film formed on the surface of the object to be treated. The rinsing liquid is not particularly limited as long as a film with a desired film thickness can be formed. As the rinsing liquid, water, an organic solvent, and an aqueous solution of an organic solvent can be used. Water is preferable as the rinsing liquid. The method of rinsing the film is not particularly limited. Typically, rinsing is performed by bringing the rinsing liquid into contact with the film by the same method as the aforementioned coating method.

[0108] The film thickness of the film obtained after rinsing is preferably, for example, 10 nm or more and 2000 nm or less, and more preferably 10 nm or more and 400 nm or less.

[0109] The thickness of the film can be adjusted by adjusting the solid content concentration of the polymerizable composition, coating conditions, the amount of rinsing liquid used, the type of rinsing liquid, the temperature of the rinsing liquid, and the like.

[0110] After rinsing, if necessary, the object to be treated is dried, and then the object to be treated is suitably used for various applications.

Examples

[0111] Hereinafter, the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited to these examples.

[0112] 〔Example 1, Example 2, and Comparative Example 1〕 In the examples and comparative examples, the following A1-1 and A1-2 in the amounts shown in Table 1 were used as the aforementioned polymerizable betaine compound (A1). In the examples and comparative examples, the following A2-1 in the amount shown in Table 1 was used as the adhesion polymerizable compound (A2). In the examples and comparative examples, 2,2'-azobis(2-methylpropionamidine) dihydrochloride was used as the water-soluble radical polymerization initiator (B1) in the amounts shown in Table 1. In the examples, the following C1 and C2 in the amounts shown in Table 1 were used as the inorganic fine particles. In the examples and comparative examples, water and propylene glycol monomethyl ether (PGME) in the amounts shown in Table 1 were used as the solvent (S).

Chemical formula

[0113] C1: Silica fine particles (containing Si-OH groups) C2: Silica fine particles surface-modified with a methacryloyl group-containing compound

[0114] The polymerizable compounds (A), water-soluble radical polymerization initiators (B1), inorganic fine particles (C), and solvents (S) of the types and amounts described in Table 1 were each mixed to obtain the polymerizable compositions of Example 1, Example 2, and Comparative Example 1. In Comparative Example 1, inorganic fine particles (C) were not used.

[0115] Using the obtained polymerizable compositions, the following evaluations were conducted.

[0116] <Water contact angle> After spin-coating the polymerizable compositions of Example 1 and Example 2 on a silicon wafer at 1000 rpm for 60 seconds, the wafer was heated at 100 °C for 10 minutes. Subsequently, the wafer surface was washed with water to form a film composed of the copolymer of the above polymerizable compound (A) and inorganic fine particles (C) on the wafer. Using 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 water contact angle was measured as the contact angle 10 seconds after dropping. The average value of the water contact angles at three points on the silicon wafer is shown in Table 1. The water contact angle of the untreated silicon wafer is 13.8°.

[0117] <Film thickness measurement> Using the polymerizable compositions of Example 1, Example 2, and Comparative Example 1, the film thickness of the film formed by the same method as the measurement of the water contact angle was measured by spectroscopic ellipsometry.

[0118] <Pencil hardness> Using the polymerizable compositions of Example 1, Example 2, and Comparative Example 1, the pencil hardness of the film formed by the same method as the measurement of the water contact angle was measured according to JIS K5600. <A

[0119]

Table 1

[0120] According to Example 1 and Example 2, when surface treatment is performed using a polymerizable composition containing a polymerizable betaine compound (A1), an adhesion polymerizable compound (A2), a water-soluble radical polymerization initiator (B1), and inorganic fine particles (C), each satisfying a predetermined requirement, it can be seen that the surface of the object to be treated can be favorably hydrophilized, and a thick, hard, and highly durable film can be formed on the surface of the object to be treated. On the other hand, when a polymerizable composition not containing inorganic fine particles (C) was used, only a very thin and low-hardness film with poor durability could be formed.

Claims

1. A polymerizable composition comprising a polymerizable compound (A), a polymerization initiator (B), inorganic fine particles (C), and a solvent (S), wherein the polymerizable compound (A) includes a polymerizable betaine compound (A1) and an adhesion polymerizable compound (A2), the polymerizable betaine compound (A1) has an ethylenically unsaturated double bond and a betaine structure, the adhesion polymerizable compound (A2) has an ethylenically unsaturated double bond and at least one adhesion group selected from the group consisting of a hydrolyzable silyl group, an amino group, a carboxy group, a cyano group, and a hydroxyl group, the polymerization initiator (B) includes a water-soluble radical polymerization initiator (B1), the average particle diameter of the inorganic fine particles (C) is 5 nm or more and 5000 nm or less, The average particle diameter is calculated from the specific surface area (m ２ / g) of the inorganic fine particles (C) determined by the BET method and the density (g / m ３ ) of the inorganic fine particles (C) using the following formula: Average particle diameter (nm) = 6 / (specific surface area (m ２ / g) × density (g / m ３ )) × 10 －９ calculated based on, the polymer of the polymerizable compound (A) has a hydrolyzable silyl group, an amino group, or a carboxy group, and the inorganic fine particles (C) have a functional group capable of forming a covalent bond with the polymer of the polymerizable compound (A), or when the inorganic fine particles (C) have the ethylenically unsaturated double bond, the inorganic fine particles (C) are copolymerizable with the polymerizable betaine compound (A1) having the ethylenically unsaturated double bond and the adhesion polymerizable compound (A2) having the ethylenically unsaturated double bond, when the polymer has a hydrolyzable silyl group, the functional group is a hydroxyl group, a carboxy group, or an amino group, a polymerizable composition, wherein when the polymer has an amino group or a carboxy group, the functional group is an epoxy group or a hydrolyzable silyl group.

2. The polymerizable composition according to claim 1, wherein the inorganic fine particles (C) are silica fine particles.

3. The polymerizable composition according to claim 1 or 2, wherein the ratio of the mass of the inorganic fine particles (C) to the mass obtained by removing the mass of the solvent (S) from the mass of the polymerizable composition is 20% by mass or more and 80% by mass or less.

4. The polymerizable composition according to any one of claims 1 to 3, wherein the ratio of the inorganic fine particles (C) to the mass of the polymerizable compound (A) is 10% by mass or more and 200% by mass or less.

5. The polymerizable composition according to claim 4, wherein the ratio of the inorganic fine particles (C) to the mass of the polymerizable compound (A) is 50% by mass or more and 150% by mass or less.

6. The polymerizable composition according to any one of claims 1 to 5, wherein the ratio of the mass of the adhesion polymerizable compound (A2) to the mass of the polymerizable compound (A) is 0.1% by mass or more and 5% by mass or less.

7. The polymerizable composition according to any one of claims 1 to 6, wherein the solid content concentration of the polymerizable composition is 0.1% by mass or more and 20% by mass or less.

8. The polymerizable composition according to any one of claims 1 to 7, wherein the water-soluble radical polymerization initiator (B1) is a water-soluble azo polymerization initiator.

9. Coating the surface of the object to be treated with the polymerizable composition according to any one of claims 1 to 8 to form a coating film; A hydrophilization treatment method for hydrophilizing the surface of an object to be treated, comprising heating the coating film to form a film on the surface of the object to be treated.

10. The hydrophilization treatment method according to claim 9, wherein the film thickness of the film is 10 nm or more and 2000 nm or less.

Images