Hydrophilic composition

Abstract

A hydrophilic composition comprising (A) 100 parts by mass of a hydrophilic copolymer containing a structural unit represented by formula (1) and a structural unit represented by formula (2), and (B) 0.001-10 parts by mass of a blocked isocyanate-based silane compound can form a coating film having excellent hydrophilicity, antifogging properties, and water resistance. # imgabs0 # (R1 represents a hydrogen atom or a methyl group, R2 represents an alkyl group having 1-6 carbon atoms, X1 represents-NH-or-O-, n represents an integer of 1-6, Y1-represents a monovalent anion, R3 represents a hydrogen atom or a methyl group, X2 represents-NH-or-O-, Y2 represents a monovalent functional group selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group, an acid anhydride group, and an alkoxysilyl group, and m represents an integer of 0-10). However, when m is 0, Y2 is a hydrogen atom. And star number * represents a bond to an adjacent structural unit).

Description

Technical Field

[0001] The present invention relates to a hydrophilic composition, and more particularly to a hydrophilic composition containing a hydrophilic copolymer. Background Art

[0002] In recent years, there has been an increasing demand for improvement in the blurring of substrates formed of organic materials such as plastics and inorganic materials such as glass.

[0003] The improvement of the blurring of the substrate is generally achieved by coating a hydrophilic film on the surface of the substrate. For example, in Patent Document 1, a coating composition to which a hydrophilic copolymer having a quaternary ammonium salt structure with high hydrophilicity is added is proposed as a coating agent capable of imparting hydrophilicity to the substrate.

[0004] However, the water resistance of coating films formed using the above coating compositions is insufficient, and surface properties such as hydrophilicity and antifogging properties may deteriorate when in contact with water, and further improvement is desired.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2018-162431 Summary of the invention

[0008] Problems to be solved by the invention

[0009] The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide a hydrophilic composition containing a hydrophilic copolymer which can form a coating film having excellent hydrophilicity, antifogging property and water resistance.

[0010] Means for solving problems

[0011] The present inventors have conducted intensive studies to achieve the above-mentioned purpose and have found that a composition comprising a specific hydrophilic copolymer and a blocked isocyanate silane compound can form a coating film having excellent water resistance and can impart sustained hydrophilicity and anti-fogging properties to substrates formed of organic materials such as plastics and inorganic materials such as glass, thereby completing the present invention.

[0012] That is, the present invention provides:

[0013] 1. A hydrophilic composition comprising:

[0014] (A) a hydrophilic copolymer comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): 100 parts by mass; and

[0015] (B) blocked isocyanate silane compound: 0.001 to 10 parts by mass,

[0016] [Chemistry 1]

[0017] \

[0018]

[0019] (In formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 Each independently represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X 1 represents -NH- or -O-, n represents an integer from 1 to 6, Y 1- represents a monovalent anion,

[0020] In formula (2), R 3 represents a hydrogen atom or a methyl group, X 2 Indicates -NH- or -O-, Y 2 is a monovalent functional group selected from a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group, an acid anhydride group and an alkoxysilyl group, and m represents an integer of 0 to 10. However, when m is 0, Y 2 is a hydrogen atom. The asterisk * indicates a bond to an adjacent structural unit.)

[0021] 2. The hydrophilic composition according to 1, wherein the (B) blocked isocyanate silane compound is represented by the following formula (4):

[0022] [Chemistry 2]

[0023]

[0024] (Where R 6 Each independently represents an alkyl group having 1 to 8 carbon atoms, L represents a divalent linking group, and X 4 Indicates -O- or -NR 7 -, Y 3 represents a hydrogen atom or a monovalent organic group, R 7 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a 3 A group that is bonded to form a ring structure, and k represents an integer of 1 to 3.

[0025] 3. The hydrophilic composition according to 2, wherein the (B) blocked isocyanate silane compound is represented by the following formula (5) or (6):

[0026] [Chemistry 3]

[0027]

[0028] (Where R 6 , R 7 , Y 3 and k have the same meanings as above, R8 and R 9 Each independently represents a hydrogen atom or a monovalent organic group, R 8 With R 9 or R 7 With Y 3 Can be connected to each other to form a ring structure. )

[0029] 4. The hydrophilic composition according to 1, further comprising at least one compound selected from the group consisting of a polyisocyanate compound, an organosilicon compound represented by the following formula (7), and an organosilicon compound represented by the following formula (8),

[0030] [Chemistry 4]

[0031]

[0032] (In formula (7), R 10 and R 11 Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, j represents an integer of 1 to 10, and i represents an integer of 1 to 3. In formula (8), R 12 , R 13 , R 14 and R 15 Each independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms, and h represents an integer of 1 to 20.

[0033] 5. A coating agent, which is composed of the hydrophilic composition according to any one of 1 to 4;

[0034] 6. A hydrophilic film formed by curing the coating agent according to 5.

[0035] Effects of the Invention

[0036] The hydrophilic composition of the present invention can form a coating film which is excellent in water resistance and can impart sustained hydrophilicity and antifogging properties to organic substrates such as plastics and inorganic substrates such as glass. DETAILED DESCRIPTION

[0037] The present invention is described in detail below.

[0038] [A] Hydrophilic copolymer

[0039] The hydrophilic copolymer (hereinafter also simply referred to as "copolymer" or "component (A)") used in the hydrophilic composition of the present invention comprises the structural unit (a) and the structural unit (b) described below.

[0040] Each structural unit of the hydrophilic copolymer is described below.

[0041] The structural unit (a) contained in the hydrophilic copolymer used in the present invention is represented by the following formula (1).

[0042] The ammonium group contained in the structural unit (a) has high hydrophilicity and low affinity for organic solvents and is therefore easily exposed on the surface of the coating film, thereby obtaining a coating film in which the hydrophilic component is fixed on the surface.

[0043] [Chemistry 5]

[0044]

[0045] (In the formula, the asterisk * has the same meaning as above.)

[0046] In formula (1), R 1 It is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0047] R 2 Each is independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 18 carbon atoms.

[0048] Just R 2 The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and cyclohexyl.

[0049] As R 2 Specific examples of the aryl group having 6 to 18 carbon atoms include phenyl, biphenyl, naphthyl, anthracenyl (anthryl), phenanthrenyl, pyrenyl, naphthacene, indenyl, azulenyl, fluorenyl, and terphenyl.

[0050] In addition, part or all of the hydrogen atoms bonded to the carbon atoms of these alkyl and aryl groups may be substituted by halogen atoms such as chlorine, fluorine, and bromine, or other substituents such as cyano groups. Specific examples thereof include chloromethyl, bromoethyl, trifluoropropyl, chlorophenyl, bromophenyl, cyanoethyl, and the like.

[0051] Among these, R 2 It is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

[0052] X 1 It is -NH- or -O-, and is preferably -NH- from the viewpoint of improving the surface hydrophilicity and hydrolysis resistance of the coating film.

[0053] n is an integer of 1 to 6, and is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3, from the viewpoint of improving the surface hydrophilicity of the coating film.

[0054] Y1- is any monovalent anion, and from the viewpoint of improving the surface hydrophilicity of the coating film, preferably a halogen anion (halogen ion), an alkyl sulfate anion (R a -OSO3 - ).

[0055] As Y 1- Specific examples of halogen anions include F - , Cl - Br - ,I - .

[0056] Y 1- The alkyl sulfate anion (R a -OSO3 - ) is a monovalent anion connected to an alkyl group and a sulfate anion, R a The alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group include the same group as R 2 The same groups as exemplified in .

[0057] Specific examples of the alkylsulfate anion include a methylsulfate anion and an ethylsulfate anion.

[0058] Of these, Cl is preferred - , an alkyl sulfate anion having 1 to 3 carbon atoms in the alkyl group, more preferably Cl - , methyl sulfate anion, ethyl sulfate anion, and more preferably Cl - .

[0059] In addition, as Y 1- , an anion represented by the following formula (9) is also preferred.

[0060] [Chemistry 6]

[0061]

[0062] In formula (9), R 16 It is a substituted or unsubstituted linear or branched alkyl group having 12 to 14 carbon atoms.

[0063] As R 16 Specific examples of the alkyl group include dodecyl (n-dodecyl, isododecyl, etc.), tridecyl (n-tridecyl, isotridecyl, etc.), tetradecyl (n-tetradecyl, isotetradecyl, etc.), and the like.

[0064] A part or all of the hydrogen atoms bonded to the carbon atoms of these alkyl groups may be substituted with a halogen atom such as chlorine, fluorine, or bromine, or with other substituents such as a cyano group.

[0065] Among these, dodecyl and tridecyl are preferred from the viewpoint of easy availability, and tridecyl is more preferred. In addition, from the viewpoint of further improving the effect of the present invention, R 16 The alkyl group having 12 to 14 carbon atoms in is preferably straight-chain. 16 It is a substituted or unsubstituted straight-chain tridecyl group, and an unsubstituted straight-chain tridecyl group is more preferable.

[0066] A is a linear or branched alkylene group having 2 to 4 carbon atoms.

[0067] Specific examples of the alkylene group of A include ethylene, trimethylene, propylene (-CH2-CH(CH3)-), tetramethylene, 1-methyltrimethylene (-CH2-CH2-CH(CH3)-), 2-methyltrimethylene (-CH2-CH(CH3)-CH2-), dimethylethylene (-CH2-C(CH3)2-), ethylethylene (-CH2-CH(CH2CH3)-), and the like.

[0068] g is the average number of added moles of -(AO)- and is a number of 2 to 50. From the viewpoint of the surface hydrophilicity of the coating film and the improvement of workability due to the reduction in the viscosity of the composition, it is preferably a number of 2 to 30, more preferably a number of 2 to 20, and even more preferably a number of 2 to 10.

[0069] That is, in the above formula (9), -(AO) g - represents polyoxyalkylene. -(AO) g - It is preferred that two or more oxyalkylene groups are contained, and more preferably oxybutylene groups (-C4H8O-). By containing such groups, the hydrophilicity of the copolymer is not excessively increased, and the affinity with organic solvents becomes good.

[0070] Furthermore, the oxybutylene group may be branched and may include at least one or both of -CH(CH2CH3)-CH2-O- and -CH2-CH2(CH2CH3)-O-. By including such a group, the affinity with organic solvents and the surface hydrophilicity of the coating film are further improved.

[0071] Furthermore, -(AO) g - preferably contains oxyethylene (-C2H4O-).

[0072] -(AO) g The ratio of the oxybutylene group in the formula (a) is preferably 3 to 90 mol%, more preferably 10 to 80 mol%, further preferably 20 to 50 mol%, further preferably 30 to 40 mol%. When the oxybutylene group has two or more structures, the ratio of the oxybutylene group represents the total ratio (mol%) of each structure.

[0073] In addition, in -(AO) g -When containing two or more oxyalkylene groups, the arrangement may be any of a random type and a block type. From the viewpoint of further improving the surface hydrophilicity of the coating film, a block type is preferred. Furthermore, in the case of a block type, there is no restriction on the order of arrangement. That is, for example, the sulfonic acid group may be connected in the order of a polyoxyethylene chain and a polyoxybutylene chain, or vice versa.

[0074] Specific examples of the anion represented by the formula (9) include those represented by the following formulae, but the anion is not limited to these.

[0075] CH3(CH2) 11 O{(CH2)4O)}2{(CH2)2O)}5SO3 -

[0076] CH3(CH2) 11 O{(CH2)4O)}3{(CH2)2O)}5SO3 -

[0077] CH3(CH2) 11 O{(CH2)4O)}4{(CH2)2O)}5SO3 -

[0078] CH3(CH2) 11 O{(CH2)4O)}5{(CH2)2O)}5SO3 -

[0079] CH3(CH2) 11 O{(CH2)4O)} 10 {(CH2)2O)} 15 SO3 -

[0080] CH3(CH2) 11 O{(CH2)4O)} 10 {(CH2)2O)} 20 SO3 -

[0081] CH3(CH2) 12 O{(CH2)4O)}2{(CH2)2O)}5SO3 -

[0082] CH3(CH2) 12 O{(CH2)4O)}3{(CH2)2O)}5SO3 -

[0083] CH3(CH2) 12 O{(CH2)4O)}4{(CH2)2O)}5SO3 -

[0084] CH3(CH2) 12 O{(CH2)4O)}5{(CH2)2O)}5SO3 -

[0085] CH3(CH2) 12 O{(CH2)4O)} 10 {(CH2)2O)} 15 SO3 -

[0086] CH3(CH2) 12 O{(CH2)4O)} 10 {(CH2)2O)} 20 SO3 -

[0087] Specific examples of the structural unit (a) represented by the above formula (1) include those represented by the following formulae, but are not limited to these.

[0088] [Chemistry 7]

[0089]

[0090] (In the formula, the asterisk * has the same meaning as above.)

[0091] The structural unit (b) contained in the hydrophilic copolymer used in the present invention is represented by the following formula (2).

[0092] The hydrolyzable silyl group contained in the structural unit (b) undergoes a crosslinking reaction with a functional group contained in the curing agent when the hydrophilic composition of the present invention contains a curing agent, or can undergo a crosslinking reaction (self-crosslinking) by itself even when no curing agent is contained. Thus, a crosslinked structure containing a hydrophilic copolymer is formed in the coating film.

[0093] [Chemistry 8]

[0094]

[0095] (In the formula, the asterisk * has the same meaning as above.)

[0096] In the above formula (2), R 3 It is a hydrogen atom or a methyl group, preferably a methyl group.

[0097] X 2 It is -NH- or -O-, preferably -O-.

[0098] Y 2 It is a group selected from a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an epoxy group, an alkoxy group (—OR) and a hydrolyzable silyl group.

[0099] As Y 2 The alkoxy group (-OR) of R includes alkoxy groups in which the alkyl group of R is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexyloxy, cyclopentyloxy, cyclohexyloxy, etc. In addition, part or all of the hydrogen atoms bonded to the carbon atom of the alkyl group of R may be substituted with halogen atoms such as chlorine, fluorine, and bromine, or other substituents such as cyano.

[0100] As Y 2 Examples of the hydrolyzable silyl group include alkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, dimethoxysilyl, diethoxysilyl, monomethoxysilyl, and monoethoxysilyl; carboxylate silyl groups such as acetoxysilyl; halogenated silyl groups such as trichlorosilyl, dichlorosilyl, and monochlorosilyl; aminosilyl; oxime silyl; and hydrosilyl.

[0101] Among these, Y 2 Preferred are a hydrogen atom and a hydroxyl group.

[0102] m is an integer of 0 to 10, preferably an integer of 0 to 6, more preferably an integer of 1 to 4, and further preferably an integer of 2 to 4. However, when m is 0, Y 2 A hydrogen atom.

[0103] In the hydrophilic composition of the present invention, (A) hydrophilic copolymer is heat-treated by being used in combination with (B) blocked isocyanate silane, so that a cross-linked structure can be formed with the blocked isocyanate silane and the copolymer. In addition, for example, if the hydrophilic copolymer is used in combination with a curing catalyst such as an acid catalyst, the copolymer itself can also undergo a cross-linking reaction (self-crosslinking). Therefore, the coating film formed by the composition comprising the hydrophilic copolymer and the curing agent has a cross-linked structure and can exert excellent water resistance.

[0104] Based on this aspect, in the above formula (2), Y 2 A hydroxy group is more preferred.

[0105] Specific examples of the structural unit (b) represented by the above formula (2) include those represented by the following formulae, but the present invention is not limited to these.

[0106] [Chemistry 9]

[0107]

[0108] (In the formula, the asterisk * has the same meaning as above.)

[0109] In the hydrophilic copolymer used in the present invention, the content of the structural unit (a) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% by mass. When the content of the structural unit (a) is less than 5% by mass, the hydrophilicity of the copolymer is insufficient, and the surface hydrophilicity of the coating film is sometimes reduced during film coating. On the other hand, when the content of the structural unit (a) exceeds 60% by mass, the hydrophilicity of the copolymer is excessively increased, and therefore the water resistance of the coating film is sometimes reduced during film coating.

[0110] In addition, in the hydrophilic copolymer of the present invention, the total content of the structural unit (a) and the structural unit (b) is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more. When the total content of the structural unit (a) and the structural unit (b) is less than 30% by mass, the contribution of the hydrophilic factor of the structural unit (a) becomes small, and sometimes the surface hydrophilicity of the coating film when it is made into a coating film is reduced. There is no particular upper limit, and it can be only the structural unit (a) and the structural unit (b), preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 65% ​​by mass or less.

[0111] The hydrophilic copolymer used in the present invention may contain, in addition to the above-mentioned structural units, a structural unit represented by the following formula (3), for example, within a range not impairing the object of the present invention.

[0112] [Chemistry 10]

[0113]

[0114] (In the formula, the asterisk * has the same meaning as above.)

[0115] In the above formula (3), R 4 It is a hydrogen atom or a methyl group, preferably a methyl group.

[0116] X 3 It is -NH- or -O-, preferably -O-.

[0117] A' is an alkylene group having 1 to 6 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

[0118] Among these, an alkylene group having 1 to 3 carbon atoms is preferred, and an ethylene group is more preferred.

[0119] R 5 is an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include the following:2 The groups are the same as those exemplified in , and among them, a methyl group is preferred.

[0120] f is an integer of 1-10, preferably an integer of 2-8, and more preferably an integer of 3-6.

[0121] In the present invention, when the hydrophilic copolymer contains other structural units, the total content thereof is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 5 to 50% by mass.

[0122] The order of the structural units contained in the hydrophilic copolymer is arbitrary, that is, the hydrophilic copolymer may be any of an alternating copolymer, a random copolymer, and a block copolymer.

[0123] In the present invention, the weight average molecular weight of the hydrophilic copolymer is preferably 1000 to 50000, more preferably 5000 to 40000, further preferably 10000 to 30000, and further preferably 15000 to 20000, from the viewpoint of improving affinity with organic solvents and hardness of the coating film. The weight average molecular weight is a value determined by gel permeation chromatography (GPC) (standard substance: polyethylene glycol / polyethylene oxide).

[0124] In addition, from the viewpoint of compatibility with organic solvents and workability, the viscosity of the hydrophilic copolymer is preferably 0.01 to 0.5 Pa·s (temperature 25° C.) The viscosity is a value measured using a rotational viscometer.

[0125] Furthermore, the glass transition temperature of the hydrophilic copolymer is preferably -10 to 50° C. The glass transition temperature is a value measured in accordance with JIS K7121.

[0126] As the hydrophilic copolymer used in the present invention, commercially available products may be used, and examples thereof include Acleto 1WX manufactured by Daisei Philharmonic Co., Ltd. and the like.

[0127] [B] Blocked isocyanate silane compounds

[0128] The blocked isocyanate group silane compound of the component (B) functions as a curing agent for the hydrophilic copolymer, and in the present invention, an organosilicon compound having a blocked isocyanate group represented by the following formula (4) is preferred.

[0129] In addition to the blocked isocyanate silane monomer, a partially hydrolyzed structure of a hydrolyzable silyl moiety or a partially hydrolyzed condensate of an oligomer formed by further intermolecular condensation also exhibits similar properties and can be used as the curing agent component of the present invention.

[0130] [Chemistry 11]

[0131]

[0132] In formula (4), R 6 Each independently represents an alkyl group having 1 to 8 carbon atoms, L represents a divalent linking group, and X 4 Indicates -O- or -NR 7 -, Y 3 represents a hydrogen atom or a monovalent organic group, R 7 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or may be combined with Y 3 A group that is bonded to form a ring structure, and k represents an integer of 1 to 3.

[0133] R 6 The alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl and n-octyl. Among them, methyl and ethyl are preferred.

[0134] Specific examples of the divalent linking group of L include alkylene, -O-, -S-, -NR-, CO-, -COO-, -NRCO-, -SO2-, and combinations thereof. R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. In addition, examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms among the alkyl groups exemplified above.

[0135] Among these, from the perspective of the availability of raw materials when producing the organosilicon compound, the divalent linking group is preferably -(CH2) n -(n is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4) represented by an alkylene group, or the -(CH2) n - is a group in which one or more methylene units are replaced by -O-, -S-, -NH-, -CO- and -COO-, and -(CH2)3-(trimethylene) is more preferred.

[0136] X 4 -O- or -NR 7 - is a group that forms a part of the protective group of the blocked isocyanate silane compound and is not particularly limited because it is released by heating.

[0137] In X 4 -NR 7 -Middle, R 7 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or may be combined with Y 3 Groups bonded to form a ring structure.

[0138] As R 7The alkyl group having 1 to 8 carbon atoms includes the following: 6 The same groups as those exemplified in , among which a linear or branched alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group or an ethyl group is more preferred.

[0139] In-NR 7 -Middle, R 7 Indicates that it can be used with Y 3 In the case of a group that is bonded to form a ring structure, -NR 7 - and Y in formula (1) 3 A nitrogen-containing heterocyclic structure is formed. In such a heterocyclic structure, it is preferred to contain 2 or more nitrogen atoms, and more preferably 2 nitrogen atoms. As the heterocyclic structure, a 5-membered ring or a 6-membered ring structure is preferred, and a 5-membered ring structure is more preferred. As such a heterocyclic structure, an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring is preferred, and a pyrazole ring is more preferred.

[0140] Furthermore, the above-mentioned ring structure may have a substituent such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carboxyl group, a hydroxyl group, an ester group, an oxo group (=O), or the like.

[0141] Preferred ring structures include the following structures, but are not limited to these.

[0142] [Chemistry 12]

[0143]

[0144] Y 3 It is a hydrogen atom or a monovalent organic group, is a group that forms a part of the protective group of the blocked isocyanate silane compound, and is not particularly limited because it is released by heating.

[0145] As Y 3 Specific examples of the monovalent organic group include a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an -OH group (excluding the case where X is -O-), N=R 17 (R 17 represents an alkylene group having 1 to 10 carbon atoms which may be substituted by an aryl group having 6 to 20 carbon atoms. ) and the like.

[0146] The monovalent hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic, and examples thereof include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms.

[0147] As specific examples of the above alkyl groups, except for R 6 In addition to the groups exemplified in , n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, eicosyl, and the like can be mentioned.

[0148] Specific examples of the aryl group include a phenyl group and a naphthyl group.

[0149] Specific examples of the aralkyl group include a benzyl group and a phenylethyl group.

[0150] Furthermore, at least a part of the hydrogen atoms in these groups may be substituted with other substituents, and examples of the other substituents include a carboxyl group, an ester group, and a hydroxyl group.

[0151] As R 17 The alkylene group may be a straight-chain, branched or cyclic alkylene group having 1 to 10 carbon atoms, which may be substituted by an aryl group having 6 to 20 carbon atoms or a heteroaryl group. Specific examples thereof include methylene, phenylmethylene, diphenylmethylene, ethylene, propylene, propane-2-ylidene, butylene, butane-2-ylidene, pentylene, 4-methylpentane-2-ylidene, hexylene, cyclohexylene, heptylene, octylene, nonylene and decylene.

[0152] Specific examples of the aryl group having 6 to 20 carbon atoms include 3 The same groups as exemplified in .

[0153] Specific examples of the heteroaryl group having 6 to 20 carbon atoms include pyrrol-1-yl, 1H-pyrrol-2-yl, imidazol-1-yl, imidazol-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyridin-2-yl and pyridin-3-yl.

[0154] In particular, the blocked isocyanate silane compound represented by the above formula (4) is preferably represented by the following formula (5) or formula (6).

[0155] [Chemistry 13]

[0156]

[0157] (Where R 6 , R 7 , Y 3 and k have the same meanings as above. )

[0158] R 8 and R 9 Each independently represents a hydrogen atom or a monovalent organic group, R 8 With R 9 or R 7 With Y 3 Can be connected to each other to form a ring structure.

[0159] As the above R 8 and R 9Examples of the monovalent organic group include a monovalent hydrocarbon group having 1 to 20 carbon atoms and a heteroaryl group having 6 to 20 carbon atoms.

[0160] Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include the following: 3 The same groups as those exemplified in , preferably alkyl groups having 1 to 20 carbon atoms and aryl groups having 6 to 20 carbon atoms, and specific examples thereof include the same groups as those mentioned above.

[0161] Examples of the heteroaryl group having 6 to 20 carbon atoms include the following: 17 The same groups as exemplified in .

[0162] As R 8 With R 9 Examples of the ring structure formed by connecting to each other include a cyclopentane ring and a cyclohexane ring.

[0163] These hydrocarbon groups or heteroaryl groups may have a substituent. Specific examples of the substituent include a carboxyl group, a hydroxyl group, and an ester group.

[0164] As R 8 -Methylene-R 9 The group represented by may include the above R 17 Among the alkylene groups exemplified in , diphenylmethylene, propane-2-ylidene, butane-2-ylidene, 4-methylpentane-2-ylidene, and cyclohexylene are preferred.

[0165] As R 7 and Y 3 The specific examples are the same as above, wherein they are preferably bonded to each other to form a ring structure together with the nitrogen atom. As the ring structure, a 5-membered ring or a 6-membered ring is preferred, and a 5-membered ring is more preferred.

[0166] The ring structure preferably has two nitrogen atoms, more preferably an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, or a 1,2,4-triazole ring, and further preferably a pyrazole ring.

[0167] Furthermore, the above-mentioned ring structure may have a substituent such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carboxyl group, a hydroxyl group, an ester group, an oxo group (=O), or the like.

[0168] Preferred ring structures include the following ones, but are not limited to these.

[0169] [Chemistry 14]

[0170]

[0171] (B) Although the following compounds are mentioned as preferable specific examples of the blocked isocyanate silane compound of the component, it is not limited to these.

[0172] [Chemistry 15]

[0173]

[0174] The hydrophilic composition of the present invention (hereinafter also simply referred to as "composition") comprises the above-mentioned components (A) and (B), and specifically, comprises 0.001 to 10 parts by mass of the component (B) per 100 parts by mass of the component (A).

[0175] When the content of the component (B) is less than the lower limit, the desired effect of improving water resistance is not achieved. When the content exceeds the upper limit, the effect is saturated and the cost-effectiveness is reduced. In addition, the influence of the original silane coupling agent on hydrophobicity tends to increase and the hydrophilicity tends to decrease.

[0176] The content of the component (A) contained in the hydrophilic composition of the present invention is not particularly limited, but is preferably 1 to 40% by mass, more preferably 10 to 25% by mass, based on the entire composition from the viewpoint of hydrophilicity.

[0177] The hydrophilic composition of the present invention may contain other components as necessary within a range not impairing the object of the present invention, and particularly preferably contains a curing agent.

[0178] The curing agent promotes the cross-linking reaction of the hydrophilic copolymer and helps to form a cross-linked structure inside the coating film. At this time, the curing agent may be introduced into the cross-linked structure or may not be introduced.

[0179] In the case of the curing agent introduced into the crosslinked structure, it is preferred that the curing agent has a functional group contained in the side chain of the hydrophilic copolymer (specifically, the functional group Y contained in the structural unit (b)) 2 (B) or (B) component alkoxysilyl) functional group or structure for cross-linking reaction. In this case, the cross-linking method can be any one of covalent bond, ionic bond, hydrogen bond or coordination bond, preferably covalent bond.

[0180] As the curing agent introduced into the cross-linked structure, it is preferred to have a functional group such as a hydrolyzable silyl group, isocyanate group, epoxy group, carbodiimide group, oxazolyl group, epoxy group, hydroxyl group, carboxyl group, amino group, a molecular structure such as a siloxane structure, a melamine structure, a metal ion, etc. in the molecule.

[0181] Preferred combinations of the functional groups of the side chains of the cross-linkable hydrophilic copolymer and the functional groups or structures of the curing agent are shown in Table 1, for example.

[0182] [Table 1]

[0183]

[0184] Examples of curing agents having a hydrolyzable silyl group include compounds having a hydrolyzable silyl group and a siloxane structure containing a hydrolyzable silyl group. Specifically, examples include compounds represented by the following formula (7), compounds represented by the following formula (8), and hydrolysis-condensation products of compounds represented by the following formula (8).

[0185] [Chemistry 16]

[0186]

[0187] In the above formula (7), R 10 and R 11 Each independently represents an alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.

[0188] R 10 and R 11 The alkyl group may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and cyclohexyl.

[0189] As R 10 and R 11 Specific examples of the aryl group include phenyl and tolyl.

[0190] Among these, R 10 Preferably, the alkyl group has 1 to 3 carbon atoms, and more preferably, the methyl group or the ethyl group. 11 An alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is more preferred.

[0191] In the above formula (7), j is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and further preferably an integer of 2 to 4.

[0192] i is an integer of 1 to 3, and preferably 3.

[0193] Specific examples of the compound represented by the formula (7) include N,N,N-tris(trimethoxysilylpropyl)isocyanurate and N,N,N-tris(triethoxysilylpropyl)isocyanurate, but are not limited to these.

[0194] In the above formula (8), R 12 , R 13 , R 14 and R 15 Each independently represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms.

[0195] In formula (8), R 12 , R 13 , R 14 and R 15 The monovalent organic group having 1 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include alkyl groups having 1 to 6 carbon atoms and alkenyl groups having 2 to 6 carbon atoms.

[0196] Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and cyclohexyl group.

[0197] Specific examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group and an allyl group.

[0198] Among these, R 12 , R 13 , R 14 and R 15 The monovalent organic group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group, from the viewpoint of hydrolyzability.

[0199] In formula (8), h represents an integer of 1 to 20, preferably an integer of 3 to 12, and more preferably an integer of 5 to 12. If h is 20 or less, the viscosity of the coating solution does not increase excessively, and a highly uniform antifogging film can be formed. In addition, if h is 1 or more, the reactivity of the compound represented by formula (5) can be easily controlled, and an antifogging film with excellent hydrophilicity can be formed.

[0200] In the present invention, the "hydrolysis condensate of the compound represented by formula (8)" means Si-OR 12 、Si-OR 13 、Si-OR 14 and Si-OR 15 A compound having a structure in which a siloxane bond (Si-O-Si) is formed in at least one of the molecules. The condensate of the compound represented by formula (8) can be formed, for example, by condensing or hydrolyzing two or more molecules of the compound represented by formula (8). For hydrolyzing, the following is R in formula (8): 12 , R 13 , R 14 and R 15 The case of methyl (-CH3) is used as an example for explanation. In one example of hydrolysis condensation, Si-OH is formed by hydrolysis of Si-OCH3, and then Si-O-Si is formed by dehydration condensation of Si-OH.

[0201] The structure of the hydrolysis-condensation product of the compound represented by the formula (8) is not particularly limited, and examples thereof include random type, linear type, ladder type, and cage type.

[0202] Furthermore, in the compound represented by formula (8) and its hydrolysis-condensation product, in R 12 , R 13 , R 14 and R 15 In the case where R contains hydrogen atoms, the hydrogen atoms may be hydrogen atoms contained in the compound added as a raw material during the production of the compound of formula (8), or may be hydrogen atoms introduced by hydrolysis. 12 , R 13 , R 14 and R 15 When at least one of the Si-OH groups in formula (8) is a hydrogen atom, at least one of the Si-OH groups in formula (8) may be a Si-OH group contained in a compound added as a raw material during the manufacture of the compound of formula (8), or may be a Si-OH group formed by hydrolysis.

[0203] The compound represented by formula (8) may be a commercially available product. The compound represented by formula (8) is available, for example, as MKC (registered trademark) Silicate (eg, MS51, MS56) manufactured by Mitsubishi Chemical Corporation.

[0204] The weight average molecular weight (Mw) of the compound represented by formula (8) is preferably 300 to 1500, more preferably 500 to 1200. The weight average molecular weight is a value determined by gel permeation chromatography (GPC) (standard substance: polyethylene glycol / polyethylene oxide).

[0205] Examples of the curing agent having an isocyanate group include aliphatic, alicyclic, or aromatic polyisocyanates.

[0206] Specific examples include isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, toluene diisocyanate, polymeric MDI, naphthalene diisocyanate, tetramethylxylylene diisocyanate, trimethylhexamethylene diisocyanate, lysine methyl diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, methylenebis(4,1-cyclohexylene)diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, adducts of diisocyanate compounds with polyol compounds such as trimethylolpropane, and isocyanate derivatives such as biuret bodies or isocyanurate bodies of diisocyanate compounds.

[0207] Among these, polyisocyanates derived from hexamethylene diisocyanate are preferred from the viewpoint of suppressing yellowing of the coating film.

[0208] The curing agent having an isocyanate group is available as a commercial product, and Duranet (registered trademark) TPA-100, TKA-100, 24A-100, 22A-75P, P301-75E, etc. manufactured by Asahi Kasei Corporation; Colonet (registered trademark) HX, HK, 2715, etc. manufactured by Tosoh Corporation; and Takenet (registered trademark) 500, 600, etc. manufactured by Mitsui Chemicals, Inc. can be used.

[0209] These may be used alone or in combination of two or more.

[0210] As the curing agent having a melamine structure, a melamine resin is preferred, and specific examples thereof include guanamine, melamine, N-butyl melamine, N-phenyl melamine, N,N-diphenyl melamine, N,N-diallyl melamine, N,N',N"-triphenyl melamine, N,N',N"-trimethylol melamine, benzoguanamine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-6 2,4-diamino-6-butyl-s-triazine, 2,4-diamino-6-benzyloxy-s-triazine, 2,4-diamino-6-butoxy-s-triazine, 2,4-diamino-6-cyclohexyl-s-triazine, 2,4-diamino-6-chloro-s-triazine, 2,4-diamino-6-mercapto-s-triazine, condensates of melamines such as Amelin (N,N,N',N'-tetracyanoethylbenzoguanamine) with formaldehyde and alcohols (e.g., methanol, etc.), etc.

[0211] The curing agent having a melamine structure is commercially available, and Uban (registered trademark) 20SE and 225 manufactured by Mitsui Chemicals, Inc.; Amidi (registered trademark) L-117-60, L-109-65, 47-508-60, L-118-60, G821-60, and J820-60 manufactured by DIC Corporation can be used.

[0212] These may be used alone or in combination of two or more.

[0213] Examples of the curing agent having an epoxy group include aliphatic, alicyclic or aromatic diepoxy compounds and triepoxy compounds.

[0214] Specific examples include 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether (bisphenol A diglycidyl ether), ethylene glycol diglycidyl ether, triglycidyl isocyanurate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene epoxy resin, biphenyl type epoxy resin, phenol novolac resin type epoxy resin, 1,5-hexadiene diepoxide, 1,4-pentadiene diepoxide, 1, 2:6,7-diepoxyheptane, 1,2:8,9-diepoxynonane, 2,2'-(1,6-hexylene)dioxirane, 1,2:7,8-diepoxyoctane, 1,5-diepoxycyclohexane, 1,2:3,4-diepoxycyclohexane, 1,2:5,6-diepoxycyclooctane, limonene dioxide, cis-1,2:4,5-diepoxy-terpene, 1,6-diepoxynaphthalene, triepoxydecane, etc.

[0215] These may be used alone or in combination of two or more.

[0216] Examples of the curing agent having an amino group include aliphatic, alicyclic or aromatic diamines, triamines and tetraamines containing primary or secondary amines.

[0217] Specific examples include hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 2-methyl-1,5-diaminopentane, 3,3-dimethylbutane-1,2-diamine, 4-methylpentane-1,2-diamine, 2,2,4,4-tetramethylcyclobutane, 2-methylcyclohexane-1,3-diamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 2,3-diaminotoluene, 2,5-dimethylbenzene-1,2-diamine, 3,4-dimethylbenzene-1,2-diamine, 2,6-dimethylbenzene-1,4-diamine, 2,4-dimethylbenzene-1,3-diamine, 3,5-dimethyl-1,2-phenylenediamine, 4-ethylbenzene-1 , 3-diamine, 2,5-dimethylbenzene-1,4-diamine, 4-methoxybenzene-1,3-diamine, 4-(1,1-dimethylethyl)-1,2-phenylenediamine, p-phenylenediamine, o-phenylenediamine, N-isopropyl-1,3-propylenediamine, N-hexylethylenediamine, 5-isopropylaminopentylamine, n-butylethylenediamine, N-tert-butylbutane-1,4-diamine, N-ethylhexane-1,6-diamine, N-isobutylethane-1,2-diamine, N-cyclohexyl-1,2-ethylenediamine, N-1-methylcyclohexane-1,4-diamine, N-methylbenzene-1,2-diamine, N-phenylethylenediamine, N-ethylbenzene-1,2-diamine, N-1-methylbenzene-1,3-diamine, 4-amino-N-methylaniline, 2-aminodiphenyl amine, 4-aminodiphenylamine, N-1,4-dimethylbenzene-1,2-diamine, N-1,5-dimethylbenzene-1,2-diamine, N-isopropyl-benzene-1,2-diamine, N-(3-aminophenyl)-N-phenylamine, N,N'-dimethyltrimethylenediamine, N,N'-diethylbutanediamine, N,N'-diisopropyl-2,3-butane-diamine, N,N'-diethyl-2-butene-1,4-diamine, N,N'-diisopropylethylenediamine, N-propyl-N'-isopropylethylenediamine, N,N'-dimethylbutane-1,4-diamine, N,N'-diethyl-1,3-propylenediamine, N,N'-diethylethylenediamine, (1R,2R)-1-N,2-N-dimethylcyclohexane-1,2- diamine, N,N'-dimethyl-1,2-cyclohexanediamine, 1-N,4-N-dimethylcyclohexane-1,4-diamine, 1,4-phenylenediamine, 1,2,4-triaminobenzene, 2,4,5-triaminotoluene, 2,4,6-triaminotoluene, 2,3,4-triaminotoluene, 3,5,6-triaminotoluene, 3-N-methylbenzene-1,2,3-triamine, 2-N-methylbenzene-1,2,3-triamine, 4-N-methylbenzene-1,2,4-triamine, 1-N-methylbenzene-1,2,4-triamine, 3-N-methylbenzene-1,3,5-triamine, 1-N',1-N"-diethylpropane-1,1,1-triamine, 4-(3,4-diaminophenyl)benzene-1,2-diamine, 1-N,1-N,2-N,2-N,3-N,3-N,4-N,4-N-octamethylbutane-1,2,3,4-tetraamine, 4-[3-amino-4-(methylamino)phenyl]benzene-1,2-diamine, etc.

[0218] These may be used alone or in combination of two or more.

[0219] Examples of the curing agent having a carbodiimide group include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, tert-butylisopropylcarbodiimide, diphenylcarbodiimide, di-tert-butylcarbodiimide, di-β-naphthylcarbodiimide, and N-isopropyl-N′-[2-(methacryloyloxy)ethyl]carbodiimide.

[0220] These may be used alone or in combination of two or more.

[0221] Examples of the curing agent having an oxazoline group include 2,2'-bis(2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, and 1,4-bis(4,5-dihydro-2-oxazolyl)benzene.

[0222] These may be used alone or in combination of two or more.

[0223] Examples of the curing agent having metal ions include organic aluminum compounds such as ethyl acetoacetate diisopropoxyaluminum.

[0224] Among these, from the viewpoint of ease of handling, a curing agent having an isocyanate group or a melamine structure is preferred, and a curing agent containing Y is more preferred. 2 The hydrophilic copolymer having a structural unit (b) of hydroxyl group is combined with a curing agent having an isocyanate group or a melamine structure, and it is further preferred to 2 The hydrophilic copolymer having structural units (b) which are hydroxyl groups is combined with a polyisocyanate or a melamine resin.

[0225] That is, a preferred embodiment of the present invention is a hydrophilic composition comprising the hydrophilic copolymer of the present invention and a polyisocyanate or melamine resin as the curing agent. 2 In the case of a combination of a hydrophilic copolymer having a structural unit (b) of a hydroxyl group and a curing agent (polyisocyanate) having an isocyanate group, the crosslinking reaction proceeds even under low temperature conditions (e.g., below 110° C.), and the composition of the present invention can be used to form a coating film on a substrate with low heat resistance, so it is particularly preferred.

[0226] On the other hand, examples of the curing agent (curing catalyst) that does not introduce a crosslinking structure include inorganic acids, organic acids, organic metal salts, and Lewis acids.

[0227] Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, and sulfamic acid.

[0228] Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p-toluenesulfonic acid, and citric acid.

[0229] Examples of the organic metal salt include lithium hydroxide, sodium hydroxide, potassium hydroxide, n-hexylamine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium formate, potassium formate, benzoyltrimethylammonium acetate, tetramethylammonium acetate, and tin octoate.

[0230] Examples of the Lewis acid include tetraisopropyl titanate, tetrabutyl titanate, triisobutoxyaluminum, triisopropoxyaluminum, aluminum acetylacetonate, tin chloride (SnCl 4 ), titanium chloride (TiCl 4 ), and zinc chloride (ZnCl 4 ).

[0231] In addition, alkyl tin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, dioctyltin dioctoate, and dioctyltin diverstcarbonate can also be preferably used.

[0232] These may be used alone or in combination of two or more.

[0233] In addition, a curing agent that introduces a crosslinking structure and a curing agent (curing catalyst) that does not introduce a crosslinking structure may be used in combination as appropriate.

[0234] When the hydrophilic composition of the present invention contains a curing agent, the content thereof is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the hydrophilic copolymer.

[0235] The hydrophilic composition of the present invention preferably further contains a hydrophilic organosilicon compound represented by the following formula (10) and / or a hydrolysis-condensation product thereof.

[0236] [Chemistry 17]

[0237]

[0238] In formula (10), R 18 and R 19Each independently represents an alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. Specific examples of these alkyl groups and aryl groups include: 3 The groups are the same as those exemplified in , and among these, a methyl group is preferred.

[0239] R 20 It is a divalent organic group containing an aromatic ring and having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, preferably a divalent organic group containing an aromatic hydrocarbon ring, more preferably a divalent organic group containing a benzene ring or a naphthalene ring, and further preferably an arylene group or aralkylene group containing a benzene ring or a naphthalene ring.

[0240] As R 20 Specific examples of the arylene group include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, naphthylene and the like.

[0241] As R 20 Specific examples of the aralkylene group include methylenephenylene, ethylenephenylene, methylenephenylenemethylene, and ethylenephenyleneethylene.

[0242] Among these, R 18 Preferred is a phenylene group, and more preferred is a 1,4-phenylene group.

[0243] R 21 and R 22 Each independently represents an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include 6 The alkyl groups having 1 to 6 carbon atoms in the groups exemplified in are the same alkyl groups, and among these, a methyl group is preferred.

[0244] X 5 It represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.

[0245] X 5 The alkylene group may be linear, branched or cyclic, and specific examples thereof include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene and cyclohexylene.

[0246] Among these, X 5 Preferred are methylene, ethylene and trimethylene, and more preferred is trimethylene.

[0247] Y 4 Represents COO - 、SO3 - , or PO4 - From the viewpoint of the durability of the obtained coating film, SO3 is preferred. - .

[0248] o is an integer of 1 to 3, and preferably 3.

[0249] Specific examples of such hydrophilic organosilicon compounds are shown below, but the present invention is not limited to these. Among these, compounds represented by formula (11) are preferred.

[0250] [Chemistry 18]

[0251]

[0252] (In the formula, Me represents a methyl group and Et represents an ethyl group.)

[0253] When a hydrophilic organosilicon compound is used, the content of the hydrophilic organosilicon compound in the hydrophilic composition of the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the hydrophilic copolymer.

[0254] The hydrophilic composition of the present invention may contain a solvent as required. The solvent is not particularly limited as long as it can dissolve or disperse the hydrophilic copolymer, the curing agent used as appropriate, the hydrophilic organosilicon compound and other additives, does not react with the components, and can be easily removed in the drying step described below.

[0255] Specific examples of the solvent include methanol, ethanol, isopropanol, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, toluene, ethyl acetate, ethyl lactate, methyl lactate, dimethyl sulfoxide, water, and the like.

[0256] For example, when polyisocyanate is used as a curing agent, it is preferable to use a solvent that does not react with an isocyanate group (for example, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone).

[0257] These may be used alone or in combination of two or more.

[0258] The hydrophilic composition of the present invention may further contain additives such as pigments, film-forming aids, fillers, toners, wetting agents, antistatic agents, pigment dispersants, plasticizers, antioxidants, flow control agents, viscosity modifiers, defoamers, ultraviolet absorbers, dispersants, etc. as needed.

[0259] The solid content concentration of the composition is preferably 5 to 80% by mass, more preferably 10 to 30% by mass, from the viewpoint of coating properties and workability.

[0260] The viscosity of the composition is preferably 0.01 to 0.05 Pa·s (temperature 25° C.) from the viewpoint of coating properties and workability. The viscosity is a value measured using a rotational viscometer.

[0261] The composition of the present invention may be a one-liquid type (one-component type) or a type in which two or more liquids are mixed before use.

[0262] The composition of the present invention can impart hydrophilicity to various substrates by being applied to the substrates.

[0263] Specific examples of the material constituting the substrate include glass; synthetic resins {polymethyl methacrylate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, ABS resin, polycarbonate resin, polystyrene resin, epoxy resin, unsaturated polyester resin, melamine resin, diallyl phthalate resin, polyimide resin, polyurethane resin, nylon resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, fluororesins (polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, perfluoroalkoxy fluororesin, tetrafluoroethylene-hexafluoropropylene copolymer resin, ethylene-tetrafluoroethylene copolymer resin, ethylene- chlorotrifluoroethylene copolymer resin, etc.), polybutadiene, polyisocyanate, SBR, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, chloroprene rubber, polysulfide, butyl rubber, etc.}; metals (iron, aluminum, stainless steel, titanium, copper, brass, alloys thereof, etc.); cellulose, cellulose derivatives, cellulose analogs (chitin, chitosan, metalloporphyrin, etc.), natural fibers such as cotton, silk, wool, regenerated fibers such as rayon, semi-synthetic fibers such as acetate, synthetic fibers such as vinylon, polyester, nylon, polyethylene, polypropylene, polyurethane, aramid fibers, etc.; composite fibers of these fibers (polyester / cotton, etc.), etc., as their forms, substrates, sheets, films, fibers, various articles using them, etc. can be listed.

[0264] The composition of the present invention can be formed into a hydrophilic coating film by applying a known coating method to form a coating film on the surface of a substrate or the like.

[0265] As the coating method, for example, rod coating, dip coating, spin coating, spray coating, flow coating, brush coating, gravure coating, roll transfer, blade coating, air knife coating, slit coating, screen coating, inkjet, flexographic printing, etc. are used. Among these, rod coating is preferred.

[0266] A cured coating film can be obtained by applying the composition onto a substrate and then heating it.

[0267] The heating temperature is preferably 40 to 250° C., more preferably 80 to 120° C. The drying time is preferably 10 seconds to 12 hours, more preferably 30 seconds to 3 hours.

[0268] Furthermore, the solvent in the composition may be removed by pre-drying under the same conditions as above.

[0269] The heating atmosphere may be any of an air atmosphere and an inert gas (eg, nitrogen, argon, etc.) atmosphere.

[0270] The thickness (dry film thickness) of the coating film of the present invention is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 1 to 10 μm.

[0271] Example

[0272] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0273] (1) Production of coating composition (hydrophilic composition)

[0274] [Example 1]

[0275] A methyl ethyl ketone-IPA (1:2, wt / wt) solution (solid content concentration: 25% by mass, denoted as A-1) of a copolymer comprising structural units represented by the following formulae (12), (13), (14), (15) and (16) as the component (A), a compound represented by the following (B-1) as the component (B), and Neostar U-830 (manufactured by Nitto Kasei Co., Ltd.) as a dioctyltin catalyst were mixed in the formulation shown in Table 2 to prepare a hydrophilic composition.

[0276] [Chemistry 19]

[0277]

[0278] (In the formula, the asterisk * has the same meaning as above.)

[0279] [Examples 2 to 7, Comparative Examples 1 to 6]

[0280] A hydrophilic composition was prepared in the same manner as in Example 1 except that the type of the component (B) was changed as shown in Table 2 and a curing agent shown in Table 2 was added.

[0281] [Table 2]

[0282]

[0283] In addition, in Table 1, the abbreviations are as follows.

[0284] B-1: Silane compound represented by the above formula (8-a)

[0285] B-2: Silane compound represented by the above formula (8-b)

[0286] B-3: Silane compound represented by the above formula (4-a)

[0287] B'-1: 3-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)

[0288] B'-2: 3-isocyanatepropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-9007)

[0289] C-1: Tris-(trimethoxysilylpropyl)isocyanurate (Shin-Etsu Chemical Co., Ltd.

[0290] System, KBM-9659)

[0291] C-2: MKC (registered trademark) Silicate MS51 (manufactured by Mitsubishi Chemical Corporation), which is a partially hydrolyzed oligomer of tetramethoxysilane

[0292] D-1: Silane compound represented by the above formula (11)

[0293] (2) Evaluation of storage stability of hydrophilic composition

[0294] 40 g of the hydrophilic composition just prepared in each of the above examples and comparative examples were weighed in a 50 mL polyethylene container and left to stand for 3 months in a thermostat (SPHH-201, Espec Co., Ltd.) set at 40°C. After 3 months, the composition was taken out from the desiccator and left to stand for 1 hour under the conditions of 25°C / 50% relative humidity, and then the composition was observed. The evaluation criteria for storage stability are as follows.

[0295] ○: The composition maintains fluidity

[0296] ×: The composition solidifies into a gel state

[0297] (3) Preparation and evaluation of coating films

[0298] The hydrophilic compositions immediately after preparation in the above-mentioned examples and comparative examples were applied to polycarbonate plates using a bar coater (No. 14) and then immediately dried at 120° C. for 1 hour to obtain hydrophilic films. The obtained films were subjected to the following tests, and the results are shown in Table 3.

[0299] [Anti-fog properties]

[0300] Air was exhaled onto each of the above films, and a case where the surface of the film was blurred was marked as ×, and a case where it was not blurred was marked as ○. Furthermore, the film was placed above a 60°C warm water bath at a height of 3 cm from the water surface for 1 minute, and a case where the surface of the film was not blurred was marked as ◎, thereby evaluating the anti-fogging property.

[0301] [Water resistance]

[0302] Each of the above films was immersed in tap water at 25° C. for 5 minutes, and the surface water was absorbed with a paper towel, followed by natural drying at 25° C. for 10 minutes, and the above antifogging property was evaluated.

[0303] Next, each film was immersed in tap water for 1 hour, and the surface water was absorbed with a paper towel, followed by natural drying at 25° C. for 10 minutes, and the above-mentioned antifogging property was evaluated.

[0304] [Moisture resistance]

[0305] Each of the above films was allowed to stand for 24 hours in a thermostatic chamber (KCL-2000W, Tokyo Rikaki Co., Ltd.) set at 50°C and 98% RH, and then naturally dried at 25°C for 10 minutes, and the above antifogging property was evaluated.

[0306] [Table 3]

[0307]

[0308] As shown in Table 3, it can be seen that the compositions of Examples 1 to 6 containing blocked isocyanate silane compounds have good storage stability, and even after the water resistance test (water immersion for 5 minutes, water immersion for 1 hour) and the humidity resistance test (50°C, 98% RH, 24 hours), they maintain excellent hydrophilicity and anti-fogging properties. In the film of Example 6, the durability is particularly excellent.

[0309] On the other hand, it can be seen that in the film of Comparative Example 1 not containing a blocked isocyanate silane compound, the anti-fogging property disappears after immersion in water for 5 minutes, and the water resistance is poor. In addition, it can be seen that the compositions of Comparative Example 2 containing an unblocked isocyanate silane compound and Comparative Example 3 containing 3-glycidyloxypropyltrimethoxysilane have poor storage stability.

[0310] In addition, it is found that the cured film obtained from the composition of Comparative Example 4 to which the blocked isocyanate silane compound was added in an excessive amount has poor anti-fogging properties.

Claims

1. A hydrophilic composition comprising: (A) a hydrophilic copolymer comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): 100 parts by mass; and (B) blocked isocyanate silane compound: 0.001 to 10 parts by mass, [Chemistry 1] In formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 Each independently represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X 1 represents -NH- or -O-, n represents an integer from 1 to 6, Y 1- represents a monovalent anion, In formula (2), R 3 represents a hydrogen atom or a methyl group, X 2 Indicates -NH- or -O-, Y 2 is a monovalent functional group selected from a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group, an acid anhydride group and an alkoxysilyl group, and m represents an integer of 0 to 10. However, when m is 0, Y 2 represents a hydrogen atom, and an asterisk * represents a bond to an adjacent structural unit.

2. The hydrophilic composition according to claim 1, wherein The (B) blocked isocyanate silane compound is represented by the following formula (4): [Chemistry 2] In the formula, R 6 Each independently represents an alkyl group having 1 to 8 carbon atoms, L represents a divalent linking group, and X 4 Indicates -O- or -NR 7 -, Y 3 represents a hydrogen atom or a monovalent organic group, R 7 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or may be combined with Y 3 A group that is bonded to form a ring structure, and k represents an integer of 1 to 3.

3. The hydrophilic composition according to claim 2, wherein The (B) blocked isocyanate silane compound is represented by the following formula (5) or (6): [Chemistry 3] In the formula, R 6 , R 7 , Y 3 and k have the same meanings as above, R 8 and R 9 Each independently represents a hydrogen atom or a monovalent organic group, R 8 With R 9 or R 7 With Y 3 Can be connected to each other to form a ring structure.

4. The hydrophilic composition according to claim 1, further comprising at least one compound selected from the group consisting of a polyisocyanate compound, an organosilicon compound represented by the following formula (7), and an organosilicon compound represented by the following formula (8), [Chemistry 4] In formula (7), R 10 and R 11 each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, j represents an integer of 1 to 10, and i represents an integer of 1 to 3, In formula (8), R 12 , R 13 , R 14 and R 15 Each independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms, and h represents an integer of 1 to 20.

5. A coating agent comprising the hydrophilic composition according to any one of claims 1 to 4.

6. A hydrophilic film formed by curing the coating agent according to claim 5.

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