Hydrophilic composition

Abstract

To provide a hydrophilic composition including a hydrophilic copolymer that yields a coating film having exceptional hydrophilicity, anti-fogging properties, and water resistance.SOLUTION: A hydrophilic composition includes (A) 100 pts.mass of a hydrophilic copolymer including structural units represented by formula (1) and structural units represented by formula (2) and (B) 0.001-10 pts.mass of a blocked isocyanate silane compound. [In formula (1), R1 represents a hydrogen atom or a methyl group, R2 each independently represent a C1-6 alkyl group, and n represents an integer of 1-6. In formula (2), R3 represents a hydrogen atom or a methyl group, X1 represents -NH- or -O-, Z1 represents a hydrogen atom, a methyl group, a hydroxyl group, a carboxy group, or an amino group, and m represents an integer of 0-10 (however, when m is 0, Z1 is a hydrogen atom or a methyl group.) An asterisk * represents bonding to an adjacent structural unit.]SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to hydrophilic compositions, coatings, hydrophilic films and coated articles. [Background technology]

[0002] In recent years, there has been an increasing demand for improvement in the fogging of substrates made of organic materials such as plastics and inorganic materials such as glass. Improvement of the fogging of a substrate is generally achieved by coating the surface of the substrate with a hydrophilic film. For example, Patent Document 1 proposes a coating composition containing a hydrophilic copolymer having a highly hydrophilic quaternary ammonium salt structure as a coating agent capable of imparting hydrophilicity to a substrate.

[0003] However, the coating film formed by the above coating composition does not have sufficient water resistance, and surface properties such as hydrophilicity and antifogging properties may deteriorate when the coating film comes into contact with water, and further improvement is desired. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2018-162431 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a hydrophilic composition (coating agent) containing a hydrophilic copolymer that provides a coating film excellent in hydrophilicity, antifogging properties and water resistance, a hydrophilic coating obtained from the composition, and a coated article having the coating. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors have conducted intensive research in order to achieve the above object, and have found that a composition containing a specific hydrophilic copolymer and a blocked isocyanate silane compound can provide a coating film that has excellent water resistance and can impart long-lasting 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.

[0007] That is, the present invention provides 1. (A) a hydrophilic copolymer including a constitutional unit represented by the following formula (1) and a constitutional unit represented by the following formula (2): 100 parts by mass, and (B) a hydrophilic composition comprising 0.001 to 10 parts by mass of a blocked isocyanate silane compound; [ka] [In formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6, In formula (2), R 3 represents a hydrogen atom or a methyl group, and X 1 represents -NH- or -O-; Z 1 represents a hydrogen atom, a methyl group, a hydroxyl group, a carboxyl group, or an amino group, and m represents an integer of 0 to 10 (provided that when m is 0, Z 1 is a hydrogen atom or a methyl group.) An asterisk * indicates a bond to the adjacent structural unit. 2. The (B) blocked isocyanate silane compound is a hydrophilic composition 1 represented by the following formula (3): [ka] (In the formula, R 4 each independently represents an alkyl group having 1 to 8 carbon atoms; L represents a divalent linking group; X 2 is -O- or -NR 5 - represents Z 2 represents a hydrogen atom or a monovalent organic group, R 5 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or Z2 represents a group capable of forming a ring structure by bonding with, 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 (4) or (5): [ka] (In the formula, R 4 , R 5 , Z 2 and k have the same meaning as above, R 6 and R 7 each independently represents a hydrogen atom or a monovalent organic group, R 6 and R 7 or R 5 and Z 2 may be linked to each other to form a ring structure. 4. The hydrophilic composition according to any one of 1 to 3, further comprising at least one compound selected from the group consisting of a polyisocyanate compound, an organosilicon compound represented by the following formula (6), and an organosilicon compound represented by the following formula (7): [ka] (In formula (6), R 8 and R 9 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 (7), R 10 , R 11 , R 12 and R 13 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 1 to 4. 6. A hydrophilic coating obtained by curing the coating agent of 5. 7. A coated article having a substrate and a hydrophilic coating 6 formed on at least one surface of the substrate directly or via one or more other layers. to provide. Effect of the Invention

[0008] The hydrophilic composition of the present invention provides a coating film which is excellent in water resistance and can impart long-lasting hydrophilicity and anti-fogging properties to substrates such as glass. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention will be specifically described below. (A) Hydrophilic copolymer The hydrophilic copolymer used in the present invention (hereinafter also referred to simply as "copolymer" or "component (A)") contains specific contents of the structural units (a) and (b) described below.

[0010] [1] Structural unit (a) The structural unit (a) is represented by the following formula (1).

[0011] [ka] (In the formula, the asterisk * has the same meaning as above.)

[0012] In formula (1), R 1 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom. R 2 are each independently an alkyl group having 1 to 6 carbon atoms. 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 groups. Among these, R 2 From the viewpoint of improving the hydrophilicity of the coating film, is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. n is an integer of 1 to 6, and n is preferably 2 or 3.

[0013] 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.

[0014] [ka] (In the formula, the asterisk * has the same meaning as above.)

[0015] [2] Structural unit (b) The structural unit (b) is represented by the following formula (2).

[0016] [ka] (In the formula, the asterisk * has the same meaning as above.)

[0017] In the above formula (2), R 3 is a hydrogen atom or a methyl group, and is preferably a methyl group. X 1 is -NH- or -O-, preferably -O-. Z 1 is a hydrogen atom, a methyl group, a hydroxyl group, a carboxyl group or an amino group, and preferably a hydrogen atom or a hydroxyl group. However, when m is 0, Z 1 is a hydrogen atom or a methyl group.

[0018] m is an integer of 0 to 10, preferably an integer of 0 to 6, more preferably an integer of 1 to 4, and even more preferably an integer of 2 to 4.

[0019] The hydrophilic copolymer used in the present invention can form a crosslinked structure between the blocked isocyanate silane and the copolymer by using (B) in combination and performing heat treatment. In addition, for example, when the hydrophilic copolymer is used in combination with a curing catalyst such as an acid catalyst, the copolymer itself can undergo a crosslinking reaction (self-crosslinking). Therefore, the coating film formed from the composition containing the hydrophilic copolymer of the present invention and a curing agent has a crosslinked structure and can exhibit excellent water resistance.

[0020] From this viewpoint, in the above formula (2), m is an integer of 1 to 4, and Z 1 However, a hydroxyl group is more preferred.

[0021] Specific examples of the structural unit (b) represented by the above formula (2) include those represented by the following formulas, but are not limited to these.

[0022] [ka] (In the formula, the asterisk * has the same meaning as above.)

[0023] 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 even more preferably 15 to 40% by mass. If the content of the structural unit (a) is less than 5% by mass, the hydrophilicity of the copolymer becomes insufficient, and the surface hydrophilicity of the coating film may decrease when the coating film is formed. On the other hand, if the content of the structural unit (a) exceeds 60% by mass, the hydrophilicity of the copolymer becomes too high, and the water resistance of the coating film may decrease when the coating film is formed. Furthermore, in the hydrophilic copolymer used in 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 even more preferably 40% by mass or more. If 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 the surface hydrophilicity of the coating film may decrease when the coating film is formed. There is no particular upper limit, and only the structural unit (a) and the structural unit (b) may be used, but it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less.

[0024] [3] Other structural units The hydrophilic copolymer used in the present invention may contain, in addition to the above-mentioned structural units, for example, a structural unit represented by the following formula (8), provided that the object of the present invention is not impaired.

[0025] [ka] (In the formula, the asterisk * has the same meaning as above.)

[0026] In the above formula (8), R 14 is a hydrogen atom or a methyl group. X 3 is -NH- or -O-, preferably -O-. A' is an alkylene group having 1 to 6 carbon atoms, specific examples of which include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene groups, etc. Among these, an alkylene group having 1 to 3 carbon atoms is preferred, and an ethylene group is more preferred. R 15 is an alkyl group having 1 to 6 carbon atoms or a hydrolyzable silyl group, and specific examples of the alkyl group having 1 to 6 carbon atoms include the above-mentioned R 2 Among them, a methyl group is preferable. Examples of hydrolyzable silyl groups include alkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, dimethoxysilyl, diethoxysilyl, monomethoxysilyl, and monoethoxysilyl groups; carboxylate silyl groups such as acetoxysilyl groups; halosilyl groups such as trichlorosilyl, dichlorosilyl, and monochlorosilyl groups; aminosilyl groups; oximesilyl groups; and hydrosilyl groups. f is an integer of 1 to 10, preferably an integer of 2 to 8, and more preferably an integer of 3 to 6.

[0027] 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 even more preferably from 5 to 50% by mass. The order of the respective structural units contained in the hydrophilic copolymer may be arbitrary, that is, the hydrophilic copolymer may be any of an alternating copolymer, a random copolymer, and a block copolymer.

[0028] In the present invention, from the viewpoint of improving the affinity with organic solvents and the hardness of the coating film, the weight average molecular weight of the hydrophilic copolymer is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, even more preferably 10,000 to 30,000, and still more preferably 15,000 to 20,000. The weight average molecular weight is a value determined by gel permeation chromatography (GPC) (standard substance: polyethylene glycol / polyethylene oxide).

[0029] From the viewpoints of compatibility with organic solvents and workability, the viscosity of the hydrophilic copolymer is preferably 0.01 to 0.5 Pa·s (at 25° C.) The viscosity is a value measured by a rotational viscometer. Furthermore, the glass transition temperature of the hydrophilic copolymer is preferably −10 to 50° C. The glass transition temperature is a value measured based on JIS K7121.

[0030] [4] Method for producing hydrophilic copolymer The hydrophilic copolymer used in the present invention can be obtained, for example, as shown in the following scheme, by polymerizing a polymerizable monomer having a (meth)acrylamide group, as represented by the following formula (9), and a polymerization initiator having a (meth)acryl group and / or a (meth)acrylamide group, as represented by the following formula (10), under an inert gas atmosphere such as nitrogen.

[0031] [ka] (In the formula, R 1 , R 2 , R 3 , X 1 , Z 1 , m, and n are the same as above.)

[0032] As the polymerizable monomer containing a (meth)acrylamide group of the above formula (9), a commercially available product may be used, such as DMAPAA (registered trademark) manufactured by KJ Chemicals Co., Ltd.

[0033] The polymerization initiator is preferably a thermal polymerization initiator, and the amount of the polymerization initiator added is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 2 to 10% by mass, based on the total mass of the monomers to be copolymerized. The polymerization initiator may be added all at once or in several portions.

[0034] The above reaction can be carried out without a solvent, but can also be carried out in an organic solvent such as methyl ethyl ketone, 1,2-dimethoxyethane, etc., if necessary, as long as the reaction is not inhibited. The reaction temperature is preferably from 0° C. to the boiling point of each solvent, and more preferably from 20 to 80° C. The reaction time is preferably from 1 to 24 hours, and more preferably from 5 to 10 hours.

[0035] The hydrophilic copolymer obtained by the above method may be mixed with additives after adjusting the solid content concentration, exchanging the solvent, or filtering, if necessary. The hydrophilic copolymer produced by polymerization may be purified by precipitation or reprecipitation with hexane or the like, and dissolved together with additives in a solvent according to the application.

[0036] (B) Blocked isocyanate silane compound The blocked isocyanate silane compound of component (B) is a component that acts as a curing agent for the hydrophilic copolymer, and in the present invention, an organosilicon compound represented by the following formula (3) is preferred. In addition to the blocked isocyanate silane alone, structures in which the hydrolyzable silyl group portion is partially hydrolyzed and partial hydrolysis condensates which have been further intermolecularly condensed to form oligomers also exhibit similar performance and can be used as the curing agent component of the present invention.

[0037] [ka]

[0038] In formula (3), R 4 each independently represents an alkyl group having 1 to 8 carbon atoms; L represents a divalent linking group; X2 is -O- or -NR 5 - represents Z 2 represents a hydrogen atom or a monovalent organic group, R 5 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or Z 2 represents a group capable of bonding to form a ring structure, and k represents an integer of 1 to 3.

[0039] R 5 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 groups, and among these, a methyl group and an ethyl group are preferred.

[0040] Specific examples of the divalent linking group of L include an alkylene group, -O-, -S-, -NR-, CO-, -COO-, -NRCO-, -SO2-, and combinations thereof. Here, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom is preferable. The alkyl group may be any of the alkyl groups exemplified above having 1 to 4 carbon atoms. Among these, the divalent linking group -(CH2) is preferred due to the availability of raw materials for producing organosilicon compounds. p -(p is an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 4), or the -(CH2) p Among these, groups in which one or more methylene units are replaced by -O-, -S-, -NH-, -CO- and -COO- are preferred, and -(CH2)3- (trimethylene group) is more preferred.

[0041] X 2 is -O- or -NR 5 However, since - is a group that forms a part of the protecting group of the blocked isocyanate silane compound and is eliminated by heating, there is no particular limitation. X 2 -NR 5 - In R5 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or Z 2 represents a group capable of bonding to form a ring structure. R 5 The alkyl group having 1 to 8 carbon atoms is the same as the above R 4 Among them, 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. -NR 5 - In R 5 Z 2 When the group represents a group capable of forming a ring structure by bonding with 5 - is Z in formula (1). 2 and form a nitrogen-containing heterocyclic structure. Such a heterocyclic structure preferably contains two or more nitrogen atoms, more preferably contains two nitrogen atoms. The heterocyclic structure is preferably a 5-membered or 6-membered ring structure, more preferably a 5-membered ring structure. Such a heterocyclic structure is preferably an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, or a 1,2,4-triazole ring, more preferably a pyrazole ring. The 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 carboxy group, a hydroxyl group, an ester group, or an oxo group (=O). Suitable ring structures include, but are not limited to, the following:

[0042] [ka]

[0043] Z 2 is a hydrogen atom or a monovalent organic group, but is not particularly limited since it is a group that forms a part of the protecting group of the blocked isocyanate silane compound and is eliminated by heating. Z 2 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-), and -N=R 17(R 17 represents an alkylidene group having 1 to 10 carbon atoms which may be substituted with an aryl group having 6 to 20 carbon atoms.) The monovalent hydrocarbon group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and examples thereof include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Specific examples of the alkyl group include R 4 In addition to the groups exemplified above, examples thereof include n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, and icosyl groups. Specific examples of the aryl group include phenyl and naphthyl groups. Specific examples of the aralkyl group include benzyl and phenylethyl groups. In addition, at least a portion of the hydrogen atoms of these groups may be substituted with other substituents, and examples of such other substituents include a carboxy group, an ester group, and a hydroxyl group.

[0044] R 17 The alkylidene group having 1 to 10 carbon atoms which may be substituted by an aryl group or heteroaryl group having 6 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methylidene, phenylmethylidene, diphenylmethylidene, ethylidene, propylidene, propan-2-ylidene, butylidene, butan-2-ylidene, pentylidene, 4-methylpentan-2-ylidene, hexylidene, cyclohexylidene, heptylidene, octylidene, nonylidene, and decylidene groups. Specific examples of the aryl group having 6 to 20 carbon atoms include the above Z 2 Examples of the groups include the same groups as those exemplified in the above. 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 groups.

[0045] In particular, the blocked isocyanate silane compound represented by the above formula (3) is preferably one represented by the following formula (4) or (5).

[0046] [ka] (In the formula, R 4 , R 5 , Z 2 and k have the same meaning as above.)

[0047] Above R 6 and R 7 Examples 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. Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include the above Z 2 Examples of the groups include the same as those exemplified in 1., but an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferred, and specific examples thereof include the same as those mentioned above. The heteroaryl group having 6 to 20 carbon atoms includes the above-mentioned R 5 Examples of the groups include the same groups as those exemplified in the above. R 6 and R 7 Examples of the ring structure formed by linking together include a cyclopentane ring and a cyclohexane ring. These hydrocarbon groups and heteroaryl groups may have a substituent, specific examples of which include a carboxy group, a hydroxyl group, and an ester group. R 6 -Methylidene-R 7 The group represented by the above R 17 Among them, diphenylmethylidene, propan-2-ylidene, butan-2-ylidene, 4-methylpentan-2-ylidene and cyclohexylidene are preferred.

[0048] R 5 and Z 2Specific examples of are the same as those mentioned above, but among them, it is preferable that they are bonded to each other to form a ring structure together with the nitrogen atom. The ring structure is preferably a 5-membered or 6-membered ring, and more preferably a 5-membered ring. Furthermore, this ring structure preferably has two nitrogen atoms, and is more preferably an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, or a 1,2,4-triazole ring, with a pyrazole ring being even more preferable. The 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 carboxy group, a hydroxyl group, an ester group, or an oxo group (=O). Suitable ring structures include, but are not limited to, the following:

[0049] [ka]

[0050] Preferred specific examples of the blocked isocyanate silane compound of component (B) include the following compounds, but are not limited to these.

[0051] [ka]

[0052] The hydrophilic composition of the present invention (hereinafter also simply referred to as the "composition") contains the above-mentioned components (A) and (B), and specifically, the component (B) is contained in an amount of 0.001 to 10 parts by mass per 100 parts by mass of the component (A). If the content of component (B) is less than the lower limit, the desired water resistance improvement effect is not achieved, whereas if the content exceeds the upper limit, the effect becomes saturated, reducing the cost-effectiveness. In addition, the hydrophobic effect of the original silane coupling agent increases, tending to reduce hydrophilicity. The content of the component (A) in the hydrophilic composition of the present invention is not particularly limited, but from the viewpoint of hydrophilicity, it is preferably 1 to 40 mass % of the total composition, and more preferably 10 to 25 mass %.

[0053] The hydrophilic composition of the present invention may contain other components as necessary within the scope of the object of the present invention, and in particular, it is preferable that the composition contains a curing agent. The curing agent promotes the crosslinking reaction of the hydrophilic copolymer and contributes to the formation of a crosslinked structure inside the coating film. In this case, the curing agent may or may not be incorporated into the crosslinked structure.

[0054] In the case of a curing agent incorporated into a crosslinked structure, the functional group contained in the side chain of the hydrophilic copolymer (specifically, the functional group Z 2 It is preferable that the copolymer has a functional group or structure that undergoes a crosslinking reaction with the alkoxysilyl group of the component (B). In this case, the type of crosslinking may be any of a covalent bond, an ionic bond, a hydrogen bond, and a coordinate bond, but a covalent bond is preferable. As the curing agent to be incorporated into the crosslinked structure, those having, in the molecule, a functional group such as a hydrolyzable silyl group, an isocyanato group, an epoxy group, a carbodiimide group, an oxazolyl group, an epoxy group, a hydroxyl group, a carboxyl group, or an amino group, a molecular structure such as a siloxane structure or a melamine structure, or a metal ion, are preferred.

[0055] Suitable combinations of the functional group of the hydrophilic copolymer side chain capable of crosslinking reaction and the functional group or structure of the curing agent are, for example, as shown in Table 1.

[0056] [Table 1]

[0057] Examples of the curing agent having a hydrolyzable silyl group include a hydrolyzable silyl group and a compound having a siloxane structure containing a hydrolyzable silyl group. Specific examples thereof include a compound represented by the following formula (6), a compound represented by the following formula (7), and a hydrolysis condensate of a compound represented by the following formula (7).

[0058] [ka]

[0059] In the above formula (6), R 8 and R 9 are each independently 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. R 8 and R 9 The alkyl group may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, and cyclohexyl groups. R 8 and R 9 Specific examples of the aryl group include phenyl and tolyl groups. Among these, R 8 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group; R 9 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. In the above formula (6), j is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and even more preferably an integer of 2 to 4. "i" is an integer of 1 to 3, and is preferably 3.

[0060] Specific examples of the compound represented by the above formula (6) include N,N,N-tris(trimethoxysilylpropyl)isocyanurate, N,N,N-tris(triethoxysilylpropyl)isocyanurate, and the like, but are not limited to these.

[0061] In the above formula (7), R 10 , R 11 , R 12 and R 13 each independently represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. In formula (7), R 10 , R 11 , R 12 and R13 The monovalent organic group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and examples thereof include an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, and cyclohexyl groups. Specific examples of the alkenyl group having 2 to 6 carbon atoms include vinyl and allyl groups. Among these, R 10 , R 11 , R 12 and R 13 From the viewpoint of hydrolysis, the monovalent organic group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.

[0062] In formula (7), h represents an integer of 1 to 20, preferably an integer of 3 to 12, and more preferably an integer of 5 to 12. When h is 20 or less, the viscosity of the coating liquid is not too high, and an anti-fogging film with high uniformity can be formed. When h is 1 or more, the reactivity of the compound represented by formula (5) is easily controlled, and an anti-fogging film with excellent hydrophilicity can be formed.

[0063] In the present invention, the term "condensation product of the compound represented by formula (7)" refers to a condensation product of the compound represented by formula (7) that is a Si-OR 10 , Si-OR 11 , Si-OR 12 , and Si-OR 13 It means a compound having a structure in which a siloxane bond (Si-O-Si) is formed in at least one of the above. The condensate of the compound represented by formula (7) can be formed, for example, by condensing or hydrolytic condensing two or more molecules of the compound represented by formula (7) with each other. Regarding hydrolytic condensation, R in formula (7) 10 , R 11 , R 12 and R 13In 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. The structure of the hydrolysis condensate of the compound represented by formula (7) is not particularly limited, and examples thereof include a random type, a linear type, a ladder type, and a cage type.

[0064] In the compound represented by formula (7) and its hydrolysis condensation product, R 10 , R 11 , R 12 and R 13 When R contains a hydrogen atom, the hydrogen atom may be a hydrogen atom contained in a compound added as a raw material during the production of the compound of formula (7), or may be a hydrogen atom introduced by hydrolysis. 10 , R 11 , R 12 and R 13 When at least one of the Si-OH groups is a hydrogen atom, at least one of the Si-OH groups in formula (7) may be a Si-OH group contained in a compound added as a raw material during the production of the compound of formula (7), or may be a Si-OH group formed by hydrolysis.

[0065] The compound represented by formula (7) may be a commercially available product. For example, the compound represented by formula (7) is available as MKC (registered trademark) silicate (for example, MS51, MS56) manufactured by Mitsubishi Chemical Corporation.

[0066] The weight-average molecular weight (Mw) of the compound represented by formula (7) is preferably 300 to 1,500, and more preferably 500 to 1,200. The weight-average molecular weight is a value determined by gel permeation chromatography (GPC) (standard substance: polyethylene glycol / polyethylene oxide).

[0067] Examples of the curing agent having an isocyanato group include aliphatic, alicyclic or aromatic polyisocyanates. Specific examples of the isocyanate include isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, tolylene diisocyanate, polymeric MDI, naphthalene diisocyanate, tetramethylxylylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, methylenebis(4,1-cyclohexylene)diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, adducts of diisocyanate compounds and polyol compounds such as trimethylolpropane, and isocyanate derivatives such as biuret and isocyanurate of diisocyanate compounds. Among these, polyisocyanates derived from hexamethylene diisocyanate are preferred from the viewpoint of suppressing yellowing of the coating film. The curing agent having an isocyanate group is commercially available, and examples thereof that can be used include Duranate (registered trademark) TPA-100, TKA-100, 24A-100, 22A-75P, P301-75E, etc. manufactured by Asahi Kasei Corporation; Coronate (registered trademark) HX, HK, 2715, etc. manufactured by Tosoh Corporation; and Takenate (registered trademark) 500, 600, etc. manufactured by Mitsui Chemicals, Inc. These may be used alone or in combination of two or more.

[0068] As the curing agent having a melamine structure, a melamine resin is preferable, and specific examples thereof include guanamine, melamine, N-butylmelamine, N-phenylmelamine, N,N-diphenylmelamine, N,N-diallylmelamine, N,N',N"-triphenylmelamine, N,N',N"-trimethylolmelamine, benzoguanamine, 2,4-diamino-6-methyl-sym-triazine, 2,4-diamino-6-butyl-sym-triazine, 2,4-diamino-6-benzol, Examples of such melamines include condensates of melamines such as 2,4-diamino-6-butoxy-sym-triazine, 2,4-diamino-6-cyclohexyl-sym-triazine, 2,4-diamino-6-chloro-sym-triazine, 2,4-diamino-6-mercapto-sym-triazine, and amerin (N,N,N',N'-tetracyanoethylbenzoguanamine) with formaldehyde and alcohols (e.g., methanol, etc.). The curing agent having a melamine structure is commercially available, and examples of the curing agent that can be used include U-BAN (registered trademark) 20SE and 225 manufactured by Mitsui Chemicals, Inc.; and Amidea (registered trademark) L-117-60, L-109-65, 47-508-60, L-118-60, G821-60, and J820-60 manufactured by DIC Corporation. These may be used alone or in combination of two or more.

[0069] Examples of the curing agent having an epoxy group include aliphatic, alicyclic or aromatic diepoxy compounds and triepoxy compounds. Specifically, 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 type 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-hexanediyl)bisoxirane, 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-p-menthane, 1,6-diepoxynaphthalene, triepoxydecane, and the like. These may be used alone or in combination of two or more.

[0070] Examples of the curing agent having an amino group include aliphatic, alicyclic or aromatic diamines, triamines, tetraamines, etc. that contain a primary amine or a secondary amine. Specifically, 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-dimethyl 2,6-dimethylbenzene-1,4-diamine, 2,4-dimethylbenzene-1,3-diamine, 3,5-dimethyl-1,2-benzenediamine, 4-ethylbenzene-1,3-diamine, 2,5-dimethylbenzene-1,4-diamine, 4-methoxybenzene-1,3-diamine, 4-(1,1-dimethylethyl)-1,2-benzenediamine, paraphenylenediamine, orthophenylenediamine, N-isopropyl-1,3-propanediamine, N-hexylethylenediamine, 5-isopropylaminoamyl amylate amine, n-butylethylenediamine, N-tertiary butylbutane-1,4-diamine, N-ethylhexane-1,6-diamine, n-isobutylethane-1,2-diamine, N-cyclohexyl-1,2-ethanediamine, 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-aminodiphenylamine, 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'-diethylbutylenediamine, 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-propanediamine, 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-benzenediamine, 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-Methyl 1-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. These may be used alone or in combination of two or more.

[0071] Examples of curing agents having a carbodiimide group include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, and N-isopropyl-N'-[2-(methacryloyloxy)ethyl]carbodiimide. These may be used alone or in combination of two or more.

[0072] 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. These may be used alone or in combination of two or more.

[0073] Examples of hardeners having metal ions include aluminum organic compounds such as aluminum ethyl acetoacetate diisopropylate.

[0074] Among these, from the viewpoint of ease of handling, a curing agent having an isocyanato group or a melamine structure is preferred. 1 It is more preferable to combine a hydrophilic copolymer containing a structural unit (b) in which Z is a hydroxyl group with a curing agent having an isocyanato group or a melamine structure. 1 It is more preferable to combine a hydrophilic copolymer containing a structural unit (b) in which is a hydroxyl group with a polyisocyanate or a melamine resin. That is, a preferred embodiment of the present invention is a hydrophilic composition containing the above hydrophilic copolymer and a polyisocyanate or a melamine resin as a curing agent. 1 In the case of a combination of a hydrophilic copolymer containing a structural unit (b) in which R is a hydroxyl group and a curing agent having an isocyanato group (polyisocyanate), the crosslinking reaction proceeds even under low temperature conditions (for example, 110°C or lower), and a coating film can be formed from the composition according to the present invention even on a substrate having low heat resistance, which is particularly preferred.

[0075] On the other hand, examples of the curing agent (curing catalyst) that is not incorporated into the crosslinked structure include inorganic acids, organic acids, organometallic salts, Lewis acids, and the like. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, and sulfamic acid. 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. 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. Examples of Lewis acids include tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, tin chloride (SnCl4), titanium chloride (TiCl4), and zinc chloride (ZnCl4). Additionally, alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, dioctyltin dioctoate, and dioctyltin diversatate can also be suitably used. These may be used alone or in combination of two or more. Furthermore, a curing agent that is incorporated into the crosslinked structure and a curing agent (curing catalyst) that is not incorporated into the crosslinked structure may be used in appropriate combination.

[0076] 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.

[0077] The hydrophilic composition of the present invention preferably further contains a hydrophilic organosilicon compound represented by the following formula (10) and / or a hydrolysis condensate thereof.

[0078] [ka]

[0079] In formula (10), R 18 and R19 are each independently 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. Specific examples of these alkyl groups and aryl groups include R 6 Examples of the groups include the same groups as those exemplified in 1. Among these, a methyl group is preferred. R 20 is a divalent organic group containing an aromatic ring having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms; a divalent organic group containing an aromatic hydrocarbon ring is preferred; a divalent organic group containing a benzene ring or a naphthalene ring is more preferred; and an arylene group or aralkylene group containing a benzene ring or a naphthalene ring is even more preferred. R 20 Specific examples of the arylene group include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, and naphthylene groups. R 20 Specific examples of the aralkylene group include methylenephenylene, ethylenephenylene, methylenephenylenemethylene, and ethylenephenyleneethylene groups. Among these, R 18 is preferably a phenylene group, more preferably a 1,4-phenylene group. R 21 and R 22 Each independently represents an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include R 6 Among the groups exemplified in 1, the same groups having 1 to 6 carbon atoms can be mentioned, and among these, a methyl group is preferred. X 5 represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. 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 groups. Among these, X 5is preferably a methylene, ethylene or trimethylene group, more preferably a trimethylene group. Z 4 is COO - , SO3 - , or PO4 - From the viewpoint of the durability of the resulting coating film, - is preferred. o is an integer of 1 to 3, with 3 being preferred.

[0080] Specific examples of such hydrophilic organosilicon compounds are shown below, but are not limited to these. Among these, the compound represented by formula (11) is preferred.

[0081] [ka] (In the formula, Me represents a methyl group, and Et represents an ethyl group.)

[0082] 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.

[0083] The hydrophilic composition of the present invention may contain a solvent as necessary. The solvent is not particularly limited as long as it can dissolve or disperse the hydrophilic copolymer, optionally the curing agent, the hydrophilic organosilicon compound and other additives, does not react with each component, and can be easily removed in the drying step described below. 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, and water. For example, when polyisocyanate is used as a curing agent, it is preferable to use a solvent that does not react with an isocyanato group (for example, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone). These may be used alone or in combination of two or more.

[0084] The hydrophilic composition of the present invention may further contain additives, such as a pigment, a film-forming aid, a filler, a toner, a wetting agent, an antistatic agent, a pigment dispersant, a plasticizer, an antioxidant, a flow control agent, a viscosity modifier, an antifoaming agent, an ultraviolet absorbing agent, and a dispersant, as necessary.

[0085] From the viewpoints of coatability and workability, the solid content concentration of the composition is preferably from 5 to 80% by mass, and more preferably from 10 to 30% by mass. The viscosity of the composition is preferably 0.01 to 0.05 Pa·s (at 25° C.) from the viewpoints of coatability and workability. The composition of the present invention may be a one-liquid type, or may be a type in which two or more liquids are mixed before use.

[0086] The composition of the present invention can impart hydrophilicity to various substrates by applying it to the substrates. Specific examples of materials constituting the above-mentioned substrate include, for example, 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, urethane 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-chlorotrifluoro ethylene copolymer resins, etc.), polybutadiene, polyisopropylene, SBR, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, neoprene rubber, polysulfide, butyl rubber, etc.}; metals (iron, aluminum, stainless steel, titanium, copper, brass, alloys thereof, etc.); cellulose, cellulose derivatives, cellulose analogues (chitin, chitosan, porphyran, 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, polyaramid fibers, etc.; composite fibers of these fibers (polyester / cotton, etc.), and the like, and examples of the form of such fibers include substrates, sheets, films, fibers, and various articles using these.

[0087] The composition of the present invention can be applied to a known coating method to form a coating film on the surface of a substrate or the like, thereby forming a hydrophilic coating film. Examples of the coating method include bar coating, dip coating, spin coating, spray coating, float coating, brush coating, gravure coating, roll transfer, blade coating, air knife coating, slit coating, screen coating, inkjet printing, and flexographic printing. Among these, bar coating is preferred.

[0088] After applying the composition onto a substrate, a cured coating film can be obtained by heating. The heating temperature is preferably 40 to 250° C., and more preferably 80 to 120° C. The drying time is preferably 10 seconds to 12 hours, and more preferably 30 seconds to 3 hours. Pre-drying may be carried out under the same conditions as above to remove the solvent from the composition. The heating atmosphere may be either an air atmosphere or an inert gas (eg, nitrogen, argon, etc.) atmosphere.

[0089] 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, and more preferably 1 to 10 μm. EXAMPLES

[0090] 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.

[0091] (1) Preparation of hydrophilic copolymer [Synthesis Example 1] Into a reactor, 258.35 g of methyl ethyl ketone, 101.55 g of DMAPAA (registered trademark, manufactured by KJ Chemicals Co., Ltd.) represented by the following formula (12), 5.81 g of hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula (13), and 3.36 g of an oil-soluble azo polymerization initiator V-59 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) represented by the following formula (14) were added, and the reaction was carried out at 80° C. for 4 hours. After the reaction, 216.00 g of 2-propanol (IPA) was added, and the mixture was filtered to obtain 360 g of a methyl ethyl ketone-IPA (3:2, wt / wt) solution (solid concentration 25 mass%, designated A-1) of hydrophilic copolymer P1 (content of structural unit (a) 93 mass%, content of structural unit (b) 7 mass%, weight average molecular weight 400,000).

[0092] [ka]

[0093] [Synthesis Example 2] Into a reactor, 258.23 g of methyl ethyl ketone, 101.55 g of DMAPAA (registered trademark, manufactured by KJ Chemicals Co., Ltd.) represented by the above formula (12), 5.76 g of HEAA (registered trademark, manufactured by KJ Chemicals Co., Ltd.) represented by the following formula (15), and 3.36 g of an oil-soluble azo polymerization initiator V-59 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) represented by the above formula (14) were added, and the reaction was carried out at 80° C. for 4 hours. After the reaction, 216.00 g of 2-propanol (IPA) was added, and the mixture was filtered to obtain 360 g of a methyl ethyl ketone-IPA (3:2, wt / wt) solution (solids concentration 25% by mass, designated A-2) of hydrophilic copolymer P2 (content of structural unit (a) 93% by mass, content of structural unit (b) 7% by mass; weight average molecular weight 420,000).

[0094] [ka]

[0095] (2) Preparation of coating composition (hydrophilic composition) [Examples 1 to 12, Comparative Examples 1 to 10] The following components were mixed in the formulations (parts by mass) shown in Tables 2 and 3 below to prepare hydrophilic compositions.

[0096] [Table 2]

[0097] [Table 3]

[0098] In Table 1, the abbreviations are as follows: A-1: Methyl ethyl ketone-IPA solution of hydrophilic copolymer P1 obtained in Synthesis Example 1 A-2: Methyl ethyl ketone-IPA solution of hydrophilic copolymer P2 obtained in Synthesis Example 2 B-1: A silane compound represented by the above formula (8-a) B-2: A silane compound represented by the above formula (8-b) B-3: A silane compound represented by the above formula (4-a) B'-1: 3-Glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-403) B'-2: 3-isocyanatepropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-9007) C-1: Tris-(trimethoxysilylpropyl)isocyanurate (Shin-Etsu Chemical Co., Ltd., KBM-9659) C-2: MKC (registered trademark) silicate MS51 (manufactured by Mitsubishi Chemical Corporation), which is a partially hydrolyzed oligomer of tetramethoxysilane. D-1: A silane compound represented by the above formula (11) Neostan U-830: Dioctyl tin catalyst (manufactured by Nitto Kasei Co., Ltd.)

[0099] (3) Evaluation of storage stability of hydrophilic composition Immediately after preparing the hydrophilic compositions according to each of the above Examples and Comparative Examples, 40 g of each composition was weighed into a 50 mL polyethylene container and left to stand in an incubator (SPHH-201, Espec Corporation) set at 40°C for 3 months. After 3 months, the composition was taken out of the dryer and allowed to stand for 1 hour under conditions of 25°C / 50% relative humidity, and then the composition was observed. The evaluation criteria for storage stability are as follows. ○: The composition maintained its fluidity ×: The composition was solidified into a gel.

[0100] (4) Preparation and evaluation of coating film Immediately after preparing the hydrophilic compositions in each of the above Examples and Comparative Examples, each was applied to a polycarbonate plate using a bar coater (No. 14), and immediately thereafter dried at 120°C for 1 hour to obtain a hydrophilic coating. The following tests were carried out on the obtained coating, and the results are shown in Table 3.

[0101] [Anti-fogging properties] Breath was blown onto each of the above coatings, and if the surface of the coating became cloudy, it was marked with an X, and if it did not become cloudy, it was marked with an O. Furthermore, the coating was placed above a 40°C warm water bath at a height of 3 cm above the water surface for 1 minute, and if the surface of the coating did not become cloudy, it was marked with an ⊚ to evaluate the anti-fogging property.

[0102] 〔water resistance〕 Each of the above coating films was immersed in tap water at 25° C. for 24 hours, the water on the surface was wiped off with a paper wiper, and then the film was naturally dried at 25° C. for 10 minutes, and the above anti-fogging properties were evaluated. Next, each coating was further immersed in tap water for 240 hours, the water on the surface was wiped off with a paper wiper, and then the coating was naturally dried at 25° C. for 10 minutes, and the anti-fogging properties were evaluated.

[0103] [Moisture resistance] Each of the coatings was left to stand for 240 hours in a thermohygrostat (KCL-2000W, Tokyo Rikakikai Co., Ltd.) set at 50° C. and 98% RH, and then naturally dried at 25° C. for 10 minutes, and the antifogging properties were evaluated.

[0104] [Table 4]

[0105] As shown in Table 4, the compositions of Examples 1 to 12 containing a blocked isocyanate silane compound have good storage stability, and maintain excellent hydrophilicity and antifogging properties even after water resistance tests (24 hours of water immersion, 240 hours of water immersion) and moisture resistance tests (50°C, 98% RH, 240 hours). It can be seen that the coating of Example 6 is particularly excellent in durability. On the other hand, the coatings of Comparative Examples 1 and 6, which do not contain a blocked isocyanate silane compound, lost their antifogging properties after 24 hours of water immersion, indicating poor water resistance. Also, the compositions of Comparative Examples 2 and 7, which contain an unblocked isocyanate silane compound, and Comparative Examples 3 and 8, which contain 3-glycidoxypropyltrimethoxysilane, are found to have poor storage stability. Moreover, it is clear that the cured films obtained from the compositions of Comparative Examples 4 and 9, in which an excessive amount of the blocked isocyanate silane compound was added, are inferior in anti-fogging properties.

Claims

1. (A) a hydrophilic copolymer including a constitutional unit represented by the following formula (1) and a constitutional unit represented by the following formula (2): 100 parts by mass, and (B) A hydrophilic composition comprising 0.001 to 10 parts by mass of a blocked isocyanate silane compound. 【Chemistry 1】 [In formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 each independently represents an alkyl group having 1 to 6 carbon atoms; n represents an integer of 1 to 6; In formula (2), R 3 represents a hydrogen atom or a methyl group; X 1 represents -NH- or -O-; Z 1 represents a hydrogen atom, a methyl group, a hydroxyl group, a carboxyl group, or an amino group, and m represents an integer of 0 to 10 (provided that when m is 0, Z 1 is a hydrogen atom or a methyl group.), and an asterisk * indicates a bond to an adjacent structural unit.

2. 2. The hydrophilic composition according to claim 1, wherein the blocked isocyanate silane compound (B) is represented by the following formula (3): 【Chemistry 2】 (In the formula, R 4 each independently represents an alkyl group having 1 to 8 carbon atoms; L represents a divalent linking group; X 2 is -O- or -NR 5 - represents Z 2 represents a hydrogen atom or a monovalent organic group; R 5 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or Z 2 represents a group capable of bonding to form a ring structure, and k represents an integer of 1 to 3.

3. 3. The hydrophilic composition according to claim 2, wherein the blocked isocyanate silane compound (B) is represented by the following formula (4) or (5): 【Chemistry 3】 (In the formula, R 4 , R 5 , Z 2 and k have the same meaning as above, R 6 and R 7 each independently represents a hydrogen atom or a monovalent organic group, R 6 and R 7 Or R 5 and Z 2 may be linked 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 (6), and an organosilicon compound represented by the following formula (7): 【Chemistry 4】 (In formula (6), R 8 and R 9 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 (7), R 10 , R 11 , R 12 and R 13 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 coating film obtained by curing the coating agent according to claim 5.

7. 7. A coated article comprising a substrate and the hydrophilic coating according to claim 6 formed on at least one surface of the substrate directly or via one or more other layers.