Hydrophilic composition

Abstract

To provide a hydrophilic composition including a hydrophilic copolymer that yields a coating film having excellent hydrophilicity, antifogging properties, and water resistance.SOLUTION: A hydrophilic composition contains (A) 100 pts.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 pts.mass of a blocked isocyanate silane compound. (R1 represents H or a methyl group, R2 represents a C1-6 alkyl group, X1 represents -NH- or -O-, n represents an integer of 1-6, Y1- represents a monovalent anion, R3 represents H or a methyl group, X2 represents -NH- or -O-, Y2 represents a monovalent functional group selected from the group consisting of H, hydroxyl groups, carboxy groups, amino groups, acid anhydride groups, and alkoxysilyl groups, m represents an integer of 0-10, and an asterisk * represents a bond to an adjacent structural unit).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In recent years, there has been an increasing demand for improving the fogging of substrates formed of organic materials such as plastics and inorganic materials such as glass. Improvement of fogging of substrates is generally achieved by coating a hydrophilic film on the surface of the substrate. For example, in Patent Document 1, a coating composition is proposed in which a hydrophilic copolymer having a highly hydrophilic quaternary ammonium salt structure is added 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 when it comes into contact with water, surface properties such as hydrophilicity and antifogging properties may deteriorate, and further improvement has been desired.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to provide a hydrophilic composition containing a hydrophilic copolymer that gives a coating film excellent in hydrophilicity, antifogging property, and water resistance.

Means for Solving the Problems

[0006] As a result of intensive studies to achieve the above object, the present inventors have found that a composition containing a specific hydrophilic copolymer and a blocked isocyanate silane compound has excellent water resistance and can provide a coating film that imparts sustainable hydrophilicity and anti-fogging properties to a substrate formed of an organic material such as plastic or an inorganic material such as glass, thereby completing the present invention.

[0007] That is, the present invention relates to 1. A hydrophilic composition comprising: 100 parts by mass of a hydrophilic copolymer containing a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2); and 0.001 to 10 parts by mass of (B) a blocked isocyanate silane compound. [Chemical formula] (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 of 1 to 6, Y 1- represents a monovalent anion, In formula (2), R 3 represents a hydrogen atom or a methyl group, X 2 represents -NH- or -O-, Y 2 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 to 10. However, when m is 0, Y 2 is a hydrogen atom. The asterisk * indicates a bond to an adjacent structural unit.) 2. The hydrophilic composition according to 1, wherein the (B) blocked isocyanate silane compound is one represented by the following formula (4). [Chemical formula] (In the formula, R 6 each independently represents an alkyl group having 1 to 8 carbon atoms, L represents a divalent linking group, X 4 is -O- or -NR7 represents -, and Y 3 represents a hydrogen atom or a monovalent organic group, and R 7 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group capable of combining with Y 3 to form a ring structure, and k represents an integer of 1 to 3.) 3. The (B) blocked isocyanate silane compound is a hydrophilic composition of 2 represented by the following formula (5) or (6),

Chemical formula

Chemical formula

[0008] The hydrophilic composition of the present invention is excellent in water resistance and can provide a coating film that imparts sustainable hydrophilicity and antifogging properties to organic substrates such as plastics and inorganic substrates such as glass. [Embodiments for Carrying Out the Invention]

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

[0010] Hereinafter, each structural unit of the hydrophilic copolymer will be described. The structural unit (a) contained in the hydrophilic copolymer used in the present invention is represented by the following formula (1). Since the ammonium group contained in the structural unit (a) has high hydrophilicity and low affinity with an organic solvent, it is likely to be exposed on the surface of the coating film, and a coating film with a hydrophilic component immobilized on the surface can be obtained.

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

[0012] In formula (1), R 1 is a hydrogen atom or a methyl group, preferably a hydrogen atom. R 2 are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms. R 2 The alkyl group having 1 to 6 carbon atoms of R may be linear, branched, or cyclic. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl groups, etc. R 2 Specific examples of the aryl group having 6 to 18 carbon atoms for R include phenyl, biphenyl, naphthyl, anthryl (anthracenyl), phenanthryl, pyrenyl, naphthacenyl, indenyl, azulenyl, fluorenyl, terphenyl group, and the like. In addition, some or all of the hydrogen atoms bonded to the carbon atoms of these alkyl groups and aryl groups may be substituted with halogen atoms such as chlorine, fluorine, bromine, or other substituents such as a cyano group. Specific examples thereof include chloromethyl, bromoethyl, trifluoropropyl, chlorophenyl, bromophenyl group; cyanoethyl group, and the like. Among these, R 2 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 even more preferably a methyl group, from the viewpoint of improving the surface hydrophilicity of the coating film.

[0013] X 1 is -NH- or -O-, and is preferably -NH- from the viewpoints of improving the surface hydrophilicity and hydrolysis resistance of the coating film. 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.

[0014] Y 1- is an arbitrary monovalent anion, and is preferably a halogen anion (halide ion) or an alkyl sulfate anion (R a -OSO3 - ) from the viewpoint of improving the surface hydrophilicity of the coating film. Y 1- Specific examples of the halogen anion of Y include F - , Cl - , Br - , I - and the like. Y 1- The alkyl sulfate anion (R a -OSO3 - ) is a monovalent anion in which an alkyl group and a sulfoxide anion are linked, and R aThe alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group are the same as those exemplified for R above. 2 Examples thereof include the same ones as those exemplified by R above. Specific examples of the alkyl sulfate anion include methyl sulfate anion, ethyl sulfate anion, and the like. Among these, Cl - , an alkyl sulfate anion having 1 to 3 carbon atoms in the alkyl group is preferred, and Cl - , methyl sulfate anion, and ethyl sulfate anion are more preferred, and Cl - is even more preferred.

[0015] Also, as Y 1- , an anion represented by the following formula (9) is also suitable.

[0016]

Chemical formula

[0017] In formula (9), R 16 is a substituted or unsubstituted linear or branched alkyl group having 12 to 14 carbon atoms. R 16 Specific examples of the alkyl group of R include dodecyl (n-dodecyl, isododecyl, etc.), tridecyl (n-tridecyl, isotridecyl, etc.), tetradecyl (n-tetradecyl, isotetradecyl, etc.) groups, and the like. Some or all of the hydrogen atoms bonded to the carbon atoms of these alkyl groups may be substituted with halogen atoms such as chlorine, fluorine, bromine, or other substituents such as cyano groups. Among these, from the viewpoint of easy availability, dodecyl group and tridecyl group are preferred, and tridecyl group is more preferred. Also, from the viewpoint of further improving the effects of the present invention, the alkyl group having 12 to 14 carbon atoms in R 16 is preferably linear. Therefore, in a preferred embodiment of the present invention, R 16 is a substituted or unsubstituted linear tridecyl group, and an unsubstituted linear tridecyl group is more preferred.

[0018] A is a linear or branched alkylene group having 2 to 4 carbon atoms. 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-), ethyl ethylene (-CH2-CH(CH2CH3)-) groups, and the like.

[0019] g is the average number of moles of addition of -(AO)-, which is a number from 2 to 50. From the viewpoints of the surface hydrophilicity of the coating film and the improvement of workability due to the decrease in the viscosity of the composition, it is preferably a number from 2 to 30, more preferably a number from 2 to 20, and even more preferably a number from 2 to 10.

[0020] That is, in the above formula (5), -(AO) g - represents a polyoxyalkylene group. -(AO) g - preferably contains two or more kinds of oxyalkylene groups, and more preferably contains an oxybutylene group (-C4H8O-). By containing such a group, the hydrophilicity of the copolymer does not become too high, and the affinity with the organic solvent becomes good. The oxybutylene group may be branched and may contain at least one or both of -CH(CH2CH3)-CH2-O- and -CH2-CH2(CH2CH3)-O-. By containing such a group, the affinity with the organic solvent and the surface hydrophilicity of the coating film are further improved. Furthermore, -(AO) g - preferably contains an oxyethylene group (-C2H4O-).

[0021] -(AO) gThe proportion of the oxybutylene group in - is preferably 3 to 90 mol%, more preferably 10 to 80 mol%, still more preferably 20 to 50 mol%, and even more preferably 30 to 40 mol%. When the oxybutylene group has two or more structures, the proportion of the oxybutylene group represents the total of the proportions (mol%) of each structure. Also, -(AO) g When - contains two or more kinds of oxyalkylene groups, the arrangement may be either a random type or a block type. From the viewpoint of further enhancing the surface hydrophilic effect of the coating film, the block type is preferred. In the case of the block type, the order of the arrangement does not matter. That is, for the sulfonic acid group, for example, it may be linked in the order of a polyoxyethylene chain and a polyoxybutylene chain, or vice versa.

[0022] Specific examples of the anion represented by formula (5) include, but are not limited to, those represented by the following formulas. CH3(CH2) 11 O{(CH2)4O)}2{(CH2)2O)}5SO3 - CH3(CH2) 11 O{(CH2)4O)}3{(CH2)2O)}5SO3 - CH3(CH2) 11 O{(CH2)4O)}4{(CH2)2O)}5SO3 - CH3(CH2) 11 O{(CH2)4O)}5{(CH2)2O)}5SO3 - CH3(CH2) 11 O{(CH2)4O)} 10 {(CH2)2O)} 15 SO3 - CH3(CH2) 11 O{(CH2)4O)} 10 {(CH2)2O)} 20 SO3 - CH3(CH2) 12 O{(CH2)4O)}2{(CH2)2O)}5SO3 - CH3(CH2) 12 O{(CH2)4O)}3{(CH2)2O)}5SO3 - CH3(CH2) 12 O{(CH2)4O)}4{(CH2)2O)}5SO3 - CH3(CH2) 12 O{(CH2)4O)}5{(CH2)2O)}5SO3 - CH3(CH2) 12 O{(CH2)4O)} 10 {(CH2)2O)} 15 SO3 - CH3(CH2) 12 O{(CH2)4O)} 10 {(CH2)2O)} 20 SO3 -

[0023] Specific examples of the structural unit (a) represented by the above formula (1) include, but are not limited to, those represented by the following formulae.

[0024]

Chemical formula

[0025] The structural unit (b) contained in the hydrophilic copolymer used in the present invention is represented by the following formula (2). When the hydrophilic composition of the present invention contains a curing agent, the hydrolyzable silyl group contained in the structural unit (b) undergoes a crosslinking reaction with the functional group contained in this curing agent, or even when the curing agent is not contained, it can undergo a crosslinking reaction (self-crosslinking) by itself. As a result, a crosslinked structure containing the hydrophilic copolymer is formed in the coating film.

[0026]

Chemical formula

[0027] In the above formula (2), R 3 is a hydrogen atom or a methyl group, and a methyl group is preferred. X 2 is -NH- or -O-, and -O- is preferred. Y 2 is a group selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, an isocyanate group, an epoxy group, an alkoxy group (-OR) and a hydrolyzable silyl group. As the alkoxy group (-OR) of Y 2 the alkyl group of R is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Specific examples thereof include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, cyclopentyloxy, cyclohexyloxy groups and the like. Further, part or all of the hydrogen atoms bonded to the carbon atoms of the alkyl group of R may be substituted with halogen atoms such as chlorine, fluorine, bromine and the like, or other substituents such as a cyano group. As the hydrolyzable silyl group of Y 2 for example, alkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, dimethoxysilyl, diethoxysilyl, monomethoxysilyl, monoethoxysilyl groups; carboxylatesilyl groups such as acetoxysilyl group; halosilyl groups such as trichlorosilyl, dichlorosilyl, monochlorosilyl groups; aminosilyl group; oximesilyl group; hydrosilyl group and the like can be mentioned. Among these, Y 2 is preferably a hydrogen atom and a hydroxyl group.

[0028] 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. However, when m is 0, Y 2 is a hydrogen atom.

[0029] In the hydrophilic composition of the present invention, the (A) hydrophilic copolymer can form a crosslinked structure with the (B) blocked isocyanate silane by performing heat treatment in combination with the (B) blocked isocyanate silane. Further, for example, when the hydrophilic copolymer and a curing catalyst such as an acid catalyst are used in combination, the copolymer itself can also undergo a crosslinking reaction (self-crosslinking). Therefore, a coating film formed from a composition containing the hydrophilic copolymer and a curing agent has a crosslinked structure and can exhibit excellent water resistance.

[0030] From such a point, in the above formula (2), Y 2 is more preferably a hydroxyl group.

[0031] Specific examples of the structural unit (b) represented by the above formula (2) include, but are not limited to, those represented by the following formula.

[0032] [Chemical formula] (In the formula, the asterisk * represents the same meaning as above.)

[0033] 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. When 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, when 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 of the present invention, the total content of the constitutional unit (a) and the constitutional 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. When the total content of the constitutional unit (a) and the constitutional unit (b) is less than 30% by mass, the contribution degree of the hydrophilic factor of the constitutional unit (a) becomes small, and the surface hydrophilicity of the coating film may decrease when it is formed into a coating film. The upper limit is not particularly limited, and it may be only the constitutional unit (a) and the constitutional unit (b), 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.

[0034] The hydrophilic copolymer used in the present invention may contain, in addition to the above constitutional units, for example, a constitutional unit represented by the following formula (3) within a range not impairing the object of the present invention.

[0035]

Chemical formula

[0036] In the above formula (3), R 4 is a hydrogen atom or a methyl group, and a methyl group is preferred. X 3 is -NH- or -O-, and -O- is preferred. A’ is an alkylene group having 1 to 6 carbon atoms, and specific examples thereof include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene groups and the like. Among these, an alkylene group having 1 to 3 carbon atoms is preferred, and an ethylene group is more preferred. R 5 is an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include the same groups as those exemplified for the above R 2 , but a methyl group is preferred among them. f is an integer of 1 to 10, preferably an integer of 2 to 8, and more preferably an integer of 3 to 6.

[0037] In the present invention, when the hydrophilic copolymer contains other constituent units, the total content is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 5 to 50% by mass. The order of each constituent unit 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.

[0038] In the present invention, from the viewpoint of improving the affinity with an organic solvent 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).

[0039] Also, from the viewpoints of compatibility with an organic solvent 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 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.

[0040] As the hydrophilic copolymer used in the present invention, commercially available products may be used, for example, Acrit 1WX manufactured by Dainippon Fine Chemical Co., Ltd., etc.

[0041] [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. In the present invention, an organosilicon compound having a blocked isocyanate group represented by the following formula (4) is preferred. In addition to the blocked isocyanate silane alone, a structure in which a part of the hydrolyzable silyl group is hydrolyzed, or a partial hydrolysis condensate that has further undergone intermolecular condensation to form an oligomer, can also exhibit the same performance and can thus be used as the curing agent component of the present invention.

[0042]

Chemical formula

[0043] In formula (4), R 6 each independently represents an alkyl group having 1 to 8 carbon atoms, L represents a divalent linking group, X 4 represents -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 group capable of combining with Y 3 to form a ring structure, and k represents an integer of 1 to 3.

[0044] R 6 The alkyl group having 1 to 8 carbon atoms of R 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, n-octyl groups, etc. Among them, methyl and ethyl groups are preferred.

[0045] Specific examples of the divalent linking group of L include those composed of 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 preferred. The alkyl group includes those having 1 to 4 carbon atoms among the alkyl groups exemplified above. Among these, from the viewpoint of the availability of raw materials for producing organosilicon compounds, as the divalent linking group, -(CH2) n-(where n is an integer from 1 to 10, preferably from 1 to 6, more preferably from 1 to 4) represents an alkylene group, or one or more methylene units in this -(CH2) n - are preferably groups in which one or more methylene units are substituted with -O-, -S-, -NH-, -CO- and -COO-, and -(CH2)3- (trimethylene group) is more preferred.

[0046] X 4 is -O- or -NR 7 -, but it is a group that forms part of the protecting group of the blocked isocyanate silane compound and is not particularly limited because it is eliminated by heating. X 4 of -NR 7 - in which R 7 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a group capable of combining with Y 3 to form a ring structure. R 7 As the alkyl group having 1 to 8 carbon atoms of R 6 the same groups as those exemplified above for R -NR 7 - in which R 7 is a group capable of combining with Y 3 to form a ring structure, -NR 7 - forms a nitrogen-containing heterocyclic structure with Y 3 in formula (1). In such a heterocyclic structure, it is preferably to contain two or more nitrogen atoms, and more preferably to contain two nitrogen atoms. As the heterocyclic structure, a 5-membered or 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 are preferred, and a pyrazole ring is more preferred. In addition, the above ring structure may have substituents such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carboxy group, a hydroxy group, an ester group, an oxo group (=O), etc. Examples of suitable ring structures include, but are not limited to, the following.

[0047] [Chemical formula]

[0048] Y 3 is a hydrogen atom or a monovalent organic group, and is a group that forms part of the protecting group of the blocked isocyanate silane compound and is eliminated by heating, and is not particularly limited. Y 3 Specific examples of the monovalent organic group of include a monovalent hydrocarbon group which may have a substituent having 1 to 20 carbon atoms, an -OH group (however, excluding the case where X is -O-), 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), and the like. 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, an aralkyl group having 7 to 20 carbon atoms, and the like. Specific examples of the alkyl group include, in addition to the groups exemplified by R 6 n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, icosyl group, and the like. Specific examples of the aryl group include phenyl, naphthyl group, and the like. Specific examples of the aralkyl group include benzyl, phenylethyl group, and the like. In addition, at least a part of the hydrogen atoms of these groups may be substituted with other substituents, and examples of the other substituents include a carboxy group, an ester group, a hydroxyl group, and the like.

[0049] R 17The C1-C10 alkylidene group which may be substituted with an aryl group or a heteroaryl group having 6 to 20 carbon atoms may be linear, branched or cyclic. Specific examples thereof include methylidene, phenylmethylidene, diphenylmethylidene, ethylidene, propylidene, propane-2-ylidene, butylidene, butane-2-ylidene, pentylidene, 4-methylpentane-2-ylidene, hexylidene, cyclohexylidene, heptylidene, octylidene, nonylidene, decylidene groups and the like. Specific examples of the aryl group having 6 to 20 carbon atoms include the groups exemplified above for Y 3 and the like. 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, pyridin-3-yl groups and the like.

[0050] In particular, the blocked isocyanate silane compound represented by the above formula (4) is preferably one represented by the following formula (5) or formula (6).

[0051] [Chemical formula] (In the formula, R 6 , R 7 , Y 3 and k represent the same meanings as described above.)

[0052] R 7 and R 8 each independently represent a hydrogen atom or a monovalent organic group, provided that R 7 and R 8 or R 7 and Y 3 may be linked to each other to form a ring structure. Examples of the monovalent organic groups for the above R 7 and R 8 include, for example, monovalent hydrocarbon groups having 1 to 20 carbon atoms, heteroaryl groups having 6 to 20 carbon atoms, and the like. Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include the above Y 3 The same groups as those exemplified in 3 can be mentioned, but an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferable, and the same specific examples as above can be mentioned for these. As the heteroaryl group having 6 to 20 carbon atoms, the same groups as those exemplified in the above R 17 can be mentioned. R 7 and R 8 Examples of the ring structure formed by connecting with each other include a cyclopentane ring, a cyclohexane ring, etc. In addition, these hydrocarbon groups and heteroaryl groups may have substituents. Specific examples of the substituents include a carboxy group, a hydroxy group, an ester group, etc. R 7 -Methylidene-R 8 Examples of the group represented by include the alkylidene groups exemplified in the above R 17 Among them, diphenylmethylidene, propane-2-ylidene, butane-2-ylidene, 4-methylpentane-2-ylidene, and cyclohexylidene groups are preferable.

[0053] R 7 and Y 3 Specific examples of are the same as above, but among them, it is preferable that these are bonded to each other to form a ring structure together with a nitrogen atom. As the ring structure, a 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring is more preferable. In addition, this ring structure preferably has two nitrogen atoms, and an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring are more preferable, and a pyrazole ring is even more preferable. In addition, the above ring structure may have substituents such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carboxy group, a hydroxy group, an ester group, an oxo group (=O), etc. Preferable ring structures include the following, but are not limited thereto.

[0054] [Chemical]

[0055] Preferred specific examples of the blocked isocyanate silane compound of component (B) include, but are not limited to, the following compounds.

[0056] [Chemical]

[0057] The hydrophilic composition of the present invention (hereinafter also simply referred to as "composition") contains the above components (A) and (B). Specifically, with respect to 100 parts by mass of component (A), component (B) is contained in an amount of 0.001 to 10 parts by mass. When the content of component (B) is less than the lower limit value, the desired water resistance improvement effect is not exhibited. When it exceeds the upper limit value, the effect is saturated, the cost-effectiveness decreases, and in addition, the hydrophobic influence of the original silane coupling agent becomes large, and the hydrophilicity tends to decrease. The content of component (A) contained in the hydrophilic composition of the present invention is not particularly limited, but from the viewpoint of hydrophilicity, 1 to 40% by mass of the whole composition is preferable, and 10 to 25% by mass is more preferable.

[0058] 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. The curing agent promotes the crosslinking reaction of the above hydrophilic copolymer and contributes to the formation of a crosslinked structure inside the coating film. At this time, the curing agent may or may not be incorporated into the crosslinked structure.

[0059] In the case of a curing agent incorporated into the crosslinked structure, the functional group contained in the side chain of the above hydrophilic copolymer (specifically, the functional group Y contained in the structural unit (b) 2It is preferably to have a functional group or structure that crosslinks with the alkoxysilyl group of the component (B). At this time, the crosslinking mode may be any of covalent bond, ionic bond, hydrogen bond or coordination bond, but covalent bond is preferred. As the curing agent incorporated into the crosslinked structure, those having 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, etc. in the molecule, a molecular structure such as a siloxane structure or a melamine structure, or a metal ion, etc. are preferred.

[0060] A suitable combination of the functional group of the hydrophilic copolymer side chain capable of crosslinking reaction and the functional group or structure of the curing agent is as shown in Table 1, for example.

[0061]

Table 1

[0062] Examples of the curing agent having a hydrolyzable silyl group include compounds having a hydrolyzable silyl group, compounds having a siloxane structure containing a hydrolyzable silyl group, etc. Specifically, compounds represented by the following formula (7), compounds represented by the following formula (8), hydrolysis condensates of compounds represented by the following formula (8), etc. are included.

[0063]

Chemical formula

[0064] In the above formula (7), R 10 and R 11 are each independently 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. R 10 and R 11The alkyl group may be linear, branched, or cyclic. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl group, and the like. R 10 and R 11 Specific examples of the aryl group of and R Among these, R 10 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and R 11 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. In the above formula (7), j is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and even more preferably an integer from 2 to 4. i is an integer from 1 to 3, preferably 3.

[0065] Specific examples of the compound represented by the above formula (7) include, but are not limited to, N,N,N-tris(trimethoxysilylpropyl)isocyanurate, N,N,N-tris(triethoxysilylpropyl)isocyanurate, and the like.

[0066] In the above formula (8), R 12 R 13 R 14 and R 15 each independently represent a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. 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 an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and the like. Specific examples of the alkyl group having 1 to 6 carbon atoms include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl group, and the like. Specific examples of the alkenyl group having 2 to 6 carbon atoms include vinyl, allyl group and the like. 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, more preferably a methyl group or an ethyl group, from the viewpoint of hydrolyzability.

[0067] In formula (8), h represents an integer of 1 to 20, preferably an integer of 3 to 12, more preferably an integer of 5 to 12. When h is 20 or less, the viscosity of the coating liquid does not become too high, and an anti-fog film with high uniformity can be formed. Further, when h is 1 or more, the reactivity of the compound represented by formula (5) can be easily controlled, and an anti-fog film excellent in hydrophilicity can be formed.

[0068] In the present invention, the "hydrolysis condensate of the compound represented by formula (8)" means a compound having a structure in which a siloxane bond (Si-O-Si) is formed in at least one of Si-OR 12 、Si-OR 13 、Si-OR 14 、and Si-OR 15 The condensate of the compound represented by formula (8) can be formed, for example, by the condensation or hydrolysis condensation of two or more molecules of the compound represented by formula (8) with each other. Regarding hydrolysis condensation, taking the case where R 12 、R 13 、R 14 and R 15 are methyl groups (-CH3) as an example, it will be described below. In an example of hydrolysis condensation, Si-OH is formed by the hydrolysis of Si-OCH3, and then Si-O-Si is formed by the dehydration condensation of Si-OH. The structure of the hydrolysis condensate of the compound represented by formula (8) is not particularly limited, and examples include random type, linear type, ladder type, cage type and the like.

[0069] In the compound represented by formula (8) and its hydrolysis condensate, R12 and R 13 and R 14 and R 15 When the hydrogen atom is contained in R, the hydrogen atom may be the hydrogen atom contained in the compound added as a raw material during the production of the compound of formula (8) or the hydrogen atom introduced by hydrolysis. That is, in formula (8), R 12 and R 13 and R 14 and R 15 If at least one of them is a hydrogen atom, at least one of the Si-OH groups in formula (8) may be the Si-OH group contained in the compound added as a raw material during the production of the compound of formula (8) or the Si-OH group formed by hydrolysis.

[0070] 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 (e.g., MS51, MS56) manufactured by Mitsubishi Chemical Corporation.

[0071] The weight average molecular weight (Mw) of the compound represented by formula (8) is preferably 300 to 1,500, 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).

[0072] Examples of the curing agent having an isocyanate group include aliphatic, alicyclic or aromatic polyisocyanates. Specifically, 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, methylene bis(4,1-cyclohexylene) diisocyanate, 1,3-bis(isocyanatomethyl) cyclohexane, adducts of diisocyanate compounds and polyol compounds such as trimethylolpropane, biuret bodies and isocyanurate bodies of diisocyanate compounds, and other isocyanate derivatives, etc. can be mentioned. Among these, from the viewpoint of suppressing yellowing of the coating film, polyisocyanates derived from hexamethylene diisocyanate are preferable. Hardening agents having isocyanate groups are commercially available and can be used, such as 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; Takenate (registered trademark) 500, 600, etc. manufactured by Mitsui Chemicals, Inc. These may be used alone or in combination of two or more.

[0073] As the curing agent having a melamine structure, a melamine resin is preferable. Specific examples 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-benzyloxy-sym-triazine, 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, melamines such as amerine (N,N,N’,N’-tetracyanoethylbenzoguanamine), condensates of formaldehyde and alcohols (for example, methanol, etc.). The curing agent having a melamine structure is commercially available, and examples thereof include Youban (registered trademark) 20SE, 225 manufactured by Mitsui Chemicals, Inc.; Amidia (registered trademark) L-117-60, L-109-65, 47-508-60, L-118-60, G821-60, J820-60 manufactured by DIC Corporation, etc. can be used. These may be used alone or in combination of two or more kinds.

[0074] As the curing agent having an epoxy group, aliphatic, alicyclic or aromatic diepoxy compounds, triepoxy compounds and the like can be mentioned. 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 novolak 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, etc. can be mentioned. These may be used alone or in combination of two or more.

[0075] Examples of the curing agent having an amino group include primary amines, aliphatic, alicyclic or aromatic diamines, triamines, tetraamines, etc. containing secondary amines. 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-dimethylbenzene-1,2-diamine, 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-isopropylaminoamylamine, n-butylethylenediamine, N-tertiarybutylbutane-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-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, and the like can be mentioned., These may be used alone or in combination of two or more kinds.,

[0076] Examples of the curing agent having a carbodiimide group include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N-isopropyl-N'-[2-(methacryloyloxy)ethyl]carbodiimide, and the like., These may be used alone or in combination of two or more kinds.,

[0077] 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, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, and the like. These may be used alone or in combination of two or more.

[0078] Examples of the curing agent having a metal ion include aluminum organic compounds such as aluminum ethyl acetoacetate diisopropylate.

[0079] Among these, from the viewpoint of ease of handling, a curing agent having an isocyanate group or a melamine structure is preferable. 2 It is more preferable to combine a hydrophilic copolymer containing a structural unit (b) in which Y is a hydroxyl group with a curing agent having an isocyanate group or a melamine structure. 2 It is even more preferable to combine a hydrophilic copolymer containing a structural unit (b) in which Y 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 hydrophilic copolymer of the present invention and a polyisocyanate or a melamine resin as the curing agent. Among them, 2 In the case of a combination of a hydrophilic copolymer containing a structural unit (b) in which Y is a hydroxyl group and a curing agent having an isocyanate group (polyisocyanate), the crosslinking reaction proceeds even under low-temperature conditions (for example, 110 ° C or lower), and a coating film can be formed on a substrate with low heat resistance by the composition according to the present invention, which is particularly preferable.

[0080] On the other hand, examples of the curing agent (curing catalyst) not incorporated into the crosslinked structure include inorganic acids, organic acids, organic metal salts, Lewis acids, and the like. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid, and the like. 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, citric acid, and the like. 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, tin octylate, and the like. Examples of the Lewis acid include tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, tin chloride (SnCl4), titanium chloride (TiCl4), zinc chloride (ZnCl4), and the like. In addition, alkyl tin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, dioctyltin dioctoate, dioctyltin dibenzoate, and the like can also be preferably used. These may be used alone or in combination of two or more. Further, a curing agent incorporated into the crosslinked structure and a curing agent (curing catalyst) not incorporated may be appropriately combined and used.

[0081] When the hydrophilic composition of the present invention contains a curing agent, the content 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.

[0082] The hydrophilic composition of the present invention preferably further contains a hydrophilic organosilicon compound represented by the following formula (10) and / or its hydrolysis condensate.

[0083]

Chemical formula

[0084] In formula (10), R 18 and R 19 are each independently 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 are the same as the groups exemplified by Y 3 respectively, but 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 an aralkylen 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, naphthylene group, etc. R 20 Specific examples of the aralkylen group include methylenephenylene, ethylenephenylene, methylenephenylenemethylene, ethylenephenyleneethylene group, etc. Among these, R 18 is preferably a phenylene group, more preferably a 1,4-phenylene group. R 21 and R 22 each independently represent an alkyl group having 1 to 6 carbon atoms. Specific examples thereof include those similar to the groups exemplified by R 6 among the groups exemplified by R X 5 represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. X 5 The alkylene group of X may be linear, branched or cyclic. Specific examples thereof include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, cyclohexylene group, etc. Among these, X 5 is preferably a methylene, ethylene, or trimethylene group, more preferably a trimethylene group. Y 4 represents COO - , SO3 - , or PO4 - However, from the perspective of the durability of the resulting coating film, SO3 - is preferred. o is an integer from 1 to 3, preferably 3.

[0085] Specific examples of such hydrophilic organosilicon compounds are shown below, but are not limited thereto. Among these, those represented by formula (11) are preferred.

[0086]

Chemical formula

[0087] When using a hydrophilic organosilicon compound, its content 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 above hydrophilic copolymer.

[0088] The hydrophilic composition of the present invention may optionally contain a solvent. The solvent is not particularly limited as long as it can dissolve or disperse the hydrophilic copolymer, optionally a 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 later. 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. For example, when using a polyisocyanate as a curing agent, it is preferable to use a solvent that does not react with the isocyanate group (for example, a ketone-based solvent such as methyl ethyl ketone, methyl isobutyl ketone, etc.). These may be used alone or in combination of two or more.

[0089] 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., if necessary.

[0090] From the viewpoints of coatability and workability, the solid content concentration of the composition is preferably 5 to 80% by mass, more preferably 10 to 30% by mass. From the viewpoints of coatability and workability, the viscosity of the composition is preferably 0.01 to 0.05 Pa·s (at a temperature of 25°C). The viscosity is a value measured by a rotational viscometer. The composition of the present invention may be a one-component type or a type in which two or more components are mixed before use.

[0091] By applying the composition of the present invention to various substrates, hydrophilicity can be imparted to these substrates. Specific examples of the material constituting the base material 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, perfluoroalkoxyfluororesin, tetrafluoroethylene - hexafluoropropylene copolymer resin, ethylene tetrafluoroethylene copolymer resin, ethylene - chlorotrifluoroethylene copolymer resin, 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 analogs (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 fiber, etc.; composite fibers of these fibers (such as polyester / cotton, etc.), etc. Examples of the form include substrates, sheets, films, fibers, various articles using these, etc.

[0092] The composition of the present invention can form a coating film on the surface of a substrate or the like by applying a known coating method to obtain a hydrophilic coating film. Examples of the coating method include, for example, bar coating method, dip coating method, spin coating method, spray coating method, float coating method, brush coating method, gravure coating method, roll transfer method, blade coating method, air knife coating method, slit coating method, screen coating method, inkjet method, flexographic printing method, etc. Among these, the bar coating method is preferred.

[0093] A cured coating film can be obtained by applying a composition onto a substrate and then heating it. 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. In addition, preliminary drying may be performed under the same conditions as above to remove the solvent in the composition. The heating atmosphere may be either an air atmosphere or an inert gas (e.g., nitrogen, argon, etc.) atmosphere.

[0094] 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.

Examples

[0095] Hereinafter, the present invention will be described in more detail by showing examples and comparative examples, but the present invention is not limited to these examples.

[0096] (1) Production of coating composition (hydrophilic composition) [Example 1] As component (A), a methyl ethyl ketone-IPA (1:2, wt / wt) solution (solid content concentration 25% by mass, designated as A-1) of Acrit 1WX (manufactured by Dainippon Fine Chemical Co., Ltd.), a copolymer containing structural units represented by the following formulas (12), (13), (14), (15) and (16), and as component (B), the compound shown in the following (B-1) and Neo-Stann U-830 (manufactured by Nitto Kasei Co., Ltd.), a dioctyltin catalyst, were mixed in the blending composition shown in Table 2 to prepare a hydrophilic composition.

[0097]

Chemical formula

[0098] [Examples 2 to 7, Comparative Examples 1 to 6] A hydrophilic composition was prepared in the same manner as in Example 1, except that the type of component (B) was changed as shown in Table 2 and the curing agent shown in Table 2 was added.

[0099]

Table 2

[0100] In Table 1, the abbreviations are as follows. B-1: Silane compound represented by the above formula (8-a) B-2: Silane compound represented by the above formula (8-b) B-3: Silane compound represented by the above formula (4-a) B’-1: 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) B’-2: 3-Isocyanatopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-9007) C-1: Tris-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-9659) C-2: MKC (registered trademark) Silicate MS51, a partial hydrolysis oligomer of tetramethoxysilane (manufactured by Mitsubishi Chemical Corporation) D-1: Silane compound represented by the above formula (11)

[0101] (2) Evaluation of storage stability of hydrophilic composition Immediately after preparation, 40 g each of the hydrophilic compositions prepared in the above Examples and Comparative Examples were weighed into 50 mL polyethylene containers and left standing in a thermostat (SPHH-201, manufactured by Espec Corporation) set at 40°C for 3 months. After 3 months, they were taken out from the dryer, left standing for 1 hour under the conditions of 25°C / 50% relative humidity, and then the state of the compositions was observed. The evaluation criteria for storage stability are as follows. ○: The composition maintained fluidity. ×: The composition solidified into a gel state.

[0102] (3) Preparation and evaluation of coating film The hydrophilic compositions prepared immediately in the above Examples and Comparative Examples were each applied to a polycarbonate plate using a bar coater (No. 14), and immediately dried at 120°C for 1 hour to obtain a hydrophilic film. The following tests were performed on the obtained films, and the results are shown in Table 3.

[0103] 〔Anti-fogging property〕 Exhaled breath was blown onto each of the above films. When the surface of the film became fogged, it was marked as ×, and when it did not become fogged, it was marked as ○. Further, the film was left standing at a height of 3 cm from the water surface above a 60°C warm water bath for 1 minute. When the surface of the film did not become fogged, it was marked as ◎, and the anti-fogging property was evaluated. 〔Water resistance〕 Each of the above films was immersed in water at 25°C for 5 minutes, the water on the surface was blotted with a paper wiper, and then naturally dried at 25°C for 10 minutes, followed by evaluation of the anti-fogging property as described above. Subsequently, each film was further immersed in water for 1 hour, the water on the surface was blotted with a paper wiper, and then naturally dried at 25°C for 10 minutes, followed by evaluation of the anti-fogging property as described above. 〔Humidity resistance〕 Each of the above films was left standing in a thermo-hygrostat (KCL-2000W, Tokyo Rika Kikai Co., Ltd.) set at 50°C and 98% RH for 24 hours. Thereafter, it was naturally dried at 25°C for 10 minutes, followed by evaluation of the anti-fogging property as described above.

[0104]

Table 3

[0105] As shown in Table 3, the compositions of Examples 1 to 6 containing the blocked isocyanate silane compound had good storage stability and maintained excellent hydrophilicity and anti-fogging property even after the water resistance test (immersion in water for 5 minutes and 1 hour) and the humidity resistance test (50°C, 98% RH, 24 hours). It can be seen that the film of Example 6 was particularly excellent in durability. On the other hand, in the coating of Comparative Example 1 that does not contain a blocked isocyanate silane compound, it can be seen that the anti-fogging property disappears after 5 minutes of water immersion, indicating poor water resistance. Also, it can be seen that the compositions of Comparative Example 2 containing an unblocked isocyanate silane compound and Comparative Example 3 containing 3-glycidoxypropyltrimethoxysilane have poor storage stability. Furthermore, it can be seen that the cured film obtained from the composition of Comparative Example 4 with an excessive addition of a blocked isocyanate silane compound is inferior in anti-fogging property.

Claims

Claim 1 (A) 100 parts by mass of a hydrophilic copolymer containing a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): and (B) 0.001 to 10 parts by mass of a blocked isocyanate silane compound: a hydrophilic composition. 【Chemical 1】 (In formula (1), R 1 represents a hydrogen atom or a methyl group, and 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 of 1 to 6, and Y 1- represents a monovalent anion, In formula (2), R 3 represents a hydrogen atom or a methyl group, X 2 represents -NH- or -O-, Y 2 is 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 to 10. However, when m is 0, Y 2 is a hydrogen atom, and when m is 1 to 10, Y 2 is a monovalent functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an acid anhydride group, and an alkoxysilyl group. The asterisk * indicates the bond to the adjacent structural unit.) Claim 2 The hydrophilic composition according to Claim 1, wherein the (B) blocked isocyanate silane compound is represented by the following formula (4). 【Chemical Formula 2】 (In the formula, R 6 each independently represents an alkyl group having 1 to 8 carbon atoms, L represents a divalent linking group, X 4 represents -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 group capable of combining with Y 3 to form a ring structure, and k represents an integer of 1 to 3.) Claim 3 The hydrophilic composition according to Claim 2, wherein the (B) blocked isocyanate silane compound is represented by the following formula (5) or (6). [Chemical Formula 3] (wherein, R 6 , R 7 , Y 3 and k represent the same meanings as described above, and R 8 and R 9 each independently represent a hydrogen atom or a monovalent organic group, provided that R 8 and R 9 or R 7 and Y 3 may be linked to each other to form a ring structure.) Claim 4 Furthermore, the hydrophilic composition according to Claim 1, 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). 【Chemical Formula 4】 (In formula (3), 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 (4), 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.) Claim 5 A coating agent comprising the hydrophilic composition according to any one of Claims 1 to 4. Claim 6 A hydrophilic film obtained by curing the coating agent according to Claim 5.

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