Hydrophilic composition

Abstract

A hydrophilic composition comprising (A) 100 parts by mass of a hydrophilic copolymer comprising a structural unit represented by formula (1) and a structural unit represented by formula (2), and (B) 0.001-10 parts by mass of a blocked isocyanate silane compound, this hydrophilic composition can form a coating film having excellent hydrophilicity, antifogging properties, and water resistance. [In formula (1), R1 represents a hydrogen atom or a methyl group, R2 each independently represents an alkyl group having 1-6 carbon atoms, 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 carboxyl group, or an amino group, and m represents an integer of 0-10 (however, when m is 0, Z1 represents a hydrogen atom or a methyl group). And star number * represents a bond to an adjacent structural unit. ]

Description

Technical Field

[0001] This invention relates to hydrophilic compositions, coating agents, hydrophilic films, and coated articles. Background Technology

[0002] In recent years, there has been a growing demand for improving the fogging performance of substrates made from organic materials such as plastics and inorganic materials such as glass.

[0003] Improving the fogging of a substrate is generally achieved by coating the surface of the substrate with a hydrophilic film. For example, in Patent Document 1, a coating composition containing a hydrophilic copolymer with a quaternary ammonium salt structure that has high hydrophilicity was proposed as a coating agent that can impart hydrophilicity to the substrate.

[0004] However, the water resistance of the coating film formed by the above coating composition is not sufficient. When in contact with water, surface properties such as hydrophilicity and anti-fogging properties sometimes deteriorate, and further improvement is desired.

[0005] Existing technical documents

[0006] Patent documents

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

[0008] The problem that the invention aims to solve

[0009] The present invention was made in view of the above-mentioned circumstances, and its object is to provide a hydrophilic composition (coating agent) comprising a hydrophilic copolymer that imparts a coating film with excellent hydrophilicity, anti-fogging and water resistance, a hydrophilic film obtained therefrom, and a coated article having the coating film.

[0010] Methods for solving problems

[0011] In order to achieve the above objectives, the inventors conducted repeated and in-depth research and found that the composition containing a specific hydrophilic copolymer and a blocked isocyanate silane compound has excellent water resistance and can form a coating film with continuous hydrophilicity and anti-fogging properties on substrates made of organic materials such as plastics and inorganic materials such as glass, thus completing the present invention.

[0012] That is, the present invention provides:

[0013] 1. A hydrophilic composition comprising: (A) 100 parts by weight of a hydrophilic copolymer comprising structural units represented by formula (1) and structural units represented by formula (2); and (B) 0.001 to 10 parts by weight of a blocked isocyanate silane compound.

[0014] [Chemistry 1]

[0015]

[0016] In equation (1), R 1 R represents a hydrogen atom or a methyl group. 2 Each of the alkyl groups independently represents an alkyl group with 1 to 6 carbon atoms, and n represents an integer from 1 to 6. In formula (2), R 3 X represents a hydrogen atom or a methyl group. 1 Indicates -NH- or -O-, Z 1 Represents a hydrogen atom, methyl group, hydroxyl group, carboxyl group, or amino group, where m represents an integer from 0 to 10 (where m is 0, Z is 0). 1 (This represents a hydrogen atom or a methyl group. The asterisk * indicates a bond with an adjacent structural unit.)

[0017] 2. The hydrophilic composition according to 1, wherein the (B) blocked isocyanate silane compound is represented by the following formula (3):

[0018] [Chemistry 2]

[0019]

[0020] (where R) 4 Each of these groups independently represents an alkyl group with 1 to 8 carbon atoms, L represents a divalent linking group, and X represents a divalent linking group. 2 Indicates -O- or -NR 5 -, Z 2 R represents a hydrogen atom or a monovalent organic group. 5 It represents hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, or substances capable of reacting with Z. 2 Groups bonded to form a ring structure, where k represents an integer from 1 to 3.

[0021] 3. The hydrophilic composition according to 2, wherein the (B) blocked isocyanate silane compound is represented by the following formula (4) or (5):

[0022] [Chemistry 3]

[0023]

[0024] (where R) 4 R 5 Z 2 And k represents 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 They can be interconnected to form a ring structure.

[0025] 4. The hydrophilic composition according to any one of 1 to 3, further comprising at least one compound selected from polyisocyanate compounds, organosilicon compounds represented by formula (6) below, and organosilicon compounds represented by formula (7) below:

[0026] [Chemistry 4]

[0027]

[0028] (In equation (6), R) 8 and R 9 Each can independently represent an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms, where j represents an integer from 1 to 10 and i represents an integer from 1 to 3.

[0029] In equation (7), R 10 R 11 R 12 and R 13 Each group independently represents a hydrogen atom or an organic group with 1 to 6 carbon atoms, where h represents an integer from 1 to 20.

[0030] 5. A coating agent comprising the hydrophilic composition according to any one of 1 to 4;

[0031] 6. A hydrophilic coating, which is a hydrophilic coating formed by curing the coating agent according to 5;

[0032] 7. A coated article having a substrate and a hydrophilic coating according to 6 formed directly or indirectly on at least one side of the substrate by one or more other layers.

[0033] The effects of the invention

[0034] The hydrophilic composition of the present invention can form a coating film with excellent water resistance and capable of imparting continuous hydrophilicity and anti-fogging properties to substrates such as glass. Detailed Implementation

[0035] The present invention will now be described in detail.

[0036] (A) Hydrophilic copolymer

[0037] The hydrophilic copolymer used in this invention (hereinafter also referred to as "copolymer" or "(A) component") contains structural units (a) and (b) described below in a specific proportion.

[0038] [1] Structural unit (a)

[0039] The structural unit (a) is represented by the following equation (1).

[0040] [Chemistry 5]

[0041]

[0042] (In the formula, the asterisk * indicates the same meaning as above.)

[0043] In equation (1), R 1 It can be a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0044] R 2 Each is an alkyl group having 1 to 6 carbon atoms.

[0045] Regarding R 2 For alkyl groups having 1 to 6 carbon atoms, they can be linear, branched, or cyclic. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, etc.

[0046] Among these, from the perspective of improving the hydrophilicity of the coating film, R 2 Preferably, it is an alkyl group having 1 to 3 carbon atoms, more preferably methyl or ethyl, and even more preferably methyl.

[0047] n is an integer from 1 to 6, with 2 or 3 being preferred.

[0048] As a specific example of the structural unit (a) represented by the above equation (1), examples can be listed that are represented by the following equation, but are not limited to these.

[0049] [Chemistry 6]

[0050]

[0051] (In the formula, the asterisk * indicates the same meaning as above.)

[0052] [2] Structural unit (b)

[0053] The structural unit (b) is represented by the following equation (2).

[0054] [Chemistry 7]

[0055]

[0056] (In the formula, the asterisk * indicates the same meaning as above.)

[0057] In the above formula (2), R 3 It can be a hydrogen atom or a methyl group, preferably a methyl group.

[0058] X 1 It can be -NH- or -O-, preferably -O-.

[0059] Z 1It can be a hydrogen atom, methyl, hydroxyl, carboxyl, or amino group, preferably a hydrogen atom or hydroxyl group. However, when m is 0, Z 1 It can be a hydrogen atom or a methyl group.

[0060] m is an integer from 0 to 10, preferably an integer from 0 to 6, more preferably an integer from 1 to 4, and even more preferably an integer from 2 to 4.

[0061] By using the hydrophilic copolymer and (B) blocked isocyanate silane in combination and subjecting them to heat treatment, a cross-linked structure can be formed between the blocked isocyanate silane and the copolymer. Furthermore, for example, if the above-mentioned hydrophilic copolymer is used in combination with a curing catalyst such as an acid catalyst, the copolymer itself can also undergo a cross-linking reaction (self-cross-linking). Therefore, the coating film formed from the composition of the present invention containing the hydrophilic copolymer and the curing agent has a cross-linked structure and exhibits excellent water resistance.

[0062] From this point of view, in the above equation (2), it is more preferable that m is an integer from 1 to 4, and Z 1 It is a hydroxyl group.

[0063] As a specific example of the structural unit (b) represented by the above equation (2), examples can be listed that are represented by the following equation, but are not limited to these.

[0064] [Chemistry 8]

[0065]

[0066] (In the formula, the asterisk * indicates the same meaning as above.)

[0067] In the hydrophilic copolymer used in this invention, the content of 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 structural unit (a) is less than 5% by mass, the hydrophilicity of the copolymer becomes insufficient, resulting in a decrease in the surface hydrophilicity of the coating film during formation. On the other hand, when the content of structural unit (a) exceeds 60% by mass, the hydrophilicity of the copolymer is excessively increased, resulting in a decrease in the water resistance of the coating film during formation.

[0068] Furthermore, in the hydrophilic copolymer used in this invention, the total content of structural unit (a) and 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. When the total content of structural unit (a) and structural unit (b) is less than 30% by mass, the contribution of the hydrophilic factor of structural unit (a) becomes smaller, and sometimes the surface hydrophilicity of the coating film decreases when it is formed. There is no particular limitation on the upper limit, and only structural unit (a) and structural unit (b) are required, 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.

[0069] [3] Other structural units

[0070] Without prejudice to the purpose of the invention, in addition to the above-described structural units, the hydrophilic copolymers used in the invention may also contain structural units, for example, represented by the following formula (8).

[0071] [Chemistry 9]

[0072]

[0073] (In the formula, the asterisk * indicates the same meaning as above.)

[0074] In the above formula (8), R 14 It can be a hydrogen atom or a methyl group.

[0075] X 3 It can be -NH- or -O-, preferably -O-.

[0076] A' is an alkylene group having 1 to 6 carbon atoms. Specific examples include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene. Among these, alkylene groups having 1 to 3 carbon atoms are preferred, and ethylene is more preferred.

[0077] R 15 It is an alkyl group having 1 to 6 carbon atoms or a hydrolyzable silyl group. Specific examples of alkyl groups having 1 to 6 carbon atoms include those related to the above-mentioned R. 2 The groups exemplified herein are the same as those groups, but methyl is preferred.

[0078] Examples of hydrolyzable silyl groups include alkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, dimethoxysilyl, diethoxysilyl, monomethoxysilyl, and monoethoxysilyl; carboxylic acid ester silyl groups such as acetoxysilyl; halosilyl groups such as trichlorosilyl, dichlorosilyl, and monochlorosilyl; aminosilyl; oxime silyl; and hydrogen silyl.

[0079] f is an integer from 1 to 10, preferably an integer from 2 to 8, and more preferably an integer from 3 to 6.

[0080] In this invention, when the hydrophilic copolymer contains other structural units, the total content of these units is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 5% to 50% by mass.

[0081] The order of the structural units contained in a hydrophilic copolymer is arbitrary; that is, a hydrophilic copolymer can be any of an alternating copolymer, a random copolymer, or a block copolymer.

[0082] In this invention, from the viewpoint of improving 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 even more preferably 15,000 to 20,000. It should be noted that the weight-average molecular weight is a value obtained using gel permeation chromatography (GPC) (standard material: polyethylene glycol-polyethylene oxide).

[0083] Furthermore, from the viewpoint of compatibility with organic solvents and workability, the viscosity of the hydrophilic copolymer is preferably 0.01–0.5 Pa·s (at 25°C). It should be noted that the viscosity is a value measured using a selective viscometer.

[0084] Furthermore, the glass transition temperature of the hydrophilic copolymer is preferably -10 to 50°C. It should be noted that the glass transition temperature is a value determined based on JIS K7121.

[0085] [4] Method for manufacturing hydrophilic copolymers

[0086] For example, as shown in the following scheme, the hydrophilic copolymer used in this invention can be obtained by polymerization in the presence of a polymerizable monomer containing (meth)acrylamide as represented by formula (9) and a polymerization initiator containing (meth)acrylamide and / or (meth)acrylamide as represented by formula (10) under an inactive gas atmosphere such as nitrogen.

[0087] [Chemistry 10]

[0088]

[0089] (where R) 1 R 2 R 3 X 1 Z 1 (m, n are the same as above.)

[0090] As the polymerizable monomer containing (meth)acrylamide in the above formula (9), commercially available products can be used, such as DMAPAA (registered trademark) manufactured by KJ Chemicals Corporation.

[0091] As a polymerization initiator, a thermal polymerization initiator is preferred. The amount of polymerization initiator added relative to the total mass of the copolymerized monomers is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 2 to 10% by mass. Furthermore, the polymerization initiator can be added all at once or in several portions.

[0092] The above reaction can also be carried out in solvent-free conditions, and can be carried out in organic solvents such as methyl ethyl ketone and 1,2-dimethoxyethane, as needed, within a range that does not hinder the reaction.

[0093] The reaction temperature is preferably 0°C to the boiling point of each solvent, more preferably 20°C to 80°C. The reaction time is preferably 1 to 24 hours, more preferably 5 to 10 hours.

[0094] The hydrophilic copolymers obtained by the above method can also be formulated with additives as needed, after adjusting the concentration of solid components, performing solvent exchange, or after filtration. Alternatively, the hydrophilic copolymers generated by polymerization can be purified by precipitation or reprecipitation with hexane or similar methods, and then dissolved together with additives in a solvent suitable for the intended use.

[0095] (B) Blocked isocyanate silane compounds

[0096] (B) The blocked isocyanate silane compound of the component acts as a curing agent for the hydrophilic copolymer. In this invention, an organosilicon compound represented by the following formula (3) is preferred.

[0097] Furthermore, in addition to the blocked isocyanate silane monomer, the partially hydrolyzed structure of the hydrolyzable silane moiety and the partially hydrolyzed condensate that becomes an oligomer by intermolecular condensation also exhibit the same properties and can therefore be used as a curing agent component of the present invention.

[0098] [Chemistry 11]

[0099]

[0100] In equation (3), R 4 Each of these groups independently represents an alkyl group with 1 to 8 carbon atoms, L represents a divalent linking group, and X represents a divalent linking group. 2 Indicates -O- or -NR 5 -, Z 2 R represents a hydrogen atom or a monovalent organic group. 5It represents hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, or substances capable of reacting with Z. 2 Groups bonded to form a ring structure, where k represents an integer from 1 to 3.

[0101] Regarding R 5 For alkyl groups having 1 to 8 carbon atoms, they can be linear, branched, or cyclic. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl, among which methyl and ethyl are preferred.

[0102] Specific examples of divalent linking groups of L include alkylene, -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, preferably a hydrogen atom. Furthermore, as alkyl groups, examples include alkyl groups having 1 to 4 carbon atoms among the alkyl groups exemplified above.

[0103] Among these, considering the availability of raw materials for manufacturing organosilicon compounds, -(CH2) is preferred as the divalent linking group. p - (p is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4) represents an alkylene group, or the - (CH2) group. p -A group obtained by replacing one or more methylene units with -O-, -S-, -NH-, -CO- and -COO-, more preferably -(CH2)3-(trimethylene).

[0104] X 2 -O- or -NR 5 However, as a group that is part of the protecting group forming the closed isocyanate silane compound, it can be removed by heating, so there is no particular limitation.

[0105] In X 2 -NR 5 -in, R 5 It represents hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, or substances capable of reacting with Z. 2 Groups that are bonded to form a ring structure.

[0106] As R 5 Alkyl groups having 1 to 8 carbon atoms can be listed as those related to the above-mentioned R. 4 The same group as the group illustrated herein, wherein preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms, more preferably a methyl or ethyl group.

[0107] In -NR 5 -in, R 5 Indicates the ability to communicate with Z 2 In the case of groups bonded to form a ring structure, -NR5 - with Z in equation (1) 2 A nitrogen-containing heterocyclic structure is formed. In such a heterocyclic structure, it is preferable to contain two or more nitrogen atoms, more preferably two nitrogen atoms. As a heterocyclic structure, a 5-membered ring or a 6-membered ring structure is preferred, more preferably a 5-membered ring structure. As such a heterocyclic structure, an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, or a 1,2,4-triazole ring is preferred, more preferably a pyrazole ring.

[0108] Furthermore, the above-mentioned ring structure may have substituents such as alkyl with 1 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, carboxyl, hydroxyl, ester, oxo (=O), etc.

[0109] The following are examples of preferred ring structures, but the options are not limited to these.

[0110] [Chemistry 12]

[0111]

[0112] Z 2 It can be a hydrogen atom or a monovalent organic group, but as a group that is part of the protecting group forming a closed isocyanate silane compound, it can be removed by heating, so there is no particular limitation.

[0113] As Z 2 Specific examples of monovalent organic groups include monovalent hydrocarbon groups having substituents with 1 to 20 carbon atoms, -OH groups (however, excluding the case where X is -O-), and -N=R groups. 17 (R) 17 This refers to alkylene groups with 1 to 10 carbon atoms that can be substituted by aryl groups with 6 to 20 carbon atoms.

[0114] As a monovalent hydrocarbon group with 1 to 20 carbon atoms, it can be straight-chain, branched, or cyclic. Examples include alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, and aralkyl groups with 7 to 20 carbon atoms.

[0115] As a specific example of the aforementioned alkyl group, besides R 4 In addition to the groups listed, other examples include n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, eicosyl, etc.

[0116] Specific examples of the aforementioned aryl groups include phenyl and naphthyl groups.

[0117] Specific examples of the aforementioned aralkyl groups include benzyl and phenylethyl.

[0118] Furthermore, at least some of the hydrogen atoms of these groups can be replaced by other substituents, such as carboxyl groups, ester groups, and hydroxyl groups.

[0119] As R 17 Alkyl groups with 1 to 10 carbon atoms that can be replaced by aryl or heteroaryl groups with 6 to 20 carbon atoms can be linear, branched, or cyclic. Specific examples include methylene, phenylmethylene, diphenylmethylene, ethylene, propylene, propane-2-ethylene, butylene, butane-2-ethylene, pentylene, 4-methylpentane-2-ethylene, hexylene, cyclohexylene, heptylene, octylene, nonylene, and decylene.

[0120] Specific examples of aryl groups with 6 to 20 carbon atoms can be listed, such as those related to the Z mentioned above. 2 The groups shown in the example are the same groups.

[0121] Specific examples of heteroaryl groups with 6 to 20 carbon atoms include pyrrolo-1-yl, 1H-pyrrolo-2-yl, imidazole-1-yl, imidazole-2-yl, pyrazole-1-yl, pyrazole-3-yl, pyridin-2-yl, and pyridin-3-yl.

[0122] In particular, the blocked isocyanate silane compound represented by the above formula (3) is preferably represented by the following formula (4) or (5).

[0123] [Chemistry 13]

[0124]

[0125] (where R) 4 R 5 Z 2 (and k represents the same meaning as above.)

[0126] As mentioned above, R 6 and R 7 The monovalent organic groups can be listed as monovalent hydrocarbon groups with 1 to 20 carbon atoms and heteroaryl groups with 6 to 20 carbon atoms.

[0127] Specific examples of monovalent hydrocarbon groups with 1 to 20 carbon atoms can be listed, such as those related to the Z mentioned above. 2 The groups exemplified herein are the same as those exemplified herein, but preferably alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 20 carbon atoms. Specific examples of these groups can be listed as being the same as those exemplified above.

[0128] As heteroaryl groups with 6 to 20 carbon atoms, examples of those related to the above-mentioned R groups can be listed. 5 The groups shown in the example are the same groups.

[0129] As R 6 With R7 The ring structures formed by interconnected rings include cyclopentane rings, cyclohexane rings, etc.

[0130] Furthermore, these hydrocarbon groups and heteroaryl groups may have substituents. Specific examples of substituents include carboxyl groups, hydroxyl groups, and ester groups.

[0131] As a result of R 6 -methylene-R 7 The groups represented can be listed as R above. 17 The alkylene groups exemplified herein are preferably diphenylmethylene, propane-2-alkylene, butane-2-alkylene, 4-methylpentane-2-alkylene, or cyclohexylene.

[0132] As R 5 and Z 2 Specific examples are the same as those described above, but preferably they are combined with each other and form a ring structure together with nitrogen atoms. As a ring structure, a 5-membered ring or a 6-membered ring is preferred, and a 5-membered ring is more preferred.

[0133] In addition, the ring structure preferably has a nitrogen atom, more preferably an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, or a 1,2,4-triazole ring, and even more preferably a pyrazole ring.

[0134] Furthermore, the above-mentioned ring structure may have substituents such as alkyl with 1 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, carboxyl, hydroxyl, ester, oxo (=O), etc.

[0135] The following are examples of preferred ring structures, but the options are not limited to these.

[0136] [Chemistry 14]

[0137]

[0138] Preferred examples of the blocked isocyanate silane compound as component (B) include the following compounds, but are not limited to these.

[0139] [Chemistry 15]

[0140]

[0141] The hydrophilic composition of the present invention (hereinafter also referred to as the "composition") comprises the above-mentioned components (A) and (B), specifically, 0.001 to 10 parts by mass of component (B) are included relative to 100 parts by mass of component (A).

[0142] When the content of component (B) is below the lower limit, the desired improvement in water resistance is not observed. When it exceeds the upper limit, in addition to the effect saturation and reduced cost-effectiveness, the original hydrophobicity of the silane coupling agent tends to increase and the hydrophilicity to decrease.

[0143] There is no particular limitation on the content of component (A) in the hydrophilic composition of the present invention, but from the viewpoint of hydrophilicity, it is preferred to be 1 to 40% by mass of the total composition, more preferably 10 to 25% by mass.

[0144] Without prejudice to the purpose of the invention, the hydrophilic composition of the invention may contain other components as needed, and particularly preferably a curing agent.

[0145] The curing agent promotes the cross-linking reaction of the aforementioned hydrophilic copolymer, which helps in the formation of cross-linked structures within the coating film. At this point, the curing agent may or may not be incorporated into the cross-linked structure.

[0146] In the case of a curing agent that can be incorporated into a cross-linked structure, it is preferable to have functional groups contained in the side chains of the aforementioned hydrophilic copolymer (specifically, functional group Z contained in structural unit (b)). 2 The functional group or structure of (B) component (alkoxysilyl group) undergoes a cross-linking reaction. In this case, the cross-linking can be any of a covalent bond, ionic bond, hydrogen bond, or coordinate bond, with a covalent bond being preferred.

[0147] As a curing agent that can be incorporated into a cross-linked structure, a curing agent having functional groups such as hydrolyzable silyl groups, isocyanate groups, epoxy groups, carbodiimide groups, oxazolyl groups, epoxy groups, hydroxyl groups, carboxyl groups, and amino groups, molecular structures such as siloxane structures and melamine structures, and metal ions are preferred.

[0148] Preferred combinations of functional groups of the side chains of crosslinkable hydrophilic copolymers with functional groups or structures of curing agents are shown in Table 1, for example.

[0149] [Table 1]

[0150]

[0151] As curing agents containing hydrolyzable silanes, examples include compounds containing hydrolyzable silanes, siloxane structures containing hydrolyzable silanes, and specifically, compounds represented by the following formula (6), compounds represented by the following formula (7), and hydrolyzed condensates of compounds represented by the following formula (7).

[0152] [Chemistry 16]

[0153]

[0154] In the above formula (6), R 8 and R 9 Each is 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.

[0155] Regarding R 8 and R 9 As for alkyl groups, they can be linear, branched, or cyclic. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, etc.

[0156] As R 8 and R 9 Specific examples of aryl groups include phenyl, tolyl, etc.

[0157] Of these, R 8 Preferably, it is an alkyl group having 1 to 3 carbon atoms, more preferably methyl or ethyl, R 9 Preferably, it is an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0158] In the above formula (6), 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.

[0159] i is an integer from 1 to 3, preferably 3.

[0160] Specific examples of compounds represented by the above formula (6) include N,N,N-tris(trimethoxysilylpropyl)isocyanurate, N,N,N-tris(triethoxysilylpropyl)isocyanurate, etc., but are not limited to these.

[0161] In the above formula (7), R 10 R 11 R 12 and R 13 Each of these groups independently represents a monovalent organic group consisting of 1 to 6 hydrogen or carbon atoms.

[0162] In equation (7), R 10 R 11 R 12 and R 13 The monovalent organic groups with 1 to 6 carbon atoms can be linear, branched, or cyclic. Examples include alkyl groups with 1 to 6 carbon atoms and alkenyl groups with 2 to 6 carbon atoms.

[0163] Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, etc.

[0164] Specific examples of alkenes with 2 to 6 carbon atoms include vinyl and allyl.

[0165] Of 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, and more preferably a methyl or ethyl group.

[0166] In formula (7), h represents an integer from 1 to 20, preferably an integer from 3 to 12, and more preferably an integer from 5 to 12. If h is less than 20, the viscosity of the coating liquid will increase excessively, and a highly uniform anti-fog film can be formed. In addition, if h is 1 or more, the reactivity of the compound represented by formula (5) can be easily controlled, and an anti-fog film with excellent hydrophilicity can be formed.

[0167] In this invention, the term "condensate of the compound represented by formula (7)" means Si-OR in the compound represented by formula (7). 10 Si-OR 11 Si-OR 12 and Si-OR 13 At least one of the compounds has a structure in which siloxane bonds (Si-O-Si) are formed. A condensate of a compound represented by formula (7) can be formed, for example, by the condensation or hydrolytic condensation of two or more molecules of the compound represented by formula (7). For hydrolytic condensation, R in formula (7) is used. 10 R 11 R 12 and R 13 Taking the case of methyl (-CH3) as an example, the following explanation will be given. In one example of hydrolysis condensation, Si-OCH3 is hydrolyzed to form Si-OH, and then Si-O-Si is formed by the dehydration condensation of Si-OH.

[0168] There are no particular restrictions on the structure of the hydrolysis condensate of the compound represented by formula (7), such as random type, linear type, ladder type, cage type, etc.

[0169] Furthermore, in the compounds represented by formula (7) and their hydrolytic condensates, R 10 R 11 R 12 and R 13 When R contains hydrogen atoms, the hydrogen atoms can be those contained in the compound added as a raw material during the manufacture of the compound in formula (7), or they can be hydrogen atoms introduced through hydrolysis. That is, in formula (7), R 10 R 11 R 12and R 13 When at least one of the atoms is a hydrogen atom, at least one of the Si-OH groups in formula (7) can be a Si-OH group contained in a compound added as a raw material during the manufacture of the compound of formula (7), or a Si-OH group formed by hydrolysis.

[0170] The compound represented by formula (7) may be a commercially available product. The compound represented by formula (7) may be obtained, for example, as MKC (registered trademark) Silicate (e.g., MS51, MS56) manufactured by Mitsubishi Chemical Co., Ltd.

[0171] The weight-average molecular weight (Mw) of the compound represented by formula (7) is preferably 300 to 1500, more preferably 500 to 1200. It should be noted that the weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) (standard substance: polyethylene glycol-polyethylene oxide).

[0172] Curing agents with isocyanate groups include aliphatic, alicyclic, or aromatic polyisocyanates.

[0173] Specifically, examples include isophorone diisocyanate, hexamethylene diisocyanate, phenyl diisocyanate, toluene diisocyanate, polyMDI, naphthalene diisocyanate, tetramethyl phenyl diisocyanate, trimethyl hexamethylene diisocyanate, lysine diisocyanate methyl ester, hydrogenated phenyl diisocyanate, diphenylmethane diisocyanate, methylene bis(4,1-cyclohexylene) diisocyanate, 1,3-bis(methyl isocyanate)cyclohexane, adducts of diisocyanate compounds with polyols such as trimethylolpropane, and isocyanurates or biuretates of diisocyanate compounds.

[0174] Among these, from the viewpoint of inhibiting yellowing of the coating, polyisocyanates derived from hexamethylene diisocyanate are preferred.

[0175] Curing agents with isocyanate groups are available as commercially available products, such as DURANATE (registered trademark) TPA-100, TKA-100, 24A-100, 22A-75P, P301-75E manufactured by Asahi Kasei Corporation; Coronate (registered trademark) HX, HK, 2715 manufactured by Tosoh Corporation; and Takenate (registered trademark) 500, 600 manufactured by Mitsui Chemicals Co., Ltd.

[0176] These can be used individually or in combination with two or more.

[0177] As a curing agent with a melamine structure, melamine resin is preferred. Specific examples include guanidineamine, melamine, N-butylmelamine, N-phenylmelamine, N,N-diphenylmelamine, N,N-diallylmelamine, N,N',N'"-triphenylmelamine, N,N',N'"-tris(hydroxymethylmelamine), benzoguanidine, 2,4-diamino-6-methyl-triazine, and 2,4-diamino-6-butyl-triazine. Condensations of melamines such as 2,4-diamino-6-benzyloxy-triazine, 2,4-diamino-6-butoxy-triazine, 2,4-diamino-6-cyclohexyl-triazine, 2,4-diamino-6-chloro-triazine, 2,4-diamino-6-mercapto-triazine, and melamine diamide (N,N,N',N'-tetracyanoethylbenzoguanidine) with formaldehyde and alcohols (such as methanol).

[0178] Curing agents with melamine structures are available as commercially available products, such as U-VAN (registered trademark) 20SE and 225 manufactured by Mitsui Chemicals Co., Ltd.; and AMIDIR (registered trademark) L-117-60, L-109-65, 47-508-60, L-118-60, G821-60, and J820-60 manufactured by DIC Co., Ltd.

[0179] These can be used individually or in combination with two or more.

[0180] Examples of epoxy-based curing agents include aliphatic, alicyclic, or aromatic diepoxides and triepoxides.

[0181] Specifically, examples include 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether (bisphenol A diglycidyl ether), ethylene glycol diglycidyl ether, triglycidyl isocyanurate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene-based epoxy resin, biphenyl type epoxy resin, phenolic varnish resin type epoxy resin, 1,5-hexadiene diepoxide, 1,4-pentadiene diepoxide, and 1,2: 6,7-Diepoxyheptane, 1,2:8,9-Diepoxynonane, 2,2'-(1,6-hexene)bisepoxyethylene, 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-oxoane, 1,6-diepoxynaphthalene, triepoxydecane, etc.

[0182] These can be used individually or in combination with two or more.

[0183] Examples of curing agents containing amino groups include aliphatic, alicyclic, or aromatic diamines, triamines, and tetraamines containing primary or secondary amines.

[0184] Specifically, examples include hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 2-methyl-1,5-diaminopentane, 3,3-dimethylbutane-1,2-diamine, 4-methylpentane-1,2-diamine, 2,2,4,4-tetramethylcyclobutane, 2-methylcyclohexane-1,3-diamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 2,3-diaminotoluene, 2,5-dimethylbenzene-1,2-diamine, 3,4-dimethylbenzene-1,2-diamine, 2,6-dimethylbenzene-1,4-diamine, 2,4-dimethylbenzene-1,3-diamine, 3,5-dimethyl-1,2-phenylenediamine, and 4-ethylbenzene-1... 3-Diamine, 2,5-Dimethylphenyl-1,4-Diamine, 4-Methoxyphenyl-1,3-Diamine, 4-(1,1-Dimethylethyl)-1,2-phenylenediamine, p-phenylenediamine, o-phenylenediamine, N-Isopropyl-1,3-Propanediamine, N-Hexylethylenediamine, 5-Isopropylaminopentylamine, n-Butylethylenediamine, N-T-Butylbutane-1,4-Diamine, N-Ethylhexane-1,6-Diamine, N-Isobutylethane-1,2-Diamine, N-Cyclohexyl-1,2-Ethylenediamine, N-1-Methylcyclohexane-1,4-Diamine, N-Methylphenyl-1,2-Diamine, N-Phenyleneethylenediamine, N-Ethylphenyl-1,2-Diamine, N-1-Methylphenyl-1,3-Diamine, 4-Amino-N-Methylaniline, 2-Aminodiphenylamine 4-Aminodiphenylamine, N-1,4-dimethylphenyl-1,2-diamine, N-1,5-dimethylphenyl-1,2-diamine, N-isopropylphenyl-1,2-diamine, N-(3-aminophenyl)-N-phenylamine, N,N'-dimethyltrimethylenediamine, N,N'-diethylbutanediamine, N,N'-diisopropyl-2,3-butanediamine, 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-phenylenediamine, 1,2,4-triaminobenzene, 2,4,5-triaminotoluene, 2,4,6-triaminotoluene, 2,3,4-triaminotoluene, 3,5,6-triaminotoluene, 3-N-methylbenzene-1,2,3-triamine, 2-N-methylbenzene-1,2,3-triamine, 4-N-methylbenzene-1,2,4-triamine, 1-N-methylbenzene-1,2,4-triamine, 3-N-methylbenzene-1,3,5-triamine, 1-N',1-N”-Diethylpropane-1,1,1-triamine, 4-(3,4-diaminophenyl)benzene-1,2-diamine, 1-N,1-N,2-N,2-N,3-N,3-N,4-N,4-N-octamethylbutane-1,2,3,4-tetramine, 4-[3-amino-4-(methylamino)phenyl]benzene-1,2-diamine, etc.

[0185] These can be used individually or in combination with two or more.

[0186] Examples of curing agents containing carbodiimide groups include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, tert-butylisopropylcarbodiimide, diphenylcarbodiimide, di-tert-butylcarbodiimide, di-β-naphthylcarbodiimide, and N-isopropyl-N'-[2-(methacryloyloxy)ethyl]carbodiimide.

[0187] These can be used individually or in combination with two or more.

[0188] Examples of curing agents containing oxazoline groups include 2,2'-bis(2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 1,3-bis(4,5-dihydro-2-oxazoline), and 1,4-bis(4,5-dihydro-2-oxazoline).

[0189] These can be used individually or in combination with two or more.

[0190] Examples of aluminum-containing organic compounds that act as curing agents containing metal ions include ethyl acetoacetate diisopropoxyaluminum.

[0191] From the viewpoint of ease of processing, curing agents having isocyanate groups or melamine structures are preferred, and those containing Z are more preferred. 1 A hydrophilic copolymer of a hydroxyl structural unit (b) combined with a curing agent having an isocyanate group or a melamine structure, further preferably containing Z 1 A hydrophilic copolymer of a hydroxyl structural unit (b) combined with a polyisocyanate or melamine resin.

[0192] That is, a preferred embodiment of the present invention is a hydrophilic composition comprising the above-mentioned hydrophilic copolymer and a polyisocyanate or melamine resin as a curing agent. Wherein, Z... 1 When a hydrophilic copolymer of a hydroxyl structural unit (b) is combined with a curing agent (polyisocyanate) having an isocyanate group, the crosslinking reaction occurs even at low temperatures (e.g., below 110°C), and the composition of the present invention can form a coating film on a substrate with low heat resistance, and is therefore particularly preferred.

[0193] On the other hand, examples of curing agents (curing catalysts) that are not bound to the cross-linked structure include inorganic acids, organic acids, organometallic salts, Lewis acids, etc.

[0194] Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, and aminosulfonic acid.

[0195] Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p-toluenesulfonic acid, and citric acid.

[0196] Examples of organometallic salts 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.

[0197] Examples of Lewis acids include tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxy, aluminum triisopropoxy, aluminum acetylacetonate, tin chloride (SnCl4), titanium chloride (TiCl4), and zinc chloride (ZnCl4).

[0198] In addition, alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctanoate, and dioctyltin ditert-tert-carbonate are also preferred.

[0199] These can be used individually or in combination with two or more.

[0200] In addition, curing agents that can be bonded to cross-linked structures can be appropriately combined with unbonded curing agents (curing catalysts).

[0201] When the hydrophilic composition of the present invention contains a curing agent, its content is preferably 0.05 to 50 parts by weight, more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the above-mentioned hydrophilic copolymer.

[0202] The hydrophilic composition of the present invention preferably further comprises a hydrophilic organosilicon compound and / or its hydrolytic condensate represented by the following formula (10).

[0203] [Chemistry 17]

[0204]

[0205] In equation (10), R 18 and R 19Each is 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 and aryl groups can be listed, including those relating to R. 6 The same groups are illustrated in the examples, among which methyl is preferred.

[0206] R 20 It is a divalent organic group containing an aromatic ring with 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, more preferably a divalent organic group containing an aromatic hydrocarbon ring, more preferably a divalent organic group containing a benzene ring or a naphthalene ring, and even more preferably an arylene or arylene alkyl group containing a benzene ring or a naphthalene ring.

[0207] As R 20 Specific examples of arylene groups include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, and naphthylene.

[0208] As R 20 Specific examples of arylene compounds include methylene phenylene, ethyl phenylene, methylene phenylene methylene, and ethyl phenylene ethylene.

[0209] Of these, R 18 Phenylidene is preferred, and 1,4-phenylene is more preferred.

[0210] R 21 and R 22 Each of the alkyl groups, representing 1 to 6 carbon atoms, can be independently represented as a specific example, along with R. 6 The groups exemplified herein are the same as those having 1 to 6 carbon atoms, among which methyl is preferred.

[0211] X 5 The alkylene group refers to an alkylene group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.

[0212] Regarding X 5 As for alkylene compounds, they can be linear, branched, or cyclic. Specific examples include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, and cyclohexylene.

[0213] Among these, X 5 Methylene, ethylene, and trimethylene are preferred, with trimethylene being more preferred.

[0214] Z 4 COO - SO3 - , or PO4 - From the viewpoint of the durability of the obtained coating, SO3 is preferred. - .

[0215] o is an integer from 1 to 3, preferably 3.

[0216] The following are specific examples of such hydrophilic organosilicon compounds, but are not limited to these. Among these, the examples represented by formula (11) are preferred.

[0217] [Chemistry 18]

[0218]

[0219] (In the formula, Me represents methyl and Et represents ethyl.)

[0220] The content of the hydrophilic organosilicon compound in the hydrophilic composition of the present invention is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the above-mentioned hydrophilic copolymer, and more preferably 0.1 to 1 part by mass.

[0221] The hydrophilic composition of the present invention may include a solvent as needed. There are no particular limitations as long as the solvent is capable of dissolving or dispersing the hydrophilic copolymer, the curing agent that may be used as appropriate, the hydrophilic organosilicon compound and other additives without reacting with the components, and can be easily removed in the drying process described later.

[0222] Specific examples of solvents 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.

[0223] For example, when using polyisocyanates as curing agents, it is preferable to use solvents that do not react with isocyanate groups (such as ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone).

[0224] These can be used individually or in combination with two or more.

[0225] The hydrophilic composition of the present invention may further include, as needed, 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, and dispersants.

[0226] Regarding the concentration of solid components in the composition, from the viewpoint of coatability and workability, it is preferably 5 to 80% by mass, more preferably 10 to 30% by mass.

[0227] Regarding the viscosity of the composition, from the viewpoint of coatability and workability, it is preferably 0.01 to 0.05 Pa·s (at 25°C).

[0228] The composition of the present invention can be a single-component type (1 liquid type) or a type in which two or more liquid components are mixed before use.

[0229] The compositions of the present invention can impart hydrophilicity to various substrates by being applied to them.

[0230] Specific examples of materials constituting the aforementioned substrate include, for instance, glass; synthetic resins {polymethyl methacrylate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, ABS resin, polycarbonate resin, polystyrene resin, epoxy resin, unsaturated polyester resin, melamine resin, diallyl phthalate resin, polyimide resin, polyurethane resin, nylon resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, fluoropolymers (polytetrafluoroethylene resin, polyvinyl chloride resin, polyvinylidene fluoride resin, perfluoroalkoxy fluoropolymer, tetrafluoroethylene-hexafluoropropylene copolymer resin, ethylene tetrafluoroethylene copolymer resin, ethylene-chlorotrifluoroethylene...} Fluoroethylene copolymer resins, etc.), polybutadiene, polyisopropylene, SBR, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, chloroprene rubber, polysulfide, butyl rubber, etc.; metals (iron, aluminum, stainless steel, titanium, copper, brass, their alloys, etc.); cellulose, cellulose derivatives, cellulose analogs (chitosan, chitosan, laver polysaccharide, etc.), natural fibers such as cotton, silk, and wool, regenerated fibers such as rayon, semi-synthetic fibers such as acetate, synthetic fibers such as vinylon, polyester, nylon, polyethylene, polypropylene, polyurethane, and aromatic polyamide fibers; composite fibers of these fibers (polyester / cotton, etc.), etc., as their forms, can be listed as substrates, sheets, films, fibers, and various items using these materials, etc.

[0231] The compositions of the present invention can be applied to form a coating film on the surface of a substrate or the like using known coating methods, thereby producing a hydrophilic coating film.

[0232] Coating methods include, for example, bar coating, dip coating, spin coating, spray coating, flow coating, brush coating, gravure coating, roller transfer printing, doctor blade coating, air knife coating, slot coating, screen coating, inkjet printing, and flexographic printing. Among these, bar coating is preferred.

[0233] A cured coating film can be obtained by applying the composition to a substrate and then heating it.

[0234] The heating temperature is preferably 40–250°C, more preferably 80–120°C. The drying time is preferably 10 seconds–12 hours, more preferably 30 seconds–3 hours.

[0235] It should be noted that pre-drying can be performed under the same conditions as described above to remove the solvent from the composition.

[0236] The heating atmosphere can be any of the following: air atmosphere or inactive gas atmosphere (such as nitrogen, argon, etc.).

[0237] There are no particular limitations on the thickness (dry film thickness) of the coating film of the present invention, which is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm.

[0238] Example

[0239] The following examples and comparative examples illustrate the invention in more detail, but the invention is not limited to these examples.

[0240] (1) Manufacturing of hydrophilic copolymers

[0241] [Synthesis example 1]

[0242] 258.35 g of methyl ethyl ketone, 101.55 g of DMAPAA (a registered trademark, manufactured by KJ Chemicals Corporation) represented by formula (12), 5.81 g of hydroxyethyl acrylate (manufactured by Tokyo Chemicals Co., Ltd.) represented by formula (13), and 3.36 g of V-59 (manufactured by Fujifilm and Kagaku Pure Chemicals Co., Ltd.) (an oil-soluble azo polymerization initiator represented by formula (14)) were added to the reactor and reacted at 80°C for 4 hours.

[0243] After the reaction, 216.00 g of 2-propanol (IPA) was added and filtered to obtain 360 g of methyl ethyl ketone-IPA (3:2, wt / wt) solution of hydrophilic copolymer P1 (containing 93% by mass of structural unit (a) and 7% by mass of structural unit (b); weight average molecular weight 400,000) (solid component concentration 25% by mass, designated as A-1).

[0244] [Chemistry 19]

[0245]

[0246] [Synthesis example 2]

[0247] 258.23 g of methyl ethyl ketone, 101.55 g of DMAPAA (a registered trademark, manufactured by KJ Chemicals Corporation) represented by the above formula (12), 5.76 g of HEAA (a registered trademark, manufactured by KJ Chemicals Corporation) represented by the following formula (15), and 3.36 g of V-59 (manufactured by Fujifilm and Kohden Chemical Co., Ltd.), an oil-soluble azo polymerization initiator represented by the above formula (14), were added to the reactor and reacted at 80°C for 4 hours.

[0248] 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 of hydrophilic copolymer P2 (containing 93% by mass of structural unit (a) and 7% by mass of structural unit (b); weight average molecular weight 420,000) (solid component concentration 25% by mass, designated as A-2).

[0249] [Chemistry 20]

[0250]

[0251] (2) Preparation of coating composition (hydrophilic composition)

[0252] [Examples 1-12, Comparative Examples 1-10]

[0253] A hydrophilic composition was prepared by mixing the following components according to the mixing compositions (parts by mass) shown in Tables 2 and 3 below.

[0254] [Table 2]

[0255]

[0256] [Table 3]

[0257]

[0258] It should be noted that the abbreviations in Table 1 are as follows.

[0259] A-1: Methyl ethyl ketone-IPA solution of the hydrophilic copolymer P1 obtained in Synthesis Example 1

[0260] A-2: Methyl ethyl ketone-IPA solution of the hydrophilic copolymer P2 obtained in Synthesis Example 2

[0261] B-1: Silane compounds represented by the above formula (8-a)

[0262] B-2: Silane compounds represented by the above formula (8-b)

[0263] B-3: Silane compounds represented by the above formula (4-a)

[0264] B'-1:3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)

[0265] B'-2:3-Isocyanate-propyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-9007)

[0266] C-1: Tris(trimethoxysilylpropyl)isocyanurate (Shin-Etsu Chemical Co., Ltd., KBM-9659)

[0267] C-2: MKC (registered trademark) Silicate MS51 (manufactured by Mitsubishi Chemical Co., Ltd.), a partially hydrolyzed oligomer of tetramethoxysilane.

[0268] D-1: Silane compound represented by the above formula (11) NEOSTANN U-830: Dioctyltin catalyst (made by Nitto Chemical Co., Ltd.)

[0269] (3) Evaluation of the storage stability of hydrophilic compositions

[0270] As in the above examples and comparative examples, after the hydrophilic composition was prepared, 40g of each composition was measured into a 50mL polyethylene container and left to stand for 3 months in a thermostat (SPHH-201, ESPEC Corp.) set at 40°C.

[0271] Three months later, the sample was removed from the dryer and allowed to stand for one hour at 25°C / 50% relative humidity before being observed. The evaluation criteria for storage stability are as follows.

[0272] ○: The composition maintains fluidity.

[0273] ×: The composition solidifies into a gel-like state.

[0274] (4) Coating preparation and evaluation

[0275] As in the examples and comparative examples described above, after the hydrophilic composition was prepared, it was coated onto a polycarbonate sheet using a rod coater (No. 14) and immediately dried at 120°C for 1 hour to obtain a hydrophilic coating. The following tests were performed on the obtained coatings, and the results are shown in Table 3.

[0276] [Anti-fog properties]

[0277] Exhaled air was sprayed onto each of the above-mentioned membranes. The condition where the membrane surface fogged up was marked as ×, and the condition where no fogging occurred was marked as ○. Then, the membrane was placed above a 40°C warm water bath at a height of 3cm above the water surface for 1 minute. The condition where no fogging occurred on the membrane surface was marked as ◎. The anti-fogging performance was evaluated.

[0278] [Water resistance]

[0279] Each of the above-mentioned films was immersed in tap water at 25°C for 24 hours, the surface water was absorbed with paper towels, and then naturally dried at 25°C for 10 minutes to evaluate the anti-fogging properties.

[0280] Next, each film was further soaked in tap water for 240 hours, the surface water was absorbed with paper towels, and then it was naturally dried at 25°C for 10 minutes to evaluate the anti-fogging properties.

[0281] [Moisture resistance]

[0282] Each of the above-mentioned films was placed in a constant temperature and humidity chamber (KCL-2000W, Tokyo Rika Kyodo Co., Ltd.) set at 50°C and 98%RH for 240 hours. Then, it was naturally dried at 25°C for 10 minutes, and the anti-fogging properties were evaluated as described above.

[0283] [Table 4]

[0284]

[0285] As shown in Table 4, the compositions of Examples 1-12 containing blocked isocyanate silane compounds exhibit good storage stability, maintaining excellent hydrophilicity and anti-fogging 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). The coating of Example 6 exhibits particularly excellent durability.

[0286] On the other hand, it was found that the anti-fogging properties of the films in Comparative Examples 1 and 6, which did not contain blocked isocyanate silane compounds, disappeared after immersion in water for 24 hours, and their water resistance was poor. In addition, it was found that the compositions of Comparative Examples 2 and 7, which contained unblocked isocyanate silane compounds, and Comparative Examples 3 and 8, which contained 3-glycidoxypropyltrimethoxysilane, had poor storage stability.

[0287] Furthermore, it is known that the cured films obtained from the compositions of Comparative Examples 4 and 9, which contain excessive amounts of blocked isocyanate silane compounds, have poor anti-fogging properties.

Claims

1. A hydrophilic composition comprising: (A) A hydrophilic copolymer comprising 100 parts by weight of structural units represented by formula (1) and structural units represented by formula (2) below. (B) Blocked isocyanate silane compounds: 0.001–10 parts by weight, [Chemistry 1] In equation (1), R 1 R represents a hydrogen atom or a methyl group. 2 Each of these groups independently represents an alkyl group with 1 to 6 carbon atoms, where n represents an integer from 1 to 6. In equation (2), R 3 X represents a hydrogen atom or a methyl group. 1 Indicates -NH- or -O-, Z 1 This represents a hydrogen atom, methyl group, hydroxyl group, carboxyl group, or amino group, where m represents an integer from 0 to 10. When m is 0, Z 1 It represents a hydrogen atom or a methyl group, and the asterisk * indicates a bond with an adjacent structural unit.

2. The hydrophilic composition according to claim 1, wherein, The (B) blocked isocyanate silane compound is represented by the following formula (3), [Chemistry 2] In the formula, R 4 Each of these groups independently represents an alkyl group with 1 to 8 carbon atoms, L represents a divalent linking group, and X represents a divalent linking group. 2 Indicates -O- or -NR 5 -, Z 2 R represents a hydrogen atom or a monovalent organic group. 5 It represents hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, or substances capable of reacting with Z. 2 Groups bonded to form a ring structure, where k represents an integer from 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), [Chemistry 3] In the formula, R 4 R 5 Z 2 And k represents 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 They can be connected to form a ring structure.

4. The hydrophilic composition according to claim 1, further comprising at least one compound selected from polyisocyanate compounds, organosilicon compounds represented by formula (6), and organosilicon compounds represented by formula (7). [Chemistry 4] In equation (6), R 8 and R 9 Each can independently represent an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms, where j represents an integer from 1 to 10 and i represents an integer from 1 to 3. In equation (7), R 10 R 11 R 12 and R 13 Each of the following groups independently represents an organic group with 1 to 6 hydrogen atoms or carbon atoms, and h represents an integer from 1 to 20.

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

6. A hydrophilic coating, which is a hydrophilic coating formed by curing the coating agent according to claim 5.

7. A coated article having a substrate and a hydrophilic coating according to claim 6 formed directly or indirectly on at least one side of the substrate by one or more other layers.

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