Antifogging agent, antifogging coating composition containing the same, and structure having cured layer of the composition

Abstract

To provide an antifogging agent having extremely improved water resistance compared with a conventional antifogging agent, and as a result, having extremely excellent durability.SOLUTION: A surfactant exhibiting antifogging properties is fixed in a coating film through a chemical bond such as an ester bond or an amide bond, and the coating film is crosslinked by a crosslinking agent and fixed to a substrate by a chemical bond.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a coatable anti-fogging agent that has high durability, a significant anti-fogging effect, and can be produced at low cost, an anti-fogging coating composition containing the same, and a structure having a layer formed by curing the composition (hereinafter, sometimes referred to as an anti-fogging agent, etc.). More specifically, the present invention relates to a novel anti-fogging agent and the like, in which, when a coating film is formed, functional groups that exhibit anti-fogging properties are chemically bonded to a polymer film formed from a polymer having a hydroxyl group and / or an amino group contained in the anti-fogging agent, and the polymer film is firmly fixed to a substrate such as a plastic substrate made of polycarbonate or the like through chemical bonds, resulting in improved durability of the anti-fogging properties of the coating film as a layer formed by curing the composition. [Background technology]

[0002] The present inventors have already invented Patent Document 1, which relates to an anti-fogging agent using a water-soluble polymer and a surface-active silane coupling agent.

[0003] However, even in lenses coated with an anti-fog coating composition liquid made from the anti-fog agent materials described in this document, the surface-active silane coupling agent that exhibits anti-fog properties is not sufficiently chemically bonded to the water-soluble polymer or the substrate plastic via silanol groups, and there is a demand for anti-fog agents with higher water resistance and abrasion resistance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-91859 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above-mentioned prior art, and an object of the present invention is to provide a highly durable anti-fog agent which has high water resistance and abrasion resistance, a high anti-fog effect, can be produced at low cost, and is suitable for use as an anti-fog coating for eyeglasses, sunglasses, goggles, helmets, etc., or as a coating for vehicle headlight covers; an anti-fog coating composition containing the same; and a structure having a layer formed by curing the anti-fog coating composition. [Means for solving the problem]

[0006] As a result of intensive research conducted by the present inventors while taking into consideration the problems of the above-mentioned conventional techniques, It is expressed by the following formula (1), and Y 1 is —CH2COOH (surfactant 1) and / or a compound represented by the following formula (1), 1 a reaction product (surfactant 3) of a compound in which is a hydrogen atom and an acid anhydride compound; a polymer having a hydroxyl group and / or an amino group; and a crosslinking agent; or It is expressed by the following formula (1), and Y 1 is a hydrogen atom (surfactant 2); a polycarboxylic acid that is a hydrolyzate of an acid anhydride compound or a crosslinking agent; and a polymer having a hydroxyl group and / or an amino group, the surfactants 1 and / or 3, or surfactant 2, etc. are more easily fixed in a coating film coated with the antifogging agent through chemical bonds such as ester bonds or amide bonds than with conventional surface-active silane coupling agents, and as a result, the above-mentioned problems can be solved, leading to the present invention. R 1 -X 1 -(CH2CH2O) m -Y 1 (1) {R in formula 1 represents an alkyl group having 1 to 20 carbon atoms (the alkyl group may be substituted with a hetero atom and / or a benzene ring and / or a group containing a double bond), X 1 is -O-, -COO-, or -CONH-, m is an integer of 1 to 30, and Y 1 represents a hydrogen atom or -CH2COOH}

[0007] That is, the present invention is characterized by the following constitution and solves the above-mentioned problems. [1] Represented by the following formula (1), Y 1 is -CH2COOH, and / or It is expressed by the following formula (1), and Y 1 a reaction product of a compound in which is a hydrogen atom with an acid anhydride compound; a polymer having hydroxyl and / or amino groups; and Contains a crosslinking agent, or It is expressed by the following formula (1), and Y 1 is a hydrogen atom; Polycarboxylic acids or crosslinking agents that are hydrolyzates of acid anhydride compounds; and Contains a polymer with hydroxyl groups and / or amino groups An anti-fogging agent characterized by: R 1 -X 1 -(CH2CH2O) m -Y 1 (1) {R in formula 1 represents an alkyl group having 1 to 20 carbon atoms (the alkyl group may be substituted with a hetero atom and / or a benzene ring and / or a group containing a double bond), X 1 is -O-, -COO-, or -CONH-, m is an integer of 1 to 30, and Y 1 represents a hydrogen atom or -CH2COOH} [2] The anti-fogging agent according to [1], wherein the acid anhydride compound contains two or more acid anhydride groups. [3] The anti-fogging agent according to [1] or [2], wherein the functional group of the crosslinking agent is a blocked isocyanate group and / or a carboxyl group. [4] An anti-fog coating composition comprising the anti-fog agent according to [1] or [2]. [5] An anti-fogging coating composition comprising the anti-fogging agent according to [3]. [6] A structure having a layer of the cured anti-fog coating composition according to [4]. [7] A structure having a layer of the cured anti-fog coating composition according to [5]. [Effects of the Invention]

[0008] When a coating film is formed using the anti-fogging agent of the present invention, surfactants 1 and / or 3, or surfactant 2, etc. are fixed to a film (polymer film) formed from the polymer having the hydroxyl group or amino group through chemical bonds such as ester bonds or amide bonds, and the polymer film is fixed to the substrate through chemical bonds with a crosslinking agent, thereby improving water resistance and abrasion resistance, and as a result, improving the durability of the anti-fogging properties. DETAILED DESCRIPTION OF THE INVENTION

[0009] The antifogging agent of the present invention is represented by the following formula (1): 1 is —CH2COOH (hereinafter, may be referred to as surfactant 1), and / or a compound represented by the following formula (1), 1 is a hydrogen atom (hereinafter, may be referred to as surfactant 2) and a reaction product of an acid anhydride compound (hereinafter, may be referred to as surfactant 3); a polymer having hydroxyl and / or amino groups; and Contains a crosslinking agent, or It is expressed by the following formula (1), and Y 1 is a hydrogen atom (surfactant 2); Polycarboxylic acids or crosslinking agents that are hydrolyzates of acid anhydride compounds; and It contains a polymer having hydroxyl groups and / or amino groups. R 1 -X 1 -(CH2CH2O) m -Y 1 (1) {R in formula 1 represents an alkyl group having 1 to 20 carbon atoms (the alkyl group may be substituted with a hetero atom and / or a benzene ring and / or a group containing a double bond), X 1 is -O-, -COO-, or -CONH-, m is an integer of 1 to 30, and Y 1 represents a hydrogen atom or -CH2COOH}

[0010] The anti-fogging agent of the present invention is characterized in that, when a coating film is formed, surfactants 1 and / or 3, or surfactant 2, etc., which exhibit anti-fogging properties, are fixed to a film (polymer film) formed from a polymer having a hydroxyl group or an amino group through chemical bonds such as ester bonds or amide bonds, and the polymer film is crosslinked and fixed to a substrate through chemical bonds such as urethane bonds or ester bonds.

[0011] In the compound represented by the formula (1) which is a raw material of the compound of the present invention, R 1 Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a palmitoleyl group, a heptadecyl group, an octadecyl group, an oleyl group, and a 4-(1,1,3,3-tetramethylbutyl)phenyl group. Of these, in consideration of the availability of raw materials, preferred are methyl, decyl, dodecyl, tetradecyl, oleyl, and 4-(1,1,3,3-tetramethylbutyl)phenyl groups.

[0012] X 1 is -O-, -COO- or -CONH-. m is a natural number of 1 to 30, and preferably 1 to 15. Y 1 is a hydrogen atom or -CH2COOH.

[0013] The compound represented by formula (1) is a surfactant, and commercially available surfactants can be used. Commercially available surfactants made of the compound represented by formula (1) usually do not have a constant number of ethylene oxide additions, and as a result, they are not a single surfactant but exist as a mixture of surfactants with different numbers of ethylene oxide additions. In the case of a mixture of compounds represented by the formula (1), m is preferably 14 or less on average.

[0014] Represented by the formula (1), Y 1 Specific examples of the compound (surfactant 1) in which is —CH2COOH include the following: C 12 H 25 O(CH2CH2O)5CH2COOH C 13 H 27 O(CH2CH2O)3CH2COOH

[0015] Represented by the formula (1), Y 1 Specific examples of the compound (surfactant 2) in which is a hydrogen atom include the following: CH3O(CH2CH2O)2H CH3O(CH2CH2O)3H CH3O(CH2CH2O)4H C 12 H 25 O(CH2CH2O)8H C 12 H 25 O(CH2CH2O)9H C 12 H 25 O(CH2CH2O) 10 H C 17 H 35 COO(CH2CH2O)9H C 17 H 33 COO(CH2CH2O)9H C 17 H 33 COO(CH2CH2O) 14 H C 17 H 35 CONHCH2CH2OH (CH3)3CCH2C(CH3)2-C6H4-O(CH2CH2O)9H (CH3)3CCH2C(CH3)2-C6H4-O(CH2CH2O) 10 H

[0016] C4F9CH2O(CH2CH2O) q H C4F9CH2CH2O(CH2CH2O)q H C6F 13 CH2O(CH2CH2O) q H C6F 13 CH2CH2O(CH2CH2O) q H Here, q represents an integer of 1 to 30.

[0017] Examples of the other raw material, an acid anhydride compound, include succinic anhydride, maleic anhydride, phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-methylhexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, cyclohex-4-ene-1,2-dicarboxylic anhydride, citraconic anhydride, 2,3-pyrazinedicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, mellitic dianhydride, tetralin dianhydride, butanetetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, mellitic anhydride, and 3-trimethoxysilylpropylsuccinic anhydride, and mixtures thereof.

[0018] Of these, preferred are succinic anhydride, pyromellitic anhydride, trimellitic anhydride, mellitic dianhydride, tetralin dianhydride, butanetetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, mellitic anhydride, 3-trimethoxysilylpropylsuccinic anhydride, and mixtures thereof.

[0019] The antifogging agent of the present invention can be obtained by adding the surfactant and the polycarboxylic acid or the crosslinking agent separately as components of the antifogging agent, without reacting the surfactant with the acid anhydride compound and then adding the reacted compound as a component of the antifogging agent. Alternatively, the surfactant and the polycarboxylic acid may be reacted separately in advance and then added as a component of the anti-fogging agent. The reaction between the surfactant and the acid anhydride compound occurs rapidly and quantitatively at room temperature, almost 100%. In contrast, the reaction with the polycarboxylic acid requires heating to about 50°C or higher, and the reaction occurs when the compound is heated after coating.

[0020] Examples of hydrolyzates of acid anhydrides include succinic acid, maleic acid, phthalic acid, 1,2-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, cyclohex-4-ene-1,2-dicarboxylic acid, citraconic acid, 2,3-pyrazinedicarboxylic acid, pyromellitic acid, trimellitic acid, mellitic acid, butanetetracarboxylic acid, and cyclobutane-1,2,3,4-tetracarboxylic acid. Examples of polycarboxylic acids include adipic acid, X-12-1135 manufactured by Shin-Etsu Chemical Co., Ltd., and mixtures thereof.

[0021] Examples of the crosslinking agent include compounds or sols in which multiple isocyanate groups, blocked isocyanate groups, carboxyl groups, and epoxy groups are bonded, and mixtures thereof. Also, polycarboxylic acids, which are hydrolyzates of acid anhydride compounds, and compounds represented by the formula (1) above, wherein Y 1 Among the reaction products of a compound in which Y is a hydrogen atom and an acid anhydride compound, a reaction product having two or more carboxyl groups can also be used as a crosslinking agent. The reaction product having two or more carboxyl groups is represented by the above formula (1), 1 is obtained by reacting a compound in which is a hydrogen atom with an acid anhydride compound containing two or more acid anhydride groups.

[0022] Examples of compounds having a plurality of bonded isocyanate groups include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and mixtures thereof.

[0023] Examples of compounds having a plurality of blocked isocyanate groups bonded thereto include the above polyisocyanate compounds bonded with a blocking agent (3,5-dimethylpyrazole, ε-caprolactam, diethylmalonic acid), and mixtures thereof.

[0024] Examples of sols having multiple blocked isocyanate groups bonded thereto include those obtained by reacting a silane coupling agent having blocked isocyanate groups bonded thereto (e.g., X-12-1308ES manufactured by Shin-Etsu Chemical Co., Ltd.) with a sol (e.g., methanol silica sol manufactured by Nissan Chemical Industries, Ltd.).

[0025] Examples of compounds having multiple bonded carboxyl groups include succinic acid, maleic acid, phthalic acid, 1,2-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, cyclohex-4-ene-1,2-dicarboxylic acid, citraconic acid, 2,3-pyrazinedicarboxylic acid, pyromellitic acid, trimellitic acid, mellitic acid, butanetetracarboxylic acid, cyclobutane-1,2,3,4-tetracarboxylic acid, adipic acid, X-12-1135 manufactured by Shin-Etsu Chemical Co., Ltd., and mixtures thereof.

[0026] Examples of sols having multiple bonded carboxyl groups include those obtained by hydrolyzing the acid anhydride groups and alkoxy groups of a silane coupling agent having bonded acid anhydride groups (e.g., X-12-967C manufactured by Shin-Etsu Chemical Co., Ltd.) and then reacting it with a sol (e.g., methanol silica sol manufactured by Nissan Chemical Industries, Ltd.).

[0027] Examples of compounds having multiple bonded epoxy groups include X-12-981S and X-12-984S manufactured by Shin-Etsu Chemical Co., Ltd., and EX-612, EX-614, EX-614B, EX-313, EX-314, EX-421, EX-512, EX-521, EX-1610, EX-321, EX-321L, EX-622 manufactured by Nagase ChemteX Co., Ltd., and mixtures thereof.

[0028] Examples of the sol having multiple epoxy groups bonded thereto include those obtained by reacting a silane coupling agent having epoxy groups bonded thereto (for example, KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.) with a sol (for example, methanol silica sol manufactured by Nissan Chemical Co., Ltd.).

[0029] Among these, preferred are sols having a plurality of blocked isocyanate groups bonded thereto and compounds having a plurality of carboxyl groups bonded thereto.

[0030] Represented by the formula (1), Y 1 Examples of reaction products of a compound in which is a hydrogen atom with an acid anhydride compound include the following: R 1 -X 1 -(CH2CH2O) m -C(O)-CH2CH2-COOH R 1 -X 1 -(CH2CH2O) m -C(O)-Ph-COOH [R 1 -X 1 -(CH2CH2O) m -C(O)-C(CH2COOH)-2 [R 1 -X 1 -(CH2CH2O) m -C(O)CH2-C(COOH)-2 R 1 -X 1 -(CH2CH2O) m -C(O)-C(CH2COOH)-C(COOH)-CCH2CO(OCH2CH2) m -X 1 -R 1 {where, R 1 , X 1 and m is the same as in formula (1), and Ph represents a 1,2-phenylene group.

[0031] The anti-fogging agent of the present invention may mainly be in the following forms (i) to (iv). (i) Represented by the above formula (1), Y 1is -CH2COOH (Surfactant 1); Polymers containing hydroxyl and / or amino groups; and Crosslinking agent Contains: (ii) Represented by the above formula (1), Y 1 is a hydrogen atom (surfactant 2) and an acid anhydride compound (surfactant 3); Polymers containing hydroxyl and / or amino groups; and Crosslinking agent Contains: (iii) · Expressed by the following formula (1), Y 1 is a hydrogen atom (surfactant 2); Polycarboxylic acids or crosslinkers that are hydrolyzates of acid anhydride compounds; and Polymers containing hydroxyl and / or amino groups Contains: (iv) Represented by the above formula (1), Y 1 is a hydrogen atom (surfactant 2) with an acid anhydride compound containing two or more acid anhydride groups (surfactant 3, which is also a crosslinker); and Polymers containing hydroxyl and / or amino groups Contains: In addition, form (i) further includes "represented by the formula (1), Y 1 is a hydrogen atom (surfactant 2) with an acid anhydride compound (surfactant 3)." Form (ii) may further include "a reaction product of a compound represented by the formula (1), Y 1 The surfactant may contain a compound in which the moiety is -CH2COOH (surfactant 1).

[0032] Generally, surfactants have the function of imparting anti-fogging properties. 1 is -CH2COOH (surfactant 1), or a compound represented by the formula (1), 1 is a hydrogen atom and an acid anhydride compound (surfactant 3), and 1The compound (surfactant 2) in which is a hydrogen atom is a component that imparts anti-fogging properties in the present invention, and has the function of imparting anti-fogging properties with particularly improved water resistance and abrasion resistance. These compounds are fixed by chemical bonding to a substrate such as a glass substrate or a plastic substrate or to an anti-fogging film, thereby making it possible to obtain an anti-fogging film with good durability.

[0033] Represented by the formula (1), Y 1 The reaction product of a compound in which is a hydrogen atom and an acid anhydride compound can be obtained, for example, by the following method. That is, represented by the formula (1), Y 1 The compound in which is a hydrogen atom is mixed with a predetermined amount of an acid anhydride compound, and the resulting mixture is left at room temperature or heated to obtain the compound.

[0034] Represented by the formula (1), Y 1 The mixing ratio of the compound in which is a hydrogen atom and the acid anhydride compound may be the same as the molar ratio of the acid anhydride group, but either one may be in excess. Preferably, they are reacted in the same molar ratio or with a slight excess of the acid anhydride compound.

[0035] The reaction temperature is from room temperature to 200°C, preferably from room temperature to 100°C. A catalyst may be used if necessary. The catalyst used may be a base catalyst (for example, DBU or pyridine).

[0036] A solvent may or may not be used. Examples of the solvent that can be used include ether solvents (tetrahydrofuran, dioxane, 1,2-dimethoxyethane, propylene glycol monomethyl ether acetate, etc.), aromatic hydrocarbons (toluene, xylene, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), and aprotic solvents (N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.). Among these, the reaction without a solvent is preferred.

[0037] The reaction time is usually preferably 1 to 72 hours, more preferably 2 to 48 hours.

[0038] The above-mentioned components that impart anti-fogging properties may be used alone or in combination. Furthermore, the component that imparts the anti-fogging function may be directly used in the next production step without being isolated after production.

[0039] Examples of polymers having a hydroxyl group or an amino group include carboxymethyl cellulose, carboxymethyl ethyl cellulose, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, dihydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, nitrocellulose, croscarmellose, ethylhydroxyethyl cellulose, chitin, chitosan, hyaluronic acid, porphyran, polyvinyl alcohol, aminoethylated acrylic polymers, polyethyleneimine, polyethyleneimine ethoxylate, and salts thereof.

[0040] Examples of hydroxypropyl cellulose include HPC-SSL, HPC-SL, HPC-L, HPC-M, HPC-H, and HPC-VH manufactured by Nippon Soda Co., Ltd.

[0041] Examples of carboxymethyl cellulose include carboxymethyl cellulose 1110, 1120, 1130, 1140, 1150, 1160, 1170, 1180, 1190, 1220, 1240, 1250, 1260, 1330, 1350, 1380, 1390, 2200, 2260, and 2280 manufactured by Daicel FineChem Ltd.

[0042] Examples of hydroxyethyl cellulose include hydroxyethyl cellulose SP200, SP400, SP500, SP600, SP850, and SP900 manufactured by Daicel FineChem Co., Ltd.

[0043] Examples of polyvinyl alcohols include those manufactured by Kuraray Co., Ltd., fully saponified products (3-98, 25-100, 60-98, etc.), intermediately saponified products (7-92, 27-96, etc.), partially saponified products (3-88, 95-88, 23-88E, 45-88E, 3-80, 48-80, L-8, L-9-78, L-10, etc.), low saponification products (5-74, etc.), K polymers (6-77KL, 32-97KL, etc.), C polymers (23-88CM, etc.), R polymers (25-98R, etc.), M polymers (5-88M, 20-98M, etc.), LM polymers (LM-10HD, LM-25, etc.), SD polymers (3-86SD, etc.), and KX polymers (105-88KX, 200-88KX, etc.).

[0044] Examples of aminoethylated acrylic polymers include NK-350, NK-380, NK-100PM, and NK-200PM manufactured by Nippon Shokubai Co., Ltd.

[0045] Examples of polyethyleneimine polymers include SP-003, SP-006, SP-012, SP-018, SP-200, HM-2000, HM-3000, and P-1000 manufactured by Nippon Shokubai Co., Ltd.

[0046] Of these, preferred are polymers having a cellulose skeleton, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, and carboxymethyl cellulose, and particularly preferred are hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, and polyethyleneimine polymers.

[0047] The anti-fogging agent of the present invention can be obtained by mixing the respective components.

[0048] The proportion of the component that imparts anti-fogging properties in the anti-fogging agent of the present invention is preferably 0.1% by mass to 200% by mass, more preferably 0.2% by mass to 150% by mass, and particularly preferably 1% by mass to 100% by mass, relative to the polymer having a hydroxyl group or an amino group.

[0049] The proportion of the crosslinking agent (including polycarboxylic acids that are hydrolysates of acid anhydride compounds) in the anti-fogging agent of the present invention is preferably 0.1% by mass to 50% by mass, more preferably 0.2% by mass to 40% by mass, and particularly preferably 1.0% by mass to 30% by mass, relative to the polymer having a hydroxyl group or an amino group.

[0050] The anti-fog coating composition of the present invention may be prepared by using the anti-fog agent of the present invention as it is, or, in order to further improve workability (handling property, coating property, etc.), it can be obtained by diluting it preferably with a solvent.

[0051] Solvents that are preferably used in the anti-fog coating composition of the present invention include water, alcoholic solvents (methyl alcohol, ethyl alcohol, isopropyl alcohol, etc.), etheric solvents (tetrahydrofuran, dioxane, 1,2-dimethoxyethane, propylene glycol monomethyl ether acetate, etc.), aromatic hydrocarbons (toluene, xylene, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), aprotic solvents (N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), and mixtures thereof. Of these, water, alcoholic solvents, etheric solvents and mixtures thereof are preferred.

[0052] The dilution ratio is preferably 5 to 50 times, more preferably 4 to 40 times, and particularly preferably 3 to 30 times by mass relative to the anti-fogging agent used.

[0053] The concentration of the total solids (surfactant, polymer having a hydroxyl group or an amino group, and crosslinking agent) relative to the solvent in the anti-fog coating composition of the present invention is usually preferably 0.1% by mass to 30% by mass, more preferably 0.15% by mass to 25% by mass, and particularly preferably 0.2% by mass to 20% by mass.

[0054] The anti-fog agent and anti-fog coating composition of the present invention can be applied to surface hydrophilization of substrates such as glass, plastics (polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ABS, polycarbonate, polystyrene, epoxy, unsaturated polyester, melamine, diallyl phthalate, polyimide, urethane, nylon, polyethylene, polypropylene, polyvinyl chloride, polybutadiene, polyisoprene, SBR, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, neoprene rubber, porsulfide, butyl rubber, etc.), metals (iron, aluminum, stainless steel, titanium, copper, brass, alloys thereof, etc.), cellulose, cellulose derivatives, cellulose analogs (chitin, chitosan, porphyra, etc.), and natural fibers (silk, cotton, etc.), as well as sheets, films, and fibers.

[0055] If necessary, a primer or a surface activation treatment such as corona discharge treatment (a method for increasing the surface energy of the substrate surface) may be used to improve adhesion to the substrate or other base material.

[0056] Examples of methods for applying the coating liquid comprising the anti-fogging coating composition of the present invention include dip coating, spin coating, flow coating, and spray coating.

[0057] After coating, the anti-fog coating composition can be heat-treated to chemically react the coating layer to obtain a cured structure. In this case, a catalyst such as an acid (paratoluenesulfonic acid), a base (potassium hydroxide, lithium hydroxide, DBU, etc.), or a metal compound (e.g., an organic titanium compound, an organic aluminum compound, an organic zirconium compound, etc.) can be added to promote the chemical reaction.

[0058] Examples of organic titanium compounds include Orgatics TC-750 manufactured by Matsumoto Fine Chemical Co., Ltd. Examples thereof include Orgatix TC-300, Orgatix TC-310, Orgatix TC-400, and Orgatix TC-500.

[0059] Examples of the organoaluminum compound include Orgatix AL3001, Orgatix AL3100, and Orgatix AL3200.

[0060] Examples of the organic zirconium compound include Orgatix ZC-126 and Orgatix ZC-300.

[0061] Of these, organic titanium compounds are preferred.

[0062] When the curing agent is a blocked isocyanate, a dissociation catalyst can be added to lower the dissociation temperature of the blocking group.

[0063] Specific examples of the dissociation catalyst include U-CAT SA603 manufactured by San-Apro Co., Ltd., and URECKO-C manufactured by Koei Chemical Industry Co., Ltd.

[0064] The heat treatment temperature is usually preferably from room temperature to 200°C, more preferably from 50 to 180°C, and particularly preferably from 100 to 150°C. The heat treatment time is usually preferably 0.05 to 48 hours, more preferably 0.1 to 36 hours, even more preferably 0.2 to 10 hours, and particularly preferably 0.5 to 5 hours.

[0065] Furthermore, in order to prevent deterioration of the coating film due to ultraviolet rays or the like when used outdoors, these anti-fog coating compositions may contain polymer stabilizers, such as antioxidants for improving durability, ultraviolet absorbers and hindered amine light stabilizers for improving weather resistance, and mixtures thereof.

[0066] Specific examples of the antioxidant include phenol-based antioxidants manufactured by ADEKA CORPORATION (e.g., ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-80, ADK STAB AO-330, etc.) and thioether-based antioxidants (e.g., ADK STAB AO-412S, ADK STAB AO-503, etc.).

[0067] Specific examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers manufactured by ADEKA CORPORATION (e.g., ADK STAB LA-24, ADK STAB LA-29, ADK STAB LA-31RG, ADK STAB LA-32, ADK STAB LA-36, ADK STAB LA-46, ADK STAB LA-F70, ADK STAB LA-1413, etc.).

[0068] Specific examples of the hindered amine light stabilizer include ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-81, ADK STAB LA-82, ADK STAB LA-87, ADK STAB LA-402AF, ADK STAB LA-40MP, and ADK STAB LA-40Si, all manufactured by ADEKA CORPORATION. [Example]

[0069] The present invention will be specifically described below with reference to examples, which are intended to illustrate the present invention but are not intended to limit the scope of the present invention.

[0070] [Synthesis Example 1] A compound represented by the above formula (1), Y 1Synthesis of reaction product (surfactant 3) of compound where is a hydrogen atom with acid anhydride compound Emulmin LS-90 (hydroxyl value 95, represented by the above formula (1)) manufactured by Sanyo Chemical Industries, Ltd. 1 is a hydrogen atom; polyoxyethylene lauryl ether), 8.89 g (33.9 mmol) of a silane coupling agent (3-trimethoxysilylpropylsuccinic anhydride, trade name X-12-967C) manufactured by Shin-Etsu Chemical Co., Ltd. was added, and the mixture was allowed to react at 60°C for 2 hours in an inert gas atmosphere to obtain 28.8 g of surfactant (A) in which one carboxyl group was bonded to the polyoxyethylene lauryl ether terminal.

[0071] [Synthesis Example 2] A compound represented by the above formula (1), Y 1 Synthesis of reaction product (surfactant 3) of compound where is a hydrogen atom with acid anhydride compound Emulmin LS-90 (hydroxyl value 95, represented by the above formula (1)) manufactured by Sanyo Chemical Industries, Ltd. 1 2.55 g (25.5 mmol) of succinic anhydride manufactured by Tokyo Chemical Industry Co., Ltd. was added to 15.0 g of a compound in which (A) is a hydrogen atom; polyoxyethylene lauryl ether), and the mixture was allowed to react at 60°C for 24 hours under an inert gas atmosphere to obtain 17.5 g of surfactant (B) in which one carboxyl group was bonded to the polyoxyethylene lauryl ether terminal.

[0072] [Synthesis Example 3] A compound represented by the above formula (1), Y 1 Synthesis of reaction products (surfactants 3, also crosslinkers) between compounds where is a hydrogen atom and acid anhydride compounds containing two or more acid anhydride groups Emulmin LS-90 (hydroxyl value 95, represented by the above formula (1)) manufactured by Sanyo Chemical Industries, Ltd. 1 is a hydrogen atom; polyoxyethylene lauryl ether) was added to 15.0 g of pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and the mixture was reacted at 60°C for 24 hours in an inert gas atmosphere to obtain 17.8 g of surfactant (C) in which two groups derived from polyoxyethylene lauryl ether and two carboxyl groups were bonded.

[0073] [Synthesis Example 4] A compound represented by the above formula (1), Y 1 Synthesis of reaction products (surfactants 3, also crosslinkers) between compounds where is a hydrogen atom and acid anhydride compounds containing two or more acid anhydride groups Emulmin LS-90 (hydroxyl value 95, represented by the above formula (1)) manufactured by Sanyo Chemical Industries, Ltd. 1 To 15.0 g of a compound in which (a) is a hydrogen atom (polyoxyethylene lauryl ether), 2.53 g (12.8 mmol) of butanetetracarboxylic anhydride manufactured by New Japan Chemical Co., Ltd. was added, and the mixture was allowed to react at 60°C for 24 hours under an inert gas atmosphere, to obtain 17.5 g of surfactant (D) in which two groups derived from polyoxyethylene lauryl ether and two carboxyl groups were bonded.

[0074] [Synthesis Example 5] Synthesis of crosslinking agent 2.5 g of methanol silica sol manufactured by Nissan Chemical Industries, Ltd., 10 g of IPA-ST-UP (isopropyl alcohol silica sol manufactured by Nissan Chemical Industries, Ltd.), 1.5 g of a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. (a silane coupling agent having a blocked isocyanate group bonded thereto; product name X-12-1308ES), 31.0 g of ethanol, and 5.0 g of water were added and heated under reflux for 24 hours to obtain 50.0 g of an alcohol dispersion of silica sol having a blocked isocyanate group bonded thereto.

[0075] Example 1 4.0 g of a 100-fold diluted solution of the surfactant (A) obtained in Synthesis Example 1 in ethanol, 4.0 g of a 2.5% ethanol solution of HPC-M (hydroxypropyl cellulose) manufactured by Nippon Soda Co., Ltd. as a polymer having hydroxyl groups, 1.0 g of an alcohol dispersion of silica sol to which blocked isocyanate groups are bonded as a crosslinking agent obtained in Synthesis Example 5, and 11.0 g of ethanol were mixed to obtain 20.0 g of an anti-fog coating composition liquid containing the anti-fog agent (form ii) of one embodiment of the present invention.

[0076] Example 2 4.0 g of a 200-fold diluted ethanol solution of the surfactant (B) obtained in Synthesis Example 2, 4.0 g of a 2.5% ethanol solution of HPC-M manufactured by Nippon Soda Co., Ltd. as a polymer having a hydroxyl group, 1.0 g of an alcohol dispersion of the silica sol to which blocked isocyanate groups are bonded as a crosslinking agent obtained in Synthesis Example 5, and 11.0 g of ethanol were mixed to obtain 20.0 g of an anti-fog coating composition liquid containing the anti-fog agent (form ii) of one embodiment of the present invention.

[0077] Example 3 4.0 g of a 200-fold diluted ethanol solution of the surfactant (C) (which also serves as a crosslinking agent) obtained in Synthesis Example 3, 4.0 g of a 2.5% ethanol solution of HPC-M manufactured by Nippon Soda Co., Ltd. as a polymer having a hydroxyl group, 1.0 g of an alcohol dispersion of the silica sol to which blocked isocyanate groups are bonded as a crosslinking agent obtained in Synthesis Example 5, and 11.0 g of ethanol were mixed to obtain 19.0 g of an anti-fog coating composition liquid containing an anti-fog agent (form ii) of one embodiment of the present invention.

[0078] Example 4 4.0 g of a 200-fold diluted ethanol solution of the surfactant (D) (which also serves as a crosslinking agent) obtained in Synthesis Example 4, 4.0 g of a 2.5% ethanol solution of HPC-M manufactured by Nippon Soda Co., Ltd. as a polymer having hydroxyl groups, 1.0 g of an alcohol dispersion of the silica sol to which blocked isocyanate groups are bonded as a crosslinking agent obtained in Synthesis Example 5, and 12.0 g of ethanol were mixed to obtain 21.0 g of an anti-fog coating composition liquid containing an anti-fog agent (form ii) of one embodiment of the present invention.

[0079] Example 5 20.0 g of an anti-fog coating composition liquid containing an anti-fog agent (Form i) of one embodiment of the present invention was obtained by mixing 4.0 g of a 200-fold diluted solution of Viewright LCA-H (polyoxyethylene lauryl ether sodium acetate; an ether carboxylic acid surfactant made from naturally occurring alcohol) manufactured by Sanyo Chemical Industries, Ltd., 4.0 g of a 2.5% ethanol solution of HPC-M manufactured by Nippon Soda Co., Ltd. as a polymer having hydroxyl groups, 1.0 g of an alcohol dispersion of silica sol to which blocked isocyanate groups are bonded as obtained in Synthesis Example 5 as a crosslinking agent, and 11.0 g of ethanol.

[0080] Example 6 4.0 g of a 200-fold ethanol diluted solution of the surfactant (B) obtained in Synthesis Example 2, 4.0 g of a 2.5% ethanol solution of HPC-M manufactured by Nippon Soda Co., Ltd. as a polymer having a hydroxyl group, 1.5 g of a 100-fold ethanol diluted solution of a VOC-free silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.: X-12-1135 (a polycarboxylic acid as a crosslinking agent; a hydrolyzate of an acid anhydride compound), and 10.5 g of ethanol were mixed to obtain 20.0 g of an anti-fog coating composition liquid containing an anti-fog agent (form ii) of one embodiment of the present invention.

[0081] Example 7 4.0 g of a 200-fold ethanol diluted solution of the surfactant (D) (which also serves as a crosslinking agent) obtained in Synthesis Example 4, 4.0 g of a 2.5% ethanol solution of HPC-M manufactured by Nippon Soda Co., Ltd. as a polymer having a hydroxyl group, 1.0 g of a 100-fold ethanol diluted solution of a VOC-free silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.: X-12-1135 (a polycarboxylic acid as a crosslinking agent; a hydrolyzate of an acid anhydride compound), and 11.0 g of ethanol were mixed to obtain 20.0 g of an anti-fog coating composition liquid containing an anti-fog agent (form ii) of one embodiment of the present invention.

[0082] Example 8 6.0 g of a 200-fold diluted ethanol solution of the surfactant (D) (which also serves as a crosslinking agent) obtained in Synthesis Example 4, 4.0 g of a 2.5% ethanol solution of HPC-M (manufactured by Nippon Soda Co., Ltd.) as a polymer having a hydroxyl group, and 10.0 g of ethanol were mixed to obtain 20.0 g of an anti-fog coating composition liquid containing an anti-fog agent (form iv) of one embodiment of the present invention.

[0083] Example 9 Emulmin LS-90 (hydroxyl value 95, represented by the above formula (1)) manufactured by Sanyo Chemical Industries, Ltd. 1 By mixing 6.0 g of a 200-fold diluted ethanol solution of a compound in which (a compound in which (b) is a hydrogen atom; polyoxyethylene lauryl ether), 4.0 g of a 2.5% ethanol solution of HPC-M manufactured by Nippon Soda Co., Ltd. as a polymer having a hydroxyl group, 1.0 g of a 100-fold diluted ethanol solution of a VOC-free silane coupling agent: X-12-1135 manufactured by Shin-Etsu Chemical Co., Ltd. (polycarboxylic acid as a crosslinking agent; hydrolysate of an acid anhydride compound), and 9.0 g of ethanol, 20.0 g of an anti-fog coating composition liquid containing an anti-fog agent (Form iii) of one embodiment of the present invention was obtained.

[0084] Example 10 4.0 g of a 200-fold diluted ethanol solution of the surfactant (C) (which also serves as a crosslinking agent) obtained in Synthesis Example 3, 4.0 g of a 2.5% ethanol solution of Epomin SP-012 (polyethyleneimine polymer) manufactured by Nippon Shokubai Co., Ltd. as a polymer having amino groups, 1.0 g of an alcohol dispersion of the silica sol having blocked isocyanate groups bonded thereto obtained in Synthesis Example 5 as a crosslinking agent, and 11.0 g of ethanol were mixed to obtain 20.0 g of an anti-fog coating composition liquid containing the anti-fog agent (Form ii) of one embodiment of the present invention.

[0085] These anti-fog coating composition solutions, and an anti-fog coating composition solution obtained by the method described in Example 3 of JP 2021-91859 A as a comparative example, were used to prepare anti-fog durability evaluation samples by the following preparation method.

[0086] <Preparation of anti-fogging evaluation sample> A polycarbonate plate {76 mm long, 26 mm wide, 1 mm thick; the surface was wiped with ethanol} was immersed in an anti-fog coating composition solution, and after removing the polycarbonate plate, the solution was drained off and the plate was heat-treated at 120°C for 1 hour to obtain a surface-modified polycarbonate plate. <Durability evaluation> A drop of water was dropped onto the obtained surface-modified polycarbonate plate, and the plate was left at room temperature for 1 hour, after which the anti-fogging properties were evaluated. <Anti-fogging evaluation> The sample was placed on a 200cc beaker half filled with 30°C hot water, with a drop of water on the side facing downwards, and left for one minute. The anti-fogging properties were evaluated based on whether or not fogging occurred. Areas where fogging occurred were judged to have "no anti-fogging properties," and areas where fogging did not occur were judged to have "anti-fogging properties."

[0087] In the surface-modified polycarbonate plate obtained from the anti-fog coating composition liquid obtained by the method described in Example 3 of JP 2021-91859 A, the anti-fog properties were lost in the areas where water had dripped, but the anti-fog properties were not lost in the surface-modified polycarbonate plate obtained from the anti-fog coating composition liquids of Examples 1 to 10.

[0088] The above results demonstrate that when surfactants 1 and / or 3, or surfactant 2, are immobilized in the coating film through chemical bonds, water resistance is improved, and as a result, it is possible to obtain a highly durable anti-fogging agent with long-lasting anti-fogging properties. [Industrial Applicability]

[0089] In comparison with conventional antifogging agents, the antifogging agent of the present invention has surfactants 1 and / or 3, or surfactant 2, which exhibit antifogging properties, fixed in a coating film formed using the antifogging agent through chemical bonds such as ester bonds or amide bonds, and the coating film is crosslinked by a crosslinking agent and fixed to the substrate through chemical bonds, thereby greatly improving water resistance and making the antifogging agent very useful as a material for forming a highly durable antifogging coating film on substrates such as plastic substrates (e.g., eyeglass lenses, sunglasses lenses, headlight covers, etc.) and glass.

Claims

1. Represented by the following formula (1), Y １ Ga-CH ２ COOH, and / or Represented by the following formula (1), Y １ is a hydrogen atom with an acid anhydride compound; a polymer having hydroxyl and / or amino groups; and Contains a crosslinking agent, or Represented by the following formula (1), Y １ is a hydrogen atom; A polycarboxylic acid or crosslinking agent which is a hydrolyzate of an acid anhydride compound; and Contains a polymer having hydroxyl groups and / or amino groups An anti-fogging agent characterized by: R １ -X １ -(CH ２ CH ２ O) ｍ -Y １ (1) {R in the formula １ represents an alkyl group having 1 to 20 carbon atoms (the alkyl group may be substituted with a group containing a hetero atom and / or a benzene ring and / or a double bond); X １ is —O—, —COO—, or —CONH—, m is an integer of 1 to 30, and Y １ is a hydrogen atom or -CH ２ represents COOH}

2. 2. The anti-fogging agent according to claim 1, wherein the acid anhydride compound contains two or more acid anhydride groups.

3. 3. The anti-fogging agent according to claim 1, wherein the functional group of the crosslinking agent is a blocked isocyanate group and / or a carboxyl group.

4. An anti-fogging coating composition comprising the anti-fogging agent according to claim 1 or 2.

5. An anti-fogging coating composition comprising the anti-fogging agent according to claim 3.

6. A structure having a layer of the cured anti-fog coating composition of claim 4.

7. A structure having a layer of the cured anti-fog coating composition according to claim 5.