Novel surface-active silane coupling agent, antifogging agent containing the same, antifogging coating composition, 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: By increasing the number of alkoxysilyl groups contained in the surface-active silane coupling agent, the surface-active silane coupling agent is more easily fixed to a coating film, a substrate, or the like through a chemical bond than a conventional surface-active silane coupling agent, and as a result, the surface-active silane coupling agent is more firmly fixed, and as a result, water resistance is improved and durability of antifogging properties is improved.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a surfactant silane coupling agent useful as a component of a coatable anti-fogging agent that has high durability, a significant anti-fogging effect, and can be produced at low cost; an anti-fogging agent containing the same; an anti-fogging coating composition; and a structure having a layer formed by curing the composition. More specifically, the present invention relates to a novel surfactant silane coupling agent that exhibits anti-fogging properties and is more easily fixed in an anti-fogging coating film through chemical bonds than conventional surfactant silane coupling agents, thereby improving the durability of the anti-fogging properties of the coating film. [Background technology]

[0002] The present inventors have already invented the inventions disclosed in Patent Documents 1 to 3, which relate to surface-active silane coupling agents and anti-fogging agents using the same. That is, the invention of Patent Document 1 relates to a surfactant represented by the following formula (2): R 5 -X 1 -(CH2CH2O) p -Y 1 (2) {R in formula 5 is an alkyl group having 1 to 20 carbon atoms, and X 1 is -O-, -COO-, or -CONH-, p is an integer of 1 to 30, and Y 1 represents a hydrogen atom, -CH2COOH. The invention relates to a surface-active silane coupling agent hydrolysate, which is a reaction product of a silane coupling agent having a functional group capable of reacting with the active hydrogen in formula (2).

[0003] The invention of Patent Document 2 relates to a raw material metal oxide sol for a modified metal oxide sol, the raw material metal oxide sol comprising, as its main component, a hydrolyzate of a surfactant silane coupling agent, a modified metal oxide sol modified with the hydrolyzate of a surfactant silane coupling agent, or a mixture and / or condensate of a hydrolyzate of a surfactant silane coupling agent and a modified metal oxide sol modified with the hydrolyzate of a surfactant silane coupling agent, and a modified metal oxide sol modified with a sulfur (S)-containing functional group.

[0004] The invention of Patent Document 3 relates to a hydrolysate and / or hydrolysis condensate of a compound represented by the following formula (1): (X) 3-k (CH3) k Si-R 1 -(YR 2 ) m -N + (R 3 )(R 4 )-Z (1) In the formula, X may be the same or different and represent an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom; k represents 0 or 1; R 1 represents an alkylene group having 1 to 5 carbon atoms, Y represents -NHCOO-, -NHCONH-, -S- or -SO2-, m represents 0 or 1, R 2 is an alkylene group having 1 to 10 carbon atoms which may contain an ether bond, an ester bond or an amide bond, or -CH2CH2N + (CH3)(Z)CH2CH2OCH2CH2-, and R 3 and R 4 represents an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and Z is (CH2) n SO3-, (CH2) n represents CO2- and O-, and n represents an integer of 1 to 5. and a surface-active silane coupling agent.

[0005] However, even in lenses coated with anti-fog coating compositions comprising the anti-fog agent materials described in these documents, the surface-active silane coupling agents that exhibit anti-fog properties may not be firmly fixed via silanol groups, and therefore water resistance and abrasion resistance may be insufficient for practical use, and therefore anti-fog agents with higher durability are desired. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2017-71724 [Patent Document 2] Japanese Patent Application Publication No. 2017-71725 [Patent Document 3] Patent No. 6590875 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above-mentioned conventional techniques, and aims to provide a surfactant silane coupling agent which has higher water resistance and abrasion resistance, a greater antifogging effect, can be produced at low cost, and is highly durable and particularly suitable for coating on substrates such as lenses for eyeglasses, etc.; an antifogging agent containing the same; an antifogging coating composition; and a structure having a layer formed by curing the composition. [Means for solving the problem]

[0008] The present inventors have conducted extensive research while taking into consideration the above-mentioned problems of the prior art. As a result, they have found that by increasing the number of alkoxysilyl groups contained in a surfactant silane coupling agent, the surfactant silane coupling agent can be more easily fixed to a substrate or the like through chemical bonds than conventional surfactant silane coupling agents in a coating film formed by applying an anti-fogging agent or anti-fogging coating composition containing the surfactant silane coupling agent, thereby solving the above-mentioned problems and arriving at the present invention.

[0009] That is, the present invention is characterized by the following constitution and solves the above-mentioned problems. [1] A surfactant (1) containing active hydrogen (1) represented by the following formula (I), a silane coupling agent (2) containing a functional group capable of reacting with the active hydrogen (1) and which induces active hydrogen (2); The surfactant silane coupling agent (3) containing the active hydrogen (2) obtained by the reaction of Furthermore, a surface-active silane coupling agent produced by reacting the active hydrogen (2) with a silane coupling agent (5) containing a functional group capable of reacting with the active hydrogen (2), or Furthermore, a surface-active silane coupling agent characterized by being obtained by reacting a silane coupling agent (5') containing a functional group capable of reacting with the active hydrogen (2) and which induces new active acid hydrogen, with the surface-active silane coupling agent containing the new active hydrogen, and by repeating the following reaction procedure (A) one or more times: Reaction procedure (A): Reaction of the produced surface-active silane coupling agent with a silane coupling agent containing a functional group capable of reacting with new active hydrogen and a group that induces other new active hydrogen. R 5 -X 1 -(CH2CH2O) p -Y 1 (I) {R in formula 5 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-, p is an integer of 1 to 30, and Y 1 represents a hydrogen atom, -CH2COOH, or -NH2. [2] The surface-active silane coupling agent according to [1], characterized in that the group that induces the active hydrogen (2) and the group that induces the new active hydrogen are each independently an acid anhydride group or an epoxy group. [3] The surface-active silane coupling agent according to [1] or [2], characterized in that the functional group capable of reacting with the active hydrogen (2) is any one functional group selected from the group consisting of an acid anhydride group, an epoxy group, an amino group, an isocyanate group, and a blocked isocyanate group. [4] An anti-fogging agent characterized by containing at least one of the surface-active silane coupling agent according to [1] or [2], its hydrolysate, and its hydrolysis condensate. [5] An anti-fogging agent comprising at least one of the surface-active silane coupling agent according to [3], its hydrolysate and hydrolysis condensate. [6] An anti-fogging coating composition comprising the anti-fogging agent according to [4]. [7] An anti-fogging coating composition comprising the anti-fogging agent according to [5]. [8] A structure having a layer formed by curing the anti-fog coating composition according to [6]. [9] A structure having a layer formed by curing the anti-fog coating composition according to [7].

[0010] The hydrolyzate means the surface-active silane coupling agent in its hydrolyzed state, and the hydrolysis condensate means one or more surface-active silane coupling agents condensed randomly or in a block form. The antifogging agent of the present invention contains at least one of the surfactant silane coupling agent of the present invention, its hydrolyzate, and its hydrolysis condensate, and is preferably the other components themselves, a mixture of each of the hydrolyzed components, or at least one of the hydrolyzed components of each component condensed randomly or in a block form, or a mixture of these. [Effects of the Invention]

[0011] According to the present invention, the operation of introducing a silane coupling agent is repeated one or more times to increase the number of alkoxysilyl groups contained in the surfactant silane coupling agent. When an anti-fogging agent or anti-fogging coating composition containing the surfactant silane coupling agent is applied to a substrate or the like to form a coating film, the surfactant silane coupling agent of the present invention is fixed to the coating film and / or the substrate through a dehydration condensation reaction between silanol groups and the silanol groups in the coating film and / or the substrate, and therefore the surfactant silane coupling agent is fixed more firmly, resulting in improved water resistance and improved durability of the anti-fogging property. DETAILED DESCRIPTION OF THE INVENTION

[0012] The surfactant silane coupling agent of the present invention is A surfactant (1) containing active hydrogen (1) represented by the following formula (I), a silane coupling agent (2) containing a functional group capable of reacting with the active hydrogen (1) and which induces active hydrogen (2); The surfactant silane coupling agent (3) containing the active hydrogen (2) obtained by the reaction of Furthermore, a surface-active silane coupling agent produced by reacting the active hydrogen (2) with a silane coupling agent (5) containing a functional group capable of reacting with the active hydrogen (2), or Furthermore, a surface-active silane coupling agent characterized by being obtained by reacting a silane coupling agent (5') containing a functional group capable of reacting with the active hydrogen (2) and which induces new active hydrogen, with the surface-active silane coupling agent containing the new active hydrogen, and by repeating the following reaction procedure (A) one or more times: Reaction procedure (A): Reaction of the produced surface-active silane coupling agent with a silane coupling agent containing a functional group capable of reacting with new active hydrogen and a group that induces other new active hydrogen. R 5 -X 1 -(CH2CH2O) p -Y 1 (I) {R in formula5 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-, p is an integer of 1 to 30, and Y 1 represents a hydrogen atom, -CH2COOH, or -NH2. In addition, when the surface-active silane coupling agent of the present invention has active hydrogen, it may be subjected to a reaction (additional reaction) with a silane coupling agent containing a functional group capable of reacting with the active hydrogen in the surface-active silane coupling agent. In this specification, the term "active hydrogen" refers to hydrogen in a hydroxyl group or a carboxyl group.

[0013] In the surfactant (1) which is a raw material of the surface-active silane coupling agent of the present invention, R 5 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.

[0014] X 1 is -O-, -COO- or -CONH-. p is a natural number of 1 to 30, and preferably 1 to 15. Y 1 is a hydrogen atom, -CH2COOH or -NH2.

[0015] As the surfactant (1), commercially available surfactants can be used. Commercially available surfactants (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. When the surfactant (1) is a mixture of compounds having different numbers of ethylene oxide added, it is preferable that p is on average not more than 14. Specific examples are shown below.

[0016] CH3O(CH2CH2O)2H CH3O(CH2CH2O)3H CH3O(CH2CH2O)4H C 12 H 25 O(CH2CH2O)5CH2COOH C 13 H 27 O(CH2CH2O)3CH2COOH 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

[0017] 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.

[0018] In the present invention, the above-mentioned raw material is reacted with a silane coupling agent (such as silane coupling agent (2) or silane coupling agent (5')) containing a functional group capable of reacting with active hydrogen in the raw material and which newly induces active hydrogen, to produce a surface-active silane coupling agent containing active hydrogen. Preferred examples of the "functional group capable of reacting with active hydrogen and deriving new active hydrogen" include silane coupling agents having an epoxy group or an acid anhydride group. By reacting the silane coupling agent having an epoxy group or an acid anhydride group with a surface-active silane coupling agent containing active hydrogen, a surface-active silane coupling agent having a functional group with active hydrogen (a hydroxyl group or a carboxyl group) can be obtained.

[0019] Examples of the silane coupling agent having an epoxy group or an acid anhydride group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride.

[0020] Of these, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are preferred.

[0021] Specific examples of the surface-active silane coupling agent (3) obtained by the reaction of the surfactant (1) with the silane coupling agent (2) include the following compounds. CH3O(CH2CH2O)3CH2CH(OH)CH2OCH2CH2CH2Si(OCH3)3 CH3O(CH2CH2O)3CH(CH2OH)CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)5CH2COOCH2CH(OH)CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)5CH2COOCH(CH2OH)CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH2COOCH2CH(OH)CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH2COOCH(CH2OH)CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH2CH(OH)CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH(CH2OH)CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)9CH2CH(OH)CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)9CH(CH2OH)CH2OCH2CH2CH2Si(OCH3)3 CH3O(CH2CH2O)3COCH2CH(COOH)CH2CH2CH2Si(OCH3)3 CH3O(CH2CH2O)3COCH(CH2COOH)CH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)8COCH2CH(COOH)CH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)8COCH(CH2COOH)CH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)9COCH2CH(COOH)CH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)9COCH(CH2COOH)CH2CH2CH2Si(OCH3)3 C 17 H 35 COO(CH2CH2O)9COCH2CH(COOH)CH2CH2CH2Si(OC2H5)3 C 17 H 33 COO(CH2CH2O)5COCH(CH2COOH)CH2CH2CH2Si(OC2H5)3 C6F 13 CH2CH2O(CH2CH2O)8CH(CH2OH)CH2OCH2CH2CH2Si(OCH3)3 C6F 13 CH2CH2O(CH2CH2O)8CH(CH2OH)CH2OCH2CH2CH2Si(CH3)(OCH3)2 (CH3)3CCH2C(CH3)2-C6H4-O(CH2CH2O)9CH2CH(OH)CH2OCH2CH2CH2Si(OCH3)3 (CH3)3CCH2C(CH3)2-C6H4-O(CH2CH2O)9CH(CH2OH)CH2OCH2CH2CH2Si(OCH3)3 (CH3)3CCH2C(CH3)2-C6H4-O(CH2CH2O) 10 COCH(CH2COOH)CH2CH2CH2Si(OCH3)3 (CH3)3CCH2C(CH3)2-C6H4-O(CH2CH2O)10 COCH2CH(COOH)CH2CH2CH2Si(OCH3)3

[0022] The surface active silane coupling agent (3) can be obtained by the following method. That is, the surfactant (1) and the silane coupling agent (2) are mixed together under anhydrous conditions either directly or in the presence of a catalyst such as an acid or a base, and the mixture is then heated at room temperature or by heating to obtain the compound.

[0023] The surfactant (1) and the silane coupling agent (2) may be mixed in an equal molar ratio, but either one may be in excess. Preferably, they are reacted in the same molar ratio or with a slight excess of the silane coupling agent (2).

[0024] The reaction temperature is from room temperature to 200°C, preferably from room temperature to 100°C. A catalyst may be used if necessary. Examples of the catalyst to be used include base catalysts (e.g., DBU, potassium hydroxide, etc.) and acid catalysts (e.g., p-toluenesulfonic acid, etc.) when the terminal of the compound represented by formula (I) of surfactant (1) is a hydroxyl group and the silane coupling agent (2) has an epoxy group.

[0025] A solvent may or may not be used. Examples of the solvent that can be used include ether solvents (tetrahydrofuran, dioxane, 1,2-dimethoxyethane, etc.), aromatic hydrocarbons (toluene, xylene, 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.

[0026] The reaction time is usually 1 to 72 hours, preferably 2 to 48 hours.

[0027] Examples of the silane coupling agent (5) include silane coupling agents having an acid anhydride group, an epoxy group, an amino group, an isocyanate group, or a blocked isocyanate group. The silane coupling agent (5) can be reacted with the surfactant silane coupling agent (3) to obtain the surfactant silane coupling agent of the present invention (hereinafter sometimes referred to as surfactant silane coupling agent I). When the above-mentioned surface-active silane coupling agent I has active hydrogen, it may be further reacted with a silane coupling agent containing a functional group (e.g., an amino group, an isocyanate group, or a blocked isocyanate group) that can react with the active hydrogen.

[0028] The silane coupling agent (5') may be a silane coupling agent having an acid anhydride group or an epoxy group. By reacting the silane coupling agent (5') with the surfactant silane coupling agent (3), a surfactant silane coupling agent containing active hydrogen can be obtained, and by repeating the reaction procedure (A) once or more times, a surfactant silane coupling agent of the present invention having a further silane coupling agent introduced therein (hereinafter, sometimes referred to as surfactant silane coupling agent II) can be obtained. After repeating the reaction procedure (A) one or more times, the surfactant silane coupling agent II may be further reacted with a silane coupling agent having an amino group, an isocyanate group, or a blocked isocyanate group.

[0029] When the functional group having active hydrogen (2) in the surface-active silane coupling agent (3) is a carboxyl group, examples of the silane coupling agent (5) include silane coupling agents having an epoxy group, an isocyanate group, a blocked isocyanate group, or an amino group, and examples of the silane coupling agent (5') include silane coupling agents having an epoxy group. When the functional group having active hydrogen (2) in the surface-active silane coupling agent (3) is a hydroxyl group, examples of the silane coupling agent (5) include silane coupling agents having an acid anhydride group, an epoxy group, an isocyanate group, or a blocked isocyanate group, and examples of the silane coupling agent (5') include silane coupling agents having an acid anhydride group or an epoxy group.

[0030] Examples of the silane coupling agent (5) having an epoxy group, an acid anhydride group, an amino group, an isocyanate group, or a blocked isocyanate group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, and X-12-1308ES (3-isocyanatepropyltriethoxysilane protected with 3,5-dimethylpyrazole). Among these, a silane coupling agent having an epoxy group or an acid anhydride group can be used as the silane coupling agent (5').

[0031] Of these, preferred are 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0032] Examples of the silane coupling agent (5') having an epoxy group or an acid anhydride group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride.

[0033] Of these, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are preferred.

[0034] Specific examples of the surfactant silane coupling agent I obtained by reacting the surfactant silane coupling agent (3) with the silane coupling agent (5), and the surfactant silane coupling agent produced by reacting the surfactant silane coupling agent (3) with the silane coupling agent (5') include the following compounds. CH3O(CH2CH2O)3CH(CH2OR 7 )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)5CH2COOCH2CH(OR 8 )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)5CH2COOCH(CH2OR 9 )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH2COOCH2CH(OR 10 )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH2CH(OR 7 )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH(CH2OR 8 )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)9CH2CH(OR 9 )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)9CH(CH2OR 10 )CH2OCH2CH2CH2Si(OCH3)3 CH3O(CH2CH2O)3COCH(CH2COOR 7 )CH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)8COCH2CH(COOR 8 )CH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)9COCH2CH(COOR 7 )CH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)9COCH(CH2COOR 8 )CH2CH2CH2Si(OCH3)3 C 17 H 35 COO(CH2CH2O)9COCH2CH(COOR 7 )CH2CH2CH2Si(OC2H5)3 C 17 H 33 COO(CH2CH2O)5COCH(CH2COOR 8 )CH2CH2CH2Si(OC2H5)3 C6F 13 CH2CH2O(CH2CH2O)8CH(CH2OR 7 )CH2OCH2CH2CH2Si(OCH3)3 C6F 13 CH2CH2O(CH2CH2O)8CH(CH2OR 8)CH2OCH2CH2CH2Si(CH3)(OCH3)2 (CH3)3CCH2C(CH3)2-C6H4-O(CH2CH2O)9CH2CH(OR 7 )CH2OCH2CH2CH2Si(OCH3)3 (CH3)3CCH2C(CH3)2-C6H4-O(CH2CH2O)9CH(CH2OR 9 )CH2OCH2CH2CH2Si(OCH3)3 (CH3)3CCH2C(CH3)2-C6H4-O(CH2CH2O) 10 COCH(CH2COOR 7 )CH2CH2CH2Si(OCH3)3

[0035] Further specific examples of the surface-active silane coupling agent I obtained by reacting the surface-active silane coupling agent (3) with the silane coupling agent (5) include the following compounds. CH3O(CH2CH2O)3CH2CH(OR 6 )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH2COOCH(CH2OR 6 )CH2OCH2CH2CH2Si(OCH3)3 (CH3)3CCH2C(CH3)2-C6H4-O(CH2CH2O) 10 COCH2CH(COOR 6 )CH2CH2CH2Si(OCH3)3 CH3O(CH2CH2O)3COCH2CH(COOR 11 )CH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)8COCH(CH2COOR 11 )CH2CH2CH2Si(OCH3)3

[0036] Specific examples of compounds obtained by subjecting the surfactant silane coupling agent II or surfactant silane coupling agent I obtained by repeating the above reaction procedure (A) one or more times to the above additional reaction include the following compounds. CH3O(CH2CH2O)3CH2CH(OR X )CH2OCH2CH2CH2Si(OCH3)3 CH3O(CH2CH2O)3CH(CH2OR X )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)5CH2COOCH2CH(OR X )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)5CH2COOCH(CH2OR X )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH2COOCH2CH(OR X )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH2COOCH(CH2OR X )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH2CH(OR X )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)6CH(CH2OR X )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)9CH2CH(OR X )CH2OCH2CH2CH2Si(OCH3)3 C 12 H 25 O(CH2CH2O)9CH(CH2ORX )CH2OCH2CH2CH2Si(OCH3)3 R X represents the following R 12 ~R 23 .

[0037] Note that R 6 ~R 23 each represents the following structure. R 6 :-CONH-CH2CH2CH2Si(OC2H5)3 R 7 :-CH2CH(OH)CH2OCH2CH2CH2Si(OCH3)3 R 8 :-CH(CH2OH)CH2OCH2CH2CH2Si(OCH3)3 R 9 :-COCH2CH(COOH)CH2CH2CH2Si(OCH3)3 R 10 :-CO-CH(CH2COOH)CH2CH2CH2Si(OCH3)3 R 11 :-NHCH2CH2CH2Si(OCH3)3 R 12 :-CH2CH(OR 7 )CH2OCH2CH2CH2Si(OCH3)3 R 13 :-CH(CH2OR 8 )CH2OCH2CH2CH2Si(OCH3)3 R 14 :-CH2CH(OR 9 )CH2OCH2CH2CH2Si(OCH3)3 R 15 :-CH(CH2OR 10 )CH2OCH2CH2CH2Si(OCH3)3 R 16 :-COCH2CH(COOR 7 )CH2CH2CH2Si(OCH3)3 R 17 :-CO-CH(CH2COR 8 )CH2CH2CH2Si(OCH3)3 R 18:-COCH2CH(COOR 9 )CH2CH2CH2Si(OCH3)3 R 19 :-CO-CH(CH2COR 10 )CH2CH2CH2Si(OCH3)3 R 20 :-CH2CH(OR 6 )CH2OCH2CH2CH2Si(OCH3)3 R 21 :-CH(CH2OR 6 )CH2OCH2CH2CH2Si(OCH3)3 R 22 :-COCH2CH(COR 11 )CH2CH2CH2Si(OCH3)3 R 23 :-CO-CH(CH2COR 11 )CH2CH2CH2Si(OCH3)3

[0038] The surface active silane coupling agent of the present invention can be obtained by the following method. That is, they can be obtained by mixing and heating each surfactant silane coupling agent with another surfactant silane coupling agent directly or in the presence of a catalyst such as an acid or a base under anhydrous conditions, and the detailed conditions are the same as those for obtaining surfactant silane coupling agent (3). These compounds can also be obtained by adding a silane coupling agent to the raw material (intermediate) surfactant silane coupling agent without isolating it and reacting it.

[0039] The reaction procedure (A) may be carried out once, or preferably repeated about 2 to 5 times, but from the viewpoint of cost, it is more preferable to repeat it 1 to 2 times.

[0040] The surface-active silane coupling agent, its hydrolysate and hydrolysis condensate of the present invention can be used by itself as an anti-fogging agent or as a component of other anti-fogging agents.

[0041] For example, by replacing the surface active silane coupling agent (component (B1)) described in Japanese Patent No. 6590875 (Patent Document 3) with the surface active silane coupling agent of the present invention, a more useful anti-fog agent and anti-fog coating composition can be obtained. In this case, the amount of the surfactant silane coupling agent (5) or (5') of the present invention added relative to the compound (component (A)) represented by formula (1) described in Patent Document 3 is 0.01% by mass to 500% by mass, preferably 0.01% by mass to 200% by mass, and particularly preferably 0.01% by mass to 200% by mass.

[0042] Furthermore, by replacing the surfactant silane coupling agent described in JP 2021-098834 A with the surfactant silane coupling agent of the present invention, a more useful surface treatment agent can be obtained.

[0043] The anti-fog coating composition of the present invention contains the anti-fog agent of the present invention, and is preferably diluted with a solvent to further improve workability (e.g., handleability and coatability).

[0044] The anti-fog coating composition of the present invention can be applied to surface hydrophilization of substrates, sheets, films, and fibers (hereinafter sometimes referred to as "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, and butyl rubber), metals (iron, aluminum, stainless steel, titanium, copper, brass, and alloys thereof), cellulose, cellulose derivatives, cellulose analogs (chitin, chitosan, porphyra, and the like), and natural fibers (silk, cotton, and the like).

[0045] If necessary, in order to improve adhesion to the substrate, etc., the substrate may be subjected to a surface activation treatment (a method for increasing the surface energy of the surface of the substrate, etc.) such as a primer or corona discharge treatment. For example, the primer may be organosilica sol or X-12-972F manufactured by Shin-Etsu Chemical Co., Ltd.

[0046] A catalyst may be used to accelerate the curing of the anti-fog coating composition of the present invention, and examples of the catalyst include metal compounds (e.g., organotitanium compounds, organoaluminum compounds, organozirconium compounds, etc.), acids, and bases.

[0047] 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.

[0048] Examples of the organoaluminum compound include Orgatix AL3001, Orgatix AL3100, and Orgatix AL3200.

[0049] Examples of the organic zirconium compound include Orgatix ZC-126 and Orgatix ZC-300.

[0050] Of these, organic titanium compounds are preferred.

[0051] 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.

[0052] After coating, the anti-fog coating composition can be heat-treated to cure the coating layer, thereby obtaining a structure. In this case, a curing catalyst such as an acid (e.g., hydrochloric acid), a base (e.g., sodium hydroxide, lithium hydroxide), or a metal compound (e.g., a titanium compound, an aluminum compound) can be added to promote curing.

[0053] The heat treatment temperature is usually preferably from room temperature to 250°C, more preferably from room temperature to 200°C, and particularly preferably from room temperature to 150°C. The heat treatment time is usually preferably 0.05 to 48 hours, more preferably 0.1 to 48 hours, and particularly preferably 0.2 to 36 hours. [Example]

[0054] 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.

[0055] [Synthesis Example 1] To 20.0 g of polyoxyethylene lauryl ether (Emulmin LS-90 (hydroxyl value: 95) manufactured by Sanyo Chemical Industries, Ltd.) as surfactant (1) represented by the above formula (I), 8.89 g (33.9 mmol) of 3-trimethoxysilylpropylsuccinic anhydride (silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., product name X-12-967C) as the silane coupling agent (2) was added, and the mixture was allowed to react at 60°C for 2 hours under an inert gas atmosphere to obtain 28.8 g of surfactant silane coupling agent (B) in which one molecule of 3-trimethoxysilylpropylsuccinic anhydride was added to polyoxyethylene lauryl ether as the surfactant silane coupling agent (3).

[0056] Example 1 To 14.4 g of the surfactant silane coupling agent (B) obtained in Synthesis Example 1, 4.0 g (16.9 mmol) of 3-glycidoxypropyltrimethoxysilane (silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM403, containing an epoxy group) was added as the silane coupling agent (5) or (5'), and the mixture was allowed to react at 90°C for 24 hours in an inert gas atmosphere to obtain 18.4 g of surfactant silane coupling agent (C), which is one embodiment of the surfactant silane coupling agent of the present invention in which one molecule each of 3-trimethoxysilylpropylsuccinic anhydride and 3-glycidoxypropyltrimethoxysilane is added to polyoxyethylene lauryl ether. The structure of the obtained compound of one embodiment of the present invention was confirmed by infrared absorption spectroscopy.

[0057] Example 2 To 9.2 g of the surfactant silane coupling agent (C) obtained in Example 1, 2.2 g (8.45 mmol) of 3-trimethoxysilylpropylsuccinic anhydride (silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., product name X-12-967C) was added as a silane coupling agent, and the mixture was allowed to react at 60°C for 2 hours in an inert gas atmosphere to obtain 11.4 g of surfactant silane coupling agent (D), which is another embodiment of the surfactant silane coupling agent of the present invention in which two molecules of 3-trimethoxysilylpropylsuccinic anhydride and one molecule of 3-glycidoxypropyltrimethoxysilane are added to polyoxyethylene lauryl ether (first reaction procedure (A)). The structure of the obtained compound according to another embodiment of the present invention was confirmed by infrared absorption spectroscopy.

[0058] Example 3 To 5.7 g of the surfactant silane coupling agent (D) obtained in Example 2, 1.0 g (4.23 mmol) of 3-glycidoxypropyltrimethoxysilane (silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM403, containing an epoxy group) was added as a silane coupling agent, and the mixture was allowed to react at 90°C for 24 hours in an inert gas atmosphere, thereby obtaining 6.7 g of surfactant silane coupling agent (E), which is another embodiment of the surfactant silane coupling agent of the present invention in which two molecules each of 3-trimethoxysilylpropylsuccinic anhydride and 3-glycidoxypropyltrimethoxysilane are added to polyoxyethylene lauryl ether (second reaction procedure (A)). The structure of the obtained compound of another embodiment of the present invention was confirmed by infrared absorption spectroscopy.

[0059] [Usage example 1] 5.20 g (25.0 mmol) of [3-(N,N-dimethylamino)propyl]trimethoxysilane (Tokyo Chemical Industry Co., Ltd.) and 3.05 g (25.0 mmol) of 1,3-propane sultone were dissolved in 10 ml of dehydrated isopropyl alcohol and heated under reflux for 2 hours. Next, 1.0 g of the surfactant silane coupling agent (B) produced in Synthesis Example 1, 10 ml of ethanol, and 5 ml of water were added, and the mixture was heated under reflux for 24 hours. Water was added to the resulting solution to obtain 50.0 g of a transparent aqueous anti-fogging solution (F).

[0060] [Usage example 2] 50.0 g of an aqueous anti-fogging solution (G) was obtained in exactly the same manner as in Use Example 1, except that the surfactant silane coupling agent (C) was used instead of the surfactant silane coupling agent (B).

[0061] [Usage example 3] 50.0 g of an aqueous anti-fogging solution (H) was obtained in exactly the same manner as in Use Example 1, except that the surfactant silane coupling agent (D) was used instead of the surfactant silane coupling agent (B).

[0062] [Usage example 4] 50.0 g of an aqueous anti-fogging solution (I) was obtained in exactly the same manner as in Use Example 1, except that the surfactant silane coupling agent (E) was used instead of the surfactant silane coupling agent (B).

[0063] The anti-fogging aqueous solutions prepared in Use Examples 1 to 4 were diluted 50 times with water to obtain anti-fogging coating composition solutions. These anti-fogging coating compositions were used to prepare samples for evaluating anti-fogging durability according to the following preparation method.

[0064] <Preparation of anti-fogging evaluation sample> A glass slide {length 76 mm, width 26 mm, thickness 1.2 mm; immersed in a saturated solution of potassium hydroxide in 2-propanol for 24 hours, then washed with water and dried (60°C, 2 hours)} was immersed in an anti-fog coating composition solution, and after removing the glass slide, the solution was drained and left at room temperature for 24 hours to obtain a surface-modified glass slide as a structure having a layer of hardened anti-fog coating composition. <Durability evaluation> A drop of water was dropped onto the resulting surface-modified slide glass, which was then dried at room temperature for 1 hour, after which a test was conducted to confirm whether the glass had anti-fogging properties. Verification test: The surface-modified glass slide was placed over a 200cc beaker half filled with 30°C hot water, with a drop of water dropped onto it, and left for one minute. The anti-fogging properties were evaluated based on whether fogging occurred or not. 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."

[0065] In Use Example 1, the coating film disappeared in the areas where water dripped, and the anti-fogging properties were lost. In contrast, in Use Examples 2 to 4, the coating film remained durable even in the areas where water dripped, and the anti-fogging properties were not lost.

[0066] The above results show that surfactants with multiple silane coupling agents chemically bonded to them have stronger bonding strength with substrates, etc. than those with only one silane coupling agent bonded to them, and as a result, it is possible to obtain highly durable anti-fogging agents with long-lasting anti-fogging properties. [Industrial Applicability]

[0067] The anti-fogging agent of the present invention has significantly improved water resistance compared with conventional anti-fogging agents, and is therefore extremely useful as a material for highly durable anti-fogging coating films for substrates such as glass and plastics for eyeglass lenses, sunglasses lenses, lenses and mirrors for optical instruments, etc. In addition to its anti-fogging properties, it also has the effect of preventing water from freezing, and when coated on the roof of a house in a cold region in winter, it can suppress or prevent snow accumulation on the roof.

Claims

1. A surfactant (1) containing active hydrogen (1) represented by the following formula (I), a silane coupling agent (2) containing a functional group capable of reacting with the active hydrogen (1) and inducing the active hydrogen (2); The surfactant silane coupling agent (3) containing the active hydrogen (2) obtained by the reaction of Furthermore, a surface-active silane coupling agent produced by reacting the active hydrogen (2) with a silane coupling agent (5) containing a functional group capable of reacting with the active hydrogen (2), or Furthermore, a surface-active silane coupling agent characterized by being obtained by reacting a silane coupling agent (5') containing a functional group capable of reacting with the active hydrogen (2) and a group that induces new active hydrogen, and then repeating the following reaction operation (A) once or more times with the surface-active silane coupling agent containing the new active hydrogen. Reaction procedure (A): Reaction of the produced surface-active silane coupling agent with a silane coupling agent containing a functional group capable of reacting with new active hydrogen and a group that induces other new active hydrogen. R ５ -X １ -(CH ２ CH ２ O) ｐ -Y １ (I) {R in the formula ５ 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—, p is an integer of 1 to 30, and Y １ is a hydrogen atom, -CH ２ COOH or -NH ２ represents.}

2. 2. The surface-active silane coupling agent according to claim 1, wherein the group that induces the active hydrogen (2) and the group that induces the new active hydrogen are each independently an acid anhydride group or an epoxy group.

3. 3. The surface-active silane coupling agent according to claim 1, wherein the functional group capable of reacting with the active hydrogen (2) is any one functional group selected from the group consisting of an acid anhydride group, an epoxy group, an amino group, an isocyanate group, and a blocked isocyanate group.

4. An anti-fogging agent comprising at least one of the surfactant silane coupling agent according to claim 1 or 2, its hydrolysate and its hydrolysis condensate.

5. An anti-fogging agent comprising at least one of the surfactant silane coupling agent according to claim 3, its hydrolysate and its hydrolysis condensate.

6. An anti-fogging coating composition comprising the anti-fogging agent according to claim 4.

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

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

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