JP4446654B2 - Antifogging agent and method for forming antifogging film - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention is used for various applications such as antifogging mirrors for bathrooms, toilets, etc., antifogging window glass or antifogging mirrors for vehicles, antifogging window glass for buildings, refrigeration, frozen showcase glass, etc. The present invention relates to an antifogging agent and a method for forming an antifogging coating for obtaining an antifogging coating excellent in visible light permeability, antifogging properties, antifogging sustaining properties, abrasion resistance, and water resistance.
[0002]
[Prior art]
  Transparent substrates such as glass and plastic have a sudden temperature change with respect to the substrate when one surface falls below the dew point due to the difference in temperature and humidity between the inner and outer surfaces of the substrate. When the water vapor comes into contact with the base material (for example, when it moves from a low temperature part to a high temperature and high humidity environment), moisture in the atmosphere adheres as water droplets, and the surface of the base material is condensed. As a result, light scattering occurs due to condensed water droplets. The occurrence of so-called “cloudiness” hinders the field of view, and safety is significantly impaired in general window glass, windshields of automobiles and aircraft, glasses, sunglasses, and the like.
[0003]
  In order to prevent the occurrence of “clouding” of a transparent substrate such as glass or plastic, conventionally, (1) applying a surfactant to the surface of the substrate to reduce the contact angle with water, A method for forming a film (see, for example, Patent Document 1), (2) A method for hydrophilizing the surface of a substrate with a photocatalyst to form water droplets in a water film (for example, see Patent Document 2), (3) A surface of the substrate for a heat source, etc. (4) A solution in which a curable resin and a hydrophilic resin, and a surfactant are mixed is applied to the surface of the substrate. A method of making water droplets into a water film by heating or curing with ultraviolet rays or electron beams to reduce the contact angle with water (Patent Documents 4 to 7), (5) Water on the substrate surface Water by increasing the contact angle How to drop repel or the like it has been considered.
[0004]
  However, although the method (1) is excellent in the initial antifogging property, there is a drawback that the surfactant flows out by contact with water and the antifogging effect is short-lived. The method (2) is advantageous in abrasion resistance because it is a film made of an inorganic material, but ultraviolet light is necessary for the development of antifogging properties, and antifogging properties are not exhibited in all environments. The method (3) is generally high in cost, and it takes time until the base material is warmed, and it takes time to develop antifogging properties and there are problems such as thermal cracking. The method (4) has a problem in that the antifogging property deteriorates with time due to the outflow of the surfactant from the film as in (1), and there is a problem in wear resistance and water resistance. In the method (5), there is no substance that can increase the contact angle to the extent that the antifogging property is exhibited. As described above, at present, an antifogging film satisfying sufficient antifogging property, antifogging durability, various durability and the like has not been obtained.
[0005]
  In particular, the antifogging coatings obtained up to now are not sufficient in abrasion resistance and water resistance, and therefore the antifogging property deteriorates with time even if the initial antifogging property is good. In other words, there is a problem with anti-fogging sustainability, which inconveniences the end user. As an attempt to improve the abrasion resistance and water resistance of antifogging coatings,ConventionalAntifogging agents and / or antifogging films having inorganic element oxides and hydrophilic polymers, or inorganic element oxides and water-absorbing polymers have been studied.
[0006]
  Patent Document 8 discloses an antifogging film in which an oxide film in which a surfactant that improves the hydrophilicity of the film is dispersed is coated. However, since the surfactant is only supported in the film, the initial antifogging performance cannot be maintained. In Patent Document 9, an antifogging agent having an alkoxy group-containing acrylic copolymer and tetraalkylsilicon is disclosed, and glass or the like is disclosed as a substrate on which the antifogging agent is coated. However, the antifogging agent does not have good adhesion to glass. Further, in addition to the antifogging property of the acrylic copolymer itself being not so high, tetraalkylsilicon has a hydrophobic property, so that the antifogging film made of the antifogging agent has a small antifogging effect.
[0007]
  Patent Document 10 discloses an antifogging agent having silylated polyvinyl alcohol and conductive metal oxide fine particles. The hydrophilicity of silylated polyvinyl alcohol and durability by reducing the adhesion of pollutants to the conductive metal fine particles due to conductivity. An anti-fogging coating with improved properties is disclosed. However, the anti-fogging treatment agent is a substantially anti-fogging film made of polyvinyl alcohol, and the wear resistance is slightly improved by the fine particles, but the anti-fogging property, wear resistance, and water resistance are not sufficient, There is a problem with long-term durability.
[0008]
  In Patent Document 11, obtained from a polymer containing a hydroxyl group, an aluminum-containing cross-linking agent such as alumina, aluminum hydroxide, and alumina hydrate, and an antifogging treatment agent having a surfactant containing a hydroxyl group and / or a siloxane group. An anti-fogging treated substrate is disclosed. However, the polymer and aluminum used in the antifogging agent are unlikely to form a strong chemical bond such as a covalent bond, and the polymer and aluminum are scattered, so that the wear resistance is not improved so much. Further, even if a polymer network is formed by some kind of chemical bond, the bond strength is weak, it is easy to cause hydrolysis, and water resistance cannot be expected. Furthermore, since the surfactant also has a weak binding force with the polymer network, the surfactant may flow out.
[0009]
[Patent Document 1]
JP 58-217578 A
[Patent Document 2]
Japanese Patent No. 2924502
[Patent Document 3]
JP 62-292109 A
[Patent Document 4]
JP-A-11-228808
[Patent Document 5]
JP-A-11-152356
[Patent Document 6]
US Pat. No. 5,877,254
[Patent Document 7]
Japanese Patent Laid-Open No. 04-211461
[Patent Document 8]
Japanese Patent Laid-Open No. 11-100284
[Patent Document 9]
JP-A-6-145453
[Patent Document 10]
JP 2001-172545 A
[Patent Document 11]
JP-A-9-151368
[0010]
[Problems to be solved by the invention]
  As described above, the improvement in anti-fogging property and the improvement in durability are contradictory, and it is difficult to improve both. In view of the above, the present invention provides an antifogging agent capable of forming an antifogging film having excellent antifogging properties, antifogging durability, abrasion resistance, and visible light transmittance, and a method for forming an antifogging film. The task is to do.
[0011]
[Means for Solving the Problems]
  In view of the above-mentioned problems, the present invention has been made by intensive studies to make use of the advantages of high durability such as wear resistance of inorganic element compounds and the excellent hydrophilicity of surfactants. That is, the antifogging agent of the present invention is at least one selected from the group consisting of coating agent A having a halogen group-containing silicon compound, preferably coating agent A having a chloro group-containing silicon compound, and a hydroxyl group, an amino group, and a mercapto group. A coating agent B having a surfactant containing a functional group reactive to a halogen group, preferably the coating agent B has a polyol, and the coating agent A is a silicon alkoxide, an aluminum alkoxide, a titanium alkoxide, It has at least one inorganic element alkoxide selected from the group consisting of zirconium alkoxide, niobium alkoxide, zinc alkoxide, and tantalum alkoxide.
[0012]
  Further, the present invention is an antifogging agent comprising the coating agent C having a polyisocyanate in addition to the coating agent A and the coating agent B. Preferably, the antifogging agent of the present invention has at least one fine particle selected from the group consisting of silica, alumina, titania, zirconia, zinc oxide, niobium oxide and tantalum oxide. Furthermore, it is preferable that the halogen group-containing silicon compound contains at least one halogen group and at least one alkoxy group.
[0013]
  The present invention is an antifogging film formed by applying and curing the antifogging agent, and the antifogging film comprises: (a) a step of preparing a substrate;
(B) a step of mixing the coating agent A and the coating agent B;
(C) The process of apply | coating the mixed coating agent to the base-material surface,
(D) The film coated on the substrate surface is cured at room temperature or a heat treatment temperature up to 250 ° C.Depending on the processIt is formed. Or
(A) preparing a substrate;
(B) the step of mixing the coating agent C after mixing the coating agent A and the coating agent B;
(C) The process of apply | coating the mixed coating agent to the base-material surface,
(D) The film coated on the substrate surface is cured at room temperature or a heat treatment temperature up to 250 ° C.Depending on the processIt is formed.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
  The antifogging agent of the present invention is an antifogging agent for forming an antifogging film on a substrate, and is selected from the group consisting of a coating agent A having a halogen group-containing silicon compound, and a hydroxyl group, amino group, and mercapto group. And coating agent B having a surfactant containing a functional group reactive to at least one halogen group. The surfactant mainly improves the hydrophilicity of the antifogging treatment agent. On the other hand, the silicon compound mainly improves the durability such as abrasion resistance of the antifogging treatment agent and becomes a matrix component of the antifogging film formed from the antifogging agent of the present invention. By mixing the coating agent A and the coating agent B, the halogen group of the silicon compound and the reactive functional group react with the halogen group of the surfactant. During the reaction process, the halogen group is eliminated and reacts with hydrogen in a functional group reactive to the halogen group, and the surfactant and the silicon compound are chemically bonded. Therefore, the anti-fogging film formed from the present anti-fogging agent can fully utilize the hydrophilicity of the surfactant, so that it exhibits excellent anti-fogging properties, anti-fogging durability, wear resistance, Excellent water resistance and visible light transmittance.
[0015]
  Examples of the halogen group-containing silicon compound include tetrachlorosilane, methyltrichlorosilane, monomethoxytrichlorosilane, monoethoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, monochlorotrimethoxysilane, monochlorotriethoxysilane, γ-chloropropyltri Methoxysilane, tetrafluorosilane, methyltrifluorosilane, monomethoxytrifluorosilane, monoethoxytrifluorosilane, dimethoxydifluorosilane, diethoxydifluorosilane, monofluorotrimethoxysilane, monofluorotriethoxysilane, γ-fluoropropyltri Methoxysilane, tetrabromosilane, methyltribromosilane, monomethoxytribromosilane, monoethoxytribromosilane, di Methoxydibromosilane, diethoxydibromosilane, monobromotrimethoxysilane, monobromotriethoxysilane, γ-bromopropyltrimethoxysilane, tetraiodic silane, methyltriiodic silane, monomethoxytriiodic silane, monoethoxytria Iodic silane, dimethoxydiaiodic silane, diethoxydiaiodic silane, mono-iodic trimethoxysilane, mono-iodic triethoxysilane, γ-iodic propyltrimethoxysilane, etc. can be adopted. It is also possible to react a halogen compound and a silicon-based compound in advance.
[0016]
  Among them, the halogen group-containing silicon compound is preferably a chloro group-containing silicon compound from the viewpoint of reactivity and economy. Tetrachlorosilane, methyltrichlorosilane, monomethoxytrichlorosilane, monoethoxytrichlorosilane, dimethoxydichlorosilane, diethoxydi Chlorosilane, monochlorotrimethoxysilane, monochlorotriethoxysilane, γ-chloropropyltrimethoxysilane and the like can be suitably employed.
[0017]
  The halogen group-containing silicon compound preferably contains at least one halogen group and at least one alkoxy group. In particular, when monomethoxytrichlorosilane, monoethoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, monochlorotrimethoxysilane, monochlorotriethoxysilane, γ-chloropropyltrimethoxysilane or the like is used, the antifogging agent of the present invention is formed. The effect of improving the adhesion of the antifogging film to the base material and the crosslinkability with other additive polyols and inorganic element alkoxides are improved, and the antifogging film formed has more wear resistance. Since it improves, it is preferable.
[0018]
  As the surfactant, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, etc. can be adopted, and it reacts with a halogen group at the side chain and / or chain end. Contains an active hydroxyl group, amino group, and mercapto group. Examples of such surfactants include amidodimonium compounds (for example, ricinoleamidopropylethyldimonium etosulphate), betaines, and aminopropyl quaternary ammonium salts (for example, ethyl sulfate lanolin fatty acid aminopropylethyldimethylammonium). Etc. can be adopted.
[0019]
  The weight ratio of the halogen group-containing silicon compound and the surfactant is preferably 95: 5 to 20:80. Outside the above range where the halogen group-containing silicon compound is small, the strength and abrasion resistance of the formed antifogging coating are small and the durability tends to be poor. On the other hand, outside the above range with a small amount of surfactant, the surface anti-fogging film formed has a low surface hydrophilicity, and it is difficult to obtain satisfactory anti-fogging properties.
[0020]
  In the coating agent A, at least one inorganic element alkoxide selected from the group of silicon alkoxide, aluminum alkoxide, titanium alkoxide, zirconium alkoxide, niobium alkoxide, zinc alkoxide, and tantalum alkoxide can be added. By adding an inorganic element alkoxide to the coating agent, silica, alumina, titania, zirconia, niobium oxide, zinc oxide, tantalum oxide, etc. can be added to the network bridge to the antifogging film to be formed. Durability such as wear resistance and water resistance can be improved. In order to improve the physical properties, the addition amount of the inorganic element alkoxide is preferably 5/95 or more by weight ratio with respect to the halogen group-containing silicon compound, but is preferably 90/10 or less. When the addition amount of 90/10 is exceeded, the surface hydrophilicity of the formed antifogging film becomes small and it is difficult to obtain satisfactory antifogging properties.
[0021]
  A polyol can be added to the coating agent B. As the polyol, a commonly used polyol can be used, and for example, a polyol exhibiting hydrophilicity and water absorption such as polypropylene glycol and polyethylene glycol is preferable. By adding the polyol, the hydrophilicity of the formed antifogging film is improved. Alternatively, water-absorbing performance can be imparted to the formed anti-fogging film, and an anti-fogging property, particularly an anti-fogging property below freezing point can be obtained. The hydroxyl groups of these polyols react with the halogen groups of the halogen group-containing silicon compound. Alternatively, during the decomposition reaction of the alkoxy group, the hydroxyl group of the polyol reacts with the silicon compound or the alkoxy group of the inorganic element alkoxide, so that the polyol can participate in network crosslinking forming an antifogging film. . At that time, an acid (for example, hydrochloric acid in the case of a chloro group) hydrochloric acid generated in the reaction process serves as a catalyst for promoting network crosslink formation. In order to improve hydrophilicity and impart water absorption performance, the amount of polyol added is preferably 25/75 or more, more preferably 80/20 or less, by weight with respect to the surfactant. When the added amount exceeds 80/20, the antifogging property, strength and abrasion resistance of the antifogging coating formed are lowered, leading to a decrease in the performance of the antifogging coating formed.
[0022]
  Moreover, the antifogging agent of this invention can be used as the antifogging agent which consists of the coating agent C which has polyisocyanate in addition to the coating agent A and the coating agent B. By adding the polyisocyanate, the isocyanate group in the polyisocyanate reacts with a hydroxyl group, an amino group, a mercapto group, or the like in the surfactant, and can participate in network crosslinking forming an antifogging film. As a result, the strength of the antifogging coating increases. Further, when the coating agent B has a polyol, the polyisocyanate also reacts with the polyol, so that network cross-linking of the polyurethane occurs, the antifogging film has elasticity derived from the polyurethane, and wear resistance is improved.
[0023]
  Such a polyisocyanate is not particularly limited as long as it is a polyisocyanate generally used for urethane resins and the like. For example, a burette type or nurate type polyisocyanate in which hexamethylene diisocyanate is a multimer is more preferable. preferable. These polyisocyanates provide better antifogging properties, film strength, and abrasion resistance. The amount of the polyisocyanate is such that the number of isocyanate groups in the polyisocyanate is 0.5 to 2 times the stoichiometry with respect to the number of hydroxyl groups, amino groups, and mercapto groups in the surfactant and polyol. Preferably, it is preferable to adjust so that it may be 0.8 times or more and 1.5 times or less. By being within the above range, the antifogging film is particularly effective in increasing the strength and improving the wear resistance.
[0024]
  At least one of these coating agent A, coating agent B, and coating agent C, or the anti-fogging agent generated after mixing is selected from the group of silica, alumina, titania, zirconia, zinc oxide, niobium oxide, and tantalum oxide. At least one kind of fine particles can be added. The addition of fine particles is preferable because the anti-fogging coating formed has more improved wear resistance. In order to further improve the wear resistance, the addition amount is 5/95 or more by weight ratio with respect to the total amount of the antifogging agent halogen group-containing silicon compound, surfactant, polyol, inorganic element alkoxide, and polyisocyanate. Although it is preferable, it is preferable that it is 40/60 or less. When the addition amount exceeds 40/60, the hydrophilicity of the surface of the antifogging coating film formed becomes small, and it is difficult to obtain satisfactory antifogging properties.
[0025]
  The antifogging agent of the present invention requires antifogging performance, for example, lenses such as glasses / cameras, window glass, vehicle glass, helmet shields, articles such as underwater glasses, or mirrors used in bathrooms. It can be applied to articles and the like that require transparency, and is preferably applied to a substrate having transparency and reflectivity and applied as an antifogging film. The anti-fogging coating formed from the anti-fogging agent of the present invention has a surfactant fixed through a covalent bond with a halogen group-containing silicon compound that is a matrix component of the coating, and the surfactant does not elute. The function of developing antifogging properties over a long period of time can be maintained, and the durability such as wear resistance is excellent.
[0026]
  A typical example of the substrate is glass. The glass is a plate glass usually used for automobiles, architectural and industrial glasses, and is a plate glass by a float method, a duplex method, a roll-out method, etc., and the manufacturing method is not particularly limited.
[0027]
  As glass types, it can be used for various colored glasses such as clear, green and bronze, various functional glasses such as UV, IR cut glass and electromagnetic shielding glass, netted glass, low expansion glass, zero expansion glass and fireproof glass. Various glass products such as glass, tempered glass or similar glass, laminated glass, multilayer glass, mirrors produced by the silvering method or vacuum film forming method, flat plates, bent plates and the like can be used. The plate thickness is preferably 1.0 mm or greater and 10 mm or less, and for automobiles is preferably 1.0 mm or greater and 5.0 mm or less. The substrate may be coated with the antifogging agent only on one side or on both sides. Further, the coating of the antifogging agent may be the whole surface or a part of the substrate surface.
[0028]
  In addition, the base material is not limited to glass, but a resin film such as polyethylene terephthalate having light transmissivity and light reflectivity, resin such as polycarbonate, metal, ceramics, etc. can be used at the time of drying and curing the antifogging agent. Anything that does not deform can be used.
[0029]
  The formation method of the antifogging film of this invention can coat | cover an antifogging film on the base-material surface by the following process.
(A) preparing a substrate;
(B) a step of mixing the coating agent A and the coating agent B;
(C) The process of apply | coating the mixed coating agent to the base-material surface,
(D) A step of curing the film coated on the substrate surface at room temperature or a heat treatment temperature up to 250 ° C.
And by anti-fogging coatingTheForm. Or
(A) preparing a substrate;
(B) the step of mixing the coating agent C after mixing the coating agent A and the coating agent B;
(C) The process of apply | coating the mixed coating agent to the base-material surface,
(D) Curing the film coated on the substrate surface at room temperature or at a heat treatment temperature up to 250 ° C.Process
And by anti-fogging coatingTheForm.
[0030]
    As means for applying the antifogging agent to the substrate surface, known means such as dip coating, flow coating, spin coating, roll coating, bar coating, spray coating, screen printing, flexographic printing, etc. can be employed. Moreover, the coating agent A, the coating agent B, the coating agent C, or the antifogging agent can have a solvent. As the solvent, toluene, xylene, dimethylformamide, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, diethylene glycol monoethyl ether acetate, or a mixed solvent thereof can be used.
[0031]
  After applying the antifogging agent to the substrate, the temperature is appropriately selected in consideration of the decomposition temperature of the raw material used at room temperature or a heat treatment temperature up to 250 ° C., preferably a heat treatment temperature of 120 ° C. to 250 ° C., about 20 minutes to 60 minutes By heating for about minutes, most of the solvent of the antifogging agent is scattered, and at the same time, the curing reaction of the antifogging agent is promoted to form a film. When the heat treatment temperature exceeds 250 ° C., carbonization of the organic component starts to occur, which is not preferable. In addition, when a halogen group-containing silicon compound and an inorganic element alkoxide containing alkoxide are used, polymerization of the halogen group-containing silicon compound and inorganic element alkoxide is accelerated by heat treatment, and a high-strength film can be produced.
[0032]
  The film thickness of the antifogging film is desirably 0.1 μm or more and 30 μm or less after the heat treatment, and if it is less than 0.1 μm, the durability tends to be inferior. There is a risk of optical distortion.
[0033]
【Example】
  Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to such examples. In addition, about the obtained anti-fogging film, quality evaluation was performed by the method shown below.
[0034]
(1) Repeated anti-fogging property
  Based on “Testing method for anti-fogging agent for spectacles” (JIS S 4030), the cloudiness when the sample for evaluation was held for 3 minutes in steam of hot water set at 43 ° C., and the room temperature (23 ° C., 63% after holding) The cloudiness due to exhalation when taken out during (RH) was visually observed, and this operation was performed for 10 cycles. A sample having no appearance abnormality and no cloudiness and having no problem with the visible light transmittance of the sample as judged by visual judgment was evaluated as acceptable (O), and a sample with fogging was determined as unacceptable (X).
[0035]
(2) Cold / antifogging properties
  After holding the sample for evaluation in a refrigerator set at 4 ° C. for 30 minutes, visually observe the appearance, cloudiness, and cloudiness due to exhalation when taken out at room temperature (23 ° C., 63% RH). For 10 cycles. A sample having no appearance abnormality and no cloudiness and having no problem with the visible light transmittance of the sample as judged by visual judgment was evaluated as acceptable (O), and a sample with fogging was determined as unacceptable (X).
[0036]
(3) Abrasion resistance
  Based on the abrasion resistance test method described in JIS R 3221, the sample for evaluation was subjected to a Taber type abrasion test with an abrasion wheel CS-10F and a load of 2.45 N, and the haze value (cloudiness value) was evaluated. In the evaluation, the initial haze value H0, the haze value H100 after 100 times, and the haze value H200 after 200 times are H0 ≦ H100 ≦ H200, and the haze value change amount ΔH (ΔH = H200−H0) was ΔH ≦ 10%, which was accepted (◯), and H100> H200 or ΔH> 10% was rejected (×).
[0037]
(4) Water resistance
  Immerse the evaluation sample in water kept at room temperature (23 ± 2 ° C) for 1 hour. After immersion, the sample that does not have any abnormal appearance and does not peel off by wiping with a nail is accepted (◯). (X).
[0038]
      Reference example1
  Coating agent A obtained by mixing 0.8 g of γ-chloropropyltrimethoxysilane with 7 g of solvent dimethylformamide, and 2.2 g of ricinoleamidopropylethyldimonium ethosulphate (surfactant) in 6 g of solvent dimethylformamide The coating agent B obtained by mixing was mixed and the antifogging agent was applied to the surface of a float glass having a glass size of 200 mm × 200 mm × 2 mm (thickness) washed in advance by a bar coating method, at a heat treatment temperature of 180 ° C. The coated film was held for 30 minutes and cured to obtain a glass substrate with an antifogging film. The obtained glass substrate with an antifogging film has a film thickness of 0.3 μm, and as shown in Table 1, all the qualities of repeated antifogging properties, anti-fogging properties, cold and antifogging properties, Taber abrasion resistance, and water resistance are obtained. It was confirmed that this was excellent.
[0039]
[Table 1]
[0040]
    Example 2
    Coating agent A obtained by mixing 2.5 g of γ-chloropropyltrimethoxysilane with 6 g of solvent dimethylformamide, 1.2 g of ricinoleamidopropylethyldimonium ethosulphate (surfactant), and trifunctional polyethylene Except for obtaining an antifogging agent by mixing 1.6 g of glycol (molecular weight 200) and 0.3 g of polyethylene glycol (PEG 1000) with 6 g of the solvent dimethylformamide and mixing with coating agent B.Reference exampleIn the same manner as in No. 1, a glass substrate with an antifogging film was obtained. The obtained glass substrate with an antifogging film has a film thickness of 3 μm, as shown in Table 1.Reference exampleSimilar to 1, it showed excellent performance in all qualities.
[0041]
    Reference example3
    Coating agent A obtained by mixing 1 g of γ-chloropropyltrimethoxysilane and 1.5 g of tetraethoxysilane in 6 g of solvent and 1.2 g of ricinoleamidopropylethyldimonium ethosulphate (surfactant) Except that the coating agent B obtained was mixed to obtain an antifogging agent.Reference exampleIn the same manner as in No. 1, a glass substrate with an antifogging film was obtained. The obtained glass substrate with an antifogging film has a film thickness of 18 μm, as shown in Table 1.Reference exampleSimilar to 1, it showed excellent performance in all qualities.
[0042]
    Example 4
  Coating agent A obtained by mixing 1 g of γ-chloropropyltrimethoxysilane with 6 g of solvent dimethylformamide, 1.2 g of ricinoleamidopropylethyldimonium ethosulphate (surfactant), and trifunctional polyethylene glycol (molecular weight) 200) 1.6 g and polyethylene glycol (PEG 1000) 0.3 g in 6 g of solvent dimethylformamide, coating agent B, polyisocyanate (24A-100: manufactured by Asahi Kasei) 5 g of coating agent C Except for obtaining an antifogging agent obtained by mixing agent A and coating agent B and then mixing coating agent C with the mixture,referenceA glass substrate with an antifogging film was obtained in the same manner as in Example 1. The obtained glass substrate with an antifogging film has a film thickness of 17 μm, and as shown in Table 1, all the qualities of repeated antifogging properties, anti-fogging properties, cold and antifogging properties, Taber abrasion resistance, and water resistance are obtained. It was confirmed that this was excellent.
[0043]
    Example 5
  1.2 g of surfactant for coating agent B, 0 g of polyethylene glycol (PEG 1000), 5 g of polyisocyanate for coating agent C, and a mixture of coating agent A, coating agent B, and coating agent C with colloidal silica (product) Glass with antifogging coating having a film thickness of 10 μm in the same manner as in Example 4 except that 2 g of the name “NPC-ST”; solid content 20%, manufactured by Nissan Chemical Co., Ltd.) was mixed to obtain an antifogging agent. A substrate was obtained. As shown in Table 1, the obtained glass substrate with an antifogging film is shown in Table 1.referenceAs in Example 1, excellent performance was exhibited in all qualities.
[0044]
    Example 6
  Glass with an antifogging coating is prepared in the same manner as in Example 2 except that methyltrichlorosilane is used as a raw material for the halogen group-containing silicon compound, the heat treatment temperature of the film coated on the substrate is 150 ° C., and is maintained for 50 minutes. A substrate was obtained. The obtained glass substrate with an antifogging film had a film thickness of 8 μm, and as shown in Table 1, showed excellent performance in all qualities as in Example 4.
[0045]
    Comparative Example 1
    Except for 0.1 g of γ-chloropropyltrimethoxysilane and 0.9 g of ricinoleamidopropylethyldimonium ethosulphate (surfactant),referenceA glass substrate with an antifogging film was obtained in the same manner as in Example 1. The obtained glass substrate with an antifogging film repeatedly failed in antifogging properties, cold / hot antifogging properties, abrasion resistance, and water resistance.
[0046]
    Comparative Example 2
  Except for using a polyisocyanate instead of a halogen group-containing silicon compound,referenceSame as Example 1. The obtained glass with an antifogging film has a film thickness of 20 μm, and as shown in Table 1, although it had excellent antifogging properties in terms of antifogging properties and anti-fogging properties at cold and warm temperatures, Water resistance was unacceptable.
[0047]
    Comparative Example 3
  Example 2 was repeated except that polycarbonate polyol was used instead of the surfactant. The obtained glass with an antifogging film had a film thickness of 20 μm, and as shown in Table 1, the antifogging property, the cold / hot antifogging property, and the wear resistance were repeatedly rejected.
[0048]
    Comparative Example 4
  A glass substrate with an antifogging film was obtained in the same manner as in Example 3 except that 9 g of tetraethoxysilane was used. The obtained glass substrate with an antifogging film was repeatedly unacceptable in terms of antifogging properties and cold / hot antifogging properties.
[0049]
【The invention's effect】
  The antifogging agent and antifogging film of the present invention can exhibit excellent antifogging properties over a long period of time by fixing the surfactant to the silicon compound matrix and making the surface of the film hydrophilic. In addition, since a silicon compound is used as the matrix, it has wear resistance and water resistance.

Claims (10)

A coating agent A having a halogen group-containing silicon compound, and a coating agent B having a surfactant containing a functional group reactive to at least one halogen group selected from the group consisting of a hydroxyl group, an amino group and a mercapto group. The coating agent B contains a polyol, and the coating agents A and B are mixed and applied to the substrate surface . The antifogging agent according to claim 1, wherein the halogen group of the halogen group-containing silicon compound is a chloro group. Coating agent A silicon alkoxide, aluminum alkoxide, titanium alkoxide, zirconium alkoxide, niobium alkoxides, zinc alkoxides, claim characterized in that it has at least one inorganic element alkoxide selected from the group of tantalum alkoxide 1 to claim 2 The anti-fogging agent in any one of. The antifogging agent according to any one of claims 1 to 3 , comprising at least one fine particle selected from the group consisting of silica, alumina, titania, zirconia, zinc oxide, niobium oxide, and tantalum oxide. The antifogging agent according to any one of claims 1 to 4 , wherein the halogen group-containing silicon compound contains at least one halogen group and at least one alkoxy group. The antifogging agent according to any one of claims 1 to 5, wherein the ratio of the halogen group-containing silicon compound to the surfactant is 95: 5 to 20:80 by weight. The anti-fogging agent according to any one of claims 1 to 6, wherein the polyol is in a range of 25/75 to 80/20 by weight with respect to the surfactant. The antifogging agent according to any one of claims 1 to 6, further comprising a coating agent C having a polyisocyanate mixed with the coating agents A and B in addition to the coating agent A and the coating agent B. . A method for forming an antifogging film using the antifogging agent according to any one of claims 1 to 7,
(A) preparing a substrate;
(B) a step of mixing the coating agent A and the coating agent B;
(C) The process of apply | coating the mixed coating agent to the base-material surface,
(D) A step of curing the film coated on the substrate surface at room temperature or a heat treatment temperature up to 250 ° C.
A method for forming an antifogging film, comprising: A method for forming an antifogging film using the antifogging agent according to claim 8,
(A) preparing a substrate;
(B) the step of mixing the coating agent C after mixing the coating agent A and the coating agent B;
(C) The process of apply | coating the mixed coating agent to the base-material surface,
(D) A step of curing the film coated on the substrate surface at room temperature or a heat treatment temperature up to 250 ° C.
A method for forming an antifogging film, comprising: