JP4043207B2 - Antifogging article and method for forming the same - Google Patents

Description

【００３４】
実施例２
実施例１と比較し、防曇性組成物の成分比が、界面活性剤２０重量％、ポリオール３０重量％、イソシアネートシラン３０重量％、コロイダルシリカ２０重量％となるように調合液を調整した以外は実施例１と同様に行った。なお、コロイダルシリカは、商品名「ＮＰＣ−ＳＴ」（固形分２０％、日産化学製）を用いた。得られた防曇性被膜付きガラスは、１６μｍの膜厚を有し、表１に示すように実施例１と同様に全ての品質において優れた性能を示した。
【００３５】
実施例３
イソシアネートシランの原料としてジエトキシジイソシアネートシランとトリエトキシイソシアネートシランを２：１(重量比)で混合したものを用いた以外は、実施例２と同様とした。得られた防曇性被膜付きガラスは、１２μｍの膜厚を有し、表１に示すように、実施例１と同様に全ての品質において優れた性能を示した。
【００３６】
実施例４
界面活性剤２０重量％、ジイソシアネートジエトキシシラン５０重量％、シリカゾル３０重量％となるように調合液を調整した以外は実施例１と同様に行った。なお、シリカゾルは、商品名「ＭＳ５１」（固形分５１％、三菱化学製）を用いた。得られた防曇性被膜付きガラスは、１４μｍの膜厚を有し、表１に示すように、実施例１と同様に全ての品質において優れた性能を示した。
【００３７】
比較例１
実施例１のイソシアネートシランの変わりに、ヘキサメチレンジイソシアネートを用いた以外は、実施例１と同様とした。得られた防曇性被膜付きガラスは、２０μｍの膜厚を有し、表１に示すように、繰り返し防曇性、冷温防曇性において優れた防曇性を有したものの、耐テーバー摩耗性、耐水性がＮＧであった。
【００３８】
【発明の効果】
以上詳述したように、本発明の防曇性物品は、防曇性、耐水拭き性、耐摩耗性が優れ長期間にわたり防曇性能を維持することが可能であり、建築用、自動車用、鏡用等に広く使用することができるとともに、比較的低温でガラスの基材表面に防曇性被膜を形成することができるので、例えば、鏡加工をしたガラス、曲げ加工、成型まで完了した自動車用ガラス等に、全面もしくは部分的に容易に成膜することもできる等の利点を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an article such as a lens for glasses / camera having anti-fogging performance, an article such as a window glass, a glass for vehicles, a shield for a helmet, an underwater eyeglass, or a mirror used in a bathroom. It is about.
[0002]
[Prior art]
Examples of methods for imparting antifogging properties to articles include, for example, (1) a method of imparting water absorption such as using a water absorbent resin or imparting water absorption capability by making an inorganic film porous, and (2) a surfactant. A method of making the surface hydrophilic, for example, applying a hydrophilic substance on the surface, using a hydrophilic substance on the substrate itself, or using titanium oxide exhibiting photocatalytic activity, (3) Various methods have been conventionally known, such as a method of making hydrophobic or applying a water repellent to the surface of a substrate or kneading a water repellent material, and (4) a method of increasing the surface temperature of an article to prevent condensation. .
[0003]
[Problems to be solved by the invention]
However, each of the conventional methods has the following problems. For example, in the method (1), when the water is absorbed, the base material swells and the strength is reduced, so that it cannot be used in a part requiring mechanical durability. If attached, the hydrophilicity will be lost, or if it is a surfactant, it will flow off easily. In addition, it is essential that the photocatalyst film be exposed to ultraviolet rays. In the method (3), the antifogging performance cannot be expected unless the contact angle is 160 ° super water-repellent (4). In this method, the antifogging effect is sufficient because it provides temporary or relatively short time antifogging properties, such as being very disadvantageous in parts that require transparency. Is expected to be sustainable Not only difficult, also in the practical use becomes costly were those employed is difficult.
[0004]
[Means for Solving the Problems]
The present invention has been made in view of the conventional problems, and by fixing a surfactant in a water-absorbing matrix by chemical bonding, it has both functions of surface hydrophilicity and water absorption and has excellent antifogging properties. An antifogging article formed with an antifogging film having high durability and having high mechanical strength by using a silicon compound in the matrix and a method for producing the same are provided. To do.
[0005]
That is, the antifogging article of the present invention comprises an antifogging property comprising an isocyanate group-containing silane compound, which is a matrix component of the coating, and an antifogging coating in which a surfactant is fixed via a urethane bond, and a glass substrate. an article, the coating film is a surface active agent and anti-fogging compositions ing include isocyanate group-containing silane compound having a reactive functional group in the isocyanate group one obtained by coating the surface of the glass base material It is characterized by being .
[0006]
The antifogging composition of the present invention comprises a polyol and / or an oxide.
[0007]
The antifogging composition is characterized in that the oxide is silica and / or silica fine particles.
[0008]
The antifogging composition comprises a polypropylene glycol-based or polyethylene oxide-based polyol.
[0009]
Furthermore, the antifogging film of the present invention is characterized in that the film thickness is 5 to 30 μm.
[0010]
In addition, the method for forming an antifogging article of the present invention is characterized in that an antifogging film is coated on the surface of a substrate by the following steps.
(A) preparing a substrate;
(B) a step of preparing a coating solution by mixing a surfactant having a reactive functional group with an isocyanate group and an isocyanate group-containing silane compound;
(C) The process of apply | coating the said coating liquid on the said base material surface, and coat | covering an antifogging film on the base material surface by heat-processing at the temperature of 120 to 250 degreeC.
[0011]
Furthermore, the method for forming an antifogging film of the present invention is characterized in that, in the step (b), a coating liquid is prepared by simultaneously mixing a surfactant and an isocyanate group-containing silane compound together with a polyol and / or an oxide. And
[0012]
Furthermore, in the method for forming an antifogging film of the present invention, in the step (b), the surfactant, the polyol, and the isocyanate group-containing silane compound are mixed and sufficiently reacted, and the oxide is removed after the isocyanate group disappears. It is characterized by being mixed.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The antifogging composition of the present invention comprises a surfactant and an isocyanate group-containing silane compound.
[0014]
The surfactant used in the present invention preferably has a functional group that reacts with an isocyanate group (—NCO). Examples of the functional group include —OH group, —NH ₂ group, —NH group, —SH group, and the like. Is mentioned. These functional groups and isocyanate group-containing silane compounds react to fix the surfactant to the matrix, and it is possible to maintain the function of developing antifogging properties over a long period of time without the surfactant eluting. Become. When a surfactant that does not have a functional group that reacts with an isocyanate group is used, the antifogging property and the cold / antifogging property may decrease even if the Taber abrasion resistance and water resistance are good.
[0015]
The isocyanate group-containing silane compound used in the present invention is not particularly limited as long as it is a silane compound having an isocyanate group. For example, tetraisocyanate silane, methyl triisocyanate silane, monomethoxy triisocyanate silane, monoethoxy triisocyanate. Examples include silane, dimethoxy diisocyanate silane, diethoxy diisocyanate silane, monoisocyanate trimethoxy silane, monoisocyanate triethoxy silane, and γ-isocyanate propyl trimethoxy silane. Furthermore, it is possible to react an organic isocyanate compound and a silicon compound in advance. In addition, it is preferable that the antifogging composition of this invention adds a polyol and / or an oxide to the said surfactant and an isocyanate group containing silane compound.
[0016]
The polyol is not particularly limited as long as it is a commonly used polyol. For example, a polyol having a hydrophilic property such as a polypropylene glycol type or a polyethylene oxide type is more preferable. By reacting these polyols with the isocyanate silane, a urethane bond is formed, and both the urethane bond part and the polyol can have a water absorbing function.
[0017]
Examples of the oxide include silica, alumina, zirconia, tantalum oxide, and the like, and silica and alumina are more preferable in terms of both hardness and hydrophilicity of the substrate. It is also possible to use oxide fine particles of alumina or silica.
[0018]
The antifogging composition of the present invention is prepared by preparing a preparation with the surfactant, isocyanate silane, and in some cases polyol and / or oxide, and further containing an alkoxy compound such as silicon, aluminum, zirconia or the condensation polymer thereof. It is also possible to mix the sol. In that case, since the isocyanate silane easily reacts with water and alcohol, the surfactant, polyol, isocyanate silane, and in some cases, the oxide may be sufficiently reacted to mix with the oxide after the isocyanate group disappears. desirable. When an oxide is added, it is preferable to use silicon alkoxide and an oxide sol that is a polycondensate thereof from the viewpoint of compatibility and liquid stability.
[0019]
The anti-fogging composition and anti-fogging film of the present invention are characterized in that the surface has hydrophilicity, and further, a polyol is added as a matrix component to provide water absorption performance so that hydrophilicity and water absorption coexist. This is more preferable particularly when the usage environment is below freezing point. In addition, even when used in other environments than the freezing point, it is preferable that hydrophilicity and water absorption coexist because the performance is improved, and these selections can be appropriately selected for the purpose of use.
[0020]
The antifogging composition 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, mirrors used in bathrooms, etc. However, it is particularly preferable to apply the antifogging composition on the surface of a substrate such as glass or resin and apply it as an antifogging film. In the case of such an antifogging coating, the surfactant is fixed via an isocyanate group-containing silane compound, which is a matrix component of the coating, and a urethane bond, and the antifogging is prevented for a long period of time without elution of the surfactant. The function of expressing sex can be maintained.
[0021]
Moreover, the formation method of the anti-fogging article | item of this invention coat | covers an anti-fogging film on the base-material surface according to the following process.
(A) preparing a substrate;
(B) a step of preparing a coating liquid by mixing a surfactant, an isocyanate group-containing silane compound, and a solvent;
(C) The process of apply | coating the said coating liquid on the said base material surface, and coat | covering an antifogging film on the base material surface by heat-processing at the temperature of 120 to 250 degreeC.
[0022]
As means for applying the coating solution to the substrate surface, known means such as dip coating, flow coating, spin coating, roll coating, spray coating, screen printing, flexographic printing, etc. can be employed. After coating, heating is performed at a relatively low temperature of 120 ° C. to 250 ° C. for about 30 to 60 minutes, whereby most of the solvent is scattered and the urethane reaction is promoted to form a film. When organoalkoxysilane is used, the polymerization of silica is accelerated by heat treatment, and a high-strength film can be produced.
[0023]
The film thickness of the antifogging film is preferably about 5 to 30 μm after heat treatment, and if it is less than 5 μm, the antifogging durability tends to be inferior. May occur.
[0024]
As a base material used for the antifogging film of the present invention, glass is typically used, and the glass is a plate glass usually used for automotive, architectural, industrial glass, etc., so-called glass. Float plate glass, etc., various glass such as clear, green and bronze, various functional glass, tempered glass and similar glass, laminated glass, multilayer glass, flat plate and bent plate It goes without saying that it can be used. The plate thickness is, for example, from about 1.0 mm to about 12 mm, preferably from about 3.0 mm to about 10 mm for construction, and from about 2.0 mm to about 5 mm for automobiles. Glass of about 0 mm or less is preferable.
[0025]
Since the anti-fogging film of the present invention can form an anti-fogging film on the surface of a glass substrate at a relatively low temperature, for example, mirror-finished glass, bending processing, automotive glass that has been completely molded, The film can be easily formed on the entire surface or partially.
[0026]
[Action]
Antifogging article of the present invention, in the coating, the surfactant can exhibit excellent anti-fogging properties over a long period by a hydrophilic fixed surface in the matrix. Further, when a silicon compound having a urethane bond and a hydrophilic polyol are used, the coating itself exhibits water absorption. By having both functions of hydrophilicity of the surface and water absorption of the matrix, it has excellent antifogging properties even in severe environments below freezing point. Further, since a silane compound is used as a matrix, swelling of the film and reduction in film strength during water absorption are suppressed, and excellent scratch resistance is obtained.
[0027]
【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.
[0028]
1) Repeated anti-fogging property “Fogging agent test method for spectacles” (JIS S 4030). Haze condition when holding sample for 3 minutes in steam of warm water set at 43 ° C. and normal temperature after holding (23 ° C., 63% RH), the cloudiness due to exhalation when taken out was observed, and this operation was performed for 10 cycles.
[0029]
2) Cold / antifogging properties After holding the sample for evaluation in a refrigerator set at 4 ° C. for 30 minutes, the appearance, cloudiness, and cloudiness due to expiration are observed when taken out at room temperature (23 ° C., 63% RH). Then, this operation was performed for 10 cycles, and a product that did not have an abnormality in appearance and did not cause fogging was regarded as acceptable.
[0030]
3) Abrasion resistance Based on the abrasion resistance test method described in JIS R 3221, the sample for evaluation was subjected to a Taber abrasion test with a wear wheel CS-10F and a load of 250 gf to evaluate the haze value (cloudiness value). 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) is ΔH ≦ 104%, which is acceptable (◯), and H100> H200 or ΔH> 10% is unacceptable (×).
[0031]
4) Water resistance The evaluation sample was immersed in water kept at room temperature (23 ± 2 ° C.) for 1 hour.
[0032]
Example 1
20% by weight of a nonionic surfactant obtained by adding an OH group to a polyoxyethylene fatty acid ester, 30% by weight of a polypropylene glycol copolymer (molecular weight 40 million), and 50% by weight of diisocyanate diethoxysilane It mixed and adjusted so that it might become the preparation liquid for anti-fogging compositions. Next, the obtained liquid mixture was formed into a film on the surface of a float glass having a glass size of 100 mm × 100 mm × 2 mm (thickness) that had been washed in advance by a dipping method to obtain a glass with an antifogging coating having a thickness of 15 μm. As a result of evaluating the obtained glass with an antifogging film, as shown in Table 1, it was confirmed that it was excellent in all the qualities of repeated antifogging properties, cold / antifogging properties, Taber abrasion resistance, and water resistance. It was done.
[0033]
[Table 1]

[0034]
Example 2
Compared to Example 1, except that the formulation was adjusted so that the component ratio of the antifogging composition was 20% by weight of surfactant, 30% by weight of polyol, 30% by weight of isocyanate silane, and 20% by weight of colloidal silica. Was carried out in the same manner as in Example 1. As the colloidal silica, a trade name “NPC-ST” (solid content 20%, manufactured by Nissan Chemical Co., Ltd.) was used. The obtained glass with an antifogging film had a film thickness of 16 μm, and as shown in Table 1, showed excellent performance in all qualities as in Example 1.
[0035]
Example 3
The same procedure as in Example 2 was performed except that diethoxydiisocyanate silane and triethoxyisocyanate silane mixed at a ratio of 2: 1 (weight ratio) were used as raw materials for isocyanate silane. The obtained glass with an antifogging film had a film thickness of 12 μm and, as shown in Table 1, showed excellent performance in all qualities as in Example 1.
[0036]
Example 4
The same procedure as in Example 1 was carried out except that the preparation liquid was adjusted to 20 wt% surfactant, 50 wt% diisocyanate diethoxysilane, and 30 wt% silica sol. As the silica sol, the trade name “MS51” (solid content 51%, manufactured by Mitsubishi Chemical) was used. The obtained glass with an antifogging film had a film thickness of 14 μm and, as shown in Table 1, showed excellent performance in all qualities as in Example 1.
[0037]
Comparative Example 1
The same procedure as in Example 1 was conducted except that hexamethylene diisocyanate was used in place of the isocyanate silane of Example 1. The obtained glass with an antifogging film has a film thickness of 20 μm and, as shown in Table 1, although it has excellent antifogging properties in terms of antifogging properties and cold / fogging properties, it is resistant to Taber. The water resistance was NG.
[0038]
【The invention's effect】
As described above in detail, the antifogging article of the present invention is excellent in antifogging properties, water wiping resistance, and abrasion resistance, and can maintain antifogging performance over a long period of time. It can be widely used for mirrors, etc., and can form an antifogging film on the surface of a glass substrate at a relatively low temperature. For example, the film can be easily formed on the entire surface or a part of the glass.

Claims (7)

An anti-fogging article comprising an isocyanate group-containing silane compound, which is a matrix component of a coating, and an antifogging coating in which a surfactant is fixed via a urethane bond, and a glass substrate. an antifogging composition comprising a surfactant and an isocyanate group-containing silane compound having a reactive functional group all SANYO obtained by coating the surface of the glass base material, the film thickness is 5~30μm Antifogging article characterized by The antifogging article according to claim 1, wherein the antifogging composition comprises a polyol and / or an oxide. The antifogging article according to claim 2, wherein the oxide is silica and / or silica fine particles. The antifogging article according to any one of claims 1 to 3, wherein the antifogging composition comprises a polypropylene glycol-based or polyethylene oxide-based polyol. The method for forming an antifogging article according to any one of claims 1 to 4 , wherein the base material surface is coated with an antifogging film by the following steps.
(A) preparing a substrate;
(B) a step of preparing a coating solution by mixing a surfactant having a reactive functional group with an isocyanate group and an isocyanate group-containing silane compound;
(C) The process of apply | coating the said coating liquid on the said base material surface, and coat | covering an antifogging film on the base material surface by heat-processing at the temperature of 120 to 250 degreeC. 6. The method for forming an antifogging article according to claim 5 , wherein, in the step (b), a coating liquid is prepared by simultaneously mixing a surfactant and an isocyanate group-containing silane compound together with a polyol and / or an oxide. . In the step (b), a surfactant, a polyol, mixing the isocyanate group-containing silane compound is sufficiently reactive, claim 5 or claim, characterized by comprising a mixture of oxides from gone isocyanate groups 6. A method for forming an antifogging article according to 6 .