WO2006093086A1

WO2006093086A1 - Antifog coated article, coating material for forming antifog coating, and method for producing antifog coated article

Info

Publication number: WO2006093086A1
Application number: PCT/JP2006/303602
Authority: WO
Inventors: Takeshi Ohara; Shizuo Ootori; Kenichi Yamada; Toyoyuki Teranishi; Kazutaka Kamitani
Original assignee: Yoo Corporation; Nippon Sheet Glass Company, Limited
Priority date: 2005-03-01
Filing date: 2006-02-27
Publication date: 2006-09-08
Also published as: JP2006239495A

Abstract

Disclosed is an antifog coated article comprising a base and an antifog coating formed on the surface of the base. The antifog coating contains phosphorus and an alkaline earth metal. Also disclosed is a coating material for forming an antifog coating which contains a phosphate compound and an alkaline earth metal. Further disclosed is a method for producing an antifog coated article wherein an antifog coating is formed by applying such a coating material onto the surface of a base. The antifog coated article is excellent in antifog properties and abrasion resistance. The method enables to efficiently produce a coating material for forming an antifog coating and an antifog coated article.

Description

Specification

Antifogging coated article, coating material for forming antifogging film, and method for producing antifogging coated article

Technical field

The present invention relates to an antifogging film-coated article, a coating material for forming an antifogging film, and a method for producing an antifogging film-covered article.

Background art

[0002] The phenomenon of the fogging of the surface of glass or other articles occurs because minute water droplets adhere to the surface of the article due to condensation or the like, and the minute water droplets diffusely reflect light. This fogging causes a significant decrease in the performance of optical parts such as glasses, goggles, and optical lenses, and becomes a design and design problem for building window glass and mirrors. In addition, vehicle window glasses such as automobiles may cause a reduction in the field of view and cause safety problems.

In order to eliminate these fogging, an anti-fogging coating is applied. There are organic and inorganic antifogging films, and organic antifogging films are excellent in antifogging performance, but have the disadvantage of low film hardness and low wear resistance. On the other hand, inorganic antifogging coatings have the advantage of high film hardness and high wear resistance, but have the disadvantage of being inferior in antifogging performance compared to organic antifogging coatings.

[0003] Various proposals have been made to solve the above-described problems. For example, an antifogging article having an antifogging film in which an organic substance and an inorganic substance are combined is proposed. . Specifically, a concavo-convex film having a metal oxide having a specific particle size as a matrix is covered on a substrate, and a layer of organosilane having a specific functional group is further formed thereon. Antifogging article (see Patent Document 1, Claims 1 and 7), an antifogging composition comprising a surfactant and an isocyanate group-containing silane compound (Patent Document 2, Claims) 1) is proposed.

However, all of these proposed antifogging articles and antifogging compositions have insufficient antifogging performance, difficulty in maintaining antifogging performance, or low film hardness. Because of poor wear resistance, and! There was a defect.

[0004] In addition, it has been proposed to use a phosphoric acid compound for the purpose of maintaining antifogging performance by imparting hydrophilicity to the membrane over a long period of time and maintaining the strength of the membrane. For example, an antifogging coating material characterized by blending a phosphoric acid compound binder and acid fine particles having an average particle diameter of 1 to 300 nm has been proposed (Patent Document 3, Claim 1). (See)

However, the proposed coating composition has poor anti-fogging maintenance performance, and has a thick film and low film hardness, resulting in poor wear resistance and disadvantages. .

Patent Document 1: Japanese Patent Laid-Open No. 11 100234

Patent Document 2: Japanese Patent Laid-Open No. 2003-73652

Patent Document 3: Japanese Patent Laid-Open No. 2003-231827

Disclosure of the invention

In view of the above problems, an object of the present invention is to provide an antifogging film-coated article excellent in antifogging performance and wear resistance, a coating material for forming an antifogging film, and a method for producing an antifogging film-coated article. Is provided.

[0007] As a result of intensive studies to achieve the above object, the present inventors have made use of an antifogging film-coated article in which an antifogging film containing phosphorus and an alkaline earth metal is disposed on a substrate. The present inventors have found that the above problems can be solved, and have completed the present invention based on the findings.

That is, the present invention

(1) An antifogging film-coated article comprising a base material and an antifogging film formed on the surface of the base material, wherein the antifogging film contains phosphorus and an alkaline earth metal Coated articles,

(2) The antifogging film-coated article according to (1), wherein the alkaline earth metal is magnesium,

(3) The antifogging film-coated article according to the above (2), wherein the ratio of magnesium to phosphorus (MgZP) in the antifogging film is 0.5 to 10,

(4) The antifogging film-coated article according to any one of (1) to (3), wherein the antifogging film has a thickness of 2 to LOOOnm, (5) The antifogging coated article according to any one of (1) to (4), wherein the initial haze value is 0.5% or less,

(6) The antifogging film-coated article according to any one of (1) to (5) above, wherein the difference in haze value before and after the Taber abrasion test is 2% or less,

(7) The antifogging film-coated article according to any one of the above (1) to (6), wherein the substrate is any one of a transparent glass plate, a resin board, or a resin film,

(8) A coating material for forming an antifogging film containing a phosphate compound and an alkaline earth metal,

(9) In the above (8), the phosphoric acid compound is at least one selected from the group power consisting of orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid and phosphate power. The coating material for forming the antifogging film as described,

(10) The above (8) or (8) wherein the alkaline earth metal is at least one compound selected from the group consisting of hydroxide, chloride, acid and sulfate. The coating material for forming an antifogging film according to 9),

(11) The antifogging film forming coating material according to the above (10), wherein the alkaline earth metal is magnesium,

(12) The coating material for forming an antifogging film according to the above (11), wherein the content ratio of magnesium and phosphorus (mass ratio of MgZP) is 0.05 to 4,

(13) Any of the above (8) to (12), wherein the coating material contains a solvent, and the total amount of alkaline earth metal and phosphorus (metal conversion) in the coating material is 0.01 to 50% by mass The antifogging film-forming coating material according to claim 1,

(14) The coating material for forming an antifogging film according to the above (13), wherein the solvent is alcohol or water, and

(15) Antifogging property in which an antifogging film-forming coating material as described in any one of (8) to (14) above is applied to the surface of the substrate and then formed into an antifogging film. Method for producing coated article,

Is to provide.

The anti-fogging film-coated article of the present invention is excellent in anti-fogging performance and abrasion resistance, and is suitably used as optical parts such as glasses, goggles and optical lenses, architectural or vehicle window glass. In addition, according to the coating material for forming an antifogging film of the present invention and the method for producing an antifogging film-coated article using the coating material for forming an antifogging film, the antifogging performance and the wear resistance are excellent. An antifogging film-coated article can be produced efficiently with high productivity.

Brief Description of Drawings

FIG. 1 is a result of composition analysis of a film-coated article produced in Example 1.

FIG. 2 is a scanning electron micrograph of the cross section of the coated article manufactured in Example 1.

FIG. 3 is a scanning electron micrograph of the surface of the coated article manufactured in Example 1. BEST MODE FOR CARRYING OUT THE INVENTION

[0010] The antifogging film in the antifogging film-coated article of the present invention is characterized by containing phosphorus and an alkaline earth metal. Phosphorus (P) and alkaline earth metal (M) in the anti-fogging coating are presumed to be bonded via oxygen, and —P—O—P—, —P—O—M—, -M- It seems that an anti-fogging film is formed by bonds such as 0 —M—.

Examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, barium, and radium. Of these, V and magnesium are preferred because they can easily form a film when combined with phosphorus compounds.

[0011] The proportion of phosphorus and alkaline earth metal in the antifogging coating is not particularly limited as long as the effect of the present invention is achieved, but the proportion of alkaline earth metal (M) and phosphorus (P) is not limited. The range of 0.5 to 10 is preferable. Here, the ratio means the ratio of the number of photoelectrons of alkaline earth metal and phosphorus detected by X-ray photoelectron spectroscopy per unit time (MZP, unit; count / sec).

When the ratio of alkaline earth metal (M) and phosphorus (P) is 0.5 or more, there is an advantage that there is sufficient wear resistance, and when it is 10 or less, there is an advantage that the antifogging maintenance property is excellent. is there. From the above viewpoint, the ratio of alkaline earth metal (M) and phosphorus (P) is more preferably in the range of 1-6.

The same is true in the case of magnesium, which is the most preferred embodiment as an alkaline earth metal, and the content ratio of magnesium and phosphorus is 0 (MgZP) as the ratio of magnesium (Mg) and phosphorus (P). It is preferably in the range of 5 to 10, and more preferably in the range of 1 to 6. The ratio of alkaline earth metal (M) and phosphorus (P) in the antifogging film is determined by X-ray photoelectron spectroscopic analysis while performing argon etching in the depth direction of the antifogging film. Elemental analysis was performed and calculated as the average value of the entire antifogging coating.

[0012] The antifogging film of the present invention may contain other components in addition to the above-described phosphorus and alkaline earth metal as long as the effects of the present invention are not impaired. Examples thereof include titania having a photocatalytic function, silica, zirconium, alumina for increasing the strength of the antifogging coating. Moreover, as long as the effects of the present invention are not impaired, the components in the base material may be diffused and present in the antifogging film. For example, when soda lime glass is used as a substrate and an antifogging film is formed thereon, the sodium component in the soda lime glass is diffused, and the sodium component may be contained in the antifogging film.

[0013] It is presumed that the phosphorus compound and alkaline earth metal in the present invention function as a water-absorbing material in the anti-fogging film, thereby forming an adsorbed water layer on the anti-fogging film. Is done. Then, it is considered that the surface of the antifogging film is made hydrophilic, thereby expressing the antifogging property. The thickness of these adsorbed water layers is considered to vary depending on the film structure of the film, and the larger the surface area of the film, the more adsorbed water can be stably held on the film. Therefore, it is preferable that the surface of the antifogging film has an uneven shape or a pore structure rather than a smooth surface. In the case of having an uneven shape, the arithmetic average roughness (Ra) force is preferably S80 nm or less, and more preferably 30 nm or less. When the arithmetic average roughness (Ra) is 80 nm or less, the initial haze value can be kept small.

[0014] The thickness of the anti-fogging film of the present invention is not particularly limited as long as the effects of the present invention are exhibited, but it is preferably 2 to: LOOOnm. If it is 2 nm or more, a sufficient adsorbed water layer can be formed, and sufficient anti-fogging performance can be obtained. On the other hand, if it is less than lOOOnm, sufficient wear resistance can be obtained. From the above viewpoint, the thickness of the antifogging film is preferably in the range of 2 to 500 nm. Furthermore, from the point of view that no interference color is recognized, it is particularly preferable to be in the range of 2 to 200 nm! /.

[0015] The antifogging film in the present invention may be directly formed on a base material, or a film having a smooth or uneven surface of a metal oxide is formed on the surface of the base material. You may form in. Special When an antifogging film is formed on a metal oxide film having irregularities on the surface, the antifogging film is also preferably formed according to the irregularities of the metal oxide film. There are no particular restrictions on the method of imparting irregularities to the metal oxide film, for example, a method of obtaining irregularities by dispersing fine particles such as acid silicate in the metal oxide, There is a method of embedding fat fine particles in a metal oxide, and obtaining irregularities by thermally decomposing and burning off the fine fat particles after film formation.

In the method of obtaining irregularities using the above heat decomposable resin fine particles, for example, heat decomposable resin fine particles are encapsulated in a matrix such as water glass, and after film formation on the substrate, Heat treatment is performed at a temperature higher than the decomposition temperature of the fine resin particles (usually higher than about 300 ° C) and lower than the heat resistance temperature of the substrate. Here, the heat-resistant temperature of the base material means the upper limit temperature at which the characteristics of the base material can be maintained, and differs depending on the type of base material used. For example, in the case of a glass substrate, it means the soft spot or devitrification temperature (usually about 600 to 700 ° C), and in the case of a plastic substrate, it means the glass transition temperature, crystallization temperature, decomposition point, etc.

[0016] Next, the antifogging film-coated article of the present invention preferably has an initial haze value of 0.5% or less. Here, the haze value is a value measured using a direct reading haze computer (“HG M-2DMJ” manufactured by Suga Test Instruments Co., Ltd.).

The anti-fogging coated article of the present invention preferably has a difference in haze value of 2% or less before and after the Taber abrasion test. Here, the Taber abrasion test is a test when the rotation of the wear wheel is 100 revolutions in the method of JIS R3212: 1998 3.7. The smaller the change in the haze ratio of the antifogging coated article, the higher the wear resistance.

[0017] The substrate used in the present invention is not particularly limited, and examples thereof include glass, resin, ceramics, plastic, and metal. Of these, the viewpoint power to ensure transparency The glass plate, the resin plate, or the resin film is particularly preferable because the glass or the resin is preferable. The thickness of the substrate is appropriately selected depending on the application and is not particularly limited, but is usually about 0.01 to about LOmm.

[0018] The film in the antifogging coated article of the present invention is formed by applying a coating material for forming an antifogging film containing a phosphoric acid compound and an alkaline earth metal to the surface of the substrate, and forming the film. Form be able to.

Hereinafter, a coating material for forming an antifogging film containing a phosphoric acid compound and an alkaline earth metal (hereinafter sometimes simply referred to as “coating material”) will be described in detail.

The phosphoric acid compound in the coating material is not particularly limited, and examples thereof include orthophosphoric acid, metal phosphoric acid, polyphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and phosphate. These may be used alone or in admixture of two or more. Among these, in particular, those having a straight chain structure are superior in water resistance, and have a strong viewpoint of strong bonds with alkaline earth metals compared to phosphates, etc. Orthophosphoric acid, polyphosphoric acid, pyrophosphoric acid, Triphosphoric acid and tetraphosphoric acid are preferred. These phosphate compounds are thought to react with alkaline earth metal (M), which will be described in detail later, to form P—O—M bonds via oxygen and increase the strength of the coating film.

[0019] The alkaline earth metal in the coating material is the same as the alkaline earth metal present in the antifogging film described above, and magnesium is particularly preferable.

In addition, various forms of alkaline earth metal starting materials can be used. For example, hydroxides, chlorides, oxides, sulfates, and the like can be used. Of these, in view of ease of handling, hydroxides or salts are preferred.

Accordingly, when magnesium is used as the alkaline earth metal, magnesium hydroxide, magnesium chloride, magnesium oxide, magnesium sulfate, etc. can be used as starting materials present in the coating material. Of these, considering the ease of handling, sodium hydroxide or magnesium salt is preferred.

[0020] The content ratio (mass ratio of MZP) of the alkaline earth metal and phosphoric acid compound in the coating material is not particularly limited as long as the effect of the present invention is achieved, but the alkaline earth metal ( It is preferably in the range of 0.05 to 4 in terms of mass ratio of M) and phosphorus (P). If the content of alkaline earth metal (M) and phosphorus (P) is 0.05 or more, sufficient wear resistance is advantageous, and if it is 4 or less, it is excellent in antifogging maintenance. There are advantages. From the above viewpoint, the content ratio of the alkaline earth metal (M) and phosphorus (P) is more preferably in the range of 0.1 to 2, particularly preferably in the range of 0.3 to 1. .

In the case of magnesium, which is the most preferred embodiment as an alkaline earth metal In the same way, the content ratio of magnesium and phosphate compound (Mg / P mass ratio) is in the range of 0.05 to 4 in terms of mass ratio of magnesium (Mg) and phosphorus (P). Preferably there is. Further preferred is a range of 0.1-2, particularly preferred is a range of 0.3-1. The content ratio of alkaline earth metal (M) and phosphorus (P) (mass ratio of MZP) was calculated by ICP emission spectrometry.

[0021] The method for applying the coating material to the substrate is not particularly limited, and a known method can be used. For example, vacuum film formation such as sputtering or vapor deposition, flow coating, dip coating, etc. Examples include wet coating such as the coating method, curtain coating method, spin coating method, spray coating method, bar coating method, roll coating method, hand coating method, immersion adsorption method, and sol-gel method. Wet coating is advantageous in that it does not require expensive equipment, and the method for producing an antifogging film-coated article of the present invention will be described in detail below using the wet coating method as an example.

[0022] The solvent of the coating material containing the phosphoric acid compound and the alkaline earth metal is not particularly limited as long as it can dissolve the phosphate compound and the alkaline earth metal. Forces preferably mentioned Water is particularly preferable. Water can be easily removed by drying at the time of film formation or by heat treatment after film formation, which is also suitable for the production environment. In addition, this solvent can be used individually by 1 type or in mixture of 2 or more types.

The total amount of alkaline earth metal such as magnesium and phosphorus (metal conversion) in the coating material is preferably in the range of 0.01 to 50% by mass. When the content is 0.01% by mass or more, there is an advantage that a film thickness of a certain level or more is secured and anti-fogging maintenance is good. There is an advantage of being good. From the above viewpoint, the total amount of alkaline earth metal such as magnesium and phosphorus is preferably in the range of 0.07 to 10% by mass.

[0023] In applying the coating material to the base material, the surface of the base material can be cleaned or surface-modified. Depending on the state of adhesion of dirt on the substrate, a phenomenon such as repelling of the solution may occur, and the film may not be uniformly formed. In such a case, cleaning is effective. Examples of the cleaning method include degreasing cleaning with an organic solvent such as alcohol, acetone, and hexane, cleaning with an alkali or acid, and polishing of the substrate surface with an abrasive. It is also preferable to perform surface treatment of the substrate in advance before forming the anti-fogging film in order to increase the hydrophilic group, which preferably has a hydrophilic group on the substrate surface. is there. Examples of the surface modification method include ultraviolet irradiation treatment, ultraviolet ozone treatment, plasma treatment, corona discharge treatment, and heat treatment.

[0024] After the coating material is applied on the substrate, it is preferably dried in the range of room temperature to 200 ° C, more preferably in the range of 100 to 200 ° C. Further, it is preferable to perform the heat treatment at a temperature higher than 300 ° C. and lower than the heat resistance temperature of the base material. Specifically, a range of 300 to 700 ° C is preferable, and a range of 300 to 500 ° C is more preferable.

Example

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples at all! /.

(Evaluation methods)

(1) Analysis of anti-fogging coating

The coating composition was evaluated by using X-ray photoelectron spectroscopy (“ESCA-5600ci” manufactured by ULVAC 'Huai Co., Ltd.). The conditions for X-ray photoelectron spectroscopy are as follows.

(a) Pretreatment method: After cutting the sample, it was fixed on a sample table using a molybdenum mask.

(b) Analysis conditions

Urrent X-ray anode; A1 Monocnromated 2mm Filament

Anode Energy; 1486.6eV

Anode Power; 150Watts

X-ray Voltage; 14kV

Stage Angle; 45 °

(c) Etching conditions

Primary ion species; Ar

Beam voltage; 3.0kV

Raster; 4 X 4mm

Etching Rate; about 1.4nm / min (SiO film equivalent) In addition, the surface structure and the cross-sectional structure of the coating were measured using a scanning electron microscope (“s

—4700 ”), with an acceleration voltage of 5 kV, irradiation current of 10 A, tilt angle of 10 degrees (cross section), 30 degrees (surface), surface observation magnification of 50,000 times, and cross-section observation magnification of 100,000 times. Observed.

(2) Evaluation of wear resistance

The anti-fogging coated article obtained in each Example and Comparative Example was subjected to an abrasion resistance test (Taber abrasion test) according to the method of JIS R3212: 19 98 3.7, and the abrasion resistance before and after the test was determined as a haze value. It was evaluated with. The test was conducted with the wear wheel rotating at 100 rotations. The haze value was measured using a direct reading haze computer (“HGM-2DM” manufactured by Suga Test Instruments Co., Ltd.). The smaller the haze value is, the better the abrasion resistance is without the appearance defects such as scratches when the film is peeled off.

(3) Evaluation of anti-fogging maintenance

The anti-fogging coated article obtained in each Example and Comparative Example was left in a room with a temperature of 20 ± 5 ° C and a humidity of 30 ± 10%. The evaluation was based on the visibility of the field of view visible through the glass. The evaluation was based on the following criteria.

◎; The appearance of cloudiness is the same as the dry state.

〇; Power with slight blurring and distortion Appearance is good.

Δ: It is better than the fogging in normal glass blown under the same conditions, but it looks bad.

X: It is equal to or less than fogging in ordinary glass blown under the same conditions, and the appearance is poor.

(4) Elemental analysis in coating materials

Quantitative analysis of phosphorus (P), magnesium (Mg), and titanium (Ti) in the coating material was performed by ICP emission spectrometry. As the measuring device, an ICP emission analyzer (“I CPS-8000” manufactured by Shimadzu Corporation) was used.

Example 1

100 parts by mass of ionized water and 1000 parts by mass of tetrasalt 匕 titanium

Four

Were mixed and stirred for 30 minutes or more to obtain a liquid A. In addition, 4000 parts by mass of ion exchange water and this A 200 parts by mass of the liquid was mixed and stirred for 30 minutes or more to obtain a liquid B. Next, 1000 parts by mass of B liquid, 70 parts by mass of polyphosphoric acid (HPO; manufactured by Kishidai Chemical Co., Ltd.), magnesium hydroxide (Mg (OH)

13 4 6

; Sigma-Aldrich Japan Co., Ltd.) 20 parts by mass were mixed and stirred. After this,

2

The precipitate was settled by standing, and the supernatant liquid was diluted 5 times with ion-exchanged water to obtain a coating material C for forming an antifogging film. The contents of magnesium and phosphorus in the coating material C were 0.166% by mass and 0.546% by mass, respectively. Further, titanium was below the detection limit.

The coating material C was applied on a cleaned glass substrate by a flow coating method at 20 ° C. and a relative humidity of 30%. Thereafter, the film was dried at room temperature for 30 minutes, further at 100 ° C for 30 minutes, and then heat-treated at 320 ° C for 30 minutes. The above evaluation was performed on this glass article. Figure 1 and Table 1 show the measurement results by X-ray photoelectron spectroscopy. Magnesium (1S orbital) and phosphorus (2p orbital) are detected as the main components of the anti-fogging coating, and it can be seen that phosphorus is present up to the part where the sputtering time is about 30 minutes. Since Si (2p orbital) saturates after about 30 minutes of sputtering time, it is considered that this is the substrate part after this point. The average ratio of magnesium and phosphorus in the antifogging film was 2.6.

Scanning electron micrographs are shown in FIGS. The glass article had an antifogging coating thickness of about 50 nm.

Next, Table 2 shows the change in haze ratio before and after the Taber abrasion test and the evaluation results of anti-fogging maintenance. It was confirmed that the film had excellent wear resistance with no appearance defects such as scratches if the film peeled off with little change in haze ratio before and after the Taber abrasion test. It was also confirmed that the anti-fogging performance was maintained even after 2 months.

Example 2

60 parts of phosphoric acid (H 3 PO; manufactured by Kishida Chemical Co., Ltd.) was added to 1000 parts by mass of the B solution prepared in Example 1.

3 4

An amount of 20 parts by mass of magnesium hydroxide (Mg (OH); supra) was mixed and stirred. After this

2

The precipitate was settled by allowing it to stand, and the supernatant was used as coating material D for forming an antifogging film. The contents of magnesium and phosphorus in coating material D were 1.32% by mass and 1.46% by mass, respectively. Titanium was below the detection limit.

This coating material D was washed on a glass substrate washed at 20 ° C and 30% relative humidity. It was applied by a one-coat method. Then, after drying at room temperature for 30 minutes, it was heat-treated at 320 ° C for 15 minutes. The above evaluation was performed on this glass article.

The thickness of the antifogging film of the obtained glass article was about 250 nm. Magnesium and phosphorus were detected as the main components of the antifogging coating, and the average ratio of magnesium and phosphorus in the antifogging coating was 2.7. Table 2 shows the changes in haze ratio before and after the Taber abrasion test and the evaluation results of anti-fogging maintenance. It was confirmed that the haze rate change before and after the Taber abrasion test was small, and that the film had excellent wear resistance with no defects in appearance such as scratches. Further, it was confirmed that the antifogging performance was maintained even after being left for 2 months.

[0028] Example 3

A glass article was obtained in the same manner as in Example 1 except that the coating material C of Example 1 was diluted 4-fold with ion-exchanged water, and was similarly evaluated. The thickness of the antifogging film of the obtained glass article was about 13 nm. Further, magnesium and phosphorus were detected as the main components of the antifogging coating, and the contents of magnesium and phosphorus in the coating material were 0.0415% by mass and 0.1365% by mass, respectively. The average ratio of magnesium and phosphorus in the antifogging film was 2.7. Table 2 shows the changes in haze ratio before and after the Taber abrasion test and the evaluation results of anti-fogging maintenance. It was confirmed that the film had excellent wear resistance with no appearance defects such as scratches if the film peeled off with little change in haze ratio before and after the Taber abrasion test. It was also confirmed that anti-fogging performance was maintained even after 2 months.

[0029] Comparative Example 1

50 parts by mass of water-soluble monobasic aluminum phosphate aqueous solution (“50L” manufactured by Taki Chemical Co., Ltd., water-soluble primary aluminum phosphate content 33% by mass) and 150 parts by mass of distilled water and 20 parts by mass of ethylene glycol monobutyl ether Added. After that, silica sol dispersion with an average particle size of 20 nm (Nissan Chemical Industry Co., Ltd. “Snowtex C”, dispersion medium; water, silica content; 20% by mass) 200 parts by mass and 500 parts by mass of ethanol were added, and anti-fogging A coating material E for forming a conductive film was obtained. The mass ratio of the water-soluble aluminum phosphate Z silica in solution E in terms of solid content was 0.329 / 0.71, and the total solid content concentration was 5.8% by mass.

This coating material E is applied to the cleaned glass substrate by the flow coating method at 20 ° C and relative humidity of 30%, and then heat-treated at 300 ° C for 1 hour for antifogging coating coated glass. I got a product. The thickness of the antifogging film of the obtained glass article was 200 nm. This glass article was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

It was confirmed that the haze rate change before and after the Taber abrasion test was large, and appearance changes such as film peeling occurred, resulting in poor wear resistance. In addition, the anti-fogging performance after standing for 2 months has declined, and it has been confirmed that the anti-fogging maintenance property is low.

[table 1]

Table 1

Mg / P = 1 792999.57 / 680049.85 = 2.6 [Table 2]

Table 2

Industrial applicability

The anti-fogging film-coated article of the present invention is excellent in anti-fogging performance and abrasion resistance, and is suitably used as optical parts such as glasses, goggles and optical lenses, architectural or vehicle window glass. Further, according to the coating material of the present invention and the production method using the coating material, an anti-fogging film-coated article excellent in anti-fogging performance and wear resistance is high! It can be manufactured efficiently and efficiently.

Claims

The scope of the claims

[I] An antifogging film-coated article comprising a base material and an antifogging film formed on the surface of the base material, wherein the antifogging film contains phosphorus and an alkaline earth metal Coated articles.

[2] The anti-fogging coated article according to claim 1, wherein the alkaline earth metal is magnesium.

[3] The antifogging film-coated article according to [2], wherein the ratio of magnesium to phosphorus (MgZP) in the antifogging film is 0.5 to 10.

[4] The antifogging film-coated article according to any one of [1] to [3], wherein the antifogging film has a thickness of 2 to: LOOOnm.

[5] The antifogging film-coated article according to any one of [1] to [4], wherein an initial haze value is 0.5% or less.

[6] The anti-fogging coated article according to any one of claims 1 to 5, wherein the difference in haze value before and after the Taber abrasion test is 2% or less.

[7] The substrate is a transparent glass plate, a resin board, or a resin film.

The antifogging film-coated article according to any one of 6 to 6.

[8] A coating material for forming an antifogging film comprising a phosphoric acid compound and an alkaline earth metal.

[9] The phosphoric acid compound is at least one selected from the group forces of orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and phosphate power. Coating material for forming anti-fogging film.

10. The antifogging property according to claim 8 or 9, wherein the alkaline earth metal starts with at least one compound selected from the group consisting of hydroxides, chlorides, oxides and sulfides. Coating material for film formation.

[I I] The coating material for forming an antifogging film according to claim 10, wherein the alkaline earth metal is magnesium.

12. The coating material for forming an antifogging film according to claim 11, wherein the content ratio of magnesium and phosphorus (mass ratio of Mg / P) is 0.05 to 4.

[13] The coating material according to any one of claims 8 to 12, wherein the coating material contains a solvent, and the total amount (metal conversion) of alkaline earth metal and phosphorus in the coating material is 0.01 to 50% by mass. Antifogging film formation Coating material.

14. The coating material for forming an antifogging film according to claim 13, wherein the solvent is alcohol and Z or water.

[15] An antifogging film-coated article which forms an antifogging film by applying the coating material for forming an antifogging film according to any one of claims 8 to 14 onto a substrate surface and forming the film. Manufacturing method.