JP7787609B2 - Treatment agent and coating method that shortens the anti-glare and anti-fouling lamination process and improves durability - Google Patents

Description

The present invention relates to an anti-glare treatment composition, a coating method for an anti-fouling treatment agent to be layered thereon, and an anti-glare and anti-fouling coating film.

2. Description of the Related Art In image display devices such as liquid crystal displays and organic EL displays, a phenomenon occurs in which visibility is reduced due to reflected images caused by light from indoor lighting devices such as fluorescent lights or external light such as sunlight.
To prevent this, it is common practice to apply anti-glare treatment (AG treatment) or anti-reflection treatment (AR treatment) to glass substrates such as cover glasses of image display devices.
The anti-glare treatment of these glass substrates is realized by forming irregularities on the surface by etching, sandblasting, coating or the like, thereby causing diffuse reflection of external light.
The etching method, which is the most common of these processing methods, uses hydrofluoric acid, which is highly corrosive and toxic to humans, posing serious challenges to the working environment and the global environment. Furthermore, there are also issues that need to be improved from the standpoints of cost and ensuring uniformity in curved display surfaces (Patent Documents 1 to 3).

As a result, relatively simple coating methods are being reconsidered as an alternative to etching methods. Among these, the method of spraying an anti-glare treatment composition makes it easy to control film thickness and optical properties by adjusting the coating conditions, and can be performed using small-scale equipment. However, a high-temperature baking process is required to dry the solvent after spraying, and further reductions in processes are expected for use in mass production (Patent Documents 4-6).

On the other hand, in applications where the surface is touched by fingers, such as touch panels, an anti-fouling layer made of a fluorine-containing organic silicon compound may be laminated on the anti-glare treatment layer to prevent stains such as fingerprints and sebum from adhering and impairing visibility and aesthetics (AF treatment).
Antifouling treatments form a highly water- and oil-repellent film to prevent dirt from adhering, but repeated wiping of the dirt can easily degrade this performance. Therefore, methods to improve the abrasion resistance and durability of the antifouling layer are needed.
To solve this problem, in order to improve the adhesion between the antiglare layer and the antifouling layer, a surface modification process such as glow discharge emission, plasma irradiation, or washing with an alkaline solution may be performed on the antiglare treatment layer before applying the antifouling treatment agent (Patent Documents 7 and 8).
However, the effect is not sufficient despite the increased number of manufacturing steps, and further improvement is required.
Furthermore, the antifouling agent exerts its effectiveness when it is evenly applied to the top surface of the previously formed AG layer. However, if foreign matter adheres to the AG layer in the previous process, it can cause poor repellency and uneven coating, so it is necessary to strictly control the inclusion of foreign matter in the baking oven.

Special Publication No. 2012-521958 Special Publication No. 2014-513029 Special Publication No. 2014-523384 JP 2018-198050 A JP 2009-058640 A JP 2017-106944 A JP 2022-007992 A Republished Patent 2019/189071

The present invention aims to solve the problems and issues of the prior art by providing an anti-glare (AG) treatment composition that can impart highly durable anti-glare and anti-fouling properties to glass materials and the like in a short period of time, a method for applying the same, and a coating film obtained by applying the same.

As a result of extensive research into the above-mentioned issues and problems, the inventors have discovered that these can be overcome by spray-coating, under certain conditions, an AG treatment agent consisting of a hydrolysis condensate of a tetraalkoxysilane compound in the presence of a strong acid catalyst and an alcohol or glycol ether organic solvent, followed by spray-coating a fluorine-containing antifouling treatment agent and then baking the spray-coated surface to form a multilayer coating film, which led to the present invention.
The present invention is characterized by the following points.
1. An anti-glare treatment composition comprising a hydrolysis condensation product of a tetraalkoxysilane compound in the presence of a strong acid catalyst, and an alcohol and/or a glycol ether organic solvent.
2. An anti-glare treatment composition comprising 5 to 50 parts by mass of a hydrolysis condensate of a tetraalkoxysilane compound relative to 100 parts by mass of the anti-glare treatment composition, and the organic solvent is one or more mixed solvents, and is present in an amount of 50 to 95 parts by mass relative to 100 parts by mass of the anti-glare treatment composition.
3. A method for forming a coating film having antiglare and antifouling properties using the antiglare treatment composition according to 1 or 2 above, characterized in that the antiglare treatment composition is spray-coated onto the surface of an article to be coated to form an antiglare treatment composition layer, and then a fluorine-containing antifouling treatment agent is spray-coated thereon, followed by baking.
4. The method for forming a coating film having antiglare and antifouling properties according to 3 above, characterized in that the antifouling treatment agent is spray-coated while the antiglare treatment composition layer is in a state where the heating residue determined after heating at 180°C for 1 hour is 74 to 95 parts by mass.
5. An antiglare and antifouling layer comprising an antiglare layer made of the antiglare treatment composition according to 1 or 2 above, and an antifouling layer made of a fluorine-containing antifouling treatment agent.

"Anti-glare treatment composition"
The composition forming the antiglare treatment agent used in the present invention is as follows.
An anti-glare treatment composition comprising a hydrolysis condensate of a tetraalkoxysilane compound in the presence of a strong acid catalyst, and an alcohol or glycol ether organic solvent, wherein the anti-glare treatment composition contains 5 to 50 parts by mass of the hydrolysis condensate of the tetraalkoxysilane compound per 100 parts by mass of the total treatment composition, and the organic solvent is one or more mixed solvents, and is present in an amount of 50 to 95 parts by mass per 100 parts by mass of the total treatment composition.

The coating method of the present invention is basically an invention in which (1) the anti-glare treatment composition of the present invention is spray-coated onto a substrate such as glass so as to achieve a predetermined state, (2) while the heat residue of the sprayed anti-glare treatment layer is in a state of 74 to 95 parts by mass when heated at 180°C for 1 hour, a fluorine-containing antifouling treatment agent is further spray-coated, and (3) a coating film is formed by baking in an oven at 150°C for 30 minutes.
As a result, the baking process is shorter than conventional processes, and a coating film having excellent durability and anti-glare and anti-fouling properties can be formed in a process that prevents cissing and unevenness in the anti-fouling layer due to contamination of the anti-glare layer.

By using the anti-glare treatment composition and coating method of the present invention, it is possible to form a coating film having excellent durability and anti-glare and anti-fouling properties using a method that is more environmentally friendly than conventional etching methods, that shortens the baking step compared to conventional spray coating methods which are an alternative to etching, and that prevents cissing and unevenness in the anti-fouling layer due to contamination of the anti-glare layer.
Specifically, as shown in the following examples, it has been confirmed that the coating surface obtained by the present invention has good haze, gloss, and contact angle with water even after being subjected to abrasion multiple times.

The present invention will now be described in more detail.
In the anti-glare treatment composition of the present invention, the hydrolysis condensation product (A) of a tetraalkoxysilane compound in the presence of a strong acid catalyst and the alcohol or glycol ether organic solvent (B) are both essential components for obtaining the anti-glare treatment composition.

"Hydrolysis condensation product (A) of tetraalkoxysilane compound in the presence of a strong acid catalyst"
Tetraalkoxysilane compounds that can be used to produce the hydrolytic condensation product (A) of a tetraalkoxysilane compound in the presence of a strong acid catalyst include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-normal-propoxysilane, and tetra-normal-butoxysilane, as well as oligomers and polymers thereof produced by hydrolytic condensation thereof.
These may be used alone or in combination of two or more. Among them, tetramethoxysilane oligomer and tetraethoxysilane oligomer are preferably used.

Commercially available tetraalkoxysilane compounds include methyl orthosilicate (manufactured by Tama Chemicals Co., Ltd.), ethyl orthosilicate (manufactured by Tama Chemicals Co., Ltd.), Wacker Silicate (registered trademark) TES28 (manufactured by Wacker Asahi Kasei Silicones Co., Ltd.), ethyl silicate 28 (manufactured by Colcoat Co., Ltd.), N-propyl silicate (manufactured by Colcoat Co., Ltd.), and N-butyl silicate (manufactured by Colcoat Co., Ltd.).
Further, examples of tetramethoxysilane oligomers include Methyl Silicate 51 (manufactured by Colcoat Co., Ltd.), MKC Silicate MS51, MKC Silicate MS56, MKC Silicate MS57, and MKC Silicate MS56S (manufactured by Mitsubishi Chemical Corporation); examples of tetraethoxysilane oligomers include Silicate 40 (manufactured by Tama Chemicals Co., Ltd.), Ethyl Silicate 40, and Ethyl Silicate 48 (all manufactured by Colcoat Co., Ltd.), and Dynasylan (registered trademark) SILBOND (registered trademark) 40 (manufactured by Evonik); examples of tetraethoxysilane polymers include HAS-1, HAS-6, HAS-10, and SS-C1 (all manufactured by Colcoat Co., Ltd.); and examples of other oligomers include, but are not limited to, EMS-485 (manufactured by Colcoat Co., Ltd.).

The tetraalkoxysilane compound is used in an amount of 1 to 70 parts by mass, preferably 20 to 60 parts by mass, per 100 parts by mass of the hydrolysis condensation product (A) of the tetraalkoxysilane compound in the presence of a strong acid catalyst. If the amount is less than 1 part by mass, the hydrolysis condensation will be insufficient, and if it exceeds 70 parts by mass, the hydrolysis condensation reaction will become unstable and a sufficient effect will not be achieved.

"Anti-fouling agent"
In the present invention, a trialkoxysilane compound (C) can be used in combination with the above in order to impart functionality such as stain resistance to the coating film itself, depending on the required properties, to an extent that does not reduce hardness.
Usable trialkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-
Glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, 1H,1H,2H,2H -nonafluorohexyltrimethoxysilane, 1H,1H,2H,2H-nonafluorohexyltriethoxysilane, 1H,1H,2H,2H-tridecafluoronormal-octyltrimethoxysilane, 1H,1H,2H,2H-tridecafluoronormal-octyltriethoxysilane, 1H,1H,2H,2H-heptadecafluorodecyltrimethoxysilane, 1H,1H,2H,2H-heptadecafluorodecyltriethoxysilane, [5,
5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl]
Examples include, but are not limited to, compounds obtained by co-condensation with trialkoxysilanes such as trimethoxysilane and [5,5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl]triethoxysilane, or tetraalkoxysilane.
These may be used alone or in combination of two or more.

"Strong acid catalyst"
The strong acid catalyst required for producing the hydrolysis condensation product (A) of a tetraalkoxysilane compound in the presence of a strong acid catalyst is an essential component for hydrolysis condensation of the tetraalkoxysilane compound.
Generally, in the hydrolysis and condensation of tetraalkoxysilane compounds, in acidic conditions, hydrolysis occurs due to an electrophilic reaction of the alkoxy group with oxygen, followed by dehydration polycondensation between adjacent SiOH groups. Therefore, the chain tends to elongate linearly due to the influence of steric hindrance. On the other hand, in basic conditions, hydrolysis occurs due to a direct nucleophilic reaction with Si, followed by three-dimensional condensation.
In the present invention, if the tetraalkoxysilane compound undergoes three-dimensional condensation and forms fine particles in the coating solution, the particles will likely adhere in powder form during application, which is thought to have a negative effect on sparkle. Therefore, the hydrolysis and condensation must be carried out in an acidic atmosphere.

Even when hydrolysis and condensation are carried out using a weak acid, there is a concern that condensation may proceed three-dimensionally. Therefore, in order to achieve the effects of the present invention, it is necessary to use a strongly acidic catalyst to carry out hydrolysis and condensation to extend the chain length in a linear manner.

The strong acid catalyst used in the present invention can be inorganic acids such as hydrochloric acid, sulfuric acid, or nitric acid, or organic acids such as p-toluenesulfonic acid, benzenesulfonic acid, or 10-camphorsulfonic acid. Among these, hydrochloric acid and nitric acid are preferred, as they do not remain in the coating film after baking.

In the present invention, the strong acid catalyst is diluted with water before addition to prevent a rapid reaction, and is preferably added in an amount of 0.1 to 10 parts by mass, and preferably 0.5 to 5 parts by mass, per 100 parts by mass of the tetraalkoxysilane compound. In other words, the strong acid catalyst is used in an amount of 0.001 to 7 parts by mass, and preferably 0.1 to 3.0 parts by mass, per 100 parts by mass of the hydrolysis condensate (A) of the tetraalkoxysilane compound in the presence of the strong acid catalyst.

Water, which is required when preparing the hydrolysis condensation product (A) of a tetraalkoxysilane compound in the presence of a strong acid catalyst, is an essential component for hydrolyzing the tetraalkoxysilane compound. In the present invention, water is used in an amount of about 1 to 5 times by mole, preferably about 2 to 4 times by mole, relative to the alkoxy groups of the tetraalkoxysilane. This is thought to promote the hydrolysis reaction while suppressing the dehydration condensation reaction due to the excess water. That is, if the amount is less than 1 times by mole relative to the alkoxy groups of the tetraalkoxysilane, hydrolysis will be insufficient, and if it exceeds 5 times by mole, liquid stability will decrease.
Furthermore, if the amount of water added is too large, the drying properties of the coating film will be reduced and unevenness will be less likely to occur. Therefore, the amount of water used is 0.1 to 60 parts by mass, preferably 10 to 40 parts by mass, per 100 parts by mass of the hydrolysis condensation product (A) of a tetraalkoxysilane compound in the presence of a strong acid catalyst.

When synthesizing the hydrolysis condensate (A) of the tetraalkoxysilane compound in the presence of a strong acid catalyst, an organic solvent is required as the solvent.
If an alcohol solvent or glycol ether solvent with a long alkyl group is used, there is a risk that a reaction may occur in which the silanol groups generated by hydrolysis are converted back into alkoxy groups. Therefore, alcohols with a short alkyl group, such as methanol and ethanol, are used.

For example, methanol (boiling point 65°C), ethanol (boiling point 78°C), normal propanol (boiling point 97°C), isopropyl alcohol (boiling point 82°C), tertiary butanol (boiling point 82°C), etc. can be used.
These alcohol solvents are used in an amount of 1 to 95 parts by mass, preferably 5 to 70 parts by mass, per 100 parts by mass of the hydrolysis condensation product (A) of a tetraalkoxysilane compound in the presence of a strong acid catalyst.
The alcohols used here affect the state of unevenness formed when sprayed as an AG treatment agent and the drying speed of the coating film, so the amount used must be determined by including it in the alcohol or glycol ether organic solvent (B).

"Alcohol or glycol ether organic solvent (B)"
When the hydrolysis condensation product (A) of a tetraalkoxysilane compound in the presence of a strong acid catalyst is sprayed as an AG treatment agent, it is diluted with an alcohol or glycol ether organic solvent (B) before use.
The alcohol or glycol ether organic solvent (B) not only serves as a solvent during the hydrolysis and condensation of the tetraalkoxysilane compound, but also plays an important role in forming a coating film having an uneven surface during spray coating.
In the present invention, when the component formed by hydrolysis and condensation of tetraalkoxysilane is spray-coated, the solvent dries and the component lands on a glass substrate or the like, forming a concave-convex shape.

If the solvent dries quickly, the film formation is poor and the coating is powdery. If the solvent dries slowly, the film formation is good, but the uneven shape becomes gentler, sufficient anti-glare properties are not achieved, and the solvent contained in the deposited coating evaporates during bake hardening, causing the coating to shrink and crack.

The blending ratio of these components can be adjusted in consideration of the spraying conditions. For example, when a glass substrate is used at room temperature, the AG treatment solution dries poorly immediately after application to the glass substrate, so that it is necessary to reduce the spray discharge amount, coating speed, atomization pressure, etc., but by further blending a large amount of a solvent with a low boiling point as the alcohol or glycol ether organic solvent (B), a uniform AG treatment layer can be obtained.
Examples of the low-boiling alcohol or glycol ether organic solvent (B) include alcohols such as methanol (boiling point 65°C), ethanol (boiling point 78°C), normal propanol (boiling point 97°C), isopropyl alcohol (boiling point 82°C), and tertiary butanol (boiling point 82°C), ketones such as methyl ethyl ketone (boiling point 80°C) and methyl isopropyl ketone (boiling point 93°C), and acetates such as ethyl acetate (boiling point 77°C) and isopropyl acetate (boiling point 89°C). Ethanol and isopropyl alcohol are preferred.

On the other hand, in order to shorten the spraying time, the glass substrate can be preheated to about 100° C. In this case, an alcohol or glycol ether-based organic solvent (B) with a high boiling point is used because the AG coating film applied to the glass substrate dries quickly.
Examples of the alcohol or glycol ether organic solvent (B) having a high boiling point include alcohols such as normal butanol (boiling point 118°C), isobutanol (boiling point 108°C), secondary butanol (boiling point 100°C), 1-pentanol (boiling point 138°C), 2-methyl-1-butanol (boiling point 128°C), 3-methyl-1-butanol (boiling point 131°C), 2-pentanol (boiling point 119°C), 1-ethyl-1-propanol (boiling point 116°C), 2-methyl-2-butanol (boiling point 102°C), normal hexanol (boiling point 157°C), ethylene glycol monomethyl ether (boiling point 124°C), ethylene glycol monoethyl ether (boiling point 135°C), ethylene glycol diethyl ether (boiling point 121°C), ethylene glycol monoisopropyl ether (boiling point 141°C), ethylene glycol Examples of the glycol ethers include glycol monobutyl ether (boiling point 171°C), propylene glycol monomethyl ether (boiling point 120°C), propylene glycol monoethyl ether (boiling point 132°C), propylene glycol mono-normal propyl ether (boiling point 149°C), and propylene glycol mono-normal butyl ether (boiling point 171°C); ketones such as methyl normal propyl ketone (boiling point 103°C) and methyl isobutyl ketone (boiling point 116°C); and acetates such as normal propyl acetate (boiling point 102°C), butyl acetate (boiling point 127°C), propylene glycol monomethyl ether acetate (boiling point 147°C), ethylene glycol monomethyl ether acetate (boiling point 145°C), and ethylene glycol monoethyl ether acetate (boiling point 156°C).

Among these, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred.
In selecting the solvent, one or more of these may be used in combination, taking into consideration the stability and drying properties of the liquid.

"Other additives"
In the present invention, if necessary, wetting agents, thickeners, pigments, dyes, conductivity imparting agents, fillers such as hollow, chain-like, or porous solid silica particles, metal fine particles, and the like can also be added to the antiglare treatment composition within a range that does not adversely affect the properties.
Among these, examples of fillers such as hollow, chain-like, porous solid silica particles include Sururia (registered trademark) 1110 (average particle size 50 nm, heating residue 20%, IPA dispersion), Sururia (registered trademark) 4110 (average particle size 60 nm, heating residue 20%, IPA dispersion, manufactured by JGC Catalysts and Chemicals Co., Ltd.), Organosilica sol IPA-ST-UP (average particle size 9-15 nm, heating residue 15%, IPA dispersion), and Organosilica sol MEK-ST-UP (average particle size 9-15 nm, heating residue 20%, MEK dispersion) (manufactured by Nissan Chemical Industries, Ltd.).

"Heating residue"
The heating residue of the product (A) of tetraalkoxysilane compounds hydrolyzed and condensed in the presence of a strong acid catalyst depends on the amount of SiO ₂ produced, and is usually 0.1 to 40 parts by mass, preferably 5 to 30 parts by mass, per 100 parts by mass of the product (A) of tetraalkoxysilane compounds hydrolyzed and condensed in the presence of a strong acid catalyst. The amount of SiO ₂ produced differs depending on whether the tetraalkoxysilane compound used is a monomer or an oligomer, and on the type of alkoxy group.
This heating residue has no particular effect as long as it is within the blending amount of the aforementioned tetraalkoxysilane compound hydrolyzed and condensed in the presence of a strong acid catalyst (A), and can be adjusted by adding an alcohol or glycol ether organic solvent (B) when applying. Therefore, the blending amount of the tetraalkoxysilane compound hydrolyzed and condensed in the presence of a strong acid catalyst (A) can be expressed in parts by mass of all materials.

"Method of manufacturing anti-glare treatment composition"
The method for producing the antiglare treatment composition of the present invention will be described below.
The method for producing the antiglare treatment composition mainly comprises preparing a hydrolysis condensation product (A) of a tetraalkoxysilane compound in the presence of a strong acid catalyst, diluting it with an alcohol or glycol ether organic solvent (B), and filtering it.
The hydrolysis and condensation of the tetraalkoxysilane compound is carried out in an organic solvent. However, if an alcohol solvent or glycol ether solvent with a long alkyl group is used, there is a concern that a reaction may occur in which the silanol groups generated by hydrolysis are converted back into alkoxy groups. Therefore, alcohols with a short alkyl group, such as methanol or ethanol, are used instead.
A tetraalkoxysilane compound is mixed in a solvent, and while stirring, a strong acid catalyst pre-diluted with water and a solvent is added dropwise. At this time, the liquid temperature is adjusted to between 10 and 60°C to suppress the hydrolysis and condensation reaction. After the dropwise addition is complete, the mixture is kept at a constant temperature of 20 to 40°C for a predetermined time to allow the hydrolysis and condensation reaction to occur.
The reaction conditions are adjusted depending on the type of alkoxy group in the tetraalkoxysilane compound, and a hydrolysis condensation product (A) of the tetraalkoxysilane compound is produced in the presence of a strong acid catalyst.
The appropriate viscosity of the hydrolysis condensate (A) of the tetraalkoxysilane compound in the presence of a strong acid catalyst is 1 to 5 mPa s as measured using a TVB15 (manufactured by Toki Sangyo Co., Ltd.) rotor No. L/Adp at a rotation speed of 100 rpm and a liquid temperature of 30°C.
Thereafter, the solution is diluted with an alcohol or glycol ether organic solvent (B) selected depending on the spray conditions, and filtered through a 1 μm filter to finish.

"Method for applying anti-glare treatment composition"
The antiglare treatment composition of the present invention exerts its effect particularly when spray-coated onto an object to be coated.
Spin coating and dip coating produce smooth coating films, not uneven ones, so the desired anti-glare properties cannot be achieved. However, because the unevenness that affects anti-glare properties varies depending on the droplets ejected from the spray, it is important to set coating conditions such as the amount of droplets ejected, temperature, and humidity.
Since the antiglare treatment composition is spray-coated and then the AF treatment agent is spray-coated, the antiglare treatment composition needs to be applied to a substrate such as glass in a predetermined state.
The heating residue of the antiglare treatment composition when applied to glass varies depending on the spray coating conditions, temperature and humidity, and substrate heating temperature, and increases from the original heating residue. If the time until the AF treatment agent is spray-coated is long, the solvent volatilizes more, and the heating residue increases further.
Therefore, it is necessary to set conditions in advance so that the heating residue of the AG treatment agent layer applied to the glass is 74 to 95 parts by mass when heated at 180°C for 1 hour. However, when actually laminating the AF treatment agent, heating at 180°C for 1 hour is not necessary.

By spray coating the anti-glare treatment agent layer sprayed under the above conditions with an AF treatment agent, it is possible to form a coating film having excellent durability and anti-glare and anti-fouling properties.
If the heating residue of the AG treatment agent layer is less than 74 parts by mass, the formation of the uneven shape of the coating film is insufficient, and antiglare properties cannot be exhibited. On the other hand, if the heating residue is more than 95 parts by mass, the AG treatment layer dries too much, which reduces the adhesion to the AF treatment layer applied later, resulting in a coating film that is inferior in abrasion resistance and durability.
The surface roughness of the AG treatment layer was measured using a laser microscope LEXT OLS4100.
(Olympus Corporation) and found that the value was 0.05 to 0.25, preferably 0.
0.75 to 0.15.

Antifouling treatment agent
The antifouling (AF) treatment agent used in the present invention is not particularly limited, and any commercially available antifouling treatment agent that can be spray-coated can be used, but from the standpoint of antifouling performance and adhesion to the AG layer, those comprising a fluorine-containing organic silicon compound are preferred.
The fluorine-containing organosilicon compound may be a fluorine-containing organosilicon compound having one or more groups selected from the group consisting of perfluoropolyether groups, perfluoroalkylene groups, and perfluoroalkyl groups.
Examples of commercially available products include Optool DSX (manufactured by Daikin Corporation), KY-100 series (manufactured by Shin-Etsu Chemical Co., Ltd.), and NB06-04 (manufactured by Katsurayama Technology Co., Ltd.).

The AF treatment agent is preferably applied by spray coating, and the same spray equipment as that used to apply the AG treatment agent can be used. When spin coating is used to apply the AF treatment agent, it is difficult to spread the AF treatment agent evenly because the AG layer is an uncured film containing solvent. Furthermore, when using vacuum deposition, sputtering, or plasma CVD methods, the pressure is reduced in the chamber, causing the AG layer to dry out too quickly, reducing adhesion to the AF layer.

"Object to be painted"
The antiglare treatment composition of the present invention can be applied to substrates such as plastics, glass materials such as glass plates and glass cloths, ceramic materials, metal materials, etc. The present invention is particularly effective on glass materials.

An example of application of the anti-glare treatment composition of the present invention to glass will be given below. A degreased and cleaned glass substrate is used at room temperature or after preheating. After spraying the anti-glare treatment composition, the AF treatment agent is subsequently sprayed and cured by baking at 150°C for about 30 minutes. While sufficient curing is achieved at about 150°C, heating to 300°C or higher is also possible to further improve the hardness of the coating film.
The present invention will be explained in more detail by way of Production Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. In the Production Examples, Examples, and Comparative Examples, parts refer to parts by mass unless otherwise specified.

"Manufacturing example"
Production Example 1
A one-liter flask was charged with 35 parts of tetraethoxysilane (40 parts by mass of SiO ₂ ) as a tetraalkoxysilane compound, 18 parts of ethanol as an alcohol solvent with a short alkyl group, and
An aqueous acid solution prepared by diluting 4 parts of 10% nitric acid as a strong acid catalyst with 20 parts of water was added dropwise to the flask, and then stirring was stopped and the mixture was stored at 30°C for 6 hours to obtain a hydrolysis condensate (A) of a tetraalkoxysilane compound.
Thereafter, while stirring with a disper, a premix of 5 parts of isobutyl alcohol, 403 parts of ethanol, and 15 parts of methanol was added as an alcohol or glycol ether-based organic solvent (B) to dilute the mixture, and the mixture was filtered through a 1 μm filter to obtain 500 parts of an AG treatment liquid (heating residue: 2.8%).

Production Example 2
500 parts of an AG treatment liquid (heating residue: 2.8%) was obtained in the same manner as in Production Example 1, except that 403 parts of propylene glycol monomethyl ether acetate was used instead of 403 parts of ethanol as the solvent for diluting the hydrolysis condensate (A) of a tetraalkoxysilane compound.

"Example"
Example 1
The AG treatment solution obtained in Production Example 1 was spray-coated onto a 50 mm × 100 mm × 2 mm soda glass plate (room temperature) that had been previously degreased with an alkaline detergent, using a precision coating machine (manufactured by Apiros Co., Ltd.) to form an AG coating film with a coating thickness of approximately 0.4 μm. The AF treatment solution NB06-04 (Katsurayama Technology Co., Ltd.) was spray-coated onto the AG coating film using the same precision coating machine (manufactured by Apiros Co., Ltd.), and then baked at 150°C for 30 minutes to form an AGAF laminated coating film.

Example 2
An AGAF multilayer coating film was formed in the same manner as in Example 1, except that the soda glass plate was heated to 100° C. as the substrate when the antiglare treatment composition was applied.

Example 3
An AGAF multilayer coating film was formed in the same manner as in Example 2, except that the antiglare treatment liquid obtained in Production Example 2 was used instead of the antiglare treatment liquid obtained in Production Example 1.

(Comparative Example 1)
The AG treatment solution obtained in Production Example 1 was spray-coated onto a 50 mm × 100 mm × 2 mm soda glass plate (room temperature) that had been previously degreased with an alkaline detergent using a precision coating machine (manufactured by Apiros Co., Ltd.) to a coating thickness of approximately 0.4 μm, and the plate was pre-dried at 120 ° C. for 20 minutes and then baked at 180 ° C. for 30 minutes to form an AG layer. Subsequently, using the same precision coating machine (manufactured by Apiros Co., Ltd.), the AF treatment agent NB06-04 (Katsurayama Technology Co., Ltd.) was spray-coated, followed by baking at 150 ° C. for 30 minutes to form an AGAF laminated coating film.

(Comparative Example 2)
The AG treatment solution obtained in Production Example 2 was spray-coated onto a 50 mm x 100 mm x 2 mm soda glass plate that had been previously degreased with an alkaline detergent using a precision coating machine (manufactured by Apiros Co., Ltd.) at a substrate temperature of 100°C so that the coating thickness would be approximately 0.4 μm. After pre-drying at 120°C for 20 minutes,
After the AG coating film was formed, the AF treatment solution NB06-04 (Katsurayama Technology Co., Ltd.) was sprayed using a precision coating machine (manufactured by Apiros Co., Ltd.) and then baked at 150°C for 30 minutes to form an AGAF laminated coating film.

(Comparative Example 3)
The AG treatment solution obtained in Production Example 1 was spray-coated onto a 50 mm x 100 mm x 2 mm soda glass plate (room temperature) that had been previously degreased with alkaline detergent using a precision coating machine (manufactured by Apiros Co., Ltd.) to a coating thickness of approximately 0.4 μm, and the plate was pre-dried at 120°C for 20 minutes and then baked at 180°C for 30 minutes to form an AG coating film. The AG coating film was washed with alkaline detergent (manufactured by Yokohama Resin Industries Co., Ltd.), then rinsed with water three times, and dried in a dryer at 50°C for 5 minutes. After alkaline washing, the AF
Treatment liquid NB06-04 (Katsurayama Technology Co., Ltd.) was sprayed using a precision coating machine (Apiros Co., Ltd.) and baked at 150°C for 30 minutes to form an AGAF multilayer coating film.

(Comparative Example 4)
The AG treatment solution obtained in Production Example 1 was spray-coated onto a 50 mm x 100 mm x 2 mm soda glass plate, which had previously been degreased with an alkaline detergent, using a precision coating machine (manufactured by Apiros Co., Ltd.) to a coating thickness of approximately 0.4 μm. The coating was pre-dried at 120 ° C for 20 minutes and then baked at 180 ° C for 30 minutes to form an AG coating film. The AG coating film was then subjected to plasma treatment for 20 minutes using a plasma generator (manufactured by Yamato Scientific Co., Ltd.). After plasma treatment, the AF treatment solution NB06-04 (Katsurayama Technology Co., Ltd.) was spray-coated using a precision coating machine (manufactured by Apiros Co., Ltd.) and baked at 150 ° C for 30 minutes to form an AGAF laminated coating film.

(Comparative Example 5)
An AGAF multilayer coating film was formed in the same manner as in Example 1, except that the AG treatment liquid obtained in Production Example 2 was used instead of the AG treatment liquid obtained in Production Example 1.

(evaluation)
Examples 1 to 3 and Comparative Examples 1 to 5 were evaluated for the following items.
The evaluation results are shown in Table 2.

(1) Haze: Haze was evaluated based on the haze value measured using a haze meter NDH7000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7136:2000.
(2) Gloss Using Microgloss 60° (manufactured by BYK), a black cloth was placed on the back of the glass substrate, and the gloss of the coating surface was measured and evaluated.
(3) Water Contact Angle The water contact angle of the coating film surface was measured and evaluated using PCA-11 (manufactured by Kyowa Interface Science Co., Ltd.).
(4) Abrasion resistance: The coating was abraded using a TL201t (manufactured by Trinity Lab Co., Ltd.) in accordance with JIS L8049:2013, and the coating film evaluations (1) to (3) were performed and evaluated.
(5) Measurement of heating residue after anti-glare treatment The weight (a) of the glass substrate after degreasing was measured, and the weight (b) was measured after applying the AG treatment agent. After that, it was dried at 180°C in a drying oven for 1 hour, and the weight (c) after baking was measured. The heating residue was calculated from the measured weight using the following formula.

The abrasion resistance test conditions for evaluation (4) are shown in Table 1.

The target value for AF performance is preferably a water contact angle of 100° or more after 10,000 abrasion cycles. Examples 1 to 3 maintained a high contact angle even after 10,000 abrasion cycles.
In Comparative Examples 1 and 2, baking was performed after application of the AG treatment agent, so the heating residue of the AG layer was higher than specified, and the contact angle after the abrasion test decreased significantly. In Comparative Example 5, a high-boiling point solvent was used to dilute the AG treatment agent, and the glass substrate was not heated before application of the AG treatment agent, so the heating residue of the AG layer was lower than specified, and antiglare properties were not exhibited. In Comparative Examples 3 and 4, the number of steps was increased compared to the other examples because a surface modification step was incorporated into the AG layer, but the contact angle after the abrasion test was equivalent to that of Examples 1 and 3.
From the above results, it was confirmed that by spraying the AG treatment agent so that the heating residue is 74% to 95% as in Examples 1 to 3, then spraying the AF treatment agent in the same manner and then baking it, it is possible to obtain a durable AGAF laminated film while reducing the overall processing time.

By using the anti-glare treatment composition and anti-glare and anti-fouling (AGAF) lamination method of the present invention, treatment time can be shortened compared to conventional methods, thereby increasing production efficiency. Furthermore, the resulting laminated coating film has excellent abrasion resistance and durability, making it extremely useful industrially.

Claims (2)

A method for forming a coating film having antiglare and antifouling properties using an antiglare treatment composition and a fluorine-containing antifouling treatment agent, comprising:
The formation method includes spray-coating the antiglare treatment composition onto the surface of an article to be coated to form an antiglare layer, and then, without baking, spray-coating the fluorine-containing antifouling treatment agent adjacent to the antiglare layer while the antiglare layer is in a state where the heating residue determined by heating the antiglare layer at 180°C for 1 hour is 74 to 95 mass%, followed by baking,
The antiglare treatment composition contains a hydrolysis condensation product of a tetraalkoxysilane compound in the presence of a strong acid catalyst, and an alcohol or a glycol ether organic solvent, and is filtered through a 1 μm filter;
The method for forming a coating film having antiglare and antifouling properties is characterized in that the fluorine-containing antifouling treatment agent contains a fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group, and a perfluoroalkyl group. The method for forming a coating film having anti-glare and anti-fouling properties described in claim 1, characterized in that the anti-glare treatment composition contains 5 to 50 parts by mass of a hydrolysis condensate of a tetraalkoxysilane compound and 50 to 95 parts by mass of the alcohol or glycol ether-based organic solvent per 100 parts by mass of the anti-glare treatment composition.