JP3274568B2 - Film-forming composition and film-forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming composition capable of effectively cutting the passage of ultraviolet rays. In addition, the vertical composition such as window glass using the composition
The present invention relates to a method of forming a coating on a glass that is in the air.

[0002]

2. Description of the Related Art Articles and interior goods placed near windowpanes, such as buildings, show windows, and automobiles, are exposed to ultraviolet rays, and thus are liable to fade or deteriorate in physical properties.
When a person is in the room, sunburn and rough skin may occur. Therefore, it is desirable to provide a means for cutting ultraviolet rays on the window glass .

[0003] As one of measures to cut off ultraviolet rays, a film formed by internally adding an ultraviolet absorber is adhered to a window glass.

As another measure against ultraviolet rays, a glass plate or a plastics plate is coated with a resin solution containing an ultraviolet absorber and then dried to form a film. Have been done.

As to the latter method, Japanese Patent Laid-Open No.
JP-A-113665 discloses a light absorbing film obtained by mixing a light absorbing agent such as an ultraviolet absorbing agent with a polymer of dimethylaminoethyl methacrylate and hydroxymethyl methacrylate, and applying the coating to a resin plate or a glass plate. It is described that the adhesion and the hardness are improved when compared with a film obtained by mixing a light absorbing agent with a conventional vinyl resin or the like. In this publication, solvents such as alcohols, ethers, ketones, esters, and hydrocarbons are used as solvents. Tables 2 and 3 of the Example
Provides detailed data on transparency, color tone and impact strength when applied to rigid vinyl chloride plates. In this publication, when applying the undiluted solution, it is sufficient to apply directly to the resin plate, but it is possible to obtain good adhesion by applying to the glass plate via a silicon-based adhesive. Is described.

[0006]

The method of adhering a film formed by adding an ultraviolet absorber internally to glass is as follows: The air bubbles are easily bitten during the operation of adhering to the glass surface, and the air bubbles do not escape for a long time.・ Since it is easy to see that the film is stuck to the glass surface, there is a problem in appearance. ・ Since the size of the film is limited, one piece of glass may be used depending on the size of the glass. There are problems such as having to carry out a splice even on a surface.

[0007] The method of forming a coating by coating a resin solution containing an ultraviolet absorber internally on the surface of a glass plate or a plastics plate is as follows.-Since an organic solvent is used for preparing the solution, the environment at the site is deteriorated.・ Because there are many cases where it is not possible to anchor the glass plate at the site, the adhesion of the coating to the glass plate is insufficient. ・ The formation of the coating reduces the transparency of the glass plate or plastics plate. There are problems such as.

The invention disclosed in Japanese Patent Application Laid-Open No. Hei 5-113665 mainly aims to improve adhesion and hardness by using a specific resin called dimethylaminoethyl methacrylate-hydroxymethyl methacrylate copolymer as a film-forming resin. ing.

However, even in this method, (a) disadvantages due to the use of an organic solvent still remain, and (b) there is a limit to improvement in adhesion, especially when applied to a glass plate. Since it is necessary to apply a chemical agent, it requires a lot of time and effort when constructing on the windows of buildings, show windows, windows of automobiles, etc., and the construction cost increases. There is a problem in that the transparency tends to be reduced when applied to such as.

[0010] The present invention, in this background under eliminate environmental problems such as in the case of the organic solvent used by using an emulsion, a good adhesion against the glass such as window glass, also good transparency And a high hardness coating
It is an object of the present invention to provide a film-forming composition and a film-forming method which are provided and are extremely suitable for on-site construction .

[0011]

Means for Solving the Problems The composition for forming a film of the present invention comprises an acrylic copolymer containing inorganic fine particles.
A group that further contains an ultraviolet absorber in a resin emulsion
The acrylic resin containing the inorganic fine particles.
Copolymer-based synthetic resin emulsions
Emulsion of monomer component in the presence of inorganic fine particles of particle size
Being an emulsion obtained by polymerization.
The ultraviolet absorber has a medium wavelength of 280 to 400 nm.
UV absorber that can absorb long-wavelength UV light
And 1 part by weight of the resin component in the synthetic resin emulsion.
The amounts of the inorganic fine particles and the UV absorber
0.05-1.5 parts by weight and 0.005-0.8 parts by weight
Part, the composition is an object of a vertical posture
Supply the coating liquid to the upper part of the surface and apply the liquid
Flow down along the surface, collecting excess liquid under the object
Coating method and no anchor treatment
Composition for direct application to glass in vertical position
It is characterized by that.

The method for forming a coating film of the present invention comprises the steps of:
Containing acrylic copolymer-based synthetic resin emulsion
A composition containing an ultraviolet absorber al, the Mu
The acrylic copolymer-based synthetic resin containing organic fine particles
Emulsions consist of inorganic fine particles with a particle size in the colloid region.
Emulsion polymerization of monomer components in the presence of
The obtained ultraviolet absorber,
Absorbs medium to long wavelength ultraviolet light from 280 to 400 nm
The synthetic resin emulsion,
Inorganic fine particles for 1 part by weight of resin in John and
The amount of each UV absorber is 0.05 to 1.5 parts by weight.
And 0.005 to 0.8 parts by weight,
A film-forming composition that satisfies all
Supply the coating liquid to the upper part of the surface of the
Allow the liquid to flow down along the surface of the object, with excess under the object
By the coating method to recover the liquid
Apply directly to glass in vertical position without treatment
It is characterized by drying to form a film.

Hereinafter, the present invention will be described in detail.

As the synthetic resin emulsion, acrylic
Ester copolymer emulsion, acrylic - acrylic copolymer including styrene copolymer emulsion
A synthetic resin emulsion is used, and an appropriate one is selected and used in consideration of weather resistance , coating strength, cost, and the like, depending on the purpose of use.

The solid content concentration of the acrylic copolymer-based synthetic resin emulsion is not particularly limited, but is usually selected from the range of 10 to 75% by weight. However, when thinning is intended, it can be further diluted with water.

As the inorganic fine particles, particles in the colloid region
Used size of the inorganic fine particles. Examples of the inorganic fine particles include various inorganic oxides or inorganic composite oxides (Si, Al, Ti,
Zr, Ce, Mg, Ca, Fe, Sn, Zn, W, S
a single oxide or a complex oxide such as b, K, Na, P, and B), and various inorganic salts (silicates, phosphates, aluminates, carbonates, and the like). Among these, colloidal silica is particularly preferred.

In the present invention, an acrylic copolymer-based synthetic resin emulsion containing inorganic fine particles is used as a copolymer.
A product obtained by emulsion polymerization of a monomer component in the coexistence of inorganic fine particles having a particle size in a royd region is used. With such a manner fine inorganic particles containing synthetic resin emulsion obtained, adhesiveness secured to the glass, in terms of transparency maintained, Karadea the benefits of the present invention is maximized
You.

The amount of the inorganic fine particles per 1 part by weight of the resin component in the synthetic resin emulsion is selected from the range of 0.05 to 1.5 parts by weight, preferably 0.1 to 1 part by weight.
If the proportion of the inorganic fine particles is too small, the desired effects cannot be obtained in terms of adhesion, transparency, hardness and the like to the object, and if the proportion is too large, it is disadvantageous in terms of adhesion and transparency.

The synthetic resin emulsion containing inorganic fine particles has a medium to long wavelength (ie, 280 to 40).
(0 nm). Examples of such ultraviolet absorbers include salicylate-based, benzophenone-based, benzotriazole-based, acrylonitrile-based, cyanoacrylate-based, metal complex-based, and composite forms thereof.

The content of the ultraviolet absorber is 0.005 to 0.8 with respect to 1 part by weight of the resin component in the synthetic resin emulsion.
Parts by weight , preferably in the range of 0.01 to 0.5 parts by weight. If the amount is too small, the desired UV cut effect cannot be obtained.On the other hand, if the amount is too large, the UV cut effect does not exceed a certain level, and the coating may be colored. Disadvantageous.

The composition for forming a film having each of the above-mentioned components may contain, if necessary, a thickener, a low-temperature stabilizer, a film-forming aid, an anti-sagging agent, a surfactant, an antifoaming agent, a coloring agent, a solvent and the like. Can be contained. When a coloring agent is contained, it is desirable to select an organic coloring agent (dye or organic pigment) so as not to lower the transparency.

[0022] The above composition can be used for an object in a vertical position.
Supply the coating liquid to the upper part of the surface and apply the liquid
Flow down along the surface, collecting excess liquid under the object
Coating method and no anchor treatment
Composition for direct application to glass in vertical position
It is. Representative examples of such glasses are building windows, show windows, automotive windows , and the like.

The above-mentioned feature, which is a kind of flow coating method,
When performing certain coating methods, use a vertical
Drying method of applying directly to a glass and then drying naturally
The law is adopted. Recover excess liquid below the object
And then re-supply it to the top of the object if necessary.
Wear.

[0024]

The composition for forming a film and the method of forming a film according to the present invention.
Is an easy-to-operate coating for glass in a vertical position.
Coating method without anchoring
What forms a film only by natural drying
Therefore, it is extremely suitable for on-site construction.

[0025] coating composition according to the present invention acrylic
Since it is based on a copolymer- based synthetic resin emulsion, environmental problems in a conventional method using an organic solvent solution are eliminated.

The inorganic fine particles contained in the film-forming composition have an effect of improving the adhesion of the film to the object and an effect of forming a high-hardness film.
The transparency of the coating is also good. In the present invention, fine particles having a particle size in the colloid region are used as the inorganic particles ,
In addition, an acrylic copolymer-based synthetic resin emulsion is obtained by polymerizing a monomer component in the presence of such inorganic fine particles.
To ensure adhesion to glass and maintain transparency.
In this respect, the above-described effects are particularly remarkable .

[0027] The ultraviolet absorbent which had been contained in the film-forming composition, so effectively block the sunlight from the outside, ultraviolet rays arrived was Iro褪<br/> the room or car through the glass, sunburn , that the undesirable phenomena such as deterioration of physical properties occurs, it is possible to effectively prevent.

[0028]

The present invention will be further described with reference to the following examples. Hereinafter, "parts" refers to parts by weight.

Example 1 Colloidal silica having a particle size of 10 to 20 μm ( co- silica) was used during emulsion polymerization for producing an acrylic copolymer emulsion.
Acrylic copolymer containing inorganic fine particles by coexisting with inorganic fine particles having a particle size in the loyd region )
It was obtained 88 parts of the system the synthetic resin emulsion. The resin content (acrylic copolymer) in this synthetic resin emulsion was 23.7.
Parts and inorganic fine particles (colloidal silica) were 14.2 parts. The weight ratio of the resin component to the inorganic fine particles is 1:
0.60, solid content (total amount of resin content and inorganic fine particles) of the synthetic resin emulsion containing inorganic fine particles is 43% by weight
Met.

Next, in this synthetic resin emulsion containing inorganic fine particles, 8 parts of an additive (a composition comprising a solvent, water, an activator and a film-forming auxiliary) and 3 parts of a benzotriazole-based ultraviolet absorber were added. In addition, they were mixed. The amount of the ultraviolet absorber added was 0.13 part with respect to 1 part of the resin in the synthetic resin emulsion containing inorganic fine particles.

As a result, the desired film-forming composition was prepared, and the coating solution comprising this composition was supplied to the upper part of the inside of the window glass in the room on the west side of the building to provide a coating solution. The operation of flowing down along the surface, collecting excess liquid on the lower side of the window glass, and supplying it to the upper portion again was repeated, and a film of the coating liquid was uniformly formed on the window glass. After this specific coating operation, the film was air-dried to form a uniform transparent film having a thickness of about 20 μm.

The adhesion of the formed film to the glass surface was excellent even though no anchor coating was performed (confirmed by a cross-cut test).
The glass surface with this coating is turbidity meter (JIS K0101)
As a result, the visible light transmittance was 92.24% and the haze was 0.5% as a result of measurement with an integrating sphere measuring instrument (NDH-300A manufactured by Nippon Denshoku Industries Co., Ltd.) based on the standard. The hardness was 3H as a result of measuring the hardness by a pencil scratch tester method specified in JIS K5400. The visible light transmittance of the glass surface when no coating was provided was 91.9.
The haze was 9% and the haze was 0.82%.

[0033] When the ultraviolet transmission amount to the glass surface after the film formation was measured using a Minolta ultraviolet intensity meter "UM-36", in the outside air that of 4000 mW / cm ^2,
35mW / at the indoor side 1cm away from the glass surface
cm ^2, and the wavelength to affect the discoloration of clothes 360nm
It was found that the ultraviolet rays up to 99% can be cut. MCPD-1000 manufactured by Otsuka Electronics Co., Ltd.
The spectral curve of the ultraviolet ray was measured by using, and it was found that 99% of the ultraviolet ray up to around 380 nm was absorbed.

Further, when the temperature at 50 cm from the window glass was measured, the temperature was 38 ° C. when no film was formed, but the room temperature was 4 to 5 ° C. when the film was formed.
It was found that it had dropped. When the thermal conductivity was measured using a wind speed thermal conductivity meter SHOTHERMTM-DII manufactured by Showa Denko KK, it was 0.12648 W / m · hr · ° C.
And the thermal conductivity of the JIS glass is 0.704 W / m ·
It was found that the thermal conductivity was considerably lower than that of hr · ° C. This is because the formed coating lowers the thermal conductivity of the glass.

COMPARATIVE EXAMPLE 1 A benzotriazole-based ultraviolet absorber was added to an acrylic copolymer emulsion obtained by polymerization without the presence of colloidal silica, so that the amount of the resin component in the emulsion was 0.13 part per 1 part. did. Thereafter, in the same manner as in Example 1, a film of the coating solution was formed on the window glass by the above-mentioned specific coating operation, and then naturally dried.

The coated glass surface had a visible light transmittance of 84.47%, a haze of 2.10% and a hardness of F.

Example 2 Colloidal silica having a particle size of 10 to 20 μm ( co- polymer) was used during emulsion polymerization for producing an acrylic copolymer emulsion.
Acrylic copolymer containing inorganic fine particles by coexisting with inorganic fine particles having a particle size in the loyd region )
It was obtained 88 parts of the system the synthetic resin emulsion. The resin content (acrylic copolymer) in this synthetic resin emulsion was 23.7.
Parts and inorganic fine particles (colloidal silica) were 14.2 parts. The weight ratio of the resin component to the inorganic fine particles is 1:
0.60, solid content (total amount of resin content and inorganic fine particles) of the synthetic resin emulsion containing inorganic fine particles is 43% by weight
Met.

Next, 8 parts of an additive (a composition comprising a solvent, water, an activator and a film-forming auxiliary) were added to 3 parts of a benzotriazole-based ultraviolet absorber and phthalocyanine blue (organic Colorant) 0.
3 parts were added and mixed. The amounts of the ultraviolet absorber and phthalocyanine blue added were 0.13 part and 0.013 part, respectively, relative to 1 part of the resin in the inorganic fine particle-containing synthetic resin emulsion.

As a result, the desired film-forming composition was prepared. The coating solution comprising this composition was supplied to the upper part of the window glass of an automobile, and allowed to flow down along the surface of the window glass. The operation of collecting the excess liquid on the lower side of the window glass and supplying it to the upper portion again was repeated to uniformly form a colored film of the coating liquid on the window glass. After this specific coating operation, the film was air-dried to a thickness of 30 μm.
Was formed.

The adhesion of the formed film to the glass surface was good even though the anchor coating was not performed. The visible light transmittance of the glass surface with the colored film is 75.34%, the haze is 5.63%,
The hardness was 2H. When the colored film is not provided, the visible light transmittance of the glass surface is 90.95%, and the haze is 0.1%.
22%.

Comparative Example 2 An acrylic copolymer emulsion obtained by polymerization without coexisting colloidal silica was mixed with 0.13 part of a benzotriazole-based ultraviolet absorber per 1 part of the resin in the emulsion, and 0.013 part of phthalocyanine blue (organic colorant) was added to 1 part and mixed.

Thereafter, in the same manner as in Example 2, a colored film was formed on the window glass of the automobile by the above specific coating operation. The visible light transmittance and the haze of the obtained glass surface with the coating were almost the same as those of Example 2, but the hardness was F, which was smaller than that of Example 2.

[0043]

Industrial Applicability The composition for forming a film and the film form of the present invention
According to the forming method, the following excellent effects are obtained.

Since it is based on an acrylic copolymer- based synthetic resin emulsion, environmental problems in the conventional method using an organic solvent solution are eliminated.

Excellent operability for glass in a vertical position
Coating method and without anchor treatment
Fabrics, and forms a film only by natural drying
It is extremely suitable for on-site construction.

Good adhesion to glass such as window glass
Good, good transparency, and gives a coating with high hardness.

The ultraviolet ray absorbing agent contained in the film-forming composition effectively blocks external sunlight.
Therefore, ultraviolet rays reach the interior and the car through the glass,
Unwanted phenomena such as fading, sunburn, deterioration of physical properties, etc. do not occur
Can be effectively prevented.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 101/00 C08L 101/00 (72) Inventor Masaki Ichinomiya 8-8 Dogo-Kita-cho, Matsuyama-shi, Ehime Japan Technical System Co., Ltd. (72) Inventor Keiro Sakamoto 888 Fujie Nakatani-cho, Akashi-shi, Hyogo Meiken Chemical Industry Co., Ltd. (56) References JP-A-56-88469 (JP, A) JP-A-56-41271 (JP, A) JP-A-52-14278 (JP, A) JP-A-64-142327 (JP, A) JP-A-58-160327 (JP, A) JP-A-6-4492 (JP, A) (58) (Int.Cl. ⁷ , DB name) G03F 7/0041 C03C 17/32 C08F 2/44 C08K 3 / 00,5 / 00

Claims (2)

(57) [Claims] 1. An acrylic copolymer containing inorganic fine particles.
UV absorber is added to the synthetic resin emulsion
The acrylic copolymer system containing the inorganic fine particles.
The resin emulsion has an inorganic fine particle size in the colloid region.
Emulsion polymerization of monomer components in the presence of particles
And the ultraviolet absorber has no medium wavelength of 280 to 400 nm.
UV absorber that can absorb long-wavelength UV light
And 1 part by weight of the resin component in the synthetic resin emulsion.
The amount of the inorganic fine particles and the amount of the ultraviolet absorber are each 0.1.
0.5 to 1.5 parts by weight and 0.005 to 0.8 parts by weight
In some embodiments, the composition comprises an upper surface of an object in a vertical position.
The coating liquid is supplied to the rollers, and the liquid flows along the surface of the object.
To remove excess liquid below the object
Vertical position without anchoring.
A composition for forming a coating film , which is a composition for directly applying to glass . 2. An acrylic copolymer containing inorganic fine particles.
UV absorber is added to the synthetic resin emulsion
The acrylic copolymer system containing the inorganic fine particles.
The resin emulsion has an inorganic fine particle size in the colloid region.
Emulsion polymerization of monomer components in the presence of particles
And the ultraviolet absorber has no medium wavelength of 280 to 400 nm.
UV absorber that can absorb long-wavelength UV light
And 1 part by weight of the resin component in the synthetic resin emulsion.
The amount of the inorganic fine particles and the amount of the ultraviolet absorber are each 0.1.
0.5 to 1.5 parts by weight and 0.005 to 0.8 parts by weight
Lying, all the conditions for satisfactory coating composition, vertical vertical
Supply coating liquid to the upper part of the surface of the object in the posture
And let the liquid flow down along the surface of the object.
By a coating method that collects excess liquid on the side, and
Direct application to glass in vertical position without anchoring
And forming the coating by air drying .