JPH09254302A - Laminated body and light transmitting body using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a laminated body, which is favorable in adhesion and excellent in durability by a method wherein inorganic film, which is made of at least one selected from the group consisting of SiO, SnO2 and Ti, and tin-added indium oxide film are laminated in the order named on a board mainly made of methacrylic resin. SOLUTION: A board is made of methacrylic resin or various additive- containing metharylic resin composition. The inorganic film formed between the board and a tin-added indium oxide film (henceforth expressed as ITO film) is made of at least one selected from the group consisting of SiO, SnO2 and Ti. As the forming method of the ITO film and the inorganic film, spattering method, vacuum metalliz metallizing method, ion plating method or the like is used. As the forming method of SiO, SnO2 is employed as a target or a volatalizing material. As the forming method of SnO, SnO2 is employed as a target or a voltalizing material. As the forming method of ITO, ITO, In2 O2 is employed as a target or a volatalizing material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having excellent adhesion and durability to a tin-doped indium oxide film and a light-transmitting body using the same.

[0002]

2. Description of the Related Art A transparent conductive film is widely known as a film having both visible light transmittance and electric conductivity, and a typical example thereof is a tin-doped indium oxide film (hereinafter referred to as "ITO film").
That is). BACKGROUND ART A laminated body in which an ITO film is laminated on a transparent base material is widely used as an electrode, a heating element by energization, an electromagnetic wave shielding material, a light transmitting body, and the like. Applications of the translucent body include automobiles, aircraft and buildings windows, screens, electromagnetic wave shield plates for monitors, liquid crystal display substrates, and the like.

As a means for forming an ITO film on a transparent substrate, a sputtering method, a vacuum vapor deposition method, an ion plating method and the like are known.

Glass has been mainly used as a base material of such a light-transmitting body, but as demand has increased, workability and productivity have been required to be improved. Therefore, in recent years, plastics, which are lighter in weight than glass and have excellent workability and productivity, have been attracting attention and used. Among them, methacrylic resin has excellent transparency and is widely used.

[0005]

However, since the methacrylic resin has insufficient adhesion to the ITO film, when a laminate of the methacrylic resin substrate and the ITO film is used as a light-transmitting body, the substrate and the ITO film are not used. There was a problem in durability such as peeling off and cracking or peeling of the film when used outdoors. Especially, when the substrate is heated to form a film (laminate) to improve the film characteristics of the ITO film such as surface resistance and transmittance, the adhesion and durability are further reduced, making it a good translucent material. I couldn't get anything.

The object of the present invention is to provide a methacrylic resin substrate which is lightweight, has excellent workability and productivity, and has excellent adhesion and durability to IT.
It is to provide a laminated body and a translucent body having an O film formed thereon.

[0007]

Means for Solving the Problems The gist of the present invention is that an inorganic film made of at least one selected from SiO, SnO ₂ and Ti and a tin-doped indium oxide film are sequentially formed on a substrate containing a methacrylic resin as a main component. It is a laminated body formed by laminating, and is also a translucent body using this laminated body.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION A substrate formed of a methacrylic resin or a methacrylic resin composition containing various additives is used as the substrate containing a methacrylic resin as a main component.

Examples of the methacrylic resin include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-methacrylate.
Examples thereof include polymers and copolymers of acrylic acid esters such as ethylhexyl acrylate, and cross-linked copolymers with glycidyl methacrylate.

In the present invention, the inorganic film formed between the ITO film and the substrate is composed of at least one selected from SiO, SnO ₂ and Ti.

The thickness of the SiO layer or SnO ₂ layer is preferably in the range of 5 nm to 50 nm, more preferably 10 nm to 20 nm.
Range. For any of the films, if the film thickness is too thin, a sufficient effect of improving the adhesiveness cannot be obtained, and if the film thickness is too thick, the adhesiveness and durability are adversely affected. Further, with respect to the SnO ₂ film, when the film thickness is made too thick, the light transmittance is lowered such that the coloring is deepened, which is not preferable for use as a light-transmitting body. Therefore, it is necessary to set the film thickness within a range that does not adversely affect the adhesiveness, durability and light transmittance.

The thickness of the Ti layer is preferably 0.5 nm to 10 nm, more preferably 1 nm to 5 nm. Like the SiO layer and the SnO ₂ layer, if the Ti layer is too thin, a sufficient effect of improving the adhesiveness cannot be obtained, and if the film thickness is too large, the adhesiveness and durability are adversely affected. However, it is necessary to set the film thickness in consideration of these. Even if the Ti layer is thinner than the SiO layer or the SnO ₂ layer, the adhesion and durability can be improved, and therefore the light transmittance of the base material is not reduced.

SiO, SnO ₂ and Ti may be used alone or in a combination of two or more kinds.

As a method for forming the ITO film and the inorganic film,
A sputtering method, a vacuum deposition method, an ion plating method and the like can be mentioned.

The sputtering method is a method of ionizing an inert gas such as argon introduced in a vacuum container and colliding it with a solid surface called a target to which a voltage is applied to knock out solid particles to form a film on a substrate. Is. DC sputtering,
It can be divided into high-frequency sputtering, ion beam sputtering and the like, but either method can be used.
Further, instead of the inert gas, a mixed gas of an active gas such as oxygen or an oxygen compound such as water and an inert gas may be used.

The vacuum vapor deposition method is a method of forming a film on a substrate by heating, melting, or sublimating a solid called an evaporation material in a vacuum container. As a method of evaporating the evaporation material, there are a resistance heating method, an electron beam method, and the like, and any method can be used. Other evaporation methods may be used as long as the evaporation material can be heated, melted, or sublimated. If necessary, an active gas such as oxygen or an oxygen compound such as water can be introduced into the vacuum container.

The ion plating method is a method of forming a film on a substrate after ionizing an evaporated material that has been heated and melted or sublimated in a vacuum container. An inert gas such as argon is introduced into the vacuum container as necessary to facilitate ionization of the evaporation material. At that time, an active gas such as oxygen or an oxygen compound such as water may be mixed with the inert gas and introduced. Depending on the evaporation method or ionization method of the evaporation material, it can be divided into direct current ion plating, high frequency ion plating and the like, and either method can be used, but other evaporation methods and ionization methods can also be adopted.

As a method of forming SiO, a method of using SiO as a target or an evaporation material, a method of using Si to oxidize into SiO during film formation, a method of using SiO ₂ to reduce during film formation, etc. However, either method may be used.

As a method of forming SnO ₂ in the present invention, there are a method of using SnO ₂ as a target or an evaporation material, a method of using Sn to oxidize SnO ₂ during film formation, and any method is available. May be used.

As a method of forming ITO, there are a method of using ITO as a target or an evaporation material, a method of using In ₂ O ₃ and a method of using In to oxidize during film formation.
Either method may be used. Also, during film formation, Sn and SnO ₂
Impurities such as may be doped or added to the target or the evaporation material.

During film formation (lamination), the substrate can be heated within a range that does not deform the substrate. In the laminate of the present invention, a protective film or the like can be formed on the ITO film as needed.

Examples of the translucent body produced from this laminated body include windows of automobiles, aircrafts and buildings, screens, electromagnetic wave shield plates for monitors, liquid crystal display substrates and the like.

[0023]

EXAMPLES The present invention will be specifically described with reference to the following examples. still,
In the examples, the laminate was evaluated under the following conditions.

(1) Evaluation Method of Adhesiveness The adhesive surface of an adhesive tape (Nichiban 1.8 cm-wide cellophane tape) is adhered to the ITO film of the laminate and slowly peeled off. The case where the ITO film is not peeled at all is indicated as ◯, the case where it is partially peeled is indicated as Δ, and the case where the entire surface is peeled is indicated as ×.

(2) Durability Evaluation Method After immersing the laminate in hot water at 60 ° C. for 24 hours, the above-mentioned peeling test is performed to evaluate the durability, and the result is similarly displayed.

Example 1 Vacuum deposition apparatus (basic specifications: manufactured by Vacuum Instrument Co., Ltd., B14C-600)
A 100 mm × 100 mm × 5 mm methacrylic resin substrate (Mitsubishi Rayon Acrylite L) was set in the vacuum chamber of, and the substrate was preheated to 80 ° C by a halogen lamp. Then, after setting the inside of the vacuum chamber to 9E-4Pa, at the film forming temperature of 80 ° C, Si
The O pellet is irradiated with an electron beam, and the S
An iO film is formed with a thickness of 30 nm, and then ITO pellets (SnO
The ITO film was obtained film was laminated body at a thickness of 300nm in ₂ 5 wt% contained) in irradiating the deposition rate 1 nm / sec electron beam.

The evaluation results of the adhesiveness and durability of the obtained laminate were both good and the adhesiveness was good. Further, in the durability evaluation, no defective appearance such as wrinkles was observed on the ITO film.

Example 2 A substrate was not preheated and was not intentionally heat-treated during film formation. A laminated body was produced in the same manner as in Example 1 except for the above conditions, and the results shown in Table 1 were obtained. It was

Example 3 A laminate was produced in the same manner as in Example 1 except that the thickness of the SiO film was 10 nm, and the results shown in Table 1 were obtained.

Example 4 A laminated body was prepared in the same manner as in Example 1 except that SnO ₂ pellets were used as the raw material of the inorganic film and the thickness of the SnO ₂ film formed between the methacrylic resin substrate and the ITO film was 10 nm. Manufacture
The results in Table 1 were obtained.

Example 5 A laminated body was manufactured in the same manner as in Example 1 except that Ti pellets were used as a raw material for the inorganic film and the thickness of the Ti film formed between the methacrylic resin substrate and the ITO film was 2 nm. Then, the results shown in Table 1 were obtained.

Comparative Example 1 A laminated body was produced under the same conditions as in Example 1 except that the inorganic film was not formed, and the results shown in Table 1 were obtained.

Comparative Example 2 A laminated body was produced under the same conditions as in Example 2 except that the inorganic film was not formed, and the results shown in Table 1 were obtained.

Comparative Example 3 A laminated body was prepared in the same manner as in Example 1 except that SiO ₂ pellets were used as the raw material of the inorganic film and the thickness of the SiO ₂ film formed between the methacrylic resin substrate and the ITO film was 30 nm. Manufacture
The results in Table 1 were obtained.

Comparative Example 4 TiO ₂ pellets were used as the raw material for the inorganic film, and the thickness of the TiO ₂ film formed between the methacrylic resin substrate and the ITO film was 30 nm.
A laminate was produced in the same manner as in Example 1 except that the above was obtained, and the results shown in Table 1 were obtained.

[0036]

[Table 1]

[0037]

The laminate of the present invention has good adhesion between the substrate and the ITO film and excellent durability. Further, a light-transmitting body using this laminate can be used in a wide range of applications.

Claims (2)

[Claims] 1. A laminate in which an inorganic film made of at least one selected from SiO, SnO ₂ , and Ti and a tin-added indium oxide film are sequentially laminated on a substrate containing a methacrylic resin as a main component. 2. A light-transmitting body using the laminate according to claim 1.