JPH01308848A - Highly adhesive heat ray reflecting glass - Google Patents

Abstract

PURPOSE:To obtain a highly adhesive heat ray reflecting glass excellent in scuff resistance by forming a ground film on a glass substrate, implanting high- energy ions into the film surface and then forming a nitride or boronitride film on the film surface. CONSTITUTION:A heat ray reflecting glass obtained by forming a ground film on a glass substrate, implanting high-energy ions into the ground film surface and forming a nitride or boronitride film on the ion-implanted film surface. Although ions of gases, such as argon, nitrogen or oxygen, or metallic atom ions, etc., obtained by evaporating a metal are usable as the high-energy ions 3, nitrogen ions are especially preferred by considering that the nitride or boronitride film is formed on the ground film 2. The ground film preferably contains at least one or more components common to those of the nitride or boronitride film.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a highly adhesive heat-reflecting glass suitable for automobiles or architecture.

[Prior Art] Conventionally, glass on which a metal layer of transition metals such as Cr and Ti is formed has low transmittance in the visible spectrum band and at the same time blocks most of the sunlight spectrum, making it suitable for solar control. They are called panels and have been used in building window glass and automobile sunroofs for the purpose of reflecting heat rays. However, these metal films did not have sufficient durability, especially scratch resistance, and also tended to have poor color change.

Nitrides such as titanium nitride, zirconium nitride, tantalum nitride, and chromium nitride are known as alternative materials for such metal films. Such nitride films have relatively low electrical resistance;
It has infrared reflective properties comparable to ordinary metal films, high hardness, and excellent chemical durability.

In addition, because it has a unique lustrous color, it is coated on metal surfaces such as stainless steel, and is also used in carbide materials, decorations, etc.

Boron nitride, which is obtained by adding boron to these nitrides, has a somewhat higher electrical resistance, but has a different color tone than pure nitride, so it is still used for decorations and the like.

[Problem to be solved by the invention] It is generally known that nitride films have high internal stress, but the above-mentioned nitrides and boronitrides are made of metal atoms such as titanium, zirconium, tantalum, and chromium. Since it is an interstitial compound in which nitrogen and boron have entered the matrix,
When such a nitride film or boronitride film is formed on a metal, the adhesion between the nitride film or boronitride film and the metal is relatively good.

However, when such a nitride film or boronitride film is formed on a glass substrate, the adhesion between the film and the glass substrate is poorer than when it is formed on a metal, making it difficult to actually use it as a heat-reflecting glass. In some cases, there was a problem in that the scratch resistance was insufficient and the film was likely to peel off.

Research has also been conducted on a method of inserting a binder layer such as an oxide film between the glass substrate and the nitride film or boronitride film to improve the adhesion of the film to the glass substrate.
No method has been found to form a nitride film or boronitride film directly on a glass substrate with high adhesion.

For this reason, although these nitride films or boronitride films have relatively good properties as heat ray reflective films, they can only be used on metal substrates and cannot be formed directly on glass. Shi4
Due to its large size, it was difficult to put it into practical use as a heat-reflecting glass.

[Means for Solving the Problems] The present invention was made to solve the above-mentioned problems, and consists of forming a base film on a glass substrate, irradiating the surface of the base film with high-energy ions, and The present invention provides a highly adhesive heat-reflecting glass in which a nitride film or a boronitride film is formed on the surface of the ion-irradiated film.

FIG. 1 shows the steps of the manufacturing method of the highly adhesive heat-reflecting glass of the present invention, in which (a) shows the first step of forming the base film 2 on the glass substrate l, and fb) shows the process of forming the base film 2 on the glass substrate l. A second step is to implant high-energy ions 3 into the surface, and (c) shows a third step to form a nitride film or boronitride film 4 on the ion-implanted film surface.

Glass substrate 1 forming base III 2 in the present invention
is not particularly limited, and soda lime silicate glass, aluminosilicate glass, borosilicate glass, lithium aluminosilicate glass, quartz glass, etc. can be used depending on the purpose of use.

Also, as the base film 2, Ti, Zr, etc. can be used depending on the purpose of use.
, Ta, Cr, Hf, Nb, A1. Mo, Ni, Fe,
Simple metals such as Go, or alloys containing at least one of these metal elements, or nitrides, borides, carbides,
Compounds such as oxides, or multi-compounds containing at least two of nitrogen, boron, carbon, and oxygen, such as boron carbide, boron nitride, etc., or a composite film of the above various substances can be used. In the present invention, considering the relationship with the nitride film or boronitride film 4 formed as a heat ray reflecting film on the base film into which high-energy ions are implanted, the base film 2 is formed of a nitride film or boronitride film. It is desirable that the base film 2 and the nitride film or boronitride film 4 contain at least one common component. This is thought to be because the state is similar to that of two layers of the same type of film, and the adhesion between the films increases. In particular, when a nitride film or a boronitride film of titanium, zirconium, tankard, chromium, or a mixture thereof is used as the nitride film or boronitride film 4, the base film 2 is made of titanium, zirconium, chromium, or a mixture thereof. Kuntar,
A metal film of chromium or a metal film of an alloy thereof is preferable.

The thickness of the base film 2 is 30 to 200, preferably 30 to 200.
100 people, particularly preferably 30 to 50 people.

If it is too thin, it will no longer function as a base film,
If it is too thick, the distance from the base film surface to the interface with the glass substrate will be long, and in order for the implanted ions to reach the interface with the glass substrate and form a mixed layer, extremely high-energy ions are required. This is because large-scale ion implantation snow making is required.

In the present invention, the method for forming the base film is not particularly limited, but physical vapor deposition methods such as sputtering method, vacuum evaporation method, and ion blating method are preferable in consideration of ease of controlling the lI thickness.

As the high-energy ions 3 injected from above the base film 2 in the second step, gaseous ions such as argon, nitrogen, and oxygen, and metal atomic ions obtained by evaporating metals can be used. Argon ions, nitrogen ions, and oxygen ions are preferred because they are easy to prepare.

Among them, considering that a nitride film or a boronitride film is formed on the base film 2 as a heat ray reflecting film in the third step of the present invention, nitrogen ions are particularly preferable. There are two types of ions, monatomic ions (No) and molecular ions (N 2''), and either one may be used.

In the present invention, a base film 2 formed on a glass substrate l
The energy of the ions implanted into the base II! It is necessary to change it depending on the film thickness of 2. The depth of ion penetration depends on the ion energy, so the energy of the ions must be selected according to the thickness of the base film so that the ions reach near the boundary between the base film and the glass substrate. . In the present invention, the energy of the implanted ions is 30 KeV or less, preferably 5 to 20 eV, particularly 10 to 15 KeV. This is because if the energy is less than this, the penetration of ions will be small (and the sputtering effect of the base film will be large), and if you try to implant ions with more energy than this, the cost of the ion gun will increase.

The upper limit of the amount of ions to be implanted is 1.0×1017
ions/cm”, preferably 58 ports x 1016io
ns/cm" or less, particularly preferably 3.Ox 10"1
Ons/cwt" or less is desirable. If it is made larger than this, the proportion of impurities mixed in will increase, the ion implantation processing time will become longer, and the quality of the base film itself will be significantly altered, which is not preferable.

Also, the lower limit of the amount of ions to be implanted is 1.0×10I
It is preferable that the amount is 8 ions/cm" or more; if it is less than this, a sufficient mixing effect cannot be obtained, so it is not preferable.

The method of implanting high-energy ions is not particularly limited as long as it can ionize atoms and provide ions with the above-mentioned energy, but using an ion gun is the best way to target f49. be. The degree of vacuum during high-energy ion implantation is set at 10-'torr or less in order to prevent scattering of the implanted ions.

The nitride film or boronitride film 4 formed as a heat ray reflective film on the base film 2 injected with high energy is particularly suitable for titanium, zirconium, tantalum, chromium, etc., considering the heat ray reflection performance and durability. Among them, a nitride film or a boronitride film containing at least one metal element is desirable.

The film thickness of the nitride film or boronitride film 4 is approximately 50 to 100%, considering the necessary heat ray reflection performance, internal stress, etc.
Preferably 0 people.

Methods for forming such a nitride film or boronitride film 4 include a sputtering method and a vacuum evaporation method.

A physical vapor deposition method such as an ion blasting method or an arc evaporation method is preferable, but is not particularly limited, and a chemical method such as a CVD method may also be used.

After ion implantation into the base film 2, a nitride film or boronitride film 4 is formed.
In order to have a sufficiently strong adhesion force, the three steps of base film formation, ion implantation, and nitride or boronitride film formation must be performed in the same vacuum apparatus without breaking the vacuum, i.e.
When processed continuously in an online vacuum device.

If the substrate is exposed to the atmosphere after forming a base film or ion implantation, which is preferable because it allows for the production of higher quality, highly adhesive heat-reflective glass, moisture and oil in the air will adhere to it, causing adhesion. This is because it causes a decrease in adhesion.

Further, a protective layer such as an oxide film or various functional layers such as a color tone adjusting film may be provided on the nitride film or boronitride film 4. Such a protective layer or functional layer may include a nitride film or It is particularly preferred that the film contains at least one common component with the boronitride film.

[Information] The present invention utilizes ion beam mixing. When ions with a certain kinetic energy are irradiated onto a solid, a sputtering phenomenon mainly occurs when the energy is low. However, when the energy is at the level proposed in this invention, the ion enters the solid, and in the solid the ion repeatedly collides with the atoms, and finally, the ion loses all of its energy, and the ion enters the solid. Stand still.

This phenomenon is explained by LSS theory (K.

Dan, Videsk, 5elsk, Mat-Fys,
Medd, 33 (1963)). Furthermore, when ions collide with atoms in a solid, those atoms are also scattered, and this process is repeated, resulting in so-called cascade collisions. If the energy to be injected is adjusted so that this cascade collision occurs near the interface between the base film and the glass substrate, mixing of atoms occurs there and a mixed layer is formed. As a result, the boundary between the base film and the glass substrate becomes disordered and unclear, and it is thought that a decrease in adhesion can be significantly prevented.

As a highly adhesive heat-reflecting glass, without a base film,
A highly adhesive heat-reflecting glass is also considered, in which a nitride film or boronitride film is created as a heat-reflecting film on a glass substrate, and then ion implantation is performed to improve the adhesion between the heat-reflecting film and the glass substrate. . However, in this case, the implanted ions pass through the heat ray reflective film, which may cause damage to the heat ray reflective film.

Therefore, in the present invention, instead of implanting ions onto a nitride film or a boronitride film, a base film is formed before creating such a heat ray reflective film, and ions are implanted from above the base film. The ground film is firmly attached to the glass substrate,
By forming the heat ray reflective film on top of it,
The present invention provides highly durable heat-reflective glass. The adhesion between the heat ray reflective film and the base film is sufficiently better than the adhesion between the heat ray reflection film and the glass substrate, and in particular,
When the base film has the same components as the heat ray reflective film, continuity of composition between the base film and the heat ray reflective film can be obtained, and very good adhesion can be obtained. In particular, when nitrogen ions are used as implanted ions, mixing occurs between the base film and the glass substrate, and at the same time, the base film itself is also nitrided to some extent, so the nitride film or boronitride film formed thereon is It is thought that the adhesion with the material film becomes stronger.

Furthermore, if mixing simply occurs between the base film and the glass substrate, it is sufficient to implant ions of an inert gas such as argon, but when nitrogen ions are implanted, mixing occurs and the mixed layer Not only is this formed, but also nitrogen forms chemical bonds within the mixed layer to form nitrides, which is thought to further improve the adhesion between the glass substrate and the underlying film.

In addition, in the heat ray reflective glass of the present invention, as described above, ions are implanted from above the base film to form a mixed layer between the base film and the glass substrate, so that the heat ray reflective film can be applied to the glass substrate. Since the adhesion force is improved, a nitride film or boronitride film can be formed with a sufficiently strong adhesion force without particularly heating the glass substrate during the production of heat ray reflective glass.

Examples of the present invention will be described below.

Example 1 A soda lime glass substrate of 0-order 2n+n thickness with a metal Ti target set on the cathode of a magnetron D and C equipped with a packet-type ion implantation device and a spackle device was polished with calcium carbonate powder, rinsed with running water, and treated with ethanol. After cleaning with the steps of rinsing and N2 drying, it was placed in the vacuum chamber of the above sputtering device, and was heated using an oil diffusion pump in step 4. Ox 10-
' Exhausted to below Torr. 2.2
2.6 on a metal Ti target in an Ar atmosphere of Torr.
■/cm” power was applied to the metal titanium film (50 people).
Then, an energy of 1 is applied on the metal film.
0KeV, ion implantation amount 8.6 x 10”1ons
Nitrogen ions were implanted under the conditions of /c. The degree of vacuum at this time was 3.2 x 10-'Torr. The amount of ion implantation was adjusted by measuring the ion current density with a Faraday cup. Finally, Ar with a total pressure of 2.2X 10-” Torr
A titanium nitride film (4
00 persons) formed a film.

The thus produced heat ray reflective glass was taken out into the atmosphere, a hang was attached to the 2IIIff+ corner part, and a tensile strength test was conducted, and it broke at 1.3 kg. A fracture surface occurred on the glass substrate, and it was confirmed that the glass substrate was broken first.

The heat ray reflective film was not peeled off.

Example 2 A zirconium boride target having a composition of Zr:B.7:3 was set on the cathode of a magnetron D, C, sputtering device similar to that in Example 1. After cleaning a 2+ nm thick soda lime glass substrate in the same manner as in Example 1,
Place it in the vacuum chamber of the above-mentioned spacking device; 2. IX 10-
A power of 1.6 W/c+n was applied to a zirconium boride target in an Ar atmosphere of "Torr" to form a zirconium boron film (70 people). On the zero-order zirconium boron film, an energy of 15 KeV and an ion implantation amount were applied. 1.
Nitrogen ions were implanted under the condition of Ox 10"1ons/ca+'.The degree of vacuum at this time was 3.OX 10-'Tor.
It was r. The amount of ion implantation was adjusted by measuring the ion current density with a Faraday cup. Finally, the total pressure is 1.8X
A mixture of Ar:N, = 88:12 at 10”” Torr was applied to a zirconium boride target at a depth of 2.617 cm in a gas atmosphere.
” power was applied, and the zirconium boronitride film (600
film was formed.

When the heat ray reflective glass thus produced was taken out into the atmosphere and subjected to the same tensile strength test as in Example 1, it broke at 1.69 kg. A fracture surface occurred on the glass substrate, and the heat ray reflective film was not peeled off.

Example 3 A soda lime glass substrate of 2+n+n thickness of zero order with a metal Cr target set on the cathode of a magnetron D and C equipped with a packet-type ion implantation device and a sputtering device was polished with calcium carbonate powder, rinsed with running water, and treated with ethanol. After cleaning with the steps of rinsing and N2 drying, it was placed in the vacuum chamber of the above sputtering device, and was heated using an oil diffusion pump in step 4. OX1
It was evacuated to below 0-'Torr. 2.2 x 10
−”2 to a metal Cr target in an Ar atmosphere of Torr.
．． A power of 4 W/cm” was applied, and a metal chromium film (50
Next, on the metal chromium film, an energy of 10 KeV and an ion implantation amount of 7.5 x 10"1o were applied.
Nitrogen ions were implanted under the condition of ``ns/cm''.The degree of vacuum at this time was 3.2 A power of 2.6 W/cm was applied to a Cr target in an Ar:Nz:9:1 mixture atmosphere with a pressure of 2.2X 1G-''Torr to form a chromium nitride film (400 people). .

The thus produced heat ray reflective glass was taken out into the atmosphere, soldered to the 2IIIQ square part and subjected to a tensile strength test, and broke at 1.1 kg. A fracture surface occurred on the glass substrate, and it was confirmed that the glass substrate was broken first.

The heat ray reflective film was not peeled off.

Comparative Example A metal Ti target was set on the cathode of a magnetron D, C, and sputtering device similar to that in Example 1. After cleaning a 2ffiII+ thick soda lime glass substrate in the same manner as in Example 1, it was placed in the vacuum chamber of the sputtering apparatus, and
Ar: N2 = 9 with a total pressure of 2.2X 10-'Torr after the 0th order was evacuated to 4.0X 10'''Torr or less.
:2.6W/ to Ti target in mixed gas atmosphere of 1
Applying power of “c+n”, titanium nitride film (400 people)
A film was formed.

When the thus produced heat ray reflective glass was taken out into the atmosphere and subjected to the same tensile strength test as in Example 1, it broke at 0.69 kg. Peeling of the heat ray reflective film was observed, and no fracture surface was observed on the glass substrate.

[Effects] The heat-reflecting glass of the present invention has a heat-reflecting film made of a nitride film or a boronitride film with a large internal stress that adheres closely to the glass substrate with sufficiently strong adhesion, and the heat-reflecting film prevents the film from peeling off. It does not cause any damage and has excellent scratch resistance. Therefore, it can be widely used as a single sheet of heat-reflecting glass for applications such as automobiles and architecture without being made into laminated or double-glazed glass.

In addition, in the present invention, a base film is first formed and ions are implanted into this base film to improve adhesion to the glass substrate. It is possible to provide a highly adhesive heat-reflecting glass that is not damaged by the ion implantation process.

[Brief explanation of the drawing]

FIG. 1 is an explanatory view showing the method for manufacturing the highly adhesive heat-reflective glass of the present invention using cross-sectional views of a glass substrate in each manufacturing process of the highly adhesive heat-reflective glass of the present invention. 1 is a glass substrate, 2 is a base film, 3 is a high-energy ion, and 4 is a nitride film or a boronitride film.

Claims (6)

[Claims] (1) High adhesion formed by forming a base film on a glass substrate, implanting high-energy ions into the surface of the base film, and forming a nitride film or boronitride film on the surface of the ion-implanted film. Heat reflective glass. (2) The highly adhesive heat-reflecting glass according to claim 1, wherein the ions implanted into the base film are nitrogen ions. (3) The highly adhesive heat-reflective glass according to claim 1 or 2, wherein the base film contains the same components as the nitride film or the boronitride film. (4) The nitride film or the boronitride film contains at least one metal element selected from the group of titanium, zirconium, tantalum, and chromium. Adhesive heat reflective glass. (5) The highly adhesive heat-reflective glass according to claim 4, wherein the base film is a metal film containing the same metal element as the nitride film or the boronitride film. (6) The highly adhesive heat-reflecting glass according to any one of claims 1 to 5, wherein the base film has a thickness of 30 to 200 Å.