JPH0818855B2 - Laminate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a laminate, particularly a laminated glass, and more particularly to a laminate in which cloudiness or the like does not occur due to aging.

[Prior Art] Laminated glass does not scatter even when broken, and has high resistance to penetration against impact force.
It is widely used as so-called safety glass for vehicle windows, sunroofs, aircraft windows, ship windows, architectural windows, and the like.

In particular, laminated glass is often used for windshields for automobiles from the viewpoint of ensuring safety.In this case, a transparent conductive film is added to the laminated glass in order to impart an antifogging function and a heat ray reflecting function at the same time. A structure interposing it on the joint surface side has already been provided. At this time, the transparent conductive film is a single-layer metal film such as Au film or Ag film, or ITO film or S film.
In addition to single-layer metal oxide films such as nO ₂ film, ITO, TiO _x , Sn
A multilayer film in which an Ag film is sandwiched between derivative films made of a metal oxide such as O _x and ZnO _x is also used. this house,
Regarding the single-layer metal film and the single-layer metal oxide film, there is a problem in the obtained color value and durability as well as the obtained resistance value. A multi-layered film in which an Ag film is sandwiched between is often used.

FIG. 3 shows an example of a conventional laminated glass structure in which a transparent conductive film is formed by a multilayer film in which an Ag film is sandwiched between dielectric films in order to impart an antifogging function and a heat ray reflecting function. is there.

According to this, in the laminated glass, a plastic intermediate film 13 made of polyvinyl butyral (hereinafter referred to as PVB) is arranged on the joint surface between the glass plate 11 located outside the vehicle and the glass plate 12 located inside the vehicle. In addition, the dielectric film 15, 17 as a dielectric between the glass plate 11 on the outside of the vehicle and the plastic intermediate film 13, for example, the Ag film 16 between the ZnOx film.
By interposing a transparent conductive film 14 composed of a three-layer film sandwiching the above, it is possible to exhibit an anti-fog function and a heat ray reflection function. The dielectric films 15 and 17 are provided to increase the visible light transmittance due to the interference effect with the metal film 16.

As the plastic intermediate film 13, the above-mentioned PVB (polyvinyl butyral), EVA (ethylene-vinyl acetate copolymer), urethane, etc. are used. Among them, PVB
Is tough, has excellent penetration resistance, has high durability for a long time, and is chemically and optically stable. Therefore, it is most suitable for laminated glass for vehicles where stability is required. Many are used. At this time, a PVB film containing a predetermined amount of water is used in order to impart excellent penetration resistance to PVB.

[Problems to be Solved by the Invention] By the way, according to the laminated glass structure as a conventional example shown in FIG. 3, since the transparent conductive film 14 is interposed on the bonding surface, the transparent conductive film 14 is energized. An antifogging function can be imparted by allowing heating. Further, since the transparent conductive film 14 itself has a heat ray reflecting function, it can be effectively functioned in energy saving measures such as reducing a cooling load.

However, the Ag film 1 is formed between the dielectric films 15 and 17 made of metal oxide.
It was found that when the laminated glass is formed with the transparent conductive film 14 formed of a multilayer film having 6 sandwiched therebetween, a part of the laminated glass may become cloudy after a long time.

[Means for Solving the Problems] The present invention has found that such white turbidity is caused by the reduction of the layer in contact with the interlayer film, while the layer in contact with the interlayer film has an energy gap of 4 eV or more. It was made by finding that such white turbidity can be prevented by using.

That is, the present invention has at least one glass plate and a plastic film bonded to the glass plate, and a single layer or a plurality of layers containing a metal film on the bonding surface between the glass plate and the plastic film. A layered product provided with a functional film consisting of, wherein the layer in contact with the plastic film in the functional film is a film having an energy gap of 4 eV or more, and from among the following (a) to (f): Laminate characterized by being a selected film, (a) SiO _x , Ta ₂ O ₅ ,, NiO, Ga ₂ O ₃ , Sb ₂ O ₃ , MgF ₂ , LiF, CaF ₂ , LaF
_At least one of Ce and CeF ₃ , (b) a film in which at least one of Ti, Ta, Hf, Mo, W, Nb, Sn, La, and Cr is added to SiO ₂ , (c) ) At least one of Zr, Ti, Hf, Sn, Ta, In and B
And (d) an oxide film containing at least one of Si and (d) an oxide containing Zr and B (ZrB _x O _y ), wherein the atomic ratio x of B to Zr in the film is 0.05 ≦ x ≦. 3 and film atomic ratio y for Zr of oxygen in the film is 2 ≦ y ≦ 6.5, (e ) an oxide containing Zr and Si a (ZrSi _x O _y) film, the Si in the film A film having an atomic ratio x to Zr of 0.05 ≦ x ≦ 19 and an atomic ratio y of oxygen in the film to Zr of 2.1 ≦ y ≦ 40, (f) an oxide containing Zr, B and Si (ZrB _x Si _y O _z ) film, wherein the atomic ratio x of B to Zr, the atomic ratio y of Si to Zr, and the atomic ratio z of oxygen to Zr in the film are 0.05 ≦ x + y ≦
19 (however, the composition of x + y-3> 0 and x-3y + 1> 0 is excluded), and the film of 2 <z <40, and at least one glass plate, and the glass plate A plastic film, and a functional film composed of a single layer or a plurality of layers including an absorption film made of at least one of nitride, boride, and carbide is provided on a joint surface between the glass plate and the plastic film. And a layer in contact with the plastic film in the functional film is a film having an energy gap of 4 eV or more, and the following (a) to
A laminated body characterized by being a film selected from among (f), (a) SiO _x , Ta ₂ O ₅ , NiO, Ga ₂ O ₃ , Sb ₂ O ₃ , MgF ₂ , LiF, CaF ₂ , LaF
_At least one of Ce and CeF ₃ , (b) a film obtained by adding at least one of Ti, Ta, Hf, Mo, W, Nb, Sn, La, and Cr to SiO ₂ (c) ) At least one of Zr, Ti, Hf, Sn, Ta, In and B
And (d) an oxide film containing at least one of Si and (d) an oxide containing Zr and B (ZrB _x O _y ), wherein the atomic ratio x of B to Zr in the film is 0.05 ≦ x ≦. 3 and film atomic ratio y for Zr of oxygen in the film is 2 ≦ y ≦ 6.5, (e ) an oxide containing Zr and Si a (ZrSi _x O _y) film, the Si in the film A film having an atomic ratio x to Zr of 0.05 ≦ x ≦ 19 and an atomic ratio y of oxygen in the film to Zr of 2.1 ≦ y ≦ 40, (f) an oxide containing Zr, B and Si (ZrB _x Si _y O _z ) film, wherein the atomic ratio x of B to Zr, the atomic ratio y of Si to Zr, and the atomic ratio z of oxygen to Zr in the film are 0.05 ≦ x + y ≦
19 (provided that the composition of x + y-3> 0 and x-3y + 1> 0 is excluded) and 2 <z <40 is provided. FIG. 1 shows a typical example of the laminate of the present invention. The sectional view of an example of laminated glass is shown. The present invention is a laminate having a functional film 4 consisting of a single layer or a plurality of layers on the joint surface between the glass plate 1 and the plastic film 3, and as the layer 8 of the functional film 4 in contact with the plastic film 3, The structural feature is that a film having an energy gap of 4 eV or more is used.

FIG. 1 is a cross-sectional view of an example of a laminated glass as a typical example of the laminated body of the present invention, which has a laminated glass structure in which a vehicle outer glass plate 1 and a vehicle inner glass plate 2 are joined via a plastic intermediate film 3. This is an example in which the functional film 4 is formed on the joint surface between the vehicle outer glass plate 1 and the plastic intermediate film 3.

The functional film 4 in the present invention has an optical function of selectively reflecting, blocking, and transmitting light in a specific wavelength range, snow melting,
Electrical functions such as electric heating for the purpose of melting ice and anti-fog, electromagnetic shielding, or antenna functions such as electromagnetic wave reception and transmission,
Examples thereof include those having various functions such as a photoelectric conversion function of a solar cell or the like, and a light-electric composite function such as light shielding by a liquid crystal or an electrochromic material.

In FIG. 1, as the functional film 4, a metal film 6 made of Ag, Au, etc. is sandwiched between dielectric films 5, 7 such as ZnO, SnO _{2 to} form a multilayer film, and a contact surface with the intermediate film 3 is formed. An example of a functional film formed by stacking films 8 having an energy gap of 4 eV or more is shown. Such a functional film has a heat ray reflection performance due to a metal such as Ag and Au, and a conductive performance due to such a metal. The dielectric films 5 and 7 are provided to increase the transmittance of the entire functional film due to the effect of interference with the metal film 6.

In the present invention, the reason for using a layer having an energy gap of 4 eV or more as a layer in contact with the intermediate film is as follows.

That is, the present inventor has conventionally used it as a dielectric film as shown in FIG. It has been found that ZnO, TiO ₂ , SnOx, ITO, etc. have an energy gap (Eg) of less than 4 eV. The wavelength range of sunlight on the surface of the earth is approximately 310 nm to 2 μm, which corresponds to energy of approximately 4 eV to 0.06 eV. Therefore, the energy gap (E
A film having g), for example, a ZnO film (Eg = 2.47 eV) is an intermediate film 3
When it is in contact with, it absorbs ultraviolet (UV) light having energy equivalent to such Eg and is reduced (Zn) in the presence of water contained in the interlayer film or water that has entered from the periphery of the laminate. ²⁺ → Zn) was confirmed.

Fig. 4 (a) shows U of ZnO film in contact with the intermediate film.
It is the measurement result by ESCA of the surface state before and after the V light is irradiated for 1000 hours. It can be seen that ZnO reduction products are present after UV irradiation.

Fig. 4 (b) shows the measurement results by ESCA before and after irradiation with UV light for 100 hours when TiO ₂ (Eg = 3.27 eV), which was used as a conventional dielectric film instead of ZnO, was in contact with the intermediate film. Similarly, the presence of a reduction product of TiO ₂ can be confirmed.

It was found that other dielectric films conventionally used as the dielectric film 15 in FIG. 3, such as CrOx (Eg <1), SnO ₂ and ITO, are also reduced.

It is presumed that such reduction is caused by the following photochemical reaction.

Then, for example, as shown in FIG. 3, when a layer 16 of a metal such as Ag which is easily oxidized is present, oxygen generated by the reaction (1) reaches the metal layer 16 through the dielectric layer 15, and the oxygen is generated. It is considered that this is the cause of the oxidation of the metal, and thus the cloudiness. For example, it is considered that Ag is oxidized to silver oxide, which causes the light to scatter and become cloudy.

Therefore, it is considered that if the layer in contact with the intermediate film has Eg of 4 eV or more, the above reaction does not occur and the metal or the like located on the opposite side does not oxidize.

In the present invention, the energy gap value is obtained by forming a film of about 1 μm on quartz glass, measuring the reflectance and the transmittance, and determining the wavelength dependence of the absorption coefficient.

In the present invention, the layer 8 in contact with the intermediate film may have an Eg of 4 eV or more for the above reason. For example, Zr, T
An oxide containing at least one of i, Hf, Sn, Ta, In and at least one of B and Si, for example, an oxide containing zirconium and silicon ZrSixOy (when x = 2, Eg = 5.6
eV), an oxide containing zirconium and boron ZrBxOy (x =
2, Eg = 5.2 eV), oxide ZrBxSiyOz containing zirconium, boron and silicon, SiOx (Eg = 8 eV), Ta ₂ O ₅
Membrane (Eg = 4.2eV), NiO (Eg = 4.2eV), Ga ₂ O ₃ (Eg = 4.6e)
V), Sb ₂ O ₃ (Eg = 4.1eV), MgF ₂ (Eg = 5.9eV), LiF (E
g = 11.3eV), CaF ₂ (Eg = 8.3eV), LaF ₃ (Eg = 5.6eV)
V), CeF ₃ (Eg = 4.1 eV), etc., and SiO ₂ , Ti, T
Examples thereof include a film added with a, Hf, Mo, W, Nb, Sn, La, Cr and the like.

In the SiOx film, x is not particularly limited, but if x is about 2, an amorphous and dense film can be formed, and the barrier property against moisture and oxygen from the intermediate film is further improved, which is particularly preferable. However, the SiOx film is a Si or SiO ₂
When forming a film from a target, since the target has almost no conductivity, it is necessary to use the RF sputtering method.The RF sputtering method has a low film forming rate, is not very good in productivity, and has a large area. It is not very suitable for forming a uniform film.

On the other hand, the ZrSixOy film, the ZrBxOy film, and the ZrBxSiyOz film have the advantage that they can be formed by the DC sputtering method.

Regarding the composition of the ZrBxOy film, the energy gap is 4e.
If the atomic ratio x of boron to zirconium is x> 3, the moisture resistance tends to be lowered, and if x ≧ 0.05, the film is an amorphous film, although it is not particularly limited as long as it is V or more. Considering the disappearance of the grain boundaries due to the amorphization, that is, the further improvement of the barrier property (barrier property against moisture and oxygen from the intermediate film), it is preferable that 0.05 ≦ x ≦ 3. Also, the atomic ratio y of oxygen to zirconium
Is 2 ≤ y ≤ 6.5 because if it is too large, the film structure becomes rough and it becomes a rough film, and if it is too small, the film becomes metallic and the transmittance decreases. Is preferred.

Similarly, the composition of the ZrSixOy film is not particularly limited as long as the energy gap is 4 eV or more, but if the atomic ratio x of silicon to zirconium is x ≧ 0.05, the film becomes an amorphous film, and the particles due to amorphization are formed. Boundary disappearance, denseness improvement, that is, further improvement of barrier property, x ≦ 19
If so, it is preferable that 0.05 ≦ x ≦ 19 in consideration of improving discharge stability in DC sputtering. Also, the atomic ratio y of oxygen to zirconium is ZrBx
For the same reason as for the Oy film, it is preferable that 2.1 ≦ y ≦ 40.

Similarly, the composition of the ZrBxSiyOz film is not particularly limited as long as the energy gap is 4 eV or more, but the atomic ratio x, y, z of boron, silicon, and oxygen to zirconium.
Is 0.05 ≦ x + y ≦ 19 (where x + y-3> 0 and x−
3y + 1> 0 is excluded). The reason is that if 0.05 ≦ x + y, the film becomes amorphous and the barrier property is further improved by eliminating grain boundaries and improving the compactness, and if x + y ≦ 19, stable film formation by DC sputtering becomes possible. Because. In addition, the film is made of ZrO ₂ , B ₂ O.
Considering it as a composite system of ₃ and SiO ₂ , B ₂ O ₃ has relatively poor chemical durability, so ZrO ₂ <25 mol% and SiO ₂ <2 in the film.
B ₂ O ₃ is contained at 5 mol% so that the balance becomes B ₂ O ₃ (that is, if Zr: B: Si: (atomic ratio) in the ZrBxSiyOz film is 1: x: y, 1 / (1 + x + y) <0.25, and y / (1 + x + y)
<0.25, in other words x + y-3> 0 and x-3y + 1>
The composition of 0) is inferior in chemical durability and is not preferable.
Further, the atomic ratio z of oxygen to zirconium is preferably 2 <y <40 for the same reason as in the ZrBxOy film.

Further, a film obtained by adding Ti, Ta, Hf, Mo, W, Nb, Sn, La, Cr or the like to SiO ₂ is also amorphous and can be formed by a DC sputtering method, which is preferable. The energy gap is
It is not particularly limited as long as it is 4 eV or more, but it is preferable that it is 4 atomic% or more with respect to the total amount with Si because DC sputtering can be stably performed using the alloy target.

Tantalum oxide Ta ₂ O _{5 is} also preferable because it becomes an amorphous and dense film and has a further barrier property against moisture and oxygen from the intermediate film. However, since it is difficult to form a stable film by the DC sputtering method, this is disadvantageous.

NiO can be formed by a direct current sputtering method from a Ni target, but since Ni is a magnetic material, magnetron sputtering is impossible and productivity is poor.

In addition, other Ga ₂ O ₃ ,, Sb ₂ O ₃ ,, MgF ₂ ,, LiF, CaF ₂ ,, LaF ₃ ,, CeF ₃
Are preferably formed by a vacuum vapor deposition method because the materials are expensive.

Other components may be added to the layer 8 in contact with the above-mentioned intermediate film for the purpose of adjusting optical constants, stability during film formation, or improvement of film formation rate. In particular, ZrBxOy, ZrSixO
With y, ZrBxSiyOz, etc., the refractive index of the film decreases from about 2.1 to about 1.5 as the amount of B or Si added to ZrOx increases, so that the desired refractive index can be obtained by controlling the film composition. Similarly, with SiO ₂ as the main component, Ti, Ta, Hf
A desired refractive index can also be obtained by controlling the amount of addition of a film added with or the like.

The film 8 having Eg ≧ 4 eV in contact with the intermediate film preferably has a film thickness of 10 Å or more. This is because if the thickness is smaller than this, the film becomes island-shaped, and it is difficult to form the film uniformly, and a portion where the film 8 is not formed occurs.

The functional film 4 of the present invention is not particularly limited, but examples thereof include the following.

FIG. 1 shows an example of a functional film having a transparent conductive film including a metal film, as described above, (glass /) dielectric film 7 / metal.
An example of a functional film having a structure of 6 / dielectric film 5 / film 8 (Eg ≧ 4 eV) (/ intermediate film) is shown. The metal 6 is Ag, Au, Pd, Cu, Pt
, And these alloys, such as Ag-Pd, Ag-Cu alloys,
The dielectric films 5 and 7 are not particularly limited, but ZnO, Ti
O _2, SnO _2, Al or the like can be used doped ZnO, SnO ₂ or ITO (indium oxide doped with tin), doped with F or Sb, etc. or the like. The functional film having such a configuration is
Since the metal film has conductivity, it can be used as an electrically heated glass by providing an electrically heating means such as a bus bar made of an electrically conductive print or the like. Further, since such a metal film is a transparent conductive film and has a heat ray shielding property at the same time, it can be used as a heat ray shielding glass when an electric heating means is not provided. As described above, the dielectric films 5 and 7 on both sides of the metal 6 are provided to improve the transmittance by using interference.

FIG. 2 is a vertical cross-sectional view showing another example of the laminated glass according to the present invention, which is an example in which a solar cell thin film is used as the functional film 4. That is, on the glass plate 1 outside the vehicle, Si
An alkali barrier film 21 made of O ₂ , Al ₂ O _3, etc., a first transparent electrode 22 made of SnO ₂ , ITO, etc., an a-Si film 23, and a back surface electrode (transparent conductive film) 26 are sequentially formed thereon. When the glass plate 1 and the glass plate 2 on the inside of the vehicle are joined together with the plastic intermediate film 3 interposed, a film 8 with Eg ≧ 4 eV is formed and a multilayer film of 21 to 26 and 8 is formed. The functional film 4 is formed.

The transparent conductive film 26 as the back electrode is the metal film 24,
The other film 25 may be composed of two layers or three or more layers,
It may be composed of only one layer composed of the metal film 24 and the like.

The metal film 24 may be a film made of Ag, Au, Pd, Al or the like, or a film made of an alloy of two or more of these. Further, as the other film 25, ZnO, ZnS, TiO ₂ , IT
A dielectric film such as O or SnO ₂ or a film made of a semiconductor such as Si can be used.

Further, as the structure of the functional film 4, the dielectric film 5 shown in FIG. 1 is formed by a film of Eg ≧ 4 eV, and (glass /) dielectric film / metal / dielectric film (Eg ≧ 4 eV) (/ intermediate It may be configured as a film). For example, (glass /) ZrSixOy / Ag / ZrSix
You may comprise like Oy (/ intermediate film). The dielectric film 7 in contact with the glass 1 does not necessarily have to be a film having Eg ≧ 4 eV.

Further, as another configuration example of the functional film 4, in order to utilize the heat ray blocking performance of the absorption film, (glass /) absorption film / film 8 (Eg
≧ 4 eV) (/ intermediate film) or (glass /) dielectric film / absorption film / dielectric film / film 8 (Eg ≧ 4 eV) (/ intermediate film). As the absorption film, a film made of nitride, boride, carbide or a mixture thereof can be used. Further, the dielectric film is for improving the transmittance in the visible region by utilizing interference, and the same film as that described in the example of FIG. 1 can be used. As a specific example,
(Glass /) TiN / ZrSixOy (/ intermediate film), (glass /) TiO ₂ / TiN / TiO ₂ / ZrBxOy (/ intermediate film), and the like. The visible light transmittance of the absorption film may increase due to oxidation (for example, TiN partially becomes TiO ₂ ), but according to this configuration, the oxidation of the absorption film is prevented.

It goes without saying that in the above-mentioned respective film configurations, other films may be interposed between the respective films, or between the films and the glass, etc. for the purpose of improving adhesiveness, adjusting optical performance and the like.

As the method for forming the functional film 4 described above, a spray method, a vacuum deposition method, a DC sputtering method, a CVD method, or the like can be used, but if the productivity and the film performance are taken into consideration, the DC sputtering method can be used. The film is preferably formed by the method.

When manufacturing a curved laminated glass having such a functional film, in addition to a method of forming a glass plate into a desired shape in advance before forming the film, the film is formed in advance. It can also be performed later by a method of shaping the glass plate into a desired shape.

In the present invention, the glass plates 1 and 2 are not particularly limited, and soda lime silicate glass plate, aluminosilicate glass plate, borosilicate glass plate, lithium aluminosilicate glass plate and the like can be used. Of these, soda lime silicate glass plate that is easily available at low cost is preferable. Further, a heat ray absorbing glass plate added with nickel, chromium, cobalt, iron, selenium or the like can also be used.

PVB (polyvinyl butyral) is used as the plastic intermediate film 3 used when joining the glass plates 1 and 2.
Alternatively, EVA (ethylene-vinyl acetate copolymer), urethane, etc. can be used, but when forming laminated glass for automobiles, it is preferable to use PVB having good penetration resistance and durability.

In the above description, the laminated glass having two glass plates has been described as an example, but the present invention can be applied to a laminated glass having three or more glass plates if necessary. When used for automobiles, the functional film 4
Is preferably formed on the joint surface of the glass plate positioned on the outermost side of the vehicle, which is located on the outer side of the vehicle.

Since the present invention is configured in this way, the function of the film 8 of Eg ≧ 4 eV formed on the surface in contact with the intermediate film 3 causes a white turbidity due to oxidation in the functional film, such as Ag. When a metal is contained, such white turbidity can be effectively suppressed.

Further, in the case where the functional film contains a material such as an absorption film whose transmittance is increased by oxidation, the present invention can prevent such an increase in transmittance.

In addition to the above effects, the present invention has the same Eg ≧ 4e as the present invention.
According to the structure in which the V film 8 is in contact with the intermediate film,
It was also found that there is an effect that the adhesive force between the functional film 4 and the intermediate film 3 does not change over time for a long period of time.

This is considered to be due to the following reasons.
That is, taking ZnO with Eg <4 eV as an example, between the ZnO and the intermediate film, for example, the PVB film, hydrogen on the surface of the intermediate film and Z
nO has a hydrogen-bonding force with oxygen, and Zn-O ...
It is linked like H-O (intermediate film), and ZnO is reduced by moisture and UV irradiation to reduce ZnO as in the above reaction.
When the bond is broken, it is considered that the hydrogen bond may not contribute to the adhesive force with the interlayer film. IT
Taking O (tin-doped indium oxide) as an example, In
It is considered that hydrogen bonding bonds such as —O ... H—O (intermediate film) are reduced and the In—O bonds are broken, so that they do not contribute to the adhesive force. The same applies to SnO _{2 and the} like. However, by using a film having an energy gap Eg ≧ 4 eV as a layer in contact with the intermediate film as in the present invention, such a film is not reduced even by UV light,
It is considered that the adhesive strength is maintained for a long time because no change occurs.

The laminated glass has been described above as an example of the laminated body of the present invention, but the laminated glass structure of the present invention can also be applied to a two-layer type laminated body including a glass plate and a plastic film. That is, it can be applied to a laminated body having a structure of glass / functional film / plastic film, and having a film having an energy gap of 4 eV or more as a layer in which the functional film is in contact with the plastic film. The plastic film may be a single plastic film made of the same material as the plastic intermediate film 3 or may be a multilayer film. For example, it may be composed of two layers such as (glass / functional film /) energy absorbing layer / self-healing layer. The energy absorbing layer and the self-repairing layer may be made of various urethanes, for example. Such an energy absorption layer is used to absorb a shock in an accident or the like and to impart good penetration resistance. A plastic film such as a polyethylene terephthalate film or a nylon film may be used instead of the self-repairing layer.

 Examples of the present invention will be described below.

[Examples] Various functional films were formed on a glass plate by a sputtering method and bonded to another glass plate via PVB to form a laminated glass. Table 1 shows the appearance of each of the laminated glasses after UV irradiation for 100 hours.

* 1 in Table 1 is the energy gap (Eg) of the layer in contact with PVB.

As is clear from Table 1, when the Eg of the layer in contact with the intermediate film is 4 eV or more as in the present invention, there is no change in appearance, and when the film of Eg <4 eV is in contact with the intermediate film. Was observed to be cloudy.

Furthermore, with respect to Samples 1 to 10 (Example), even when the UV light was irradiated for 1000 hours, the initial adhesive strength was hardly changed. On the other hand, with respect to Samples 11 to 14 (Comparative Examples), a slight change in the adhesive strength was observed after irradiation with UV for 1000 hours.

[Effects of the Invention] As described above, according to the present invention, in a laminate in which a functional film is formed between an intermediate film and glass, a film having Eg ≧ 4 eV is used as a layer in contact with the intermediate film. Is not reduced by UV light and the moisture contained in the interlayer film, and therefore, when the functional film contains a metal that becomes cloudy due to oxidation or an absorption film that increases transmittance, Even if it exists, it is possible to prevent such cloudiness and increase in transmittance, and it is possible to provide a stable laminate that does not change for a long period of time.

Further, the laminate of the present invention does not change in adhesive strength over a long period of time and has high long-term reliability.

INDUSTRIAL APPLICATION This invention can implement | achieve the laminated body which formed the functional film which has a desired function and which was excellent in long-term reliability, and it is suitable not only for construction but especially for the application for vehicles where reliability is required. Can be used.

[Brief description of drawings]

1 and 2 are longitudinal sectional views showing an embodiment of a laminated body according to the present invention. FIG. 3 is a longitudinal sectional view showing an example of a conventional laminated glass. FIGS. 4 (a) and 4 (b) show the results of ESCA measurement of the surface states of the ZnO film and the TiO ₂ film in contact with the intermediate film before and after UV light irradiation for 1000 hours and 100 hours, respectively. 1,2 …… Glass plate, 3 …… Plastic film, 4 …… Functional film, 5,7,15,17 …… Dielectric film, 6,16,24 …… Metal film, 8 …… Eg ≧ 4eV film

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Claims (2)

[Claims] 1. At least one glass plate, and a plastic film bonded to the glass plate, wherein the bonding surface between the glass plate and the plastic film is a single layer or a plurality of layers containing a metal film. Which is a film having an energy gap of 4 eV or more, and which is selected from the following (a) to (f): A laminated body, which is a film that is formed. (A) SiO _x , Ta ₂ O ₅ ,, NiO, Ga ₂ O ₃ ,, Sb ₂ O ₃ , MgF ₂ , LiF, CaF ₂ ,, LaF
_At least one of Ce and CeF ₃ , (b) a film in which at least one of Ti, Ta, Hf, Mo, W, Nb, Sn, La, and Cr is added to SiO ₂ , (c) ) At least one of Zr, Ti, Hf, Sn, Ta, In and B
And (d) an oxide film containing at least one of Si and (d) an oxide containing Zr and B (ZrB _x O _y ), wherein the atomic ratio x of B to Zr in the film is 0.05 ≦ x ≦. 3 and film atomic ratio y for Zr of oxygen in the film is 2 ≦ y ≦ 6.5, (e ) an oxide containing Zr and Si a (ZrSi _x O _y) film, the Si in the film A film having an atomic ratio x to Zr of 0.05 ≦ x ≦ 19 and an atomic ratio y of oxygen in the film to Zr of 2.1 ≦ y ≦ 40, (f) an oxide containing Zr, B and Si (ZrB _x Si _y O _z ) film, wherein the atomic ratio x of B to Zr, the atomic ratio y of Si to Zr, and the atomic ratio z of oxygen to Zr in the film are 0.05 ≦ x + y ≦
A film of 19 (however, excluding the composition of x + y-3> 0 and x-3y + 1> 0), and 2 <z <40. 2. At least one glass plate and a plastic film bonded to the glass plate, and at least a nitride, boride, or carbide is formed on the bonding surface between the glass plate and the plastic film. A laminated body provided with a functional film consisting of a single layer or a plurality of layers including an absorption film made of one kind, wherein the layer in contact with the plastic film in the functional film is a film having an energy gap of 4 eV or more, and A laminated body, which is a film selected from the following (a) to (f). (A) SiO _x , Ta ₂ O ₅ ,, NiO, Ga ₂ O ₃ ,, Sb ₂ O ₃ , MgF ₂ , LiF, CaF ₂ ,, LaF
_At least one of Ce and CeF ₃ , (b) a film in which at least one of Ti, Ta, Hf, Mo, W, Nb, Sn, La, and Cr is added to SiO ₂ , (c) ) At least one of Zr, Ti, Hf, Sn, Ta, In and B
And (d) an oxide film containing at least one of Si and (d) an oxide containing Zr and B (ZrB _x O _y ), wherein the atomic ratio x of B to Zr in the film is 0.05 ≦ x ≦. 3 and film atomic ratio y for Zr of oxygen in the film is 2 ≦ y ≦ 6.5, (e ) an oxide containing Zr and Si a (ZrSi _x O _y) film, the Si in the film A film having an atomic ratio x to Zr of 0.05 ≦ x ≦ 19 and an atomic ratio y of oxygen in the film to Zr of 2.1 ≦ y ≦ 40, (f) an oxide containing Zr, B and Si (ZrB _x Si _y O _z ) film, wherein the atomic ratio x of B to Zr, the atomic ratio y of Si to Zr, and the atomic ratio z of oxygen to Zr in the film are 0.05 ≦ x + y ≦
A film of 19 (however, excluding the composition of x + y-3> 0 and x-3y + 1> 0), and 2 <z <40.