JPH0338278A - Preparation of ultrathin film laminate - Google Patents

Abstract

PURPOSE:To continuously and easily prepare a ultrathin film laminate by bringing the ultrathin film formed by developing a polymer solution on the surface of the water into contact with the surface of a temporary support preliminarily coated with a liquid and subsequently transferring the same to the surface of a solid substrate. CONSTITUTION:A liquid supply tank 18 storing a liquid 11 is provided at a position before the contact of a ultrathin film 5 with a temporary support base material 9 and a coating roll 10 is provided in the liquid supply tank 18 so that at least the roll part thereof is brought into contact with the liquid 11 and the surface of the temporary support base material 9. By rotating the coating roll 10, the liquid 11 is adhered to the surface of the coating roll 10 and applied to the surface of the temporary support base material 9. Subsequently, the ultrathin film 5 is temporarily laminated to the coating surface of the base material 9 and finally laminated to the surface of a solid substrate 20. Therefore, the homogenous ultrathin film laminate of the solid substrate 20 can be continuously prepared by the support base material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an ultra-thin film laminate in which a uniform ultra-thin film is formed on a solid substrate.

[Conventional technology]

Several methods have already been proposed and put into practice for producing ultra-thin films. In particular, the method for producing the thinnest ultra-thin film is a method in which a thin film is deposited on the surface of a supporting liquid, and is a discontinuous method similar to the method for producing monomolecular thin films using the Langmuir-Prodgett method, which has two partition rods that partition the liquid surface. The manufacturing method is mentioned (JP-A-50-41958, JP-A-51-8).
No. 9564 (described in Japanese Patent Publication No. 9564), and a method in which the above-mentioned discontinuous manufacturing method has been improved to a continuous manufacturing method is described in U.S. Pat.

[Problem to be solved by the invention]

Regarding the above discontinuous production method, it is ultimately possible to produce ultra-thin films in a monomolecular state such as the Langberry Nier-Blodgett film, but from an industrial standpoint such as production, the above continuous film production method is The continuous film forming method is useful, and especially in order to obtain long ultra-thin films. However, all of the currently proposed continuous film forming methods are methods that can only be applied when the supporting base material of the ultra-thin film is a flexible film-like base material, and the supporting base material is a solid substrate, especially a large area solid material. It is not possible to continuously and uniformly stack ultra-thin films on a substrate.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for continuously and easily manufacturing an ultra-thin film laminate in which ultra-thin films are homogeneously laminated on a fixed substrate.

[Means to solve the problem]

In order to achieve the above object, the method for producing an ultra-thin film laminate of the present invention involves spreading a polymer solution on a water surface to form an ultra-thin film, bringing this ultra-thin film into contact with the surface of a temporary support substrate, and then ,
In a method for manufacturing an ultra-thin film laminate in which an ultra-thin film is attached and integrated by transfer to the surface of a solid substrate, a liquid is applied to the surface of the temporary support substrate before the ultra-thin film is brought into contact with the surface of the temporary support substrate. The structure is as follows.

[Effect]

That is, the present inventors have conducted a series of studies in order to obtain an ultra-thin film laminate in which ultra-thin films are uniformly stacked on a solid substrate. As a result, first, before bringing the ultra-thin film formed on the water surface into contact with the surface of the temporary support substrate and temporarily laminating it, when a liquid was applied to the surface of the base material in contact with the ultra-thin film, the layer was laminated on the temporary support substrate. The present invention was achieved by discovering that an ultra-thin film can be easily transferred to a solid substrate as a supporting and supporting base material. In the above manufacturing method, by controlling the amount of liquid applied to the temporary support base material, even extremely thin films can be uniformly transferred and laminated onto the solid substrate.

In particular, by using a liquid with relatively low volatility as the liquid applied to the surface of the temporary support substrate, the ultra-thin film temporarily laminated on the surface of the temporary support substrate can partially adhere directly to the temporary support substrate. It is possible to uniformly transfer the image onto a solid substrate without any problems. In addition, by applying the liquid in a predetermined pattern to the temporary support base material, only the ultra-thin film in the predetermined portion where the liquid has been applied is transferred and laminated onto the solid substrate, making it possible to layer the ultra-thin film in a pattern onto the solid substrate. becomes.

The polymer solution used in this invention is obtained using a polymer and a developing solvent.

Examples of the above-mentioned polymers include all those that can form a thin film by a water surface development method.For example, polyolefin polymers such as polybutene, polypentene, polymethylpentene, and polyhexene, cellulose derivatives such as cellulose acetate and nitrocellulose, Halogenated vinyl polymers such as polyvinyl fluoride, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, acrylic polymers such as polymethyl methacrylate and polyethyl methacrylate, aromatic and aliphatic polyamides, various polyamides and their precursors Examples include boria fruit acid, polystyrene, polycarbonate, polyorganosiloxane and its derivatives, and liquid crystal polymers.

Further, the developing solvent is not particularly limited as long as it is an organic solvent that dissolves the polymer. however,
When sufficient water surface developability cannot be obtained with one type of solvent, it is also effective to add a second organic solvent as a development aid. Such developing aids include aliphatic, cycloaliphatic or aromatic ketones, esters, alcohols, amines,
Examples include aldehydes, peroxides, and mixtures thereof.

The above polymer (A) and developing solvent (including developing aid) (B
) is A/B=0.5/99.5 by weight.
It is preferable to set it to 30/70.

The method for manufacturing the ultra-thin film laminate of the present invention is carried out, for example, as follows. That is, as shown in FIG. 1, the polymer solution is discharged onto the water surface 4 in the water tank 3 from the nozzle 2 of the metering pump 1 filled with the polymer solution, and the ultra-thin film 5 formed on the water surface 4 is 1st゜2nd. By means of the third roller 6.7.8, it is applied to the substrate surface of the sheet-like temporary support substrate 9 that moves continuously in the six directions of the arrows. Next, the temporary support base material 9 on which the ultra-thin film 5 is temporarily laminated is brought into contact with the surface of the solid substrate 20 adhered to the lower surface of the sheet-like base material 19 moving in the direction of arrow B on the roller 8, and the solid Ultra-thin film 5 on the surface of the substrate 20
This is done by transferring the . In such a continuous film forming method, the liquid 11 is applied between the first roller 6 and the second roller 7, that is, before the ultra-thin film 5 contacts the temporary support base 9, as shown in the figure. A liquid supply tank 18 is installed to store the liquid, and a coating roll 10 is installed in the liquid supply tank 18 so that the roll portion contacts at least the liquid 11 and the surface of the temporary support base 9 . Then, by rotating the coating roll 10, the coating roll 1
The liquid 11 in the liquid supply layer 18 adheres to the surface of the temporary support base material 9, and the liquid 11 is applied to the surface of the temporary support base material 9. In this way, in the above manufacturing method, when laminating the ultra-thin film 5 on the solid substrate 20,
First, the liquid 11 is applied to the surface of the temporary support base material 9, and the ultra-thin film 5 is temporarily laminated on the coated surface, and then the ultra-thin film 5 is laminated on the surface of the solid substrate 20, so that the support base material is the same as the solid substrate 20. A homogeneous ultra-thin film laminate can be continuously produced, which is the greatest feature of the present invention.

Note that the moving speed of the solid base t7i20 is preferably the same as the moving speed of the temporary support base material 9.

That is, if the moving speeds of the two are different from each other, wrinkles, cracks, etc. will occur in the ultra-thin film 5 transferred onto the solid substrate 20.

Furthermore, the solid group I! i! The 20 migration methods are as follows:
As shown in the figure, a method of attaching the solid substrate 20 to the surface of the sheet-like base Fi 19 by adhesion or suction or the like and transferring the sheet-like base material 19 can be mentioned, but the method is not particularly limited to this.

Further, the material for forming the coating roll IO is not particularly limited, but for example, resin, glass, or metal can be used. Furthermore, a porous material can be used to easily impregnate the liquid 11. Also, the surface of the coating roll 10 may be a smooth surface or an uneven surface.

The liquid applied to the temporary support base material 9 may be water or various organic solvents, which do not dissolve the ultra-thin film type 5 material and the support base material 9, and especially have a boiling point. It is preferable to use a liquid of 80°C or higher; in other words, if the boiling point is lower than 80°C, the liquid will volatilize and the temporary This is because the supporting base material 9 and the ultra-thin film 5 come into direct contact with each other, making it impossible to transfer the ultra-thin film 5 to the solid substrate 20 well.

Examples of the organic solvents mentioned above include alcohols such as isopropyl alcohol, butyl alcohol, glycerin, :L ketone glycol, ketones such as methyl isobutyl ketone and cyclohexanone, esters such as butyl acetate and propyl acetate, benzene, toluene, xylene, and liquid Hydrocarbons such as paraffin, methoxyethanol, ethoxyethanol.

Examples include polyfunctional compounds such as diethylene glycol and diethylene glycol monomethyl ether, polar solvents such as dimethylacetamide, dimethylformamide, and dimethyl sulfoxide, and the like.

These organic solvents may be used alone, or the temporary support base 9
Two or more types may be used in combination to improve uniform coating properties.

The amount of the liquid 11 applied to the temporary support base material 9 is as follows:
It is preferable to set the amount to 0.1 to 10 g/rrr. In other words, if the amount of the liquid 11 applied is less than 0.1 g/rrr, the uniform coating property of the liquid 11 may deteriorate or the liquid 11 may partially volatilize. As a result, the ultra-thin film 5 comes into direct contact with the temporary support base material 9. On the other hand, the amount of application is Loglof
This is because if it exceeds this, the temporarily laminated ultra-thin film 5 may peel off unevenly from the temporary support base material 9.

Examples of the temporary support base material 9 on which the ultra-thin film 5 as described above is temporarily laminated include plastic films, metal foils, film materials, and the like.

Further, examples of the solid substrate 20 on which the ultra-thin film 5 temporarily adhered to the temporary support base material 9 is attached and integrated include a glass plate, a transparent electrode plate, an inorganic crystal plate, a metal plate, a plastic plate, and the like.

In addition, as a method of pre-coating the liquid 11 on the surface of the temporary support base material 9, in addition to the method of coating by providing a coating roll 10 and a liquid supply tank 18, which are a liquid coating device as shown in FIG. 1, for example, One example is a method of applying the liquid 11 using a porous roll 12 whose outer peripheral layer is made of an elastic plastic material, as shown in FIG. 2(A). In the porous roll 12, a hollow metal shaft body 12a is used. This shaft body 12a has a porous roll 1
Holes 12b are formed at predetermined intervals only in the portion forming the shaft body 12, and when in use, the liquid 11 is directed into the shaft body 12a in the direction of the arrow X.
It flows into the porous roll 1 through the hole 12b in the direction shown in
2 is carried out. Then, the liquid 11
As shown in FIG. 2(B), the porous roll 12 impregnated with The liquid 11 is applied to the surface of the temporary support base material 9 by rotating.

Furthermore, as a method of applying the liquid 11 on the surface of the temporary support base material 9 in advance, for example, a method of applying the liquid 11 using an apparatus as shown in FIG. 3 can be mentioned. That is, liquid 1
A liquid supply tank 18 containing 1 is installed. Then, one end of the porous sheet 13 is immersed in the liquid supply tank 18, and the other end is brought into contact with the surface of the temporary support base material 9. In this way, by immersing one end of the porous sheet 13 in the liquid 11, the liquid 11 reaches the other end of the porous sheet 13 due to capillary action.
The liquid 11 is applied to the surface of the temporary support base 9 in contact with the liquid 11 . As shown in FIG. 4, instead of the liquid supply tank 18, a metering pump 14 filled with the liquid 11 is used, and one end of the porous sheet 13 is attached to the stationary pump 14 to quantitatively feed the liquid 11 into the porous pores. sex sheet 1
The method of applying the liquid 11 to the surface of the temporary support base material 9 using such a metering pump 14 and the porous sheet 13, which may be supplied to the liquid 11 as shown in FIG. be exposed. In addition, as the porous sheet 13,
Various porous materials such as paper, cloth, and nonwoven fabrics can be used, but materials that do not dissolve in the liquid 11 are preferable.

Further, as still another method of applying the liquid 11 on the surface of the temporary support base material 9 in advance, for example, as shown in FIG. The liquid 11 is applied by performing a series of steps in which a guide roll 16 is provided, the temporary support base material 9 is immersed in the liquid 11, and then the temporary support base material 9 coated with the liquid 11 is passed through the guide roll 17. Here is a method. Alternatively, as shown in FIG. 6, there is a method in which a spraying device 21 is installed in the liquid supply tank 18 and the liquid 11 is applied in advance by spraying the liquid 11 in the form of a mist onto the surface of the temporary support base 9. can give.

In the above manufacturing method, the liquid 11 is applied to the temporary support base material 9.
By applying the coating in a predetermined pattern, the transfer stacking of the ultra-thin film 5 onto the solid substrate 20 can be patterned. The method of applying the liquid 11 in a pattern to such a temporary support base material 9 is not particularly limited, but for example, applying the liquid 11 as shown in FIGS. 1 and 2 (A) may be used. Application roll 10 or application roll 12
In the case of applying liquid 11 at regular intervals, the application roll 10.12 is brought into contact with the temporary support base 9 intermittently.
-'t- coating method, screen printing method, and various inkjet printing methods are used.

In this way, the position where the liquid 11 is applied in advance to the surface of the temporary support base material 9 using the above-mentioned various devices can be set before the ultra-thin film 5 developed and generated on the water surface 4 comes into contact with the surface of the temporary support base material 9. Although not particularly limited, contact between the temporary support base material 9 and the ultra-thin film 5 (
In other words, if the coating device for the liquid 11 is too far away from the point of contact between the temporary support base material 9 and the ultra-thin film 5, the liquid 11 applied to the surface of the temporary support base material 9 will be This is because it will volatilize before it comes into contact with the thin film 5, making it difficult to obtain the effects of the present invention.

Note that the liquid 11 adhering to the surface of the ultra-thin film 5 transferred onto the solid substrate 12 may be vaporized by heating and drying as necessary, or may be washed with a volatile solvent or the like and then dried. It may be vaporized.

〔Effect of the invention〕

As described above, in the method for producing an ultra-thin film laminate of the present invention, before the ultra-thin film formed on the water surface is brought into contact with the surface of the temporary support base material, a liquid is applied to the surface of the temporary support base material that will be in contact with the ultra-thin film. After coating and temporarily laminating on a temporary support base material, the ultra-thin film is transferred to the solid substrate and integrated, so the ultra-thin film is evenly transferred onto the solid substrate to produce a homogeneous ultra-thin film laminate. can do. Therefore, in the above manufacturing method, a homogeneous ultra-thin film laminate can be easily manufactured, especially on a large solid substrate. Further, by applying the liquid to the surface of the temporary support base material in a predetermined pattern, it becomes possible to transfer the ultra-thin film to the solid substrate in a pattern.

Next, examples will be described together with comparative examples.

[Example 1] A stainless steel water tank 3 having a width of 60 C1 and a length of 100 cm as shown in FIG. 1 was prepared, and was filled with ion-exchanged water as a supporting liquid. Also, as a polymer solution, 3.
0.1 mole of 3',4.4'-biphenyltetracarboxylic dianhydride and 0.1 mole of 2.2-(4,4'-bis(p-aminophenoxy)diphenyl]hexafluoropropane.
at a concentration of 25 in dimethylacetamide using 1 mol.
% by weight of polyamic acid was synthesized. The polyamic acid thus obtained was adjusted to have a polymer concentration of 5% by weight, dimethylacedo/acetophenone = 1/l (weight ratio), and the polyamic acid solution was pumped into a metering pump.
The polyamic acid was supplied to the water surface from the nozzle 2 and discharged onto the water surface 4 at a flow rate of 1.0 m/sin to form a film with a film thickness of 100 mm.
Film 5 was produced. Next, as a temporary support base material, a thickness of 25μ
- the polyethylene terephthalate (PET) film 9 of the first. 12 by the second and third rollers 6.7.8
While continuously moving at a speed of m/sin, the above-mentioned produced boria fruit acid ultra-thin film 5 was brought into contact and an ultra-thin polyamic acid film was temporarily laminated thereon. In the temporary lamination step, as shown in FIG. 1, a toluene supply tank 18 containing toluene 11 is installed at a position approximately 10 CI+ above the point of contact between the produced polyamic acid ultra-thin film 5 and the PET film 9, and In the toluene supply tank 18, P is in contact with the toluene 11.
A sponge-like roll 10 was provided so as to be in contact with both sides of the ET film 9. And the above sponge-like roll lO
By rotating the sponge roll IO, toluene 11 was impregnated with toluene 11, and toluene 11 was applied to the surface of the PET film 9 at a coating rate of approximately 1 g/ryf. Next, the boria super thin film 5 laminated on the PET film 9 coated with toluene 11 is transferred to the PET film 9 by the 30th layer 8 at a uniform speed, forming a striped transparent electrode group Fi.
(Electrode width 200um+.

The polyamic acid ultra-thin film 5 was transferred onto the transparent electrode substrate 20 in contact with the surface of the transparent electrode substrate 20 (with an interval of 50 um, 30 m x 40 ann), and was adhered and integrated to produce an ultra-thin polyamic acid film laminate.

The point where the solvent in the polyamic acid solution spread on the water surface is approximately 40 CIl away from the polyamic acid solution supply point toward the roller 7, and the ultra-thin boria-acid film 5 is attached to the PET film 9. The point where the polyamic acid solution is attached and integrated is approximately 80 cm from the polyamic acid solution supply point to the roller 7 side.
It is a remote location.

[Comparative example]

Luene was not applied to the surface of PET FUSIFIL 19.

Other than that, the ultra-thin polyamic acid film was transferred to the transparent electrode substrate in the same manner as in Example 1.

[Example 2] A transparent electrode substrate was formed by using a silicon wafer (3 inches in diameter (7,
62C11)), the toluene in the liquid applied to the temporary support substrate 9 was replaced with isopropyl alcohol, and the amount of liquid applied was changed from 1 g/nf to 3 g/rrf. Except for the above, a polyamic acid ultra-thin film laminate was produced in the same manner as in Example 1.

[Example 3] Polyamic acid solution, which is a polymer solution, is mixed with a cyclohexene solution of polymethylpentene at a concentration of 5% by weight, PET film is coated with aluminum foil, and liquid toluene to be coated on a temporary support substrate is mixed with diethylene glycol monomethyl ether. Furthermore, the transparent electrode substrate is made of glass T7i (120asX 1
20m). In addition, the amount of the polymer solution supplied onto the water surface was set to 1. Od/+win, and the film forming speed was changed to 5 m/inch. Other than that, a laminate in which ultra-thin polymethylpentene films having a thickness of 300 mm was laminated was obtained in the same manner as in Example 1.

[Example 4] A polyamic acid solution, which is a polymer solution, was added to a cyclohexanone solution of polyvinyl chloride with a concentration of 10% by weight, a PET film was added to a polypropylene film (thickness 50 μm), and the liquid to be applied to the polypropylene film was added to toluene. A transparent electrode substrate was placed on a polymethacrylate plate (thickness: 5 aam, 150 aa x 150 aa) in liquid paraffin.
m) was replaced. In addition, the supply amount of the polymer solution onto the water surface was 1.3 urn/win, and the film forming speed was 13 m/s.
Changed to in. Other than that, the thickness was 4 as in Example 1.
A laminate in which ultra-thin polyvinyl chloride films were laminated was obtained.

[Example 5] As a method of applying toluene 11 to the PET film surface 9, as shown in FIG. A method was used in which toluene 11 was applied in an amount of 2 g/rrf with the end touching the surface of PET film 19.

Furthermore, the size of the transparent electrode substrate was changed from 30 tm x 40 mm to 300 m x 200 m. Other than that, a polyamic acid ultra-thin film laminate was obtained in the same manner as in Example 1.

[Example 6] PET film 19 surface sopropyl alcohol 11
As shown in FIG. 6, a spraying device 15 is installed in a liquid supply tank 18 that stores isopropyl alcohol 11, and isopropyl alcohol 11 is applied to PET.
A method was used in which the surface of FUSIFIL 19 was sprayed at a rate of 13 g/sin. Other than that, a polyamic acid ultra-thin film laminate in which the solid substrate was a silicon wafer was obtained in the same manner as in Example 2.

[Example 7] As a method of applying diethylene glycol monomethyl ether 11 to the surface of aluminum foil 9, as shown in FIG.
A method is used in which one end of the polyester nonwoven fabric 13 is attached as a porous sheet to a metering pump 14 filled with diethylene glycol monomethyl ether 11, the other end is brought into contact with the surface of aluminum foil 9, and diethylene glycol monomethyl ether 11 is applied at a coating rate of 11 g/rd. there was. Other than that, the polymethylpentene ultra-thin film 5 was transferred onto a glass plate in the same manner as in Example 3 to produce an ultra-thin film laminate. Note that the amount of diethylene glycol monomethyl ether 11 supplied to the polyester nonwoven fabric 13 was 7 g/sin.

[Example 8] As a method of applying toluene 11 to a PET film 9, as shown in FIG.
A method was used in which toluene 11 was applied in a pattern of 150 m x 100 squares by contacting the PET film 9 at regular intervals. Further, the ultra-thin polyamic acid film 5 was transferred by setting the toluene 11 applied portion to be located at the center of the transparent electrode substrate. Furthermore, PET
The amount of toluene 11 supplied to the film 9 is 0.6 g/r.
It was set as yf. Except for the above, a polyamic acid ultra-thin film laminate was produced in the same manner as in Example 5.

[Example 9] The isopropyl alcohol in the liquid applied to the temporary support base material 9 was replaced with methanol. Except for the above, a polyamic acid ultra-thin film laminate was produced in the same manner as in Example 2.

The stacking states of the example products and comparative products thus obtained were visually evaluated, and the results are shown in the table below.

(Left below) Book 1: Center part 15 of a 300m x 200m transparent electrode substrate
The ultra-thin film was laminated only on the 0m+X100m area.

*2: However, since methanol is relatively volatile,
In some cases, some parts were not transferred.

From the results in the above table, it can be seen that the ultra-thin films were uniformly and satisfactorily laminated on the solid substrate in all of the example products. However, in the comparative product, since the ultra-thin film was in close contact with the temporary support base material, transfer and lamination onto the solid substrate was not performed and an ultra-thin film laminate could not be obtained.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing one embodiment of the present invention, and FIG. 2 (A
) is a vertical cross-sectional view of a porous roll used in another embodiment of the present invention, FIG. 2(B) is a partial explanatory diagram showing a liquid application method using the roll, and FIG. FIG. 4, FIG. 5, and FIG. 6 are partial explanatory views showing a liquid applying method according to another embodiment of the present invention. 1... Metering pump 2... Nozzle 3... Water tank
4...Water surface 5...Ultra-thin film 9...Temporary support base material
10... Application roll 11... Liquid 18... Liquid supply tank 20... Solid substrate

Claims (9)

[Claims] (1) A polymer solution is spread on the water surface to form an ultra-thin film, this ultra-thin film is brought into contact with the surface of a temporary support substrate, and then transferred to the surface of a solid substrate to adhere and integrate the ultra-thin film. A method for producing an ultra-thin film laminate, which comprises applying a liquid to the surface of the temporary support substrate before bringing the ultra-thin film into contact with the surface of the temporary support substrate. (2) The amount of liquid applied to the surface of the temporary support base material is 0.
The method for producing an ultra-thin film laminate according to claim 1, wherein the thickness is 1 to 10 g/m^2. (3) The method for producing an ultra-thin film laminate according to claim (1) or (2), wherein the liquid applied to the surface of the temporary support substrate has a boiling point of 80°C or higher. (4) Any one of claims (1) to (3), wherein the application of the liquid to the surface of the temporary support base material is performed by bringing a roll with the liquid adhered to the roll surface into contact with the surface of the temporary support base material. The method for producing an ultra-thin film laminate described in Section 1. (5) Any one of claims (1) to (3), wherein the application of the liquid to the surface of the temporary support base material is performed by bringing a porous sheet impregnated with the liquid into contact with the surface of the temporary support base material. A method for producing an ultra-thin film laminate described in . (6) The ultra-thin film laminate according to any one of claims (1) to (3), wherein the application of the liquid to the surface of the temporary support base material is performed by immersing the temporary support base material in the liquid. Manufacturing method. (7) The liquid according to any one of claims (1) to (3), wherein the liquid is applied to the surface of the temporary support base material by spraying the liquid in a mist onto the surface of the temporary support base material. Method for manufacturing thin film laminates. (8) The temporary support base material is a plastic film, a metal foil,
The method for producing an ultra-thin film laminate according to any one of claims (1) to (7), which is a film material. (9) Claims (1) to (9) wherein the solid substrate is a glass plate, a transparent electrode plate, an inorganic crystal plate, a metal plate, or a plastic plate.
8) The method for producing an ultra-thin film laminate according to any one of item 8).