JPH0396348A - Manufacture of extrathin film laminate - Google Patents

Abstract

PURPOSE:To continuously manufacture an extrathin film laminate of a homogeneous state on a solid substrate even if a supporting base material is the substrate by temporarily laminating an extrathin film formed on water surface once in contact with the surface of a temporarily supporting base material, then transferring the film to the substrate, and integrally adhering it. CONSTITUTION:Polymer solution is discharged from a nozzle 2 of a quantitative pump 1 on water surface 4 in a water tank 3, and an extrathin film 5 formed on the surface 4 is adhered to the surface of a sheetlike temporarily supporting base material 9 continuously fed by rollers 6, 7, 8 in a direction of an arrow A. Then, the material 9 temporarily laminated with the film 4 is brought into contact with the surface of a solid substrate 10 adhered to the lower surface of a sheetlike bass material 11 fed between the roller 8 and a retaining roller 12 in a direction of arrow B to transfer the film 5 to the surface of the substrate 10. When the material 9 is once introduced into water and removed from the water through the roller 7, the film 5 is temporarily laminated on the surface of the material 9. Accordingly, a water layer is formed therebetween, and not brought into close contact therewith. Accordingly, the film 5 can be easily transferred to the substrate 10.

Description

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

[Prior Art] Several methods for producing ultra-thin films have already been proposed and put into practice. In particular, the method for manufacturing the thinnest ultra-thin film is to deposit a thin film on the surface of a supporting liquid, using a discontinuous method similar to the Langmuir-Blodgett method for manufacturing monomolecular thin films using two partition rods that separate the liquid surface. The manufacturing method is mentioned (JP-A-50-41958, JP-A-51-8).
(described in Publication No. 9564). Further, the above-mentioned discontinuous manufacturing method has been improved to a continuous manufacturing method as described in US Pat.

[Problem that the invention seeks to solve]

Although the discontinuous manufacturing method described above can ultimately produce ultra-thin monomolecular films such as the Langmuirb jet film, from an industrial standpoint such as production, the continuous film manufacturing method described above is The continuous film forming method is useful, and especially in order to obtain long ultra-thin films. However, although the currently proposed continuous film forming method can easily produce a uniform ultra-thin film, there are problems in the process of laminating the ultra-thin film grown on the water surface onto the supporting substrate surface. There is. Various attempts are being considered to solve the above problems.

By the way, all of the currently proposed continuous film forming methods are methods that can be applied only when the supporting substrate of the ultra-thin film is a flexible film-like substrate, and cannot be applied to solid substrates, especially large-area solid substrates. It is not possible to continuously and uniformly laminate ultra-thin films.

The present invention was made in view of the above circumstances, and an object of the present invention is to provide a method for continuously manufacturing an ultra-thin film laminate in which ultra-thin films are uniformly laminated on a solid substrate.

[Means for solving problems]

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 generate an ultra-thin film, and once bringing this ultra-thin film into contact with the surface of a temporary support substrate. The structure is such that the layers are temporarily laminated and then transferred onto the surface of a solid substrate.

[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, firstly, the ultra-thin film formed on the water surface is brought into contact with the surface of the temporary support substrate and temporarily laminated, and then when this temporarily laminated ultra-thin film is transferred to the solid substrate surface, the support substrate is transferred to the solid substrate. The present invention was achieved by discovering that an ultra-thin film laminate can be easily obtained. In particular, when an ultra-thin film is laminated when the temporary support substrate is taken out of water, a layer of water is formed between the temporary support substrate and the ultra-thin film, which prevents the transfer of the ultra-thin film onto the solid substrate. becomes very easy.

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

The above-mentioned polymers include all those that can be formed into a thin film by a water surface spreading method. For example, polyolefin polymers such as polyptene, polybentene, polymethylpentene, and polyhexene, cellulose derivatives such as cellulose acetate and nitrocellulose, and vinyl polyfluoride. Vinyl halide polymers such as polyvinylidene difluoride, polyvinyl chloride, and polyvinylidene chloride, acrylic polymers such as polymethyl methacrylate and polyethyl methacrylate, aromatic and aliphatic polyamides, various polyimides and their precursor polyamic acids, and polystyrene. , polycarbonate, polyorganosiloxane and its derivatives, liquid crystal polymer, etc.

The developing solvent is not particularly limited as long as it is an aqueous solvent that dissolves the polymer.

However, if 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,
Examples include alicyclic or aromatic ketone esters, alcohols, amines, aldehydes, peroxides, and mixtures thereof.

The above polymer (A) and developing solvent (including developing aid) (B)
The mixing ratio of ) is A/B=0.5/9 by weight.
It is preferable to set it to 5 to 30/70.

The method for manufacturing the ultra-thin film laminate of the present invention is carried out, for example, as described in the following. That is, the above-mentioned polymer solution is spread on a water surface to form an ultra-thin film, the resulting ultra-thin film is attached to the surface of a temporary support base material, and then the ultra-thin film is transferred onto the surface of a solid substrate. Attachment of the ultra-thin film to the surface of the temporary support substrate and transfer to the surface of the solid substrate are carried out by pouring the polymer solution into the water tank 3 from the nozzle 2 of the metering pump 1 filled with the polymer solution, as shown in the drawing. released onto the water surface 4,
The support base material of the sheet-like temporary support base material 9 is transferred continuously in the direction of the arrow A by the first, second, and third rollers 6, 7.8. Adhere to the surface.

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 IO adhered to the lower surface of the sheet-like base material 1l, which moves between the rollers 8 and the press rollers 12 in the direction of arrow B. The ultra-thin film 5 is then transferred onto the surface of the solid substrate 10. In such a continuous film forming method, as shown in the figure, the temporary support base material 9 is once introduced into water and when taken out from the water via the rollers 7, the ultra-thin film 5 is temporarily laminated on the surface of the temporary support base material 9. . After such a step, a layer of water is formed between the temporary support base material 9 and the ultra-thin film 5, so the ultra-thin film 5 is not directly in close contact with the temporary support base material 9. Therefore, the next step of transferring the ultra-thin film 5 onto the solid base FilO is easily performed.

In this way, in the above manufacturing method, when laminating the ultra-thin film 5 on the solid substrate 10, the ultra-thin film 5 is first temporarily laminated on the surface of the temporary support base material 9, and then the ultra-thin film 5 is laminated on the surface of the solid substrate IO. Therefore, a homogeneous ultra-thin film laminate whose supporting base material is the solid substrate 10 can be continuously manufactured.

Note that the moving speed of the solid substrate 10 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 10.

Further, as a method of transferring the solid substrate 10, as shown in the figure, the solid substrate 10 is attached to the surface of the sheet-like substrate 11 by a method such as adhesive or suction, and the above-mentioned sheet-like substrate 1
An example of this method is to migrate the data, but the method is not particularly limited to this method.

And super FjIH like above! Examples of the temporary support base material 9 on which the materials 5 are temporarily laminated include a film-like material.

Further, as the solid substrate 10 on which the ultra-thin film 5 temporarily adhered to the temporary support base material 9 is attached and integrated, a plastic plate,
Examples include metal plates, inorganic crystal plates, ceramic plates, and glass plates.

In addition, the ultra-thin B'J5 temporarily laminated on the temporary support base material 9
The roller-shaped material of the roller 8 used to transfer the image onto the solid substrate 10 is not particularly limited, but an elastic material such as metal or resin material can be used. especially,
If there are irregularities on the surface of the solid substrate IO to which the ultra-thin film 5 temporarily laminated on the temporary support base material 9 is attached and integrated, it is preferable to use an elastic body as the shape or material of the roller 8. That is, if a high-hardness roller made of metal or the like is used as the roller 8, if there are irregularities on the surface of the solid substrate IO, the ultra-thin film 5 will not be laminated following the irregularities, and the transfer lamination will not be performed properly.

The elastic body may be one that allows the ultra-thin film 5 to follow the surface of the solid substrate 10 where there are irregularities, and J
Hardness measured by IS-K-6 301 is JrS
．． It is desirable to use rubber with an angle of 50° or less, preferably JIS, 30' or less. For example, diene rubber, olefin rubber, acrylic rubber, urethane rubber. Polysulfide rubber, silicone rubber, fluorine rubber, natural rubber, etc. are used. Alternatively, if the hardness of the elastic body is moderately low, the transfer and lamination properties on the solid substrate 10 are better, and the elastic modulus is 100 kg/mm" or less, preferably 50 kg/mn".
It is desirable to use the following foams: For example, polyethylene foam, polystyrene foam, polyurethane foam. Plastic foams such as vinyl chloride foam, polyvinyl alcohol foam, urea resin foam, epoxy resin foam, phenol resin foam, and rubber foam are used.

The roller-shaped elastic material or material may be used as it is to form the roller 8, or may be wound around the surface of the roller 8. The thickness of the elastic body varies depending on the height of the unevenness on the solid substrate 10 on which the thin film 5 is transferred and laminated, the material of the elastic body, etc., but is more than IM, preferably 1
It is 0 mm or more.

〔Effect of the invention〕

As described above, in the method for producing an ultra-thin film laminate of the present invention, the ultra-thin film formed on the water surface is temporarily laminated by contacting the surface of the temporary support substrate, and then the ultra-thin film is transferred to the surface of the solid substrate. Because of this, even if the supporting base material is solid W+ffl, a homogeneous ultra-thin film laminate can be continuously manufactured on the solid substrate.

Next, examples will be described together with comparative examples.

[Example 1] A stainless steel water tank 3 having a width of 60 cm and a length of loo 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.
3',4.4'-biphenyltetracarboxylic dianhydride O. 1 mole and 0
．． 1 mol of polyamic acid was used to synthesize polyamic acid at a concentration of 10% by weight in dimethylacetamide F. The thus obtained polyamic acid was converted into dimethylacetamide/acetophenone-1/1 (weight ratio) with a polymer concentration of 5%.
This polyamic acid solution is supplied to the metering bomb 1 and applied from the nozzle 2 onto the water surface 4 at a rate of 1.0 ml/mi.
The polyamic acid was discharged at a flow rate of n to produce an ultra-thin polyamic acid film 5 with a thickness of 100 ml. Next, as a temporary support base material, a thickness of 25μ
The polypropylene film 9 of
While continuously moving the film at a speed of 12 m/min using the rollers 6, 7.8, the ultra-thin polyamic acid film 5 was brought into contact with it and temporarily bonded. Next, an indium tin oxide (IT○) vapor-deposited glass plate (30 mm x 40 mm, thickness 3 mm, electrode width 200 mm) was attached to 1 liter of belt-shaped support base material.
μm, interval 50 μm) 10 in the direction of arrow B at a constant speed with the temporary support base material 9, and between the roller 8 and the pressing roller l2, the polyamic acid ultra-thin film 5 is transferred from the temporary support base material 9 to the solid substrate 10. An ultra-thin polyamic acid film laminate was manufactured by transferring and adhering the mixture. The obtained ultra-thin film laminate was one in which the polyamic acid ultra-thin film 5 was uniformly laminated over the entire surface of the solid substrate 10.

[Example 2] A polyamic acid solution, which is a polymer solution, was added to a cyclohexanone solution of polyvinyl chloride with a polymer concentration of 5% by weight.
A silicon wafer (3 inches in diameter (7
．． 62cm>). In addition, the supply rate of the polymer solution onto the water surface was set to 1.5rd/min, and the film forming speed was set to 5m/m.
Changed to in. Other than that, the thickness was 7 as in Example 1.
A laminate in which an ultra-thin polyvinyl chloride film of 0.000% was laminated on a silicon wafer was obtained. The obtained laminate was one in which an ultra-thin polyvinyl chloride film was uniformly laminated over the entire surface of the silicon wafer.

(Example 3) Polyamic acid solution, which is a polymer solution, is cyclohexene of polymethynolebenthene with a concentration of 5% by weight. Add ITO to the liquid
The vapor-deposited glass plate was replaced with a normal glass plate (150+n+nX15
0n+m, thickness 2mm). Further, the amount of the polymer solution supplied onto the water surface was changed to 1.3 ml/min, and the film forming speed was changed to 8 m/min. Other than that, a laminate was obtained in the same manner as in Example 1, in which an ultra-thin polymethylbentene film having a thickness of 300 mm was laminated on a glass plate. The obtained laminate was a polymethylpentene ultra-thin film uniformly laminated on the entire temporary surface of the glass.

[Example 4] ■ TO vapor-deposited glass plates with the same thickness and laminated area of 30 rrm
×40m [ll was changed to 200mn+X200mm.

Other than that, a laminate was obtained in the same manner as in Example 1, in which an ultra-thin polyamic acid film having a thickness of 100 mm was laminated on an ITO vapor-deposited glass plate. In the obtained laminate, the polyamic acid ultrathin film is IT
The O vapor-deposited glass plate was uniformly laminated over the entire surface.

[Comparative example]

An ITO substrate (30 am x 40 mm, thickness 3 mm) is attached to the surface of polypropylene film 9, which is a temporary support base material, between rollers 6 and 7, and the ultra-thin film that is formed directly on the water surface without being laminated by transfer is coated with ITO. Laminated on the substrate. Then, an ultra-thin film laminate was obtained using the same film forming conditions as in Example 1. In this method, the ITO substrate is rolled 7
The uniformity of the ultra-thin film decreased due to vibration of the device and film. Furthermore, many wrinkles were observed in the ultra-thin film in the obtained laminate, and a homogeneous laminate could not be obtained.

[Example 5] Polypropylene foam (elastic modulus 3 kg/+nm", thickness 0 mm) was used as the surface shape material of the roller 8 that transferred the ultra-thin film 5 on the temporary support base material 9 onto the solid substrate 10. ,
Further, as the solid substrate 10 on which the ultra-thin film 5 is laminated, an ITO substrate having lttm irregularities on the laminated surface was used. Other than that, a laminate was obtained in the same manner as in Example 1, in which an ultra-thin polyamic acid film having a thickness of 100 was laminated on a TO substrate having irregularities. The obtained laminate was one in which an ultra-thin polyamic acid film was uniformly laminated over the entire temporary surface of the ITO base.

[Brief explanation of drawings]

The drawings are explanatory diagrams showing one 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...solid substrate

Claims (7)

[Claims] (1) A polymer solution is spread on a water surface to form an ultra-thin film, and this ultra-thin film is temporarily laminated by contacting the surface of a temporary support base material, and then transferred to a solid substrate surface. A manufacturing method for ultra-thin film laminates. (2) Claim (1) wherein the temporary lamination is performed by laminating an ultra-thin film formed on the water surface on the surface of the temporary support base material when the temporary support base material is introduced into water and then taken out from the water surface. ) The method for manufacturing the ultra-thin film laminate described in (3) Claim (1) wherein the temporary supporting base material is a film-like base material.
) or the method for producing an ultra-thin film laminate described in (2). (4) The method for producing an ultra-thin film laminate according to any one of claims (1) to (3), wherein the solid substrate is a plastic plate, a metal plate, an inorganic crystal plate, a ceramic plate, or a glass plate. (5) The ultra-thin film laminate according to any one of claims (1) to (4), wherein the jig used when transferring the ultra-thin film on the temporary support base material onto the solid substrate surface is an elastic body. How the body is made. (6) The method for producing an ultra-thin film laminate according to (5), wherein the elastic body is made of rubber, and the rubber has a hardness of 50° or less as measured according to JIS-K-6301. (7) Claim (5) wherein the elastic body is made of a foam, and the foam has an elastic modulus of 100 kg/mm^2 or less.
) The method for manufacturing the ultra-thin film laminate described in