JPH02180663A - Manufacture of laminate and its device - Google Patents

Abstract

PURPOSE:To manufacture a laminate with good accumulated films efficiently by bringing a base surface into contact with a monomolecular film surface while being retained horizontally and separating off, transferring a monomolecular film section to the base surface and repeating such transfers. CONSTITUTION:When a laminate consisting of a plurality of monomolecular films is manufactured on a base 1, a monomolecular film of a material to be accumulated is formed on the fluid level. Also, a grating-shaped sectioning board 10 having traverse dimension of a through-hole 11 for taking in and out the base 1 surface into the through-hole 11 is applied from above said monomolecular film surface and monomolecular film section substantially equal to the base surface dimension are divided in respective through-hole 11 of the sectioning board 10. The base 1 surface is brought into contact from above and separated off therefrom while being retained horizontally, and the monomolecular film section is transferred to the base 1 surface. The transfer of the monomolecular film section to the base 1 surface is repeated and a plurality of monomolecular films are accumulated on the base.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to the production of a laminate, and more particularly, to a laminate in which a cumulative multilayer film (Langmuir-Prodgett film, LB film) is laminated on a solid substrate. Regarding the body.

[Prior technology] When an amphipathic organic substance that has a parent group and a hydrophobic group in one molecule is dissolved in a folding solvent such as chloroform and spread on the water surface, the solvent evaporates and a film of the organic substance is formed. . When the area of the water surface where the organic film is formed is narrowed with a frame (barrier), the amphipathic molecules will form regular structures on the water surface, with their hydrophilic groups facing the water side and their hydrophobic groups facing the air side. A film with a thickness of one molecule, that is, a monomolecular film, is formed.

A cumulative multilayer film (Langmuir-Prodgett film,
It is called LB film). A laminate in which this cumulative multilayer film is laminated on a solid substrate can be used for various sensors, functional elements, display elements, memory, etc.
It can be applied to recording media, coating materials, liquid crystal alignment films, nonlinear optical elements, insulating films for resist switching elements for ultra-fine patterns, selective transmission films, etc.

Conventionally, a laminate in which a cumulative multilayer film is laminated on a solid substrate is generally manufactured by two methods: a vertical dipping method and a horizontal deposition method. In the vertical immersion method, as schematically shown in Figure 3, the immersed hydrophilic solid substrate 1 is vertically maintained while maintaining a monomolecular film of amphiphilic molecules having hydrophilic and hydrophobic groups on the water surface. The monomolecular film 2 is transferred to the surface of the substrate by pulling it up [FIG. 3(a)], and then the monomolecular film 2 is further transferred to the hydrophobic base surface of the amphiphilic molecules on the substrate by pulling the substrate vertically down [FIG. 3(a)]. FIG. 3(b)), and this process is repeated to obtain a laminate 4 having a cumulative multilayer film 3 [FIG. 3(C)].

If the substrate is hydrophobic, the process is reversed. On the other hand, in the horizontal adhesion method, as schematically shown in FIG. 4, the monomolecular film state is maintained on the water surface, and while the solid substrate 1 is held horizontally, the substrate surface 1 is attached to the monomolecular film 2 on the water surface. The monomolecular film 2 is transferred to the substrate surface by bringing it into contact with the substrate and then pulling it up [Fig. 4(a)].
This process is repeated to obtain a laminate 4 (FIG. 4(b)) having a cumulative multilayer film 3.

[Problems to be Solved by the Invention] However, the vertical immersion method does not necessarily have good working efficiency, and furthermore, there are many restrictions on the material of the substrate due to immersion. In the case of horizontal deposition, there are visible waves on the water surface when the substrate touches and leaves the water surface. This disordered state accumulates on the board, so
The monomolecular film has a disordered structure, and the obtained LB film also exhibits a disordered structure.

Furthermore, in the case of highly fluid monolayers, when the substrate is removed from the water surface, surface pressure is applied if the substrate is not completely horizontal, so as shown in Figure 5, part of the monolayer may As a result, a non-uniform accumulated film is formed on the substrate surface.

This invention was made based on the above background,
The objective is to provide a method and an apparatus for manufacturing a laminate having a uniform and good cumulative film in large quantities and efficiently.

[Means for Solving the Problems] As a result of various studies to solve the above problems, the inventors of the present invention discovered that, in the horizontal deposition method, before transferring a monomolecular film to a substrate surface, The present invention was completed based on the discovery that it is effective to achieve the object of the present invention if the monomolecular film is divided into desired dimensions in advance.

That is, the method for producing a laminate of the present invention is a method for producing a laminate in which a plurality of monomolecular films are accumulated on a substrate, and includes: (a) depositing a monomolecular film of a substance to be accumulated on the liquid surface; (b) Apply a lattice-like partition plate having transverse dimensions of through-holes that allow easy entry and exit from the substrate surface to the monomolecular film surface from above, and place the monomolecular film portion into the partition plate. (c) contact the divided monomolecular film portion surface from above while holding the substrate surface horizontally, and pull it away to transfer the monomolecular film portion to the substrate surface; (d) The method is characterized in that the transfer of the monomolecular film portion onto the substrate surface is repeated to accumulate a plurality of monomolecular films on the substrate.

In a preferred embodiment of the method according to the invention, the substrate is
By sequentially moving it into each of the through holes of the partition plate, the transfer of step (c) can be repeated.

In another preferred embodiment of the method according to the invention, each of the plurality of substrates is simultaneously inserted into each through-hole, and then the partition plate is moved to partition the monolayer portion into each through-hole of the partition plate. (A) Step, (C7) Step and (C)
The process can be repeated.

An apparatus for manufacturing a laminate according to one embodiment of the present invention is an apparatus for manufacturing a laminate in which a plurality of monomolecular films are accumulated on a substrate, and the substrate surface can be easily taken in and out of a through hole. It is characterized in that it has a lattice, and the frame of the lattice divides the monomolecular film on the liquid surface into a plurality of monomolecular film portions whose dimensions are essentially equal to the substrate surface dimensions.

Another aspect of the apparatus for manufacturing a laminate according to the present invention is to contact the monomolecular film partial surface defined by the through hole of the apparatus of the above aspect from above while holding the substrate surface horizontally, and then pull it away. This method is characterized by being equipped with an automatic control device that transfers the molecular film portion onto the substrate surface.

This invention will be explained in more detail below.

Manufacturing Apparatus The partition plate in this invention is an apparatus for manufacturing a laminate in which a plurality of monomolecular films are accumulated on a substrate, and is a lattice in which the transverse dimension of the through holes is such that it can be easily taken in and out of the substrate surface. The lattice frame divides the monomolecular film on the liquid surface into a plurality of monomolecular film portions that are substantially equal in size to the substrate surface.

The cross-sectional shape of the through-hole in the partition plate is selected and changed as appropriate depending on the shape of the substrate to be taken in and taken out. Such shapes include rectangles, squares, parallelograms, circles, ellipses, triangles, and combinations of these shapes.

The cross-sectional dimensions including the cross-sectional shape and cross-sectional area of the throughhole are:
It is designed so that boards can be easily taken in and out horizontally.

It is desirable that the frame of the partition plate be as thin as possible in order to reduce disturbances in the liquid surface that occur when it comes into contact with the liquid surface or when it is separated. The material of this frame is solvent resistant, corrosion resistant,
Selected in consideration of cleanability and mechanical strength. Examples of such materials include fluororesins such as polytetrafluoroethylene, polyvinylidene fluoride, and copolymerized fluororesins;
Other examples include resins such as polypropylene, composites made of these resins reinforced with metal, and materials with mechanical strength coated with the above resins.

FIG. 1 shows a specific example of a partition plate 10 that can be used as a partition plate in the present invention. In this example, width 3
A framework is formed by a frame 11 with a thickness of 5 mm, and a plurality of rectangular through holes 12 of 15 mm x 40 m+* are formed in the frame.

The present invention is not limited to the above example, and various modifications are possible.

For example, in another aspect of the manufacturing apparatus according to the present invention, the monolayer portion surface divided into the through holes of the partition plate is brought into contact with and separated from above while holding the substrate surface horizontally. An automatic control device may be provided to transfer the membrane portion to the substrate surface.

A manufacturing apparatus according to this modification is shown in FIG.

In this example, the substrate 1 is sequentially moved into and out of each of the through holes 12 of the partition plate 10 by an automatic control device (controlled via the arm 13), and the transfer of the step (c) is repeated.

Manufacturing method In the method for manufacturing a laminate of the present invention, first, a monomolecular film of the substance to be accumulated is formed on the liquid surface (a).

The substance to be deposited in this invention is appropriately selected depending on the use of the laminate, but it must have at least the ability to form a monomolecular film. For example, long-chain fatty acids such as arachidic acid, long-chain alkyl derivatives of functional molecules, certain functional polymers, and amphiphilic organic substances that have a hydrophilic group and a hydrophobic group in one molecule, such as biopolymers, etc. be.

The liquid that is the subphase is at least insoluble or poorly soluble with respect to the substance to be accumulated, and has no adverse chemical effect. Such liquids include water, glycerin, and heavy metal-containing buffers.

A conventional method can be applied to form a monomolecular film on the liquid surface. For example, a tank can be filled with water to form a liquid level, and then the substance to be accumulated can be spread over the liquid surface in a film, and a barrier can be moved along the liquid level to narrow the film.

Next, in the method of the present invention, a lattice-like partition plate is applied to the monomolecular membrane surface from above to partition the monomolecular film portion into each through hole of the partition plate (opening).

Furthermore, while holding the substrate surface horizontally, it is brought into contact with the divided monomolecular film portion surface from above and pulled away, thereby transferring the monomolecular film portion onto the substrate surface (c).

The transfer of the monomolecular film portion onto the substrate surface is repeated to accumulate a plurality of monomolecular films on the substrate (2).

(d) The process can be carried out in various ways.

For example, the transfer of step (c) can be repeated by sequentially moving the substrate into each of the through holes of the partition plate. In this embodiment, one or more portions of the substrate are sequentially moved in and out of each through-hole at the same time to accumulate a plurality of monolayers.

In another embodiment, a number of substrates corresponding to the number of through-holes are moved in and out of each through-hole at the same time, and then the partition plate is moved to the new monolayer surface and the substrates are moved into and out of each through-hole at the same time. It moves in and out of the pores and accumulates multiple monolayers. In this aspect,
Steps (a), (b) and (c) are repeated.

[Function] The present invention having the above configuration operates as follows.

In the method for producing a laminate of the present invention, when the grid-like partition plate is applied to the monomolecular film surface, the frame portion of the partition plate directly contacts the monomolecular film and cuts or destroys the monomolecular film portion. , or attached thereto, the through-hole portion does not come into contact with the monomolecular membrane and maintains the membrane as it is. Therefore, a monomolecular membrane portion having an area corresponding to the cross-sectional dimension of the through-hole is defined and surrounded by the through-hole. When this divided monomolecular film portion is brought into contact with the substrate surface from above and pulled away from the liquid surface, the monomolecular film portion adheres to the substrate surface and is transferred.

During this contact and separation, waves may be generated on the liquid surface, but since the frame portion of the partition plate remains on the liquid surface, it works to suppress the generation of waves and calm the waves that occur.

In addition, the transverse dimension of the through-hole is made slightly larger than the substrate surface so that the substrate can be taken in and out horizontally, but it is made to be the same dimension as the substrate surface, so when the substrate is separated, the excess monomolecular film Prevent from adhesion.

[Effect of the invention] The following effects can be obtained by this invention.

In the manufacturing method according to claim 1, since the monomolecular film portion is fixed in the through hole, the liquid level that may occur when the substrate surface is brought into contact with the monomolecular film surface and when it is separated is avoided. It is possible to suppress the waves and prevent the accumulation of a disordered monolayer, resulting in an LB film having a good film structure. Furthermore, since the portion of the monomolecular film that is the same as the substrate size is transferred, it is possible to prevent excess monomolecular film from wrapping around, which is a problem with conventional methods, and to achieve high-quality L.
A B film is formed.

In claim 3, since a large number of substrates are operated simultaneously, a stack with <LB films can be manufactured with greater efficiency.

With the manufacturing apparatus according to the fourth aspect, it is possible to manufacture a laminate having a good LB film, and since the structure is simple, it can be obtained at a low cost, and troubles such as failure can be easily eliminated.

In the manufacturing apparatus according to the fifth aspect, since an automatic control device such as a robot is used, reproducibility can be improved and work efficiency can be significantly improved.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples.

Example Under the conditions shown below, alkylammonium-Ni (
A mixed monomolecular film was formed by mixing dmit)2 and arachidic acid in a ratio of 1=1.

Equipment: Lauda PIImvaa
ge Temperature: 22°C Humidity: 40% Developing solvent: Benzene/acetonitrile-1/1 solution concentration: 5X10-4 M subphase:
Pure water subphase temperature: 25°C Barrier compression speed: 2 cm/min Surface pressure: 20 dyne/cm The monomolecular film was partitioned by placing the partition plate shown in Figure 1 on the obtained monomolecular film. Arachic acid L
Five layers of the B film were deposited horizontally on a hydrophobically treated glass substrate.

As a result, a good LB film was obtained, with no ripples occurring when the substrate came into contact with each other and no excess monomolecular film spreading. Furthermore,
By simply placing the partition plate on the liquid surface, the partitioned monomolecular film can be divided into 2 parts.
I was able to form one sheet.

In addition, the location to which the board should be moved becomes clear, improving work efficiency.

COMPARATIVE EXAMPLE A monomolecular film having the same composition as the example was used to accumulate an LB film using the vertical dipping method. However, the monomolecular film did not flow and the substrate penetrated, making it impossible to accumulate.

[Brief explanation of the drawing]

Fig. 1 is a plan view of a partition plate that can be used in the manufacturing method according to the present invention, Fig. 2 is a schematic diagram showing an apparatus that can be used in the manufacturing method according to the invention, and Fig. 3 explains the vertical immersion method. FIG. 4 is an explanatory diagram for explaining the horizontal adhesion method, and FIG. 5 is an explanatory diagram for explaining the problems of the conventional horizontal adhesion method. 1... Substrate, 2... Monomolecular film, 3... LB film, 4
... Laminate, 10... Partition plate, 11... Through hole,
12...Frame, 13...Arm.

Claims (1)

[Claims] 1. A method for manufacturing a laminate in which a plurality of monomolecular films are accumulated on a substrate, the method comprising forming a monomolecular film of a substance to be accumulated on a liquid surface and transmitting the material through the substrate surface. A lattice-like partition plate having a transverse dimension of the through-hole that can be easily inserted into and out of the through-hole is applied from above to the monomolecular film surface to cover a portion of the monomolecular film that is substantially equal to the surface dimension of the substrate. It is partitioned into each through-hole of the partition plate, and the partitioned monomolecular film portion is brought into contact with and separated from above while holding the substrate surface horizontally, and the monomolecular film portion is transferred to the substrate surface. A method for producing a laminate, comprising repeating the transfer of the molecular film portion onto the substrate surface to accumulate a plurality of monomolecular films on the substrate. 2. The method for manufacturing a laminate according to claim 1, wherein the substrate is sequentially moved into each of the through holes of the partition plate, and the monomolecular film portion is repeatedly transferred to the substrate surface. 3. The step of repeatedly inserting each of the plurality of substrates into each of the through holes at the same time, and then moving the partition plate to partition the monomolecular film portion into each of the through holes of the partition plate is repeated. A method for manufacturing a laminate. 4. An apparatus for manufacturing a laminate in which a plurality of monomolecular films are accumulated on a substrate, which has a lattice that allows the substrate surface to be easily taken in and out of through holes, and the frame of the lattice is An apparatus characterized in that a monomolecular film on a surface is divided into a plurality of monomolecular film portions having substantially the same dimensions as the substrate surface. 5. Automatically transferring the monomolecular film portion to the substrate surface by contacting and separating the monomolecular film portion defined by the through hole from above while holding the substrate surface horizontally in the apparatus according to claim 4. An apparatus for manufacturing a laminate, comprising a control device.