JPH09302285A - Production of composition for forming polymer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a compsn. for forming a polymer film whereby a polymer film having nonlinear optical properties, a uniform thickness, and a smooth surface can be simply formed on a substrate and whereby fine particles can be dispersed in a high concn. in the film. SOLUTION: This process provides a compsn. which can give a polymer film contg. a high concn. of fine particles dispersed therein. The compsn. is prepd. by dissolving, in an org. solvent, a polymer composite contg. a finely pulverized metal or metal oxide or both of them dispersed therein, centrifuging the resultant soln. contg. dispersed fine particles to separate a precipitate, and mixing the precipitate with a binder resin and an org. solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a composition for molding a polymer film, and more specifically, it is possible to coat a base material to prepare a polymer film in which high concentration fine particles are dispersed. The present invention relates to a method for producing a polymer film molding composition having non-linear optical characteristics.

[0002]

_2. Description of the Related Art Fine particles of metal such as gold, CuCl, Cu ₂
It is known that a semiconductor ultrafine particle such as O dispersed in a glassy matrix has a third-order nonlinear optical effect. The non-linear optical effect depends on the particle size and concentration of the fine particles, and it is said that it is preferable to disperse the fine particles at a high concentration.

As the above-mentioned production method, 1) a mixture of a metal compound and a silicon alkoxide is hydrolyzed,
Sol-gel method of dispersing fine particles in glass by heating and condensation, 2) Impregnation method of impregnating porous glass with a solution of a metal compound and heating to disperse fine particles in glass, 3) Metal and glass Sputtering method in which fine particles are dispersed in glass by sputtering at the same time, 4) Ion implantation method in which metal ions are injected into a glass substrate and heat treatment is performed to grow fine particles, 5) Metal compound and glass are mixed and once melted After that, there is a melt precipitation method in which heat treatment is performed to precipitate fine particles in glass.

[0004]

However, a problem common to the sol-gel method, the impregnation method, the sputtering method, the ion implantation method, and the melt precipitation method is that the fine particles are very easily aggregated. It becomes difficult to increase the concentration of fine particles in the composite, and further, the productivity is extremely deteriorated. Further, the low concentration of the fine particles indicates that the ratio of the fine particles contributing to the physical properties of the composite is small, which makes the use of the composite extremely narrow. Especially,
It is not suitable for optical integrated circuits, image memories, etc. that utilize the third-order nonlinear optical effect.

In general, when a material having a large third-order nonlinear susceptibility χ (3) is used, the incident light intensity required to induce an optical bistable response can be small, and not only high integration can be achieved, but also It is said that a quick response switch will be possible. Therefore, attention is focused on particles having a high concentration of fine particles and a large third-order nonlinear susceptibility χ (3). The present inventors have paid attention to such a problem, and have a non-linear optical characteristic, and can easily produce a polymer film having a smooth surface with a uniform thickness on a substrate, and further An object of the present invention is to provide a method for producing a composition for molding a polymer film, which is capable of dispersing a high concentration of fine particles in a molecular film.

[0006]

That is, the features of the present invention are as follows.
In a method for producing a polymer film-forming composition capable of producing a polymer film having a high concentration of fine particles dispersed therein, finely divided metal or metal oxide, or both of them are dispersed in a polymer. Preparation of a polymer film-forming composition in which a polymer composite is dissolved in an organic solvent, the fine particle dispersion solution is centrifuged to prepare a precipitate, and a binder resin and an organic solvent are added to the precipitate and mixed. On the way. In the present invention, a thermodynamically unstable metastable polymer layer is prepared, a metal layer is adhered to the surface of the polymer layer, and then the polymer is heated to increase the metastable state. It also includes a polymer composite obtained by micronizing the metal of the metal layer by stabilizing the molecular layer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the fine particle dispersion solution used in the present invention, since the fine particles of metal or metal oxide, or both fine particles interact strongly with the polymer, the solution state or the polymer Dispersion is very stable below the melting temperature. Therefore, the precipitate obtained by centrifuging the fine particle dispersion solution does not cause aggregation of the fine particles of the metal or the metal oxide, and a polymer film molding composition having an increased fine particle concentration can be obtained. .

First, the polymer composite used in the present invention is
It is a fine particle of metal dispersed in a polymer. The manufacturing method is, firstly, to mold the polymer layer into a thermodynamically unstable state. Specifically, this is a vacuum evaporation method in which a polymer is heated in a vacuum to melt and evaporate to solidify a polymer layer on a substrate, or the polymer is melted at a melting temperature or higher and is left in this state. There is a melting and quenching solidification method in which the polymer layer is immediately attached to liquid nitrogen or the like to be rapidly cooled and a polymer layer is attached onto the substrate.

In the case of the vacuum vapor deposition method, a vacuum degree of 10 ⁻⁴ to 10 ⁻⁶ Torr is used, a vapor deposition rate is 0.1 to 100 μm / min, and preferably 0.5 to 5 μm, using an ordinary vacuum vapor deposition apparatus.
At m / min, a polymer layer can be obtained on a substrate such as glass. In the melting quenching and solidification method, a polymer is melted and cooled at a rate higher than the critical cooling rate inherent to the polymer to obtain a polymer layer. The obtained polymer layer is placed in a thermodynamically unstable metastable state, and shifts to an equilibrium state with the passage of time.

The polymer used in the present invention is, for example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 69, polyethylene terephthalate (PET),
Polyvinyl alcohol, polyphenylene sulfide (P
PS), polystyrene (PS), polycarbonate, polymethylmethacrylate, etc., and those having a molecular cohesive energy of 2000 cal / mol or more are preferable. The polymer includes a crystalline polymer and an amorphous polymer which are generally referred to. As for the molecular cohesion energy, see Chemical Chemistry Handbook, edited by The Chemical Society of Japan (issued in 1974)
On page 890.

Next, the thermodynamically unstable metastable polymer layer is transferred to the step of bringing the metal layer into close contact with the surface thereof. In this step, a metal layer is deposited on the polymer layer by a method such as depositing a metal on the polymer layer using a vacuum vapor deposition apparatus, or directly adhering a metal foil or a metal plate to the polymer layer. The metals include Au, Ag, Cu,
Ti, V, Cr, Mn, Fe, Ni, Zn, Cd, Y,
There are W, Sn, Ge, In and Ga, and there is no particular limitation.

The composite in which the metal layer and the polymer layer are in close contact with each other is heated at a temperature not lower than the glass transition point and not higher than the melting point of the polymer to bring the polymer layer into a stable state. As a result, the metal of the metal layer is 100 nm or less and has a maximum particle size distribution in the region of 1 to 10 nm, or Cu ₂ O, Fe ₃
Fine particles of metal oxides such as O ₄ , ZnO and Y ₂ O ₃ are diffused and permeated into the polymer layer, and this state continues until the polymer layer is completely relaxed and adheres to the polymer layer. The metal layer also decreases in its thickness and eventually disappears. The fine particles are distributed in the polymer layer without being aggregated.

In the present invention, the method for producing the polymer composite is not limited to the above-mentioned method, and for example, a gas phase method belonging to the melt vaporization method, a liquid phase method belonging to the precipitation method, a solid phase method or a dispersion method is used. There is a method of producing ultrafine particles and mechanically mixing the ultrafine particles with a polymer composed of a solution or a melt, or a method of simultaneously evaporating the polymer and metal and mixing them in a gas phase.

The obtained polymer composite is mixed and dissolved in a solvent consisting of an organic solvent such as metacresol, dimethylformamide, dichloroethane, chloropropanol and the like to obtain a fine particle dispersion solution in which fine particles are dispersed. Since the particles have a small particle size and have an interaction with the polymer, separation, precipitation and aggregation of the particles do not occur in the solution. In this case, the content of fine particles is 0.01 to 60.
% By weight.

Next, the fine particle dispersed solution is separated into a precipitate and a supernatant by a centrifuge, and the supernatant is removed to remove the precipitate. The precipitate is paste-like and contains fine particles of metal or metal oxide dispersed without agglomeration. In this precipitate, high-concentration fine particles of at least 70% by weight or more are dispersed. In addition, 3 in the supernatant
Fine particles with a low concentration of 0% by weight or less are dispersed. The concentration of fine particles in the precipitate depends on the rotation speed and time of the centrifuge.

A binder resin and an organic solvent are added to the precipitate. This binder resin is used to form a polymer film having a smooth surface, for example, nitrocellulose, ethyl cellulose, cellulose acetate, cellulose such as butyl cellulose, acrylics such as methyl acrylate, polyethylene terephthalate, Examples thereof include polyesters such as polycaprolactone, polyethers such as polyoxymethylene, polycarbonates, polyvinyls such as polystyrene, polybutadiene and polyisoprene. When a composite is used, the polymer may be the same as the binder resin.

The organic solvent is a high boiling solvent such as meta-cresol, carbitol, dimethylformamide, dimethylimidazolidinone, terpinol, diacetone alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc.,
One kind or two or more kinds can be used.

In the method for producing a polymer film molding composition of the present invention, a precipitate obtained by centrifuging a fine particle dispersion solution and a binder resin prepared by dissolving an organic solvent in an organic solvent in advance are mixed, A paste-like composition can be obtained by stirring. When the paste-like polymer film-forming composition thus prepared is coated on a substrate such as a quartz glass plate using an applicator, a polymer film having a uniform thickness and a smooth surface is formed. It

[0019]

Next, the present invention will be described in more detail with reference to specific examples. Example 1 Using a vacuum evaporation apparatus, 5 g of nylon 11 polymer pellets were put into a tungsten board, and 10 ^-6 Torr
Reduce the pressure. Then, a voltage is applied to heat the tungsten board in vacuum to melt the polymer, and 10 ^-4 to 10 ^-6 T is formed on the substrate (glass plate) placed on the evaporation source.
A polymer layer of a vapor-deposited film having a thickness of about 5 μm was obtained at a rate of vacuum of orr at a rate of about 1 μm / min. The molecular weight of the polymer layer is about 1/2 to 1/10 of the polymer pellet.

Further, the gold chip was put in a tungsten board, heated and melted, and vapor deposition was performed at a vacuum degree of 10 ^-4 to 10 ^-6 Torr to deposit a gold vapor deposition film on the polymer layer. This was taken out of the vacuum evaporation apparatus and left in a thermostat kept at 120 ° C. for 10 minutes to obtain a composite.

The obtained composite was dissolved in meta-cresol and well stirred to prepare a fine particle dispersion solution, which was placed in a centrifuge and centrifuged at a predetermined minute speed for 1 hour.
After centrifugation, the supernatant was removed to remove paste-like precipitates having various gold concentrations, and the precipitates were mixed with a solution of ethyl cellulose dissolved in carbitol at 5% by weight and stirred to form a polymer film. A composition for use was obtained.

A quartz glass plate was coated with the above composition using an applicator and then dried in an oven at 120 ° C. for 10 minutes to remove the organic solvent to obtain a film. The light absorption spectrum of this film was measured with Hitachi, Ltd. UV-3300. Further, the particle size of the fine gold particles in the film was calculated using the Scherrer's formula from the full width at half maximum of the 111 _AU diffraction line of the X-ray diffraction pattern measured using a RINT X-ray diffraction device manufactured by Rigaku Corporation. Table 1 shows the results.

Comparative Example 1 The supernatant obtained in Example was mixed with a solution prepared by dissolving 5% by weight of ethyl cellulose in carbitol and stirred to obtain a polymer film-forming composition. After coating the above composition on a quartz glass plate using an applicator, apply this at 120 ° C.
Was dried in an oven for 10 minutes to remove the organic solvent and obtain a film. The characteristics of the film are also shown in Table 1.

Comparative Example 2 In the same manner as in Example 1, the paste-like precipitate obtained by removing the supernatant was taken out, and the precipitate was coated on a quartz glass plate by using an applicator, which was then 120 °. The organic solvent was removed by drying in an oven of C for 10 minutes. However, a film having a smooth surface could not be obtained.

[0025]

[Table 1]

As a result, it was revealed by centrifugation that the composition obtained contained a high concentration of fine particles,
Further, the produced film also has a smooth surface and all exhibit gold plasmon absorption, and it can be seen from the measurement of the particle size that the gold fine particles are dispersed in the matrix without being aggregated.

Further, the third-order nonlinear optical effect of the above film was measured. A 1064 nm laser beam of YAG laser GCR-3 manufactured by Spectra Physics was irradiated from one side of the film, and the light transmitted through the film was collected using a quartz lens placed on the opposite side of the film. The collected light is Y
After passing through a filter for blocking the 1064 nm laser light of the AG laser, the monochromator extracts the light in the wavelength range around 354.7 nm, which is the third light,
The intensity of light was detected by a photomultiplier tube. At this time, as a comparative sample, a synthetic quartz plate (reference example), which is a standard sample for Comparative Example 1 and the third-order nonlinear optical effect measurement, was also measured. The results are shown in Table 2.

[0028]

[Table 2]

As a result, as shown in Table 2, generation of the third-order light of 345.3 nm was observed from the film of Example 1, and the light intensity was higher than that of the quartz glass plate. This shows that the film of the present invention has a nonlinear optical effect.

[0030]

INDUSTRIAL APPLICABILITY As described above, in the method for producing a composition for polymer film molding of the present invention, the fine particle dispersion solution strongly interacts with the fine particles of the metal or metal oxide and the fine particles of the solution or the polymer. Since it is very stably dispersed below the melting point temperature, the precipitate obtained by centrifuging the fine particle dispersion solution does not aggregate metal or metal oxide fine particles and increases the concentration of fine particles. A composition for forming a molecular film can be obtained, and a polymer film having a smooth surface with a uniform thickness can be easily prepared on a substrate by adding and mixing a binder resin and an organic solvent. In addition, it has the effect of nonlinear optical characteristics.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshio Yamaguchi 3-8-3 Takakuradai, Suma-ku, Kobe 51-303 (72) Inventor Masahiro Irie 1-29-4-404 Kasuga Park, Kasuga-shi, Fukuoka

Claims (2)

[Claims] 1. A method for producing a polymer film molding composition capable of producing a polymer film having a high concentration of fine particles dispersed therein, wherein a finely divided metal or metal oxide, or both of them are used as a polymer. The polymer composite dispersed therein is dissolved in an organic solvent, the fine particle dispersed solution is centrifuged to form a precipitate, and a binder resin and an organic solvent are added to the precipitate and mixed. A method for producing a polymer film molding composition comprising: 2. The polymer composite is prepared by forming a thermodynamically unstable metastable polymer layer, and adhering a metal layer to the surface of the polymer layer, and then heating the polymer. The method for producing a polymer film-forming composition according to claim 1, which is obtained by stabilizing the metastable polymer layer to form fine particles of the metal in the metal layer.