JPH05331626A - Production of organic photochromic film - Google Patents

Abstract

PURPOSE:To produce the org. photochromic film having excellent durability, colorability and decolorability, etc., by forming a plasma polymerized film of an org. photochromic compd. alone or combined with a high-polymer resin on the surface of a substrate consisting of glass, etc. CONSTITUTION:The substrate 8 consisting of the glass, etc., is mounted on a supporting base 7 in a vacuum vessel 1 and a nonpolymerizable inorg. gas 3, such as Ar is introduced into this vessel. A high-frequency voltage is impressed to a coiled induction coupling type electrode 4 to generate a discharge. Simultaneously, the org. photochromic compd. 10a and high-polymer resin 10b packed in evaporating sources 9a, 9b are heated to evaporate by a power source 11 and to cause plasma excitation, by which the polymerized film thereof is formed on the substrate 8. The plasma polymerized film of the org. photochromic compd. is formed at 500 to 5000Angstrom thickness on the surface of the substrate 8 by setting the gaseous pressure in the vacuum vessel 1 at a 10<-2> to 10<-5>n range in such a case. The org. photochromic film having a good photochromic function is stably formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an organic photochromic film. For more details,
This invention forms an organic photochromic film excellent in various properties such as durability and color fading by plasma polymerization.
The present invention relates to a method for manufacturing a new organic photochromic film.

[0002]

2. Description of the Related Art Conventionally, the photochromic property in which the hue reversibly changes upon irradiation with ultraviolet rays has been applied to, for example, accessories, displays, sunglasses, goggles, photometers, optical filters, recording media and the like.
When imparting a photochromic function to such an industrial product, conventionally, a photochromic compound is kneaded into a base material, or a photochromic compound or a polymer resin mixed with a photochromic compound is applied to the base material. ing.

[0003]

However, in the case of the method of kneading the photochromic compound into the base material, the difference in the thickness of the base material causes light and shade during coloring, and when used as an optical material such as a lens, the appearance is There is a drawback that it is not preferable. On the other hand, in the case of the method of applying to the substrate, there is a problem that the addition amount and the application amount of the photochromic compound must be increased in order to obtain a good photochromic function. Also,
In the case of the method of mixing the photochromic compound with the polymer resin and applying the mixture, there is a problem that the photochromic function is lost depending on the solvent.

The present invention has been made in view of the above circumstances, solves the drawbacks of the conventional photochromic film manufacturing method, and is excellent in various characteristics such as durability and color fading property. It is an object of the present invention to provide a new method for producing an organic photochromic film, which is capable of producing.

[0005]

In order to solve the above-mentioned problems, the present invention aims to form a plasma polymerized film alone or a composite of an organic photochromic compound and a polymer resin on a substrate surface. A method for producing a characteristic organic photochromic film is provided.

The organic photochromic compound that can be used in the present invention is not particularly limited. For example, fluquid derivatives such as fluquid and diphenyl fluquid, triphenyl fluquid, spiropyrans and spiropyran derivatives such as benzospiropyran, spirooxazine and spironaphtho. Examples thereof include spirooxazine derivatives such as oxazine, stilbene, hydrazone, osazone, salicylaldehyde, biimidazolyl, bianthrone, azobenzene, thioindigo, trimethylmethane, polynatine, thionine, viologen and derivatives thereof.

Examples of the polymer resin include acrylic resins such as polymethylmethacrylate having excellent weather resistance, and fluororesins such as fluorinated ethylene propylene copolymer. In the present invention, the organic photochromic compounds exemplified above are formed on the surface of a substrate such as plastic or glass by plasma polymerization.

Examples of plastic substrates include polyethylene terephthalate, polyethylene naphthalate,
Examples thereof include films of polyether sulfone, polyether ether ketone, polycarbonate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polypropylene and the like. A plasma polymerized film of an organic photochromic compound alone or a plasma polymerized polymer of an organic photochromic compound and a polymer resin is simultaneously formed on the surface of these substrates, or a composite plasma polymerized film in which these polymerized films are sequentially laminated is formed. In any case, the substrate may be plasma-treated prior to film formation in order to improve adhesion.

When forming a plasma polymerized film on a substrate, for example, a coil (4) -shaped inductively coupled electrode or a parallel plate-shaped capacitively coupled electrode is placed in a vacuum container (1) as shown in FIG. The provided high frequency excitation type ion plating device can be used. At the time of plasma polymerization, a non-polymerizable inorganic gas such as argon or nitrogen is vacuumed through a gas introduction valve (3) under a reduced pressure atmosphere evacuated by a vacuum pump (12) through an exhaust pipe (2). It is introduced into (1) and a high frequency voltage is applied to the electrode (4) from a high frequency power source (6) to generate a discharge. Further, the organic photochromic compound (10a) and the polymer resin (10) filled in the evaporation sources (9a) and (9b).
Each of b) is heated and evaporated by applying a voltage from a resistance heating power source 11, and plasma is excited to form a polymerized film on the substrate 8 supported by the substrate support 7. In this case, the organic photochromic compound (10
Plasma polymerization of a) and polymeric resin (10b) is 1
It is preferable to carry out at a gas pressure of 0 ^-2 to 10 ^-5 Torr. When the gas pressure is higher than 10 ^-2 Torr, the energy of accelerating particles (ions and electrons) becomes small, and a uniform film is not formed even though the total number of accelerating particles is large. On the other hand, 10 ^-5
When the gas pressure is lower than Torr, the energy of the accelerated particles increases, but the total number of accelerated particles reaching the substrate (8) decreases, and the film formation rate decreases.

The high frequency power source (6) is usually several hundreds kH.
Those having a frequency of z to several tens of MHz can be used, and 13.56 MHz is exemplified as a preferable example. Further, the high frequency power may be in the range of 10 to 200 W. There is no particular limitation on the film thickness of the organic photochromic compound (10a) plasma-polymerized on the substrate (8) or a composite film of the organic photochromic compound (10a) and the polymer resin (10b), but a thickness of 500 to 5000Å Therefore, it is preferable to select it appropriately.

[0011]

EXAMPLES Examples will be shown below to describe the method for producing an organic photochromic film of the present invention in more detail. Example 1 A plasma polymerized film of an organic photochromic compound was formed on a polyethylene terephthalate (PET) film using the ion plating apparatus illustrated in FIG. 1 by the steps shown below.

First, the PET film is set on the substrate support (7) in the vacuum container (1), and then the exhaust pipe (2).
1 × 10 ^-5 To the inside of the device with the vacuum pump (12) connected to
The pressure was reduced to rr or less. After this, the gas introduction valve (3) is opened to introduce argon gas, and the atmospheric pressure is set to 4 × 10 ⁻⁴ To
It was adjusted to rr and discharged. Then, under the condition of high-frequency power of 50 W, a plasma-polymerized film of spironaphthoxazine filled in the resistance heating evaporation source (9a) was formed on the PET film surface for 10 seconds. When the film thickness was repeatedly measured by a reflection interferometer, it was 620 Å.

The colorability of the film thus obtained was measured by a Macbeth reflection densitometer for the blue color density after irradiation with a UV lamp for 3 minutes. Table 1 summarizes the above results.

[0014]

[Table 1]

As is clear from comparison with Comparative Examples described later, it was confirmed that the value was as large as 0.557 and the coloring density was high. Example 2 As in Example 1, the atmospheric pressure in the vacuum container (1) was set to 4 ×.
After adjusting to 10 ⁻⁴ Torr and discharging the introduced argon gas, spironaphthoxazine charged in the resistance heating evaporation source (9 a) was charged with P for 10 seconds under the condition of high frequency power of 50 W.
Plasma polymerization was performed on the surface of the ET film. Then, on this plasma-polymerized film, a fluorinated ethylene-propylene copolymer (manufactured by Daikin Industries, Ltd.) as a polymer resin filled in another evaporation source (9b) was added at a gas pressure of 1 × 10.
^The film was formed under the conditions of ^-3 Torr and high frequency power of 100 W for 3 minutes.

The same measurement as in Example 1 was performed on the obtained film. The results are shown in Table 1. As is clear from comparison with Comparative Examples described later, it was confirmed that the performance of the film produced by the method of the present invention was superior to that of the conventional product. The thickness of the plasma polymerized film is
It was 1500Å.

Comparative Example 1 Polyester resin [Vylon 280 manufactured by Toyobo Co., Ltd.]
On the other hand, a solution prepared by adding 1 wt% of an organic photochromic compound spironaphthoxazine and dissolving it in a mixed solvent of toluene / methyl ethyl ketone was applied to a PET film by a Meyer bar.

The same measurement as in Examples 1 and 2 was performed on the film thus produced. The results are also shown in Table 1. The Macbeth reflection densitometer had a low value of 0.147. The coating thickness after drying was 4 μm, which was 20 times or more the thickness of Examples 1 and 2. Comparative Example 2 A film was produced by coating in the same manner as in Comparative Example 1 except that 5 wt% of spironaphthoxazine, an organic photochromic compound, was added.

The results are also shown in Table 1. The coloring density was lower than in Examples 1 and 2, and the film thickness was also thick. Of course, the present invention is not limited to the above examples.
It goes without saying that various aspects are possible in terms of details such as the type of the substrate and the organic photochromic compound, discharge and reaction conditions.

[0020]

As described in detail above, according to the present invention, an organic photochromic film having a thin film thickness of about 1/20 or less as compared with the coating type, fast coloring, and a high concentration and good plasma polymerization can be obtained. Be done.

[Brief description of drawings]

FIG. 1 is a cross-sectional view illustrating an ion plating device that can be used in the method for producing an organic photochromic film of the present invention.

[Explanation of symbols]

 1 vacuum container 2 exhaust pipe 3 gas introduction valve 4 coil electrode 5 matching box 6 high frequency power supply 7 substrate support 8 plastic or glass substrate 9a, 9b evaporation source 10a organic photochromic compound 10b polymer resin 11 resistance heating power supply 12 vacuum pump

Claims (4)

[Claims] 1. A method for producing an organic photochromic film, which comprises forming a plasma polymerized film of an organic photochromic compound alone or a composite of an organic photochromic compound and a polymer resin on a surface of a substrate. 2. The method according to claim 1, wherein the plasma polymerized film of the organic photochromic compound is formed by high frequency excitation type ion plating. 3. The method according to claim 1, wherein the plasma polymerization is carried out within a gas pressure range of 10 ⁻² to 10 ⁻⁵ Torr. 4. The film thickness of the plasma-polymerized film of an organic photochromic compound is in the range of 500 to 5000Å.
2 or 3 manufacturing method.