JPS62226134A - Photochromic optical material - Google Patents

Abstract

PURPOSE:To obtain the titled material having improved durability by mounting one or more of coating layers or films on a surface of a film, a layer or a plastic sheet contg. an org. photochromic substance, thereby isolating almost completely the org. photochromic substance from oxygen. CONSTITUTION:The one or more layers of the coating layers or films are mounted on the surface of the film, the layer or the plastic sheet contg. the org. photochromic substance. The titled material is controlled a permeable amount of oxygen by adjusting a film thickness of the 1st layer. By providing the coating film or layer subsequent to the 2nd layer, the permeable amount of oxygen is controlled, thereby enabling to give various kinds of value added, such as the use of an antireflection film composed of inorg. or org. substances, and endowments of dyeability, a cloud-resisting and a rubbing-resisting properties to the titled material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photochromic optical material that has improved durability by blocking organic photochromic substances from acid rice.

[Prior art]

A photochromic substance is a substance that reversibly changes color and fades when irradiated with light. Organic Photochromic Substances Among Photochromic Substances Among the most important types, organic photochromic substances have been extensively studied because they exhibit a wide variety of color tone changes. However, a major drawback of organic photochromic materials is that their cyclic durability is very short. The main reason for this drawback is that the structure of the photochromic material itself is unstable, as well as its unstable horizontal position, so that it is easily susceptible to oxidative decomposition by oxygen. Various methods have been tried to solve this problem. For example, in order to prevent the oxidation component m caused by oxygen, there have been disclosed methods using an antioxidant as in JP-A-58-113203, and methods using a singlet oxygen quencher as in JP-A-58-173181. ing. In addition, as in JP-A-51-87177, the surface of a photochromic material in the form of particles is coated with an entirely inorganic substance, and JP-A-58
A method of suppressing contact with oxygen from the outside has been disclosed, such as providing an inorganic vapor-deposited substance on the surface of a substrate containing a 7-vital substance such as No. 54457.

[Problem that the invention seeks to solve]

However, antioxidants and heavy ring oxygen quenchers have their own durability problems, and these substances often have a negative effect on the rate of coloring and fading of photochromic materials. Next, there is a method of suppressing contact between oxygen and the photochromic substance, but since the shielding substance is an inorganic substance that is not in a bulk state, it is relatively easy for oxygen to pass through, and a great effect cannot be obtained. Therefore, the present invention is intended to solve the latter problem in particular, and its purpose is to almost completely shield oxygen and organic photochromic substances and improve durability.

[problem; means to solve it]

That is, this book relates to a photochromic optical material characterized by having one or more coating layers or all coatings on the surface of a film, layer, or plastic containing an organic photochromic substance.

It is a well-known fact that organic photochromic compounds are generally decomposed by oxygen (especially singlet oxygen), and in some cases, the bond cleavage of metallic substances (e.g., spiropyran, spirooxazine compounds, etc.) is significant. It is.

The present invention makes it possible to solve this problem by providing an oxygen-impermeable barrier on the surface of the film, layer or plastic containing the organic photochromic substance in order to suppress decomposition due to oxygen. Ta.

In the barrier used in the present invention, that is, the coating layer or coating film, the first layer is made of a heat-curable or photo-curable coachib material. For example, there are a wide variety of resins such as silicone resins, melamine resins, acrylic resins, urethane resins, fluorine resins, alkyd resins, organic resins, and silicone resins.

The selection of coating materials from among these coating materials is determined depending on the substrate to be used and the purpose of use (for example, one with excellent scratch resistance, heat resistance, and dyeability).

It is also effective to incorporate into the coating material an antioxidant, an oxygen quencher, an ultraviolet absorber that takes into account the light absorption characteristics of the photochromic substance, and the like.

In the present invention, the amount of oxygen permeation can be adjusted by controlling the film thickness t of the first layer. Further, by providing a coating film or a coating layer after the second layer, it is possible to further suppress the amount of oxygen permeation and obtain various added values. Examples include antireflection films made of inorganic or organic substances, imparting dyeability, imparting antifogging properties, and improving scratch resistance.

The coating methods for the Oi layer or coating film described above include flow coating, spray method, dipping method, spinner method, OVD method, vacuum evaporation method, plasma CvD method, sputtering method, etc. The choice should be made according to the production volume.

The organic photochromic substances used in the present invention are almost all substances (substances that decompose with oxygen), such as dithizone compounds, spiropyran compounds, spirooxazine compounds, phenazine compounds, and phenothiazines. There are a wide variety of compounds, including fulgide-based compounds, phenoxyanthraquinone-based compounds, aminoazobenzene-based compounds, and salicylideneaniline-based compounds.

These organic photochromic substances can be mixed into a synthetic resin, immersed in it, dissolved or dispersed in a coating material (resin similar to the above-mentioned coating layer or ridged film), and applied to a base material, or completely dissolved in a polymer. There are various methods such as dissolving or dispersing it in a solution to form a film.The synthetic resins used here include acrylic resin, polyethylene 4'A 1j, polycarbonate resin, polystyrene resin, vinyl chloride, In addition, adding antioxidants, heavy ring oxygen quenchers, and ultraviolet absorbers to these resins and coating materials is effective in extending the lifespan of photochromic materials. .

The object of the present invention can be achieved by the method described above.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 [Production of photochromic substrate] 1,3.3.4.5-pentamethyl-9'-methoxy-
Spiroindoline-naphthoxazine 5ft Methicine chloride 1952 was dissolved and kept at 20°C, and a flat plate of polycarbonate resin with a thickness of 2 mm was immersed in this solution for 5 minutes, and then dried at 50°C.

[Coating of coating layer]

In a reaction vessel equipped with a stirring device, 5 oar of colloidal silica (manufactured by Catalysts & Chemicals Industry Co., Ltd. “Oscar 123”) was added.
2)% Propylene glycol diglycidyl ether 3
02 (Anacol EX-911 manufactured by Nagashio Sangyo ■), j
- glycidoxyglobiltrimethoxysilane 100f,
A mixed solution of 0.5f of ethanol 340 tough flow control agent and 5ff of magnesium perchlorate was kept at 20°C and stirred, and further (30P'ii of LO5N hydrochloric acid was added,
Stirring was continued for 5 hours to obtain a coating liquid for lamination.

The photochromic group washed with isopropyl alcohol was completely immersed in this solution, and by the dipping method,
Apply at a liquid temperature of 10℃ and a pulling speed of 20cm/''.
Heat curing was performed at 100° C. for 3 hours. The film thickness was 3 μm.

Performance evaluation of this photochromic optical material was conducted as follows and shown in Table 1.

(1) Color and transmittance The colors are visually classified by color, and the transmittance is measured using a photochromic lens dimming tester HK223 (manufactured by Hasegawa Bee Co., Ltd.).The average transmittance before and after one irradiation test (400-75
0 nm) are shown in Table 1, respectively.

(2) Durability: 20 hours on a xenon long life fade meter (FAL-25AI manufactured by Suga Test Instruments Co., Ltd.)
After exposure for 50 hours, 100 hours, and 200 hours, (1
) All performance evaluations of transmittance are shown in Table 1.

(3) I with scratch-resistant steel wool (#0000)
K9 load hook 10 reciprocating surface? The scratches on the surface were evaluated according to the following ranks and are shown in Table 1.

A: There is no scratch at all in the area of 1 crn x 3 strokes.

B: 1 to 10 scratches within the above range.

C: 10 to 100 scratches are made within the above range.

D = Countless scratches, but a smooth surface remains.

E: No smooth surface remained due to scratches on the surface.

(4) Dyeable Bidisperse Dye Terrasil Black B (manufactured by Chipagaiki Co., Ltd.) 2f'i Dispersed in warm water at 85° C., average light attenuation rate vi after soaking a lens in this solution for 5 minutes is shown in Table 1.

[Example 2] The photochromic optical material obtained in Example 1 was provided with antireflection Ill shown below. The photochromic optical material is cleaned with acetone, and then a film structure of 810. The layer is λ/4. Zr
The total thickness of the 01 and 5101 layers is λ/4, Z r
The O2 layer is λ/4. An antireflection layer was provided so that the uppermost layer had a sitM of λ/4 (λ=520 nm).

The obtained photochromic optical material was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[Comparative Example 1] Comparative Example 1 was a photochromic substrate at the [manufacture of photochromic substrate] stage of Example 1, and the evaluation method was the same as that of Example 1, and the results are shown in Table 1.

[Comparative Example 2] Comparative Example 2 was obtained by providing the antireflection film of Example 2 on the photochromic substrate in the [manufacture of photochromic substrate] stage of Example 1, and the evaluation method was the same as that of Example 1. The results are shown in Table 1.

[Example 3] [Fabrication of photochromic substrate] Adamantane-2-ylidene (2/-methy, -3'-
furfuryl) ethyldene; succinic acid 0.1? .

diisopropyl peroxydicarbonate) 2.54 and diethylene glycol bis(allyl carbonate) 9
7.59 was mixed, poured into a space consisting of a glass mold and a gasket made of ethylene-vinyl acetate copolymer designed to have a thickness of 21aI, and heated at 60°C for 8 hours at 80°C.
The polymerization was completed in 10 hours, and the mold was released after the polymerization.

[*Kama of the covering layer]

The photochromic substrate was washed with inpropyl alcohol and then coated with Chemitron H/B using ethyl acetate as a solvent using the spin code method (Sold by Precision Entabrise).
was applied to a film thickness of 4 μm. After applying, UV
Curing was carried out using a sterilizing lamp GL-10 manufactured by Clamp Toshiba ■ for an irradiation distance of 10ffi% and an irradiation time of 5 minutes.

The obtained photochromic optical material was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[Comparative Example 3] Comparative Example 6 is a case in which the photochromic substrate in the [manufacturing of photochromic substrate] stage of Example 5 was subjected to mV irradiation treatment without providing a moderated layer. 1, and the results are shown in Table 1.

[Example 4] (Production of photochromic substrate) Tetramethoxysilane 6 was placed in a reactor equipped with a pressing device.
29, j-aminopropyltrimethoxysilane 41? ,
Bis(methyldimethoxysilylprobyl)epoxysuccinate 219. Isopropyl alcohol 103f, silicone Wm activator (LIPi) was added to 0, Q5' at room temperature with vigorous stirring, and 52 g of tetrahydrochloric acid water bath solution was added over 1 hour, and stirring was continued for an additional 2 hours. Add magnesium perchlorate [Llf, 1.3.5
-) One portion of dimethylindolino-5'-nitro-8'-methoxybenzopyrylosubiran was added, and the mixture was stirred.

Two layers of acrylic resin gold were immersed in this coating liquid, and the dipping method was applied to F.
! It was coated at n/- and heat-cured at 100°C for 6 hours. The film thickness was 2 μm.

[Painting without coating]

The photochromic radical was immersed in a mixed solution of 200 tons of hexamethoxymethylolmelamine 60y1 (Hitaloy)'2400 (Hitachi Chemical product name) 40f% F-) luenesulfone α7f1 ethylceron, and dipping at a temperature of 20°C. , pulling speed 15 cm/
xiM and heat-cured at 90° C. for 8 hours. The film thickness was 4 μm.

What is the evaluation method for the obtained photochromic optical material? It was carried out in the same manner as in 111, and the results are shown in Table 1.

[Comparative Example 4] Comparative Example 4 was prepared on a photochromic substrate in the [manufacture of photochromic substrate] stage of Example 4, and the evaluation method was the same as that of Example 7ffl 1flJ 1, and the results are shown in Table 1.

〔Effect of the invention〕

As described above, in the present invention, by cutting off oxygen km, it has become possible to dramatically improve the long-term durability of photochromic performance. This allows various organic photochromic materials to be used in applications requiring durability (
It can now be used for eyeglass lenses, window glass, etc.). In addition, as added value, it is possible to provide all performances such as scratch resistance, chemical resistance, and antireflection, and the effect is tremendous.

Claims (3)

[Claims] (1) A photochromic optical material characterized in that one or more coating layers or films are provided on the surface of a film, layer, or plastic containing an organic photochromic substance. (2) The photochromic optical material according to claim 1, wherein the coating layer or the first layer of the coating film is made of a thermosetting or photocuring coating material. (3) The photochromic optical material according to claim 1, wherein the coating layer or the second and subsequent layers of the coating film are a thermosetting or photocuring coating material or an inorganic vapor-deposited film.