JPH0323586B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a resin optical member that has both polarizing properties and dimming properties and is used, for example, as a lens, sunglasses, or goggles.

[Conventional technology]

In general, polarized lenses and sunglasses block the polarized light that occurs when natural light is reflected, thereby achieving an anti-glare or light-reducing effect.
In recent years, these characteristics have been used to prevent polarized light or glare, especially when outdoors, for example, to prevent polarized light reflected from the snow surface when skiing, to prevent diffusely reflected light from the water surface when fishing, or to prevent glare from automobiles. In addition to sunglasses to prevent drivers from being dazzled, they have begun to be used in a variety of other fields, such as sunglasses and fashion lenses for the purpose of reducing light.

Conventional polarized lenses and sunglasses have the above-mentioned unique functions, but polarized lenses or sunglasses equipped with a polarizing film have a light attenuation rate determined by the characteristics of the polarizing film. I ended up
It is not possible to obtain a dimming function according to the intensity of incident light.

On the other hand, lenses and sunglasses made of resin have recently begun to be widely used due to their features such as lightness, workability, and impact resistance. It was difficult to assign In other words, silver halide, which is commonly used to impart a light control function to inorganic glass lenses, has poor compatibility with resins, and spiropyran, a typical organic compound with a light control function, has a relatively high secondary Since fading is extremely slow in polymeric substances with a transition temperature and is not practical, and general spirooxazine compounds also have advantages and disadvantages, they are not necessarily suitable as organic compounds for imparting light control function to resin optical members. It wasn't satisfying.

Therefore, there is a demand for resin optical members, especially resin lenses, resin sunglasses, and goggles, that have both polarizing and dimming functions that are sufficient for sunlight and other light even in outdoor natural environments. was.

In response to the need for an excellent resin optical member that can sufficiently and stably exhibit both of these two functions over a long period of time, and a method for manufacturing the same, the inventors of the present invention have developed a system that provides polarization and dimming properties. Although an optical member with this function was proposed in Japanese Patent Application No. 164812/1987, this method mainly requires the process of attaching lenses and fixing a light control film to the surface of the lens. , it was a complex process that required multiple steps to be carried out sequentially.

In addition, regardless of the above-mentioned patent applications, there is a strong desire for a manufacturing method that can manufacture optical members having good polarization properties and light control effects through simple steps.

[Purpose of the invention]

In response to the above-mentioned demands, the present invention provides a resin optical member that has both a polarization function and a light control function using a specific organic photochromic substance, and has both excellent polarization and light control properties, and in particular, such a resin optical member. It is an object of the present invention to provide a method for manufacturing resin lenses, sunglasses, and goggles having these characteristics through simple steps.

[Structure of the invention]

In the method of the present invention, a radically polymerizable monomer that provides a polymer for optical members contains an organic photochromic substance having a dimming effect and a radical polymerization initiator that does not cause the organic photochromic substance to deteriorate at polymerization temperature. Inject the polymer composition into a cast polymerization container equipped with a polarizing film inside,
The method is characterized in that the monomer is polymerized in this cast polymerization container at a temperature at which the polarizing film does not deteriorate.

〔effect〕

According to the method of the present invention, the polarizing effect of the polarizing film embedded in the resin body, and
An optical member made of resin that has both a light control function that can adjust the amount of light depending on the intensity of incident light, which is achieved by containing a unique organic photochromic substance in the resin body, that is, an anti-glare member. A resin optical member embodied as a lens or sunglasses, which has both function and dimming function and is very useful from the viewpoint of protecting the eyes, can be manufactured in a single process and therefore very easily. And it can be manufactured at low cost. The monomer is a radical polymerizable monomer, the radical polymerization initiator is a radical polymerization initiator that does not deteriorate the organic photochromic substance at the polymerization temperature, and the polarizing film is polymerized at a temperature that does not deteriorate the polarizing film. The functions of both the organic photochromic material and the organic photochromic substance are not sacrificed, and a state in which good polarizing and dimming effects can be achieved can be reliably obtained.

[Specific description of the invention]

In the method of the present invention, the main body of the resin optical member, that is, the resin body part, is formed by polymerizing a monomer that provides a polymer for optical members by a casting polymerization method, also called a cast polymerization method. ,Form. When carrying out this cast polymerization, a polarizing film is placed inside a cast polymerization container usually called a mold, and an organic photochromic substance having a light control effect is added to the monomer. Let it be included. Therefore, when the polymerization of the monomers is completed, an optical member having both a polarizing function and a light control function can be manufactured without substantially requiring any other steps.

The monomer that provides the polymer for optical members used in the present invention is particularly limited as long as it is a radically polymerizable monomer that effectively exhibits the polarizing effect by the polarizing film and the dimming effect by the organic photochromic substance, which will be described later. Monomers that provide resin materials used for ordinary resin lenses or sunglasses can be used.

Specific examples of such monomers include, for example,
Mention may be made of various methacrylates and acrylates. Such methacrylates and acrylates may have substituents or side chains consisting of aliphatic groups, aromatic groups, alicyclic groups, etc., or may have substituents such as chlorine, bromine, etc. It may also be urethane methacrylate or urethane acrylate bonded through urethane groups.

In addition to the above, examples include vinyl compounds such as styrene and α-methylstyrene, and monomers used as raw materials for allyl resins such as diethylene glycol bisallyl carbonate.

These monomers may be used alone or in the form of a monomer composition in which two or more monomers are combined. However, in this latter case it is important that the entire monomer composition can be polymerized with a common radical polymerization initiator and under common polymerization conditions.

In the present invention, various polarizing films can be used. Specific examples include an iodine-polyvinyl alcohol polarizing film called a so-called thin film type polarizing film, a highly dichroic dye-polyvinyl alcohol polarizing film, and intramolecular dehydration or dehydrochlorination of polyvinyl alcohol, polyvinyl chloride, etc. Examples include so-called polyvinylene-based polarizing films that have a polyene structure and obtain polarizing properties through conjugated double bonds, and others.

Iodine-polyvinyl alcohol polarizing films are mainly neutral or blue in color, and dye-based polyvinyl alcohol polarizing films are preferably used in the present invention especially when coloring is desired. In order to protect the polarizing film, a protective layer may be formed by laminating another transparent film, such as a protective film made of cellulose acetate film, on both surfaces or one surface of the polarizing film. A polarizing film provided with such a protective layer is prevented from being adversely affected by solvents, organic photochromic substances, and others contained in the monomer composition during polymerization treatment, so that its polarizing function is not inhibited. never be done.

The organic photochromic substance used in the present invention is not particularly limited as long as it can exhibit an effective light control effect. Typical examples include thioindigos, azobenzene dyes, diallylthiocarbazone metal complexes that exhibit photochromism due to isomerization, and those that exhibit photochromism based on intramolecular hydrogen transfer. , aromatic nitro compounds such as dinitrobenzylpyridine, various chromone derivatives,
Salicylideneaniline and other compounds that exhibit photochromism due to ionic or radical dissociation include leuco compounds of triphenylmethane dyes, various imidazole dimers, tetraphenylhydrazines, various spiropyran compounds, and spirooxazine compounds. , a compound having a chromene ring or a pyran ring, a fulgide compound, and the like, but the present invention is not limited to these.

However, in the present invention, it is particularly preferable to use at least one or two or more spirooxazine compounds represented by any of the following structural formulas (), (), and () as the organic photochromic substance.

(In the formula, R ¹ and R ² represent a hydrogen atom, a halogen atom, a cyano group, a lower alkyl group, a lower alkoxy group, and R ³ represents a lower alkyl group, a lower alkoxyalkyl group, various substituted arylalkyl groups, (-
CH ₂ ) _—o COOR (R represents a lower alkyl group), and the number of carbon atoms other than the carbon atoms constituting the aromatic nucleus in each of R ¹ , R ² and R ³ is 6 or less. ) Specific examples of the spirooxazine compounds include 1,3,3-trimethylspiro[indoline-
2,3′-(3H)-naphtho[2,1-b](1,4)
oxazine], 5-chloro-1,3,3-trimethylspiro[indoline-2,3'-(3H)naphtho[2,1-
b](1,4)oxazine], 1,3,3,5-tetramethyl-9'-methoxyspiro[indoline-2,3'-(3H)-naphtho[2,1-b](1,4 ) oxazine], 1-isopropyl-3,3,5-trimethylspiro[indoline-2,3'-(3H)naphtho[2,
1-b](1,4)oxazine], 1-(p-chlorobenzyl)-3,3-dimethylspiro[indoline-2,3'-(3H)naphtho[2,
1-b](1,4)oxazine], 1-(β-methoxyethyl)-3,3-dimethyl-9'-methoxyspiro[indoline-2,3'-
(3H)-naphtho[2,1-b](1,4)oxazine], 1,3,3-trimethylspiro[indoline-
2,3′-(2H)fenanthro[9,10-b](1,
4) Oxazine], 1,3,3-trimethylspiro[indoline-
2,3′-(2H)pyrido[3,2-f](1,4)
benzoxazine], and others, but are not limited to these, of course.

In natural environments, these spirooxazine compounds stably exhibit a dimming function that repeatedly changes color and fading due to irradiation and removal of light over a long period of time, and especially when used under sunlight. Its excellent light control function is maintained over a long period of time, and its effect is stable even at relatively high temperatures.

The above organic photochromic substances can be used alone or in combination of two or more.

Specifically, the method of the present invention is performed as follows. First, select a monomer that provides a polymer for optical members with properties appropriate for the intended use, and mix it with an organic photochromic substance, a radical polymerization initiator described below, and a necessary solvent, so that these are uniformly mixed. A dispersed monomer composition is prepared. On the other hand, an appropriate polarizing film is separately formed, this polarizing film is held in a cast polymerization container by an appropriate means, and the monomer composition is poured into the cast polymerization container. In other words, in a state where the polarizing film is immersed in the monomer composition, the monomer composition is polymerized at a temperature that does not deteriorate the polarizing film to polymerize the monomers, and after the polymerization is completed, the inside is The resin optical member fixed with the polarizing film embedded therein is taken out from the cast polymerization container.

In the monomer composition, the organic photochromic substance is preferably contained in a proportion of 0.01 to 30 parts by weight based on 100 parts by weight of the monomer.

The polymerization treatment of the monomer composition is the same as the usual radical polymerization method, but the polymerization temperature is set at a temperature that does not deteriorate the polarizing film, and a radical polymerization initiator that does not deteriorate the organic photochromic substance at this polymerization temperature is used. Polymerization treatment is then carried out. If the polymerization temperature is high, the polarizing film may deteriorate and cause discoloration or unevenness, and depending on the radical polymerization initiator used, organic photochromic substances may deteriorate at the polymerization temperature and lose their effectiveness. As a result, effective polarizing or dimming effects may not be obtained. For example, when a peroxydicarbonate-based radical polymerization initiator such as diisopropyl peroxydicarbonate is used, the organic photochromic substance in particular is degraded during the polymerization reaction, and its light control effect may be significantly reduced.

The radical polymerization initiator used in the present invention is selected from peroxyesters, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxyketals, ketone peroxides, azo compounds, etc. It is preferable that the 10-hour half-life temperature is 100°C or less. Among these, peroxyesters, diacyl peroxides, and azo compounds are particularly preferably used. Specific examples of such radical polymerization initiators include lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxypivalate, t-butylperoxyneodecanoate, and t-butylperoxyneodecanoate.
-butyl peroxylaurate, t-butyl peroxy-2-ethylhexanoate, azbisisobutyronitrile, benzoyl peroxide,
Examples include 1,1-bis(t-butylperoxy)cyclohexanone, 2,2-bis(t-butylperoxy)octane, and others.
It is not limited only to these.

Here, the "10-hour half-life temperature" for a radical polymerization initiator refers to the temperature at which the amount of initiator becomes 1/2 after 10 hours have passed, but radical polymerization starts when the 10-hour half-life temperature exceeds 100℃. When a radical polymerization initiator is used, it is necessary to raise the temperature of the system to about 130°C or higher in order to eliminate the activity of the radical polymerization initiator at the end of the actual polymerization process. As a result, the organic photochromic substance may deteriorate, or the polarizing film may deteriorate and its function may be inhibited. However, when using a radical polymerization initiator with a 10-hour half-life temperature of 100° C. or lower, it is possible to reliably obtain an optical member having the desired properties without such risks. That is, the polymerization can advantageously be carried out at a temperature below 100°C, and the temperature elevation treatment is also sufficient at a temperature below 130°C, preferably below 110°C, so that neither the organic photochromic material nor the polarizing film deteriorates. I have nothing to do.

In the present invention, the container for cast polymerization may be a mold or formwork designed according to the purpose of the optical member to be finally obtained, such as a plate-shaped, lens-shaped, cylindrical, prismatic, conical, etc. can be used. The material may be any suitable material such as inorganic glass, plastic, or metal.

During the actual polymerization process, antistatic agents, colorants, heat stabilizers, antioxidants, ultraviolet absorbers, and other additives are added to the monomer composition depending on the expected use of the final optical member. It is also possible to contain auxiliary materials.

The polymer obtained by the above polymerization process can be used as it is as an optical member for lenses or sunglasses, or if necessary, it can be subjected to finishing treatments such as cutting, polishing, and other mechanical processing for ordinary optical members. Of course, it is also possible to apply

Furthermore, it is practical to perform various hard coat treatments to increase surface hardness, such as forming a silicone hard coat or an organic ultraviolet curing hard coat, metal oxide vapor deposition, sputtering, etc. This is highly desirable. It is also possible to apply a non-reflective coating using multi-coating of metal salts and metal oxides.

Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 Commercially available polyvinyl alcohol-iodine complex polarizing film (neutral gray color, degree of polarization 94.6%, single transmittance
45.8%) was hot-press molded into a spherical lens shape, which was then held in a glass lens mold.

On the other hand, 70 parts by weight of 2-ethylhexyl methacrylate and 30 parts by weight of ethylene glycol dimethacrylate.
parts by weight, and 1, which is an organic photochromic substance.
3,3-trimethylspiro[indoline-2,
2 parts by weight of 3'-(3H)naphtho[2,1-b](1,4)oxazine] and the radical polymerization initiator t-butylperoxy-2-ethylhexanoate (10-hour half-life temperature 73℃) to obtain a monomer composition, this monomer composition was poured into the mold holding the polarizing film, and the temperature was raised to 40℃.
Polymerization treatment was carried out by sequentially increasing the temperature from 90°C to 80°C over 16 hours, thereby producing a resin lens with a center thickness of 1.7 mm in which the organic photochromic substance was dissolved in the resin body and a polarizing film was embedded.

This lens has a polarizing film of 94.2% and a single transmittance of
It was 36% gray.

When this lens was exposed to sunlight, it gradually turned dark green. Furthermore, when this lens was left in direct sunlight for 3 minutes and the single transmittance was measured immediately thereafter, it had changed to 25%, indicating that it had an effective light control function as well as a polarizing effect. Furthermore, when the colored lens was left in a dark place, the color tone and single transmittance almost returned to their original state after 3 minutes had passed.

In addition, the value of the single transmittance in the above is 150W
Using the instantaneous multi-photometering system "MCPD-100" (manufactured by Otsuka Electronics Co., Ltd.) that uses a xenon lamp as a light source,
It was obtained by calculating the average value of the transmittance of light with a wavelength of 610 to 620 nm.

Comparative Example 1 The polymerization process was carried out in exactly the same manner as in Example 1, except that in the polymerization treatment, the treatment temperature was raised sequentially from 40 °C to 80 °C over 16 hours, and then further raised to 150 °C over 2 hours. A resin lens was manufactured.

The internal polarizing film of this lens had changed from neutral gray color to brown, and showed almost no polarizing effect.

Comparative Example 2 In the polymerization treatment, 1 part by weight of diisopropyl peroxydicarbonate (10 hour half-life temperature 45°C) was used instead of 1 part by weight of t-butylperoxy-2-ethylhexanoate as a polymerization initiator. A resin lens was manufactured in the same manner as in Example 1 except for this.

This lens was yellow in color and showed no dimming effect at all. This is thought to be due to the organic photochromic material being degraded by the polymerization initiator.

Example 2 Using the same method as in Example 1, a commercially available multi-color polarizing film (blue color, degree of polarization 91%, single transmittance 40%) with a protective layer made of cellulose acetate film provided on the surface was shaped into a spherical shape. It was hot press molded and held in a glass mold.

On the other hand, 60 parts by weight of methyl methacrylate and 2,
2-bis(4-methacryloxyethoxy-3,5
40 parts by weight of -dibromophenyl)propane and the organic photochromic substance 1,3,3-trimethylspiro[indoline-2,2'-(2H)phenanthro[9,10-b](1,4)oxazine]. 1.6
parts by weight and 0.4 parts by weight of azobisisobutyronitrile (10 hour half-life temperature 100°C or less), which is a polymerization initiator, to prepare a monomer composition, and this monomer composition was mixed with the above-mentioned It is injected into a glass mold and polymerized by increasing the temperature from 40°C to 80°C over 20 hours, thereby dissolving the organic photochromic substance in the resin body and embedding the polarizing film. manufactured a 1.2mm resin lens.

This lens has a polarization degree of 88% and a single transmittance of 37
% of blue color.

When this lens was exposed to sunlight, the blue color of the polarizing film became much deeper. Furthermore, when this lens was left in direct sunlight for 3 minutes and the single transmittance was measured immediately thereafter, it changed to approximately 32%, indicating that it had an effective light control function as well as a polarizing effect. Furthermore, when the colored lens was left in a dark place, the color tone and single transmittance almost returned to their original state after 3 minutes had passed.

Example 3 A polyvinyl alcohol-iodine complex polarizing film similar to that used in Example 1 (neutral gray color, degree of polarization 94.6%, single transmittance 45.8%) was hot press molded into a spherical lens shape, and this was It was held in a glass lens mold.

On the other hand, 40 parts by weight of methyl methacrylate and α-
20 parts by weight of methylstyrene, 40 parts by weight of bifunctional polymerizable urethane acrylate formed by urethane bonding of 2 equivalents of isophorone diisocyanate and 1 equivalent of hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexanoate (10 hours). 0.8 parts by weight (half-life temperature 73℃) and 5-chloro-
1,3,3-trimethylspiro[indoline-
2,3′-(3H)-naphtho[2,1-b](1,4)
Oxazine] was mixed with 1.8 parts by weight to obtain a monomer composition, this monomer composition was poured into the mold holding the polarizing film, and polymerized by a method similar to Example 1. Thus, a resin lens with a center thickness of 1.7 mm was manufactured, in which an organic photochromic substance was dissolved in the resin body and a polarizing film was embedded.

This lens has a polarization degree of 92% and a single transmittance of approximately
It was 40% gray.

When this lens was exposed to sunlight, it gradually turned dark green. Furthermore, when this lens was left in direct sunlight for 3 minutes and the single transmittance was measured immediately thereafter, it had changed to 32%, indicating that it had an effective light control function as well as a polarizing effect. Furthermore, when the colored lens was left in a dark place, the color tone and single transmittance almost returned to their original state after 3 minutes had passed.

Comparative Example 3 In the polymerization treatment, instead of 1 part by weight of t-butylperoxy-2-ethylhexanoate, 2,000 ml of t-butylperoxy-2-ethylhexanoate having a 10-hour half-life temperature of 135°C was used as a polymerization initiator.
Using 1 part by weight of 2,4-trimethylpentyl-2-hydroperoxide, the temperature was lowered to 125°C because polymerization cannot be practically achieved at temperatures below 80°C.
A resin lens was produced in the same manner as in Example 1, except that the polymerization treatment was carried out at 145°C and the temperature was finally raised to 145°C.

This lens was strongly colored and showed no light modulating or polarizing effect.

Claims (1)

[Scope of Claims] 1 A radically polymerizable monomer that provides a polymer for optical members contains an organic photochromic substance having a dimming effect and a radical polymerization initiator that does not cause the organic photochromic substance to deteriorate at polymerization temperature. A monomer composition is injected into a cast polymerization container in which a polarizing film is arranged, and the monomer is polymerized in the cast polymerization container at a temperature at which the polarizing film does not deteriorate. A method for manufacturing a resin optical member. 2. The resin optical member according to claim 1, wherein the organic photochromic substance is at least one type of spirooxazine compound represented by any of the following structural formulas (), (), and (). manufacturing method. (In the formula, R ¹ and R ² represent a hydrogen atom, a halogen atom, a cyano group, a lower alkyl group, a lower alkoxy group, and R ³ represents a lower alkyl group, a lower alkoxyalkyl group, various substituted arylalkyl groups, (-
CH ₂ ) _—o COOR (R represents a lower alkyl group), and the number of carbon atoms other than the carbon atoms constituting the aromatic nucleus in each of R ¹ , R ² and R ³ is 6 or less. ) 3 The radical polymerization initiator is selected from peroxyesters, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxyketals, ketone peroxides and azo compounds, and has a half-life of 10 hours. The method for manufacturing a resin optical member according to claim 1, wherein the temperature is 100°C or less.