JPH01163287A - Optical material having dimming action - Google Patents

Abstract

PURPOSE:To obtain an optical material having dimming action and applicable to sunglasses, concave spectacle lens, goggle, etc., by compounding a polyisocyanate resin with a specific amount of a spiroxazine compound. CONSTITUTION:The objective optical material can be produced by compounding (A) a resin produced by polymerizing a polyisocyanate and a polyfunctional monomer produced by reacting a phenolic compound with a hydroxyl compound having polymerizable unsaturated bond or a monomer composition containing >=20wt.% of said monomer with (B) 0.001-20wt.% of one or more spiroxazine compounds of formula I-III [R<1> and R<2> are H, halogen, cyano, lower alkyl or lower alkoxy; R<3> is lower alkyl, lower alkoxyalkyl, arylalkyl or -(CH2)n- COOY (Y is lower alkyl)].

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polyfunctional monomer obtained by reacting a polyisocyanate compound with a phenolic compound and a hydroxy compound having a polymerizable unsaturated bond, or The present invention relates to an optical material having a dimming effect, which is obtained by incorporating a specific spirooxazine compound, which is an organic photochromic substance, into a resin body obtained by polymerizing a monomer composition containing a functional monomer.

[Prior art]

Photochromism is a phenomenon in which a reversible color change occurs in a certain compound when it is irradiated with light containing ultraviolet light, such as sunlight or light from a mercury lamp, and then removed, and this function is applied to optical materials. As a result, an optical material having a dimming effect M can be obtained. For example, those applied to lenses are generally known as photochromic lenses, and are widely used in sunglasses, prescription glasses, goggles, etc.

[Problem that the invention seeks to solve]

Conventionally, lenses with such a dimming function have been limited to lenses made of inorganic glass containing minute silver halide particles, but lenses made of resin have recently become widely used. This lens has not yet been put into practical use.

The reason for this is that inorganic substances such as silver halide particles have low compatibility with resins, and therefore cannot be uniformly dispersed in sufficient amounts in resins, and it is thought that inorganic substances such as silver halide particles have high compatibility with resins. This is because there are few stable and useful organic photochromic compounds.

For example, spiropyran compounds, the most common organic photochromic compounds, show useful photochromism in organic solvents, but fade in polymeric materials with relatively high second-order transition temperatures that are widely used as optical materials. The speed of light control is extremely slow, and the resulting light control materials are therefore subject to significant limitations in their applications.

On the other hand, Japanese Patent Publication No. 45-28892 states that in general non-crosslinked polymers, regardless of their secondary transfer temperature,
It has been disclosed that spirooxazine compounds exhibit photochromic effects. However, as pointed out in Japanese Patent Publication No. 49-48631, this spirooxazine compound exhibits good color change and fading upon irradiation and removal of light at a low temperature of about 10°C; Otherwise, it has the disadvantage that it fades at a high rate at higher temperatures, so that it is virtually uncolored. In general, optical materials that have a light control effect, such as photochromic lenses, are designed to change color or change color when exposed to strong light from the sun, etc., in order to control the transmission of that light. Therefore, it is natural that spirooxazine compounds are required to have a sufficient coloring effect even in an environment with a temperature slightly higher than room temperature. The use of photochromic substances for optical materials having photoactivity is limited.

Under these circumstances, a photochromic hard coat layer containing an organic photochromic substance made of a specific spirooxazine compound together with a phenolic compound such as a phenol resin or a phenol compound has been developed, especially in an environment at a temperature higher than room temperature. It is disclosed in JP-A-62-151802 that it stably exhibits a sufficient coloring action. However, with this technology, since organic photochromic substances and phenolic compounds are contained in the hard coat layer provided as the surface layer of the resin lens body, it is difficult to obtain sufficient durability for the hard coat layer. However, when used in practical use for a long period of time, there is a drawback that there is a large possibility that the hard coat layer may be missing or cracked.

Apart from such reasons, it is desirable that the resin body itself of a photochromic optical material such as a photochromic lens made of resin has a photochromic effect. Therefore, it is considered that the resin body contains both the above-mentioned spirooxazine compound and a phenol compound that improves its photochromic effect. Specifically, the spirooxazine compound and
A possible method is to blend a phenolic compound with a monomer for producing a resin optical material and polymerize it.

However, this method proved to be far from practical. That is, the hydroxyl group of the phenolic compound present in the monomer composition inhibits the polymerization reaction of the monomer,
Therefore, it becomes considerably difficult to obtain the desired polymer. Furthermore, even if a polymerization reaction is possible and a cured polymer is formed, the phenolic compound is merely contained in a dispersed state in the polymer forming the resin body, so the state is not stable. Stable phenolic compounds become liberated or detached easily or over time, and as a result, it is difficult to obtain a good coloring effect over a long period of time, and it is difficult to obtain a uniform dimming effect. In some cases, it may not be possible.

As mentioned above, to date, optical materials such as resin photochromic lenses that have a good light control effect themselves and maintain excellent secondary light effect even after long-term use have been developed. Not discovered.

SUMMARY OF THE INVENTION An object of the present invention is to provide an optical material made of resin which itself has a good light control function, and which shows little deterioration of the light control function over time and is excellent in durability.

[Means and actions for solving problems]

The optical material of the present invention contains a polyfunctional monomer obtained by reacting a polyisocyanate compound with a phenolic compound and a hydroxy compound having a polymerizable unsaturated bond, or at least 20% by weight of the polyfunctional monomer. In the resin body obtained by polymerizing the monomer composition, at least one spirooxazine compound represented by any one of the following general formulas (I), (II), and (I[I) has a molecular weight of 0,001 to 20%. It is characterized by being contained in a proportion of 1%.

General formula (I) General formula (n) General formula (III) (wherein, R1 and R2 represent a hydrogen atom, a halogen atom, a cyan group, a lower alkyl group, or a lower alkoxy group, which may be the same, and R3 is Lower alkyl group, lower alkoxyalkyl group, various substituted arylalkyl groups, +CH2
Bottom C○0Y (Y represents a lower alkyl group), R
The number of carbon atoms other than the carbon atoms constituting the aromatic nucleus in each of 1, R2 and R3 is 6 or less. ) The optical material of the present invention is composed of a resin body, and the polymer or copolymer forming this resin body allows the spirooxazine compound contained in the resin body to exhibit a good coloring effect. Because it is made by polymerizing a polyfunctional monomer to which a phenolic compound is bonded, during production, the polymerization reaction of the monomer is not inhibited because the hydroxyl groups of the phenolic compound are blocked. The desired polymerization can be smoothly achieved, and the phenolic compound component can be reliably incorporated into the three-dimensional crosslinked structure as part of the molecules of the polymer or copolymer to be formed. As a result, the phenolic compound component is liberated,
There is no separation or decomposition, and therefore the good photochromic effect of the spirooxazine compound due to the phenolic compound component is stably exhibited over a long period of time, making it possible to obtain an optical material with extremely excellent durability. .

The present invention will be explained in detail below.

The polymer or copolymer forming the optical material of the present invention is
It is obtained by polymerizing a polyfunctional monomer obtained by reacting a polyisocyanate compound with a phenolic compound and a hydroxy compound having a polymerizable unsaturated bond through a urethanization reaction.

The polyisocyanate compound for obtaining the above-mentioned polyfunctional monomer is a compound having two or more incyanate groups. Specific examples of the polyisocyanate compounds used in the present invention include hexamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate methyl ester, Diisocyanate compounds such as xylylene diisocyanate, tolylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and 4.4°-diphenylmethane diisocyanate can be mentioned;
Examples of the polyfunctional incyanate compound include a biuret-forming reaction product of hexamethylene diisocyanate, a cyclic trimer of hexamethylene diisocyanate, a reaction adduct of hexamethylene diisocyanate and trimethylolpropane, and ethyl 2-incyanate=2. 6-
Diucyanate ethylhexanoate, 1.6.11
- Undecane triisocyanate, the reaction adduct of inphorone diisocyanate and trimethylpropane, the reaction adduct of xylylene diisocyanate and trimethylolpropane, the reaction adduct of bis(isocyanatemethyl)cyclohexane and trimethylolpropane, and others. Can be done.

Among the above polyisocyanate compounds, preferred are:
These include xylene diisocyanate, inphorone diisocyanate, hexamethylene diisocyanate, a cyclic trimer of hexamethylene diisocyanate, and others. In particular, a cyclic trimer of hexamethylene diisocyanate not only does not have the property of yellowing, but also can form an optical material with excellent coloring properties.

In addition, the phenolic compound bonded to the polyfunctional monomer by the urethanization reaction is not particularly limited, and may be -valent phenols or polyvalent phenols, but It is necessary to have at least one hydroxyl group that undergoes a urethanization reaction with the above polyisocyanate compound.

This phenolic compound is not limited to one consisting only of a phenol nucleus, but may also have one or more benzene nuclei like naphthol.

Of course, these phenolic compounds may have their nuclear-bonded hydrogen substituted with an alkyl group, a halogen group, etc., and in particular those of the following general formulas (rV), (V) and (VI). It is preferable to use one or more of the hydrous acid group aromatic compounds represented by any of the above.

General formula (V) (However, X is an alkyl group having 1 to 5 carbon atoms or a halogen atom other than fluorine, a is an integer of 0 to 5, b is an integer of 1 to 3, (Indicates an integer.) As specific examples of the above phenolic compounds, especially p-t
Alkyl-substituted phenols such as -butylphenol, 2.6-di-t-butyl-4-methylphenol, and 2.4.6-di-t-butylphenol are preferably used. Furthermore, phenol compounds with high molecular weight and high polarity are generally particularly suitable for more effectively exhibiting the photochromism of the spirooxazine compound described below, and for example, bisphenol A represented by the general formula (■) or a derivative thereof is preferred. Specifically, bisphenol A1 tetrabromobisphenol A1 2-(4-hydroxyethoxyphenyl)2- to which one of the hydroxyl groups, nietile oxide, is added.
(4-hydroxyphenyl)propane and the like can be preferably used.

In addition, the hydroxy compound, which is a component that imparts polyfunctionality by bonding with the polyisocyanate compound through a urethanization reaction, has a polymerizable unsaturated bond and an active hydroxyl group, and includes, for example, allyl alcohol, methacrylic alcohol, An acrylic ester or methacrylic ester containing a hydroxy group represented by the IE general formula (■) can be used.

General formula (■) H, C: C-C-0-R'+OH).

Here, p: an integer of 1 to 3 R4 = water S atom or methyl group R5, or a substituted or unsubstituted alkylene group having 2 to 12 carbon atoms.

Examples of the above acrylic esters or methacrylic esters include 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxybrobyl methacrylate, 3-hydroxypropyl methacrylate, 4-
Hydroxybutyl methacrylate, 2-hydroxy-3
-chloropropyl acrylate, and others.

In addition to the above, various polyols such as polyester polyols and polyether polyols having polymerizable unsaturated bonds can also be used, and the polyols are not limited to those shown here. These may be used alone or in combination of two or more.

Among the above, particularly preferred hydroxy compounds are allylalconopemethacrylic alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl methacrylate.

A polyfunctional monomer can be obtained by subjecting the above-mentioned polyisocyanate compound, phenol compound, and hydroxy compound to a urethanization reaction. Here, the ratio of the polyisocyanate compound to the phenol compound and the hydroxy compound is 4 to 80 equivalent %, preferably 10 to 60 equivalent % of the phenol compound based on the total hydroxyl groups, based on the total isocyanate groups of the polyisocyanate compound. The hydroxy compound is used in an amount corresponding to 96 to 20 equivalent %, preferably 90 to 40 equivalent %, based on the total hydroxyl groups. In this urethanization reaction, the temperature is usually room temperature to 200°C, and the reaction time is 5 to 3
Although the reaction time is assumed to be 0 hours, the reaction time can also be shortened by using a known urethanization reaction promoting catalyst.

In order to obtain the optical material having a light control effect of the present invention, it is sufficient to polymerize the polyfunctional monomer obtained as described above mixed with the spirooxazine compound described below. In order to adjust various properties of the optical material, such as refractive index, specific gravity, impact resistance, dyeability, and other properties, the above-mentioned polyfunctional polymer can be copolymerized with other monomers. However, it is necessary to contain at least 20% by weight of the above-mentioned polyfunctional monomer in the total monomers. In practice, by using a monomer composition containing a polyfunctional monomer of 30 to 70% by weight, an optical material can be obtained that has excellent light control properties and excellent properties such as sufficient heat resistance and solvent resistance. This is preferable because it can be done.

The type of monomer that can be copolymerized with the above-mentioned polyfunctional upper layer is not particularly limited, and as long as it does not inhibit the function of the optical material having a light control effect, the final optical material Depending on the purpose, one type or two or more types of known materials can be used.

In the present invention, the spirooxazine compound blended into the polyfunctional monomer or monomer composition is a compound represented by any one of the aforementioned general formulas (I), (n), and (I(I)). Representative examples of such spirooxazine compounds include 1.3.3-)dimethylspiro[indoline-2,3'-naphtho[2,1-b]
(I,4)-oxazine], 1,3.3.5-tetramethylspiro[indoline-2,3°-naphtho[2,1-
b) (I,4)-oxazine], 5-chloro-1,3,3-)dimethylspiro[indoline-2,3'-naphtho(2,1-b) (I,4)-oxazine], 5 -methoxy-1,3,3-)dimethylspiro[indoline-2,3°-naphtho(2,1-b) (I,4)-
oxazine], 1-isopropyl-3,3-dimethylspiro[indoline-2,3'-naphtho[:2.1-b) (I,4)-
oxazine], 1.3.3-)dimethylspiro[indoline-2,2°-(2H)phenanthro(9,10-b](I,4)-
oxazine], 1.3.3-)dimethylspiro[indoline-2,3゛-(3H)-pyridoC3,2-f] (I,4)-benzoxazine], 1-isopropyl-3,3-dimethyl Spiro[indoline-2,3'-(3H)-pyrido[3,2-f)(I,
4)-benzoxazine], 1,3.3.5-tetramethylspiro[indoline-
2,3'-(3H)-pyrido(3,2-f](I,4
)-benzoxazine], 9°-methoxy-1,3,3-trimethylspiro[indoline-2,3”-(3H)-pyridoC3,2-f](
I,4)-benzoxazine].

The reason why the spirooxazine compounds represented by general formulas (I), (II), and (I) exhibit remarkable coloration is that in the copolymer containing a highly polar phenolic compound component, ions are removed by light irradiation. This is thought to be because the isomer of the color-forming spirooxazine compound produced by dissociation comes to exist relatively stably, and therefore the color-forming state is maintained well.

The content of the spirooxazine compound is o, oot ~ 20
A particularly preferred range is 0.05 to 10% by weight. The content of spirooxazine compound is 0.001 weight 1
If it is less than 20% by weight, the coloring effect will not be sufficient, while if it exceeds 20% by weight, polymerization will be inhibited and the optical material itself may become opaque.

The polymer or copolymer forming the optical material of the present invention is
It can be obtained by polymerizing an appropriate mixture or composition of the above polyfunctional monomer, other monomers used as necessary, and the above spirooxazine compound, but this polymerization is usually carried out by radical polymerization initiation. This can be done by using an agent.

As the polymerization method, a method used in normal radical polymerization can be used. However, since the resulting copolymer is cross-linked, it is virtually impossible to perform any treatment that involves melting or dissolving it, so optical materials can be produced directly by casting polymerization using a casting container. It is desirable to do so.

As this cast polymerization method, well-known techniques can be used as they are. Casting containers can be plate-shaped, lens-shaped,
Cylindrical, prismatic, conical, spherical, and other molds, molds, and other objects designed according to the purpose are used. The material may be any suitable material such as inorganic glass, plastic, or metal.

In the case of the cast polymerization method, all of the polyisocyanate compound, phenol compound, and hydroxyl compound for the above-mentioned polyfunctional monomer, and other monomers added as necessary are mixed in a suitable casting container. The urethane-forming reaction is first carried out to produce a polyfunctional monomer. It is not necessary to carry out the urethanization reaction of the phenolic compound and the urethanization reaction of the hydroxy compound at the same time, and they may be carried out separately and consecutively. This is preferable because it makes it easy to control the binding ratio. A required amount of spirooxazine compound is added to and mixed with the polyfunctional monomer thus obtained, and then a polymerization initiator is further added, and if necessary, polymerization is carried out by heating. Other monomers can also be added after the multifunctional monomer is formed. It is also possible to carry out a certain degree of polymerization in a separate container, and then charge the resulting prepolymer or syrup into a casting container to complete the polymerization.

Each monomer and polymerization initiator may be mixed in their entire amounts at once, or may be mixed in stages. Depending on the intended use of the resulting optical material, the 7-mer composition may contain antistatic agents, colorants, fillers, ultraviolet absorbers, antioxidants, heat stabilizers, and other auxiliary materials. can.

Another example of an advantageous polymerization process is suspension polymerization, in which a mixture or prepolymer of polyfunctional monomers and other monomers, spirooxazine compounds, and polymerization initiators is suspended in water. It's legal. This method is suitable for obtaining optical materials used as spherical lenses of various particle sizes.

Even when using this suspension polymerization method, well-known techniques can be utilized as they are.

The resulting polymer or copolymer is heated to complete any incomplete polymerization or to increase hardness, or to remove any strain that may have occurred within the copolymer by casting polymerization. Needless to say, annealing and other post-processing can be performed to remove the .

The optical material of the present invention can be directly obtained as a final product by the cast polymerization method as described above, or can be cut into a final product by cutting it from a lump of the polymer or copolymer. You can also get something like this. By subjecting the resulting optical material to surface polishing, antistatic treatment, and other post-treatments as necessary, the inherent properties of the optical material can be further improved or improved, or the desired characteristics can be further improved. can be given the following properties. Furthermore, when an optical material is used as a lens, in order to increase the surface hardness of the lens, the surface may be coated with an inorganic or organic hard coating agent by means such as dipping, an anti-reflective coating may be applied, and various other methods may be used. Of course, it is also possible to dye with the following dyes.

〔Effect of the invention〕

The optical material of the present invention contains a phenolic compound having a three-dimensional crosslinked structure, which is effective in ensuring that the color-forming isomer produced by ionic dissociation of a spirooxazine compound by light irradiation exists stably in the resin body. It is contained as a part of the molecule in polymers, and as a result, a sufficiently good photochromic effect can be obtained even at room temperature or higher temperature conditions, and a sufficiently high rate of color change and fading can be obtained for practical use. Since the phenolic compound component is almost never liberated, detached, or deteriorated, its good light control effect can be stably exhibited without deterioration even after long-term use. Since the material itself has a light modulating effect, it does not have the problems that occur in lenses formed with a hard coat layer having a light modulating effect, and has sufficiently high durability.

Therefore, the optical material of the present invention is most typically implemented as a photochromic lens and can be used for sunglasses, prescription glasses, various goggles, etc. Also, depending on the properties of the resin body obtained, it can be used as an optical filter, etc. It is a useful material that can be applied as window spring stained glass and other optical materials having a light control function.

〔Example〕

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

Example 1 Cyclic trimer of hexamethylene diisocyanate 31.57 parts by weight Bisphenol A 7.14 parts by weight 2-hydroxyethyl methacrylate 16.29 parts by weight 1
．． 3-Butylene glycol dimethacrylate) 20.00 parts by weight Inbutyl methacrylate 20.00 parts by weight α-methylstyrene 5.00 parts by weight I! The mixture of the above substances is maintained at 60°C, and 0.05 parts by weight of n-butyltin dilaurate, which is a urethanization reaction promoting catalyst, is added and reacted, and the polyfunctional monomer containing the phenolic compound component is added to the mixture. It was generated inside. In the above,
The molar ratio of cyclic trimer of hexamethylene diisocyanate:bisphenol A:2-hydroxyethyl methacrylate is 2:1:4.

This polyfunctional monomer mixture is added as a spirooxazine compound (1,3.3-)! 232 parts by weight of J methyl spiro[indoline-2,3°-naphtho[2,1-b] (I,4)-oxadi and 1 part by weight of t-butylperoxypivalate as a polymerization initiator were added. The mixed solution was injected into a glass mold for making lenses, and heated at 50°C for 10 hours, at 60°C for 5 hours, at 80°C for 2 hours, and then at 80°C for 10 hours.
Polymerization was carried out under varying reaction conditions at 0° C. for 2 hours, thereby producing a thin blue transparent photochromic lens with a center thickness of 1.7 mm.

When this photochromic lens was exposed to sunlight, it gradually turned a deep blue color. Furthermore, we have developed an instantaneous multi-photometering system rMcPD-100J (
(manufactured by Otsuka Electronics), the wavelength of this photochromic lens is 605 ~
When the parallel light transmittance for 615 nm light was measured immediately before leaving it in direct sunlight and immediately after leaving it in direct sunlight for 3 minutes, it was 68% and 37%, respectively, and a large color tone change was observed. It was confirmed that it has a dimming function.

When the colored photochromic lens was left in a dark place for 3 minutes, it recovered to its original color tone and parallel light transmittance.

On the other hand, when we conducted an accelerated exposure test using this photochromic lens as a sample using a weather meter "Super Long Life Sunshine Weather Meter" (manufactured by Suga Test Instruments Co., Ltd.), we found that even after 300 hours, it was not exposed to direct sunlight. Parallel light transmittance before and after leaving for 3 minutes is 75%
It was confirmed that the brightness of the light changed from 45% to 45%, demonstrating the same excellent light control effect as at the initial stage.

The surface hardness of this photochromic lens was rH when measured using the pencil hardness specified in JIS K-5400, and it was completely insoluble in organic solvents such as ethanol, methyl ethyl ketone, tetrahydrofuran, and toluene.

Comparative Example 1 Cyclic trimer of hexamethylene diisocyanate 31.01 parts by weight 2-hydroxyethyl methacrylate 23.99 parts by weight 1
．． 3-Butylene glycol dimethacrylate) 20.00 parts by weight Inbutyl methacrylate) 20.00 parts by weight α-
6 parts of a mixture of 5 parts and 5 parts of methylstyrene
The temperature was maintained at 0°C, and 0.05 parts by weight of n-butyltin dilaurate was added in the same manner as in Example 1 to produce a polyfunctional monomer containing no phenolic compound component in the mixed liquid. In the above, the molar ratio of the cyclic trimer of hexamethylene diisocyanate to 2-hydroxyethyl methacrylate is 1:3.

1.3.3-)limethylspiro[indoline-
232 parts by weight of 2,3'-naphtho[2,1-b] (I,4)-oxadi and 1 part by weight of t-butylperoxypivalate as a polymerization initiator were added, and this mixed solution was used to manufacture lenses. A photochromic lens having a center thickness of 1.7 mm was produced in exactly the same manner as in Example 1 by injecting the mixture into a glass mold for use in the market.

Regarding this lens, the parallel light transmittance before and after leaving it in direct sunlight for 3 minutes was measured in exactly the same manner as in Example 1, and the parallel light transmittance only changed from 64% to 54%, compared to the photochromic lens of Example 1. In comparison, the light control effect was inferior.

On the other hand, when this photochromic lens was used as a sample and an accelerated exposure test was conducted using a weather meter in the same manner as in Example 1,
After 150 hours, the parallel light transmittance before and after being left in direct sunlight for 3 minutes only changed from 72% to 66%, and the coloring effect was extremely small.

As described above, it is clear that the lens of Comparative Example 1 does not fully exhibit the light control function of the spirooxazine compound compared to the lens of Example 1 because the resin lens body does not contain a phenolic compound. .

The pencil hardness of the lens of Comparative Example 1 was "H", and it was completely insoluble in organic solvents such as ethanol, tetrahydrofuran, and toluene.

Comparative Example 2 Cyclic trimer of hexamethylene diisocyanate 28.8 G parts by weight 2-hydroxyethyl methacrylate 22.28 parts by weight 1.
3-Butylene glycol dimethacrylate) 18.57 parts by weight Inbutyl methacrylate) 18.57 weight 1 tfl
A mixed solution of 4.64 parts by weight of lSα-methylstyrene was maintained at 60°C, and 0.05 parts by weight of n-butyltin dilaurate was added in the same manner as in Example 1 to obtain a polyfunctional monomer containing no phenolic compound component. It was produced in a mixed solution. In the above, the molar ratio of cyclic 31 hexamethylene diisocyanate to 2-hydroxyethyl methacrylate is 1:3.

To this mixed liquid, 7.14 parts by weight of bisphenol A,
1.3.3-) IJ methyl spiro [indoline-2,3°-naphthocarving, 1-b] as a spirooxazine compound
2 parts by weight of (I,4)-oxazine] and 3 parts by weight of t-butyl peroxyvivalate were added, and this mixed solution was poured into a glass mold for lens production, in exactly the same manner as in Example 1. Thus, a blue, transparent photochromic lens with a center thickness of 1.7+nm was obtained.

The reason why the amount of 1 in the polymerization initiator is greater than in Example 1 is that if it is less than 2 parts by weight, polymerization will be insufficient because it will partially dissolve in the organic solvent, so the amount of 1 in the polymerization initiator is increased to 3 parts by weight. As a result, a copolymer completely insoluble in organic solvents such as ethanol, methyl ethyl ketone, tetrahydrofuran, and toluene was obtained. However, even if the pot of polymerization initiator contained 3 parts by weight, the pencil hardness was about "3B".

Regarding this lens, the parallel light transmittance before and after leaving it in direct sunlight for 3 minutes, measured in exactly the same manner as in Example 1, changed from 65% to 32%, and it was as effective as the photochromic lens of Example 1. It is recognized that it has a light control effect,
When the colored photochromic lens was left in a dark place for 3 minutes, it recovered to its original color tone and parallel light transmittance.

On the other hand, when this photochromic lens was used as a sample and an accelerated exposure test was conducted using a weather meter in the same manner as in Example 1,
After 20 hours, the parallel light transmittance before and after being left in direct sunlight for 3 minutes changed from 63% to 55%, and after 50 hours, it changed from 70% to 64%, indicating a dimming effect. was observed to decrease rapidly.

The reason for this is that the photochromic lens does not incorporate a phenolic compound into the three-dimensional crosslinked structure of the copolymer that forms the resin lens body, compared to that of Example 1.
This is presumed to be because the phenolic compound elutes and is eliminated over time, and the color stability of the spirooxazine compound is rapidly lost within a short period of time.

Example 2 Cyclic trimer of hexamethylene diisocyanate 31.866 parts by weight Bisphenol A 10.81 parts by weight 2-hydroxyethyl methacrylate 12.33 parts by weight 2-ethylhexyl methacrylate 15.00 parts by weight Methyl methacrylate) 25 .00 parts by weight of styrene A mixture of 5 parts by weight or more of substances is maintained at 60°C, and 0.05 parts by weight of n-butyltin dilaurate is added and reacted to mix a polyfunctional monomer containing a phenolic compound component. It was formed in the liquid. In the above, the molar ratio of the cyclic trimer of hexamethylene diisocyanate:bisphenol A:2-hydroxyethyl methacrylate is 4:3:6.

Add 5-chloro-1,3,3-) to this mixture! J Methylspiro[indoline-2,3゛-naphtho[2,1-b(
232.0 parts by weight of I,4)-oxadi and 1 part by weight of t-butylperoxypivalate were added, and using this mixed solution, the center thickness was 2.3 m in exactly the same manner as in Example 1.
A photochromic lens of m was manufactured.

Regarding this photochromic lens, when the parallel light transmittance was measured before and after leaving it in direct sunlight for 3 minutes in the same manner as in Example 1, it changed from 71% to 39%. In addition, when we conducted a 300-hour accelerated exposure test using a weather meter, the parallel light transmittance before and after being left in direct sunlight for 3 minutes changed from 74% to 48%, indicating that the dimming function was as effective as the initial one. was confirmed to be maintained. When the colored photochromic lens was left in a dark place for 3 minutes, it recovered to its original color tone and parallel light transmittance.

The surface hardness of this photochromic lens is "H" on the pencil hardness scale.
It was completely insoluble in organic solvents such as ethanol, methyl ethyl ketone, tetrahydrofuran, and toluene.

Example 3 Inphorone diisocyanate 24.94 parts by weight 0.
0゛-Biphenol 10.45 parts by weight 2-Hydroxyethyl methacrylate 14.611 parts Dicyclopentenyloxyethyl acrylate 20.00 parts by weight Ethylene glycol dimethacrylate 10.00 parts by weight Styrene 10.00 parts by weight or more The mixed solution was maintained at 60° C., and 0.05 parts by weight of n-butyltin dilaurate was added and reacted to produce a polyfunctional monomer containing a phenolic compound component in the mixed solution. In the above, the molar ratio of inphorone diisocyanate: 0.0°-biphenol: 2-hydroxyethyl methacrylate is 2:1:2.

Add 1.3.3-)limethylspiro[indoline-2,3°-naphtho2.1-b(I,4)-] to this mixture.
A blue transparent photochromic lens with a center thickness of 2.3 mm was obtained in the same manner as in Example 1 by adding 31.0 parts of Oxadif and 1.5 parts by weight of lauroyl peroxide. .

Regarding this photochromic lens, when we measured the parallel light transmittance before and after leaving it in direct sunlight for 3 minutes in the same manner as in Example 1, it changed from 82% to 47%. After a 300-hour accelerated exposure test using a meter, the parallel light transmittance before and after being left in direct sunlight for 3 minutes changed from 85% to 54%, maintaining the same effective dimming function as at the initial stage. This was recognized.

Comparative Example 3 Isophorone diisocyanate 18.22 parts by weight 2-
Hydroxyethyl methacrylate 21.33 parts by weight Dicyclopentenyloxyethyl acrylate 20.00 parts by weight 3 Ethylene glycol dimethacrylate 10.00 parts by weight Styrene A mixture of 10.00 parts by weight or more of substances was kept at 60°C, and dilauric acid n- 0.05 parts by weight of butyltin was added and reacted to produce a polyfunctional monomer containing no phenolic compound component in the mixed solution. In the above, the molar ratio of inphorone diisocyanate:2-hydroxyethyl methacrylate is 1:2.

To this mixture, 10.45 parts by weight of 0,0゛-biphenol and 1,3,3-trinotylspiro[indoline-2
, 1.0 parts by weight of 3°-naphtho[2,1-bco(I,4)-oxazine] and 4.0 parts by weight of lauroyl peroxide, and using this mixed solution, the procedure of Example 1 was carried out. A blue transparent resin lens with a center thickness of 2.3 mm was obtained using the same method. In addition, when the amount of lauroyl peroxide was 3.0 parts by weight or less, polymerization was inhibited, and a copolymer having resistance to organic solvents could not be obtained.

Regarding this lens, when we measured the parallel light transmittance before and after leaving it in direct sunlight for 3 minutes in the same manner as in Example 1, it changed from 80% to 46%, compared to the photochromic lens of Example 3. The light control effect was not inferior. However, in an accelerated exposure test using a weather meter, 20
After time has passed, the parallel light transmittance before and after leaving it in direct sunlight for 3 minutes changes from 80% to 58%, and further increases by 58%.
After 0 hours, the rate changed from 82% to 72%, indicating a rapid decline in secondary light function.

From the results of Example 3 and Comparative Example 3 above, when the phenolic compound is incorporated into the three-dimensional crosslinked structure of the copolymer forming the resin lens body, the durability of the light control effect by the spirooxazine compound is It is clear that it has a significant effect on

Example 4 Inphorone diisocyanate 13.93 parts by weight Tetrabromobisphenol A 17.03 parts by weight 2-hydroxypropyl methacrylate 9.04 parts by weight 2-ethylhexyl methacrylate 25.00 parts by weight Ethylene glycol dimethacrylate 10.00 parts by weight Styrene A mixed solution of 25.00 parts by weight or more of substances is kept at 60°C, and 0.05 parts by weight of n-butyltin dilaurate, which is a urethanization reaction promoting catalyst, is added and reacted. The functional monomer was formed into the mixture and concentrated. In the above, the molar ratio of inphorone diisocyanate:tetrabromobisphenol A:2-hydroxypropyl methacrylate is 2:1:2.

1,3.3-)limethylsubiro[indoline-
231 parts by weight of 2,3'-naphtho[2,1-b] (I,4)-oxadi and 2 parts by weight of t-butylperoxypivalate as a polymerization initiator were added, and this mixed solution was used to manufacture lenses. Pour into a glass mold for 1 hour at 50℃.
5 hours, 10 hours at 60°C, 2 hours at 80°C and 10 hours.
Polymerization was carried out under varying reaction conditions at 0° C. for 2 hours, thereby producing a thin blue transparent photochromic lens with a center thickness of 1.7 mm.

When this photochromic lens was exposed to sunlight, it gradually turned a deep blue color. Regarding this photochromic lens, when the parallel light transmittance was measured before and after leaving it in direct sunlight for 3 minutes in the same manner as in Example 1, it changed from 88% to 48%. When this colored photochromic lens was left in a dark place for 3 minutes, it recovered to its original color tone and parallel light transmittance. In addition, after a 200-hour accelerated exposure test using a weather meter, the parallel light transmittance of this photochromic lens before and after being left in direct sunlight for 3 minutes was 89% to 56%.
It was confirmed that the effective dimming function was maintained as in the initial stage.

The surface hardness of this photochromic lens was "H" as measured by the pencil hardness specified in JIS K-5400, and it was completely insoluble in organic solvents such as ethanol nope methyl ethyl ketone, tetrahydrofuran, and toluene.

Comparative Example 4 Isophorone diisocyanate 17.48 parts by weight 2-
Hydroxypropyl methacrylate) 13.48 parts by weight 2
- Ethylhexyl methacrylate (25.00 parts by weight ethylene glycol dimethacrylate) 10.00 parts by weight styrene A mixed solution of 25.00 parts by weight was kept at 60°C, and dilauric acid n-
0.05 parts by weight of butyltin was added to produce a polyfunctional monomer containing no phenolic compound component in the mixed solution. In the above, the molar ratio of inphorone diisocyanate:2-hydroxypropyl methacrylate is l
:2.

Add 9.0% of tetrabromobisphenol A to this mixture.
4 parts by weight and 1.3.3 as spirooxazine compound
-) Limethylspiro[indoline-2,3'-naphtho[2,1-bco(I,4)-oxadi (231 parts by weight) and 3 parts by weight of t-butyl peroxyvivalate were added, and this mixture was mixed into a lens. Injected into a glass mold for production, using exactly the same method as in Example 1, to a center thickness of 1.7 mm.
A green, transparent photochromic lens was obtained.

The reason why the amount of polymerization initiator is larger than in Example 1 is that if it is less than 2 parts by weight, polymerization will be insufficient because it will partially dissolve in the organic solvent, so the amount of polymerization initiator is set to 3 parts by weight. As a result, a copolymer completely insoluble in ethanol, methyl ethyl ketone, tetrahydrofuran, toluene, etc. was obtained.

However, even if the amount of polymerization initiator is 3 parts by weight, the pencil hardness is 2B.
” was about the extent.

Regarding this lens, the parallel light transmittance before and after leaving it in direct sunlight for 3 minutes, measured in exactly the same manner as in Example 1, changed from 86% to 48%, and it was as effective as the photochromic lens of Example 1. It is recognized that it has a light control effect,
When the colored photochromic lens was left in a dark place for 3 minutes, it recovered to its original color tone and parallel light transmittance.

On the other hand, when this photochromic lens was used as a sample and an accelerated exposure test was conducted using a weather meter in the same manner as in Example 1,
After 20 hours, the parallel light transmittance before and after being left in direct sunlight for 3 minutes changed from 84% to 57%, and after 50 hours, it changed from 82% to 72%, indicating a dimming effect. It was observed that the parallel light transmittance of the lens itself was also decreasing.

The reason for this is that the photochromic lens does not incorporate a phenolic compound into the three-dimensional crosslinked structure of the copolymer that forms the resin lens body, compared to that of Example 4.
Elution and desorption of phenolic compounds occur over time, and the color stability of spirooxazine compounds is rapidly lost within a short period of time.Moreover, the eluted and desorbed phenolic compounds cloud the lens. It is assumed that

Example 5 1,3,3-trimethylspiro[indoline-2,3°
-(3H)-pyrido[3,2-f] (I,4) -
A photochromic lens having a center thickness of 2.3 cm was prepared in exactly the same manner as in Example 1 by adding 231.0 parts by weight of benzoxadi and 1 part by weight of t-butyl peroxypivalate.

Regarding this photochromic lens, when the parallel light transmittance was measured before and after leaving it in direct sunlight for 3 minutes in the same manner as in Example 1, it changed from 64% to 23%. When this lens was left in a dark place for 3 minutes, it recovered to its original color tone and parallel light transmittance.

In addition, when we conducted a 300-hour accelerated exposure test using a weather meter, the parallel light transmittance before and after being left in direct sunlight for 3 minutes changed from 69% to 36%.
It was assumed that the effective dimming function would be maintained as in the initial stage.

The surface hardness of this photochromic lens was "H" on the pencil hardness scale, and it was completely insoluble in organic solvents such as ethanol, methyl ethyl ketone, tetrahydrofuran, and toluene.

Claims (1)

[Claims] 1) A polyfunctional monomer obtained by reacting a polyisocyanate compound with a phenolic compound and a hydroxy compound having a polymerizable unsaturated bond, or containing at least 20% by weight of the polyfunctional monomer. The following general formula (
At least one spirooxazine compound represented by any one of I), (II) and (III) is 0.00
An optical material having a dimming effect, characterized in that the content thereof is 1 to 20% by weight. General formula (I) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (III) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R ^1 and R^2 represent a hydrogen atom, a halogen atom, a cyano group, a lower alkyl group, or a lower alkoxy group, which may be the same, and R^3 represents a lower alkyl group, a lower alkoxyalkyl group, or various substituted arylalkyl groups. , ■
CH_2■_nCOOY (Y 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. ) 2) The phenolic compound has the following general formula (IV) or (V)
The optical material having a light modulating effect according to claim 1, which is at least one kind of a hydrous acid group aromatic compound represented by any one of (VI) and (VI). General formula (IV) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (V) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (VI) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (However, X an alkyl group having 1 to 5 carbon atoms or a halogen atom other than fluorine; a is an integer of 0 to 5; b is an integer of 1 to 3; c, d, e, and f are integers of 0 to 4).