JPH01170904A - Polarizing sheet having photochromic property - Google Patents

Abstract

PURPOSE:To provide both functions of a photochromic property and polarization function with a single sheet by providing a film having the photochromic property and a specific thickness to at least at part of a substrate having the polarization function. CONSTITUTION:The film having the photochromic property and 0.1-30mum thickness is provided to at least a part of the substrate having the polarization function. The thickness of the film having the photochromic property is preferably >=0.1mum, more preferably >=2mum in order to prevent the unequal coloration densities by the film thickness. Moreover, the film thickness is preferably <=30mum, more preferably <=25mum in terms of the ease and uniformity of coating. The polarizing sheet which has excellent colorability and decolorability and both functions of the photochromic property and the polarization function is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polarizing sheet having photochromic properties.

[Conventional technology] Products with various functions have been developed to make objects easier to see and protect the eyes. Among them, in order to automatically control the amount of light such as sunlight that enters the eyes, it is possible to automatically control the amount of light such as sunlight that enters the eyes. Much research has been done on so-called photochromic compounds that change to a colored state and their applications. On the other hand, attempts have been made to use polarizing sheets to reduce glare caused by reflected light and to make the reflective surface itself easier to see.

Many proposals have already been made regarding the use of such a sheet having photochromic properties or a sheet having a polarization function alone.

[Problems to be Solved by the Invention] However, there is no known sheet that satisfies both functions at the same time, and an object of the present invention is to provide a single sheet that has both functions.

[Means for Solving the Problems] The present invention has the following configuration to achieve the above object.

"A polarizing sheet with photochromic properties, characterized by having a film having photochromic properties with a thickness of 0.1 to 30 μm on at least a part of the substrate with polarizing properties." Here, what is the substrate with polarizing properties? , is a substrate that has the function of converting electromagnetic waves that vibrate perpendicularly to the direction of propagation of light, generally called natural light, into light that has a certain vibrational bias, which is a collection of light from vibrating surfaces in all directions. The types include linear polarizing plates, circular polarizing plates, and elliptically polarizing plates. In particular, a linear polarizing plate is preferably used for the purpose of removing reflected light, for example, removing unpleasant glare reflected from water surfaces, glass surfaces, road surfaces, etc.
The photochromic coating of the present invention is particularly preferred since it controls the light beam m.

Further, as a specific example of the substrate having the above-mentioned polarizing function, a film made by stretching polyvinyl alcohol and then adsorbing iodine is a preferable polarizing substrate because it is inexpensive and easily available. It is not particularly limited as long as it has the following.

On the other hand, such polarizing films also have heat resistance, water resistance,
In order to provide sufficient chemical resistance, polarization durability, etc., it is generally preferable to use a composite material sandwiched with various substrates. As the substrate used for the sandwich, glass and various plastics, especially plastics having no birefringence, are preferably used.

Among such plastics, thermoplastic resins such as acrylic plates, acetyl celluloses, and thermosetting resins such as diethylene glycol bisallyl carbonate polymer plates are particularly preferably used in terms of moldability and flexibility.

In the case of linearly polarized light, those having a degree of polarization expressed by the following formula (I>) of 70% or more are preferably used from the viewpoint of polarization performance.

V <%)=Fp/Fx100 (I> where V is the degree of polarization, F is the polarized light flux, and Fp is the light flux for vibration in either the vertical or horizontal direction.

In the present invention, a coating having a photochromic property with a thickness of 0.1 to 30 μm is provided on at least a part of the substrate having a polarizing function. Of course, other photochromic compounds can also be used. Specific examples of such photochromic compounds include, for example, G,
l-1, written by BITOWN, “PHO CHO CHRO
Wiley Interscience
e, New York (1971) and Special Publications 1972-288
Publication No. 92, Japanese Patent Publication No. 49-48631, Japanese Patent Application Publication No. 1977
5-36284, JP 61-53288, JP 61-161286, JP 61-16
1287, JP 61-233079, JP 61-243087, JP 61-2686
No. 86, JP 62-33184 @ JP, JP 62-153288, JP 62-164685
Examples are given in the publication.

In particular, a photochromic compound represented by the following general formula (A) is particularly preferably used from the viewpoint of color developing/fading property, repetition resistance, etc.

is selected from hydrogen, a C1-C8 alkyl group, an alkoxy group, and a halogen. R1 is selected from the group consisting of a C1-C6 alkyl group and a C7-C20 substituted or unsubstituted aralkyl group. R2 and R3 are each hydrogen,
an alicyclic group selected from the group consisting of 01 to C5 alkyl groups, phenyl groups, hepano- or di-substituted phenyl groups, benzyl groups, or containing 6 to 8 carbon atoms (including spiro carbon atoms) in combination; A cyclic ring selected from a formula ring, a norbornyl group, and an adamantyl group. R4, R5,
R6, R7 and R8 are each hydrogen, 01 to C5
selected from alkyl groups, alkoxy groups, halogens, nitro groups, cyano groups, droxy groups, halogenated alkyl groups of 01 to C5, alkoxycarbonyl groups, and amino groups. ) Specific examples of such spirooxazine compounds include 1-benzyl-3,3-dimethylspiro[indolino-2,3
' -[3H]naphtho[2,1-bl(1,4)oxazine], 1-(4-methoxybenzyl)-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[
2,1-bl (1゜4)oxazine1.1-(2-
methylbenzyl)-3,3-dimethylspiro[indolino-2゜3'-[3H]naphtho[2,1-bl (
1,4)oxazine], 1-(3-methylbenzyl)-
3゜3-dimethylspiro[indolino-2,3'-[
3H conaphtho[2,1-bl (1,4)oxazine], 1-(4-methylbenzyl)-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,
1-bl (1,4>oxazine).

1-(3,5-dimethylbenzyl)-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2
, 1-bl (1,4)oxazine].

1- (2,4,6-drimethylbenzyl)-3゜3-
Dimethylspiro[indolino-2,3'-[3H conaphtho[2,1-bl (1,4)oxazine], 1-
(4-chlorobenzyl)-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-bl
(1,4)oxazine].

1-(4-bromobenzyl)-3,3-dimethylspiro[indolino-2,3'-[3H]naphtho[2,1-
bl (1,4>oxazine], 1-(2-fluorobenzyl)-3,3-dimethylspiro[indolino-2
,3'-[31-1]naphl~[2,1-bl (
1,4>oxazine], 1-(3-fluorobenzyl)
-3,3-dimethylspiro[indolino-2,3' -
[31-(]naphtho[2,1-bco(1,4>oxazine)], 1-(4-fluorobenzyl)-3,3-dimethylspiro[indolino-2,3'-[31-1]naph 1~[2,1-bl (1,4>okylysine]
, 1-(2,4-difluorobenzyl 13,3-dimethylspiro[indolino-2,3'-[311]nut[2,1-bl (1,4>oxylidine]), 1-
(2,3,4,5,6-pentafluorobenzyl)-3
,3-dimethylspiro[indolino-2゜3'-[3
11] naph l-[2,,1-bl (1,4)oxazine], 1-(/4-cyanobenzyl)-3°3-dimethylspiro[indolino-2,3'-[3H]nut[2 , 1-bl (1,4>7J Quizazine], 1-(
/l-trifluoromethylbenzyl)-3,3-dimethylspiro[indolino2.3'-[3H]naphtho[
2,1-b] (1゜4)7Jkisu゛jin], 1-
(4-nitrobenzyl)-3,3-dimedylspiro[indolino-2,.

3'-[31-1] naphtho[2,1-b] (1,4
)Axazine], 1-(2-phenylethyl)-3,3
- Dimedyl Spiro [Indolino-2゜3'-[31-1
] Naf l-[2,1-b] (1,4)Δchilidine 1
．． 1-(3-phenylpropyl)-3,3-dimedylspiro[indolino-2,3'-[3H] naph 1-[2,
1-b] (1,4>oxazino], 1-<2-naphthyl)-3,3-dimedylsubiro[indolino-2,3
'-[3H]nut[2,1-b] (1,4) oxyridine] and the like.

Moreover, it is also possible to use not only one type of these photochromic compounds, but also two or more types (7).

These photochromic compounds are used by being dispersed in an organic polymer matrix, but the organic polymer is not particularly limited as long as it has good compatibility with the photochromic compound. Specific examples of usable organic polymers include acrylic resin, polyurethane resin, epoxy resin, melamine resin, polyvinyl acetate, polycarbonate,
Polystyrene resin, celluloses such as cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.
Further examples include polyvinyl alcohol, urea resin, and nylon resin. In addition, each of these resins has 2
It is also possible to use one or more types in combination, and it is also possible to perform three-dimensional crosslinking by adding various curing agents, crosslinking agents, etc. In particular, those using organic polymers such as matrices made by cross-linking acrylic resins with hydroxyl and carboxyl groups in their side chains with melamine resins, and matrices made by cross-linking acrylic resins with amino groups etc. in epoxy resins as organic polymers. The repetition resistance of the photochromic compound, the rate of color development and fading, and when a hard coat is provided on the film, the resistance to solvents when coating the hard coat layer,
This is particularly preferred from the viewpoint of adhesion to the hard coat film.

In addition, the film thickness of the coating having A tochromic property (according to the present invention) is 0.1 μm or more, preferably 2 μm or more, from the viewpoint of color density after light irradiation and prevention of color density unevenness due to film thickness. This is desirable. Also, paint 15
In terms of ease of application, uniformity, etc., the thickness is preferably 30 μm or less, preferably 25 μm or less.

The amount of the F711" chromic compound contained in the F4 tochromic coating should be determined based on the required performance, especially the relationship with the coloring density. For lenses, it is preferably 0.1 to 20%, more preferably 0.5 to 15%, and if it is less than 1%, color development at room temperature. Poor C degree.

If the amount exceeds 20%, it becomes necessary to increase the amount of solvent m relative to the matrix resin due to solubility, making it difficult to obtain a sufficient coating thickness.

The method of coating the substrate with the film in the present invention is to apply a coating composition consisting of a mixed solution of the above matrix resin and photochromic compound by dipping or spin coating. Various methods can be applied, such as a method in which the photochromic compound is applied to the matrix resin, and then the photochromic compound is incorporated into the matrix resin using a dyeing method or the like.

Various organic solvents can be used as the solvent when applied as a coating composition, specifically various alcohols, ketones, ethers, esters,
Aromatic (halogenated) hydrocarbons, aliphatic (halogenated) hydrocarbons, cellosolves, various formamides,
It is not particularly limited as long as it dissolves both the matrix resin and the photochromic compound, such as sulfoxides.

In the present invention, it is preferable to further coat the above-mentioned film with a film having hard coat properties. Among these, the film is preferably a polyorganosilolone having hard coat properties. The polyorganosiloxane having the following properties is not particularly limited as long as it can improve the scratches and scratches of the film due to its chromic properties and is crosslinked, but it has the adhesion to the film,
A polyorganosilokinone-based cured film obtained from silicon compound J3 and/or its hydrolyzate, represented by the following general formula (b), is preferably used because it can be cured at low temperatures and for a short time. Ru.

(Here, R12 and R13 each represent an alkyl group, an alkenyl group, an aryl group, or a halogen, a glycide group, an epoxy group, an amino group, a mercap group, a (meth)acrylic Δx group, or a cyano group. (Y is a hydrolyzable group, a and b are 0 or 1).

Organosilicon compound represented by general formula (b)
Or as specific representative examples of its hydrolyzates, tetrasilicates such as methyl silicate-1. Alkoxysilanes and their hydrolysates, as well as methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane,
Methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane,
Phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-
Chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3.3.3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyl 1-rimethoxysilane, γ-aminopropyltriethoxysilane, γ-7 minoprovil 1 - ethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane,
β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltrimethoxysilane, α-glycidoxyethyltrimethoxysilane , α−
Glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β -glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriproboxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxy Silane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane,
δ-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(
3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane
-Epoxycyclohexyl)ethyltrimethoxyethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3
, 4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl>butyltriethoxysilane, etc.), 1-realkoxysilane, triazyl Oxysilane or triphenoxysilanes or their hydrolysates and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyljethoxysilane, phenylmethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ
-chloropropylmethyldiethoxysilane, dimethyljethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldie-1-oxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyljethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-7minopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyljethoxysilane, glycidoxymethylmethyldimethoxysilane,
Glycidoxymethylmethyljethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyljethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane , α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyljethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyl Dimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldipropoxysilane Sidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyljethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyljethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, dialkoxysilane, diphenoxysilane or diacyloxysilane or their hydrates An example is decomposition products.

It is also possible to add one type or two or more types of these organosilicon compounds.

It is preferable to use such an organosilicon compound by hydrolyzing it in terms of low temperature curing and shortening of curing time. Hydrolysis can be carried out by conventional hydrolysis methods, such as by adding pure water, an acidic aqueous solution such as hydrochloric acid, sulfuric acid, or acetic acid, or an alkaline aqueous solution such as caustic soda, caustic potash, or calcium hydroxide. The temperature during hydrolysis is not particularly limited, and there is no problem in controlling it to either a low temperature or a high temperature depending on the purpose.

Curing of the organosilicon compound and/or its hydrolyzate is usually carried out by heating, and various curing catalysts are added for the purpose of shortening the heating time and curing at a low temperature. Examples of the curing catalyst include alkali metal salts of carboxylic acids and chelate compounds of aluminum, titanium, zirconium, and the like.

In particular, aluminum chelate compounds such as acetylacetone aluminum salt are preferably used from the viewpoints of stability of the composition, transparency and no coloration.

Furthermore, among the organosilicon compounds represented by (b) above, R12°R13 is an alkyl group having 1 to 4 carbon atoms, an alkenyl group, etc. from the viewpoint of adhesion with a photochromic coating, improvement of surface hardness, heat resistance, weather resistance, etc. , or an organic group having a phenyl group, an epoxy group, or a glycidoxy group.

The thickness of the polysiloxane coating applied to the present invention may be sufficient as long as it prevents the photochromic coating from becoming easily damaged, and should be determined in relation to the coating that has photochromic properties. 0 from the meaning
．． It is 2 μm or more, preferably 0.5 μm or more. Further, from the viewpoint of preventing cracks from occurring due to bending during processing, etc., the thickness is 50 μm or less, preferably 30 μm or less.

Such film thickness is usually controlled by diluting with a solvent, but it can also be controlled by coating conditions.

The solvent that can be used is not particularly limited as long as it can dissolve the composition uniformly, but water, lower alcohols, etc. may be used in order to prevent the elution and decomposition of the photochromic compound contained in the coating. Preferably used. These solvents can be used as a mixed solvent of two or more.

In the present invention, it is possible to pre-treat the photochromic film in advance for the purpose of improving the adhesion with the photochromic film when coating the polysiloxane film. Examples of the pretreatment method include activated gas treatment, particularly low-temperature plasma treatment, in order to prevent decomposition of the photochromic compound in the photochromic coating and significantly improve adhesion. The type of gas used for the activated gas treatment should be selected appropriately depending on the type of organic polymer in the photochromic coating.
Generally, it is preferred to use oxygen gas.

The polarizing sheet made of the photochromic film and polysiloxane film formed as described above has sufficient photochromic properties in addition to the polarizing function, and the surface is not easily scratched, so there are no practical problems at all. However, in order to roughly improve the durability, especially the fatigue resistance of the photochromic property, it is preferable to add a singlet oxygen quencher to the photochromic film and/or the polysiloxane film. Many known compounds can be used as singlet oxygen quenchers, but Ni salt compounds and/or hindered amine compounds are particularly effective for spirooxazine compounds, which are photochromic compounds represented by general formula (A). can be mentioned. In particular, N1 chelate compounds such as acedelacetone nickel salt are preferably used from the viewpoint of stability of the coating composition used for preparing the photochromic film.

The conditions of use for these singlet oxygen quenchers are
Although it is optimized depending on the environment, etc., from the viewpoint of the effect of addition and the coloring of the photochromic film, it is usually determined that It is used in a range of 1 part by weight to 200 parts by weight.

Furthermore, it is also possible to add ultraviolet absorbers, antioxidants, dyes, etc. to the photochromic coating and polysiloxane coating, respectively, as required.

In a preferred embodiment of the present invention, a coating composition that forms a photochromic film or a polysiloxane film is applied to a polarizing plate made of plastic or colored plastic, so that polarized light has photochromic properties and hardness in addition to its ability. Examples include a method of imparting coating properties. When performing such coating, it is effective to add various surfactants, such as silicone surfactants and fluorine surfactants, for the purpose of improving the uniformity and smoothness of the coating.

In addition, since the obtained polarizing sheet has flexibility, it is possible to bend it, so it is also a preferred embodiment to make it into a single-lens lens for goggles at a low cost by processing and heat bending. It is. Additionally, when used in goggles, applying an anti-fog coating to the inner surface is also a useful application.

[Examples] Examples are shown below, but the present invention is not limited to these examples.

Example 1 (1) Preparation of photochromic coating (a) Preparation of coating composition Copolymer (OH value: 10) of methyl methacrylate/butyl methacrylate/butyl acrylate/hydroxyethyl methacrylate/acrylic acid toluene/
50% by weight solution of butyl acetate (50150 weight ratio) 30
009 was roughly diluted to 25% by weight with methyl ethyl ketone, a silicone surfactant was added, and 1-(3-methylbenzyl)- was added as a photochromic compound.
3゜3-dimethylspiro[indolino-2,3'-[3
150.0 CI of naphtho[2,1-b] (1,4)-oxazine] and 9 oq of hindered amine were added and sufficiently stirred and dissolved to obtain a coating composition.

(b) Coating and drying The coating composition obtained in (a) above was coated on a plastic polarizing plate (manufactured by Sanritsu Electric Co., Ltd., HC2-4-7
5 types, thickness 0.75mm, 310X87 (mm
) using the dip method at a pulling speed of 20 cm/min. The coated lenses were dried and cured at 65°C for 4 hours.

(2) Performance test The following tests were conducted. The results are shown in Table 1.

(b) Adhesion test As a test method, 100 goblets reaching the substrate at an angle of 1° are placed on the coating surface of the sheet with a steel knife, and cellophane adhesive tape (product name: Cellotape Panichiban Co., Ltd. The product) was firmly attached and rapidly peeled off in a 90 degree direction to check for peeling of the coating.

(b) Photochromic performance After irradiating with light using a chemical lamp as an excitation light source to develop color, the irradiation was stopped and the state of color development and rate of decolorization at that time was observed with the naked eye I2. All showed uniform color development.

(c) Durability test: 40 hours using a fade meter manufactured by Suga Test Instruments Co., Ltd.
The coloring state of the photochromic performance after irradiation was observed.

Example 2 On the plastic polarizing plate having the photochromic film obtained in Example 1, a polysiloxane film was roughly applied.

(1) Preparation of polysiloxane coating (a) Preparation of coating composition In a reactor equipped with a rotor, 240 g of γ-glycidoxypropyltrimethoxysilane and 240 g of γ-glycidoxypropylmethyljethoxysilane were added. Pour 1,470 g of vinyltriethoxysilane, and while stirring using a magnetic stirrer, 510 g of a 0.05N hydrochloric acid aqueous solution.
was added dropwise while maintaining the liquid temperature at 10° C., and after the completion of the addition, stirring was continued for an additional 30 minutes to effect hydrolysis.

Acetylacetonaluminum [56.0 g] was added as a curing agent to the obtained hydrolyzate, and 710.03 g of ethanol/water (80/20 hydrogen ratio) was added as an additional solvent.
After adding 6.03 of a silicone surfactant and stirring thoroughly, a coating composition was obtained.

(b) Coating and drying example 1. The paint obtained in the previous section <1> and (a) was applied to the polarizing plate having the photochromic film obtained in <1) using a dip method at a pulling rate of 10 cIt/min, and dried at 65°C for 15 hours. , curing was performed.

(2) Performance test A test similar to Example 1 was conducted. The results are shown in Table 1.

Furthermore, the following tests were conducted.

(a) Friction resistance test Using steel wool #0OOO, friction was applied under a load of 200 (1/d) to examine the scratch resistance.

As a result, there was no damage at all.

(b) Heat resistance, moist heat resistance test Heat resistance: After being left in an ao'c hot air oven for 2 hours, changes in appearance, adhesion, and photochromic properties were examined.

Moisture and heat resistance: After being left for one week under high humidity at 40° C. and 90% R1-1, changes in appearance, adhesion, and photochromic properties were examined.

As a result, it was found that it had very excellent performance in both heat resistance and moist heat resistance.

(c) Punching test A goggle-shaped single-lens lens was punched using a press machine, and a curved surface was processed using a rough wooden mold. The appearance after processing was examined, especially the presence or absence of cracks and wrinkles on the surface.

As a result, there was no change at all before the test, and neither cracks nor wrinkles were observed.

Table 1 Application Example The polarizing sheet having photochromic properties obtained in Example 2 was cut into the shape of a single-lens lens by press working.

Thereafter, a curved surface was processed using heat bending, and the material was attached to a goggle frame. When I stood on the slopes of a ski resort wearing the goggles I had created and looked at the gap, I was able to clearly recognize the shape of the gap and was able to ski safely. This effect is due to the polarizing function and photochromic function of the goggles of the present invention.

[Effects of the Invention] The polarizing sheet having photochromic properties obtained by the present invention has the following effects.

1. It has both photochromic properties with excellent color development and erasing properties and polarization function.

2. It has chromic properties to Fo1 with excellent repeatability.

3. It is a composite material with high surface hardness and excellent practical durability.

4. It is a composite with excellent heat resistance, water resistance, and acid resistance.

5. Color development after light irradiation can be freely selected from a wide range.

Patent applicant Higashi Shi Co., Ltd. Company proceedings 1, Case description 1985 Patent application No. 331441 @ 2, Name of invention Polarizing sheet with photochromic properties 3, Person making amendment Relationship with the case Patent application Address: 2-2-1 Hikibashi Muromachi, Chuo-ku, Tokyo Name (
315) Toshi Co., Ltd. 5, Number of inventions increased by amendment None 6, Specification in the "Detailed explanation of the invention" section of the specification subject to the amendment Yamanaka (1) Page 4, line 12, "To solve the problem"" is corrected to "to solve".

(2) Page 11, line 13, "Oxazine] etc."
1,4) oxazine], 1,3,3-trimethylspiro "indolino-2,3"-[31-pyrido[2,1-
bl(L4)benzoki1nadine] etc.”

(3) Page 13, line 5, F0.1 μm or more” is changed to “0.1
It needs to be larger than μm.''

<4) Page 13, line 7, r30 μm or less” was changed to “30
It needs to be less than μm.''

(5) Page 15, line 15, “hydrogens” is replaced with “hydrogen group”
I will correct it.

(6) On page 16, line 17, "Trieto" is corrected to "Trimet".

<7> On page 26, line 4, "with flexibility" is corrected to "with flexibility."

(8) Page 27, line 15 (correct “-lens” to “sheet”.

Claims (8)

[Claims] (1) A polarizing sheet having photochromic properties, characterized in that it has a coating having a photochromic property with a thickness of 0.1 to 30 μm on at least a portion of a substrate having a polarizing function. (2) A polarizing sheet having photochromic properties according to claim (1), wherein the substrate having a polarizing function is an organic plastic. (3) A polarizing sheet having photochromic properties according to claim (1), wherein the coating is an organic polymer containing a spirooxazine compound represented by the following general formula (A). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(a) (However, R_2 and R_3 selected from the group consisting of an alkyl group and a substituted or unsubstituted aralkyl group of C_7 to C_2_0.
each of which is selected from the group consisting of hydrogen, C_1 to C_5 alkyl groups, phenyl groups, mono- or di-substituted phenyl groups, benzyl groups, or combined with 6 to 8 carbon atoms (spiro carbon atoms). alicyclic rings, including
It is selected from a cyclic ring selected from a norbornyl group and an adamantyl group. R_4, R_5, R_6, R_7 and R_
8 is each hydrogen, C_1 to C_5 alkyl group,
It is selected from an alkoxy group, a halogen, a nitro group, a cyano group, a hydroxy group, a halogenated alkyl group of C_1 to C_5, an alkoxycarbonyl group, and an amino group. ) (4) A polarizing sheet having photochromic properties according to claim (1), wherein the coating is a composition containing a singlet oxygen quencher. (5) A polarizing sheet having photochromic properties according to claim (4), wherein the singlet oxygen quencher is a Ni salt compound. (6) A polarizing sheet having photochromic properties according to claim (4), wherein the singlet oxygen quencher is a hindered amine compound. (7) A polarizing sheet having photochromic properties according to claim (1), wherein the polarizing sheet is a lens. (8) A polarizing sheet having photochromic properties as set forth in claim (1), wherein the polarizing sheet is a single-lens lens.