JPS61228402A - Photochromic plastic product and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photochromic synthetic plastic articles, particularly photochromic optical elements such as lenses. More particularly, the present invention relates to methods of making photochromic synthetic plastic articles. Photochromism is a reversible phenomenon exhibited by compounds that change color when exposed to ultraviolet light and then return to their original color or state upon removal of the ultraviolet light source. Compounds exhibiting this property are called photochromic compounds.

Several methods have been used to incorporate photochromic compounds into synthetic plastic host materials. For example, U.S. Pat.
No. 2.898 describes the preparation of photosensitive compositions by suspending photochromic benzospiropyran in a pre-prepared polyester resin. US Patent No. 3
．． No. 666.352 describes the production of photochromic sunglass lenses by dispersing a mercury thiocarbazone compound in a solidified plasticized vinyl chloride-vinyl acetate copolymer and laminating this copolymer between two plastic or glass layers. are doing.

U.S. Pat. No. 3,508,810 discloses the manufacture of a safety glass unit by incorporating a hephotochromic mercury dithizonate or benzospiropyran compound in a polyvinyl butyral membrane sealed between two glass plates of the unit. It is listed. In one embodiment, a glass plate is coated with a photochromic benzospiropyran compound, a polyvinyl butyral plastic film is placed on the photochromic coating, a second glass plate is placed on the polyvinyl butyral film, and the composite is coated with a polyvinyl butyral plastic film. the structure in an autoclave,
Temperature of 135'C (275"F) and 1034kPa
(150 psig) pressure. Similarly, U.S. Pat. No. 3,522,143 discloses that by kneading or mixing a photochromic metal dithizonate compound into the membrane before sheeting or by applying the photochromic material as a coating onto one surface of the membrane. The production of materials suitable for use as lamina or interlayers in laminated safety glass units is described.

U.S. Pat. No. 4,173,672 discloses that two
Describes decorative safety glass consisting of two sheets of glass. The thermoplastic polymer is decorated by transferring the color print to the thermoplastic polymer by heat or pressure from a temporary cellulose support sheet, such as a printing paper carrying a color print made with organic or inorganic colorants. until the organic or inorganic colorant is impregnated into the intervening thermoplastic film.
Heat and pressure are applied to the two glass sheets and the intervening decorative membrane.

US Pat. No. 4,268,134 describes the production of light M laminated photochromic lenses by interposing a photochromic glass sheet between two optically clear plastic layers. U.S. Pat. No. 4,289,497 describes a gradient photochromic lens in which photochromic substances are imbibed into the lens by dipping the synthetic plastic lens into a solution of the photochromic compound.

U.S. Pat. No. 4,286,957 utilizes conventional "thermal transfer" techniques to integrate photochromic materials into synthetic organic polymeric host materials. With this technology,
After applying the photochromic compound to the surface of the organic host, it is heated at 180-220°C for 30-45 seconds to integrate the photochromic substance into the host material by thermal transfer. From the published melting point ranges of several benzospiropyrans described in this patent, it is clear that the heating temperature of 180-220°C described in this patent exceeds the melting temperature of such benzospiropyrans. It is.

The present invention relates to the advantageous incorporation of (at least one) photochromic compound into synthetic plastic materials (inc.
In one embodiment of the method of the present invention, a relatively thin, A substantially dry, uniform film is applied to at least one surface of the synthetic plastic material. The photochromic material is then incorporated into the plastic material by substantially uniformly heating the resin film at a temperature below the melting temperature of the photochromic material.

Next, the resin film depleted of photochromic substances is removed from the surface of the plastic material.

The above method can be used for sunglasses, ski goggles, sun visors, camera lenses, optical filters, lens blanks,
Photochromic plastic films and sheets useful for optical applications such as automobile windshields and ophthalmic lenses.
As used herein, "optical elements" include lenses and transparencies that enable the production of castings.
sparencies).

According to one embodiment of the method of the present invention, a thin, solid matrix of polymeric organic resin having a photochromic substance, such as a spiro(indoline) type photochromic compound, dissolved therein. A substantially dry, uniform film is applied to at least one major surface of the synthetic plastic host material, such as a substantially flat surface. The plastic material to which the film is applied may be substantially flat or may have some degree of curvature, such as the convex and/or concave surfaces of a lens. As used herein, the term "major surface" or "flat surface" refers to one or more surfaces (flat or curved) other than the side surfaces of the host material, depending on the thickness of the plastic host material. ) shall mean. Preferably, the membrane is applied to at least one major surface, more preferably both major surfaces, of a substantially planar prefabricated synthetic plastic host material.

Application of the photochromic substance-containing resin film to the receptor surface is carried out in a manner that results in a substantially uniform thickness, substantially dry, substantially spotless film or coating. Substantially mottled means substantially free of drops, bumps, streaks, spots, spots, etc. of solidified resin caused by non-uniform film thickness or non-uniform solvent removal.

The thickness of the membrane is not critical, but is typically about 0.0127-0
．． 0762 (0,5-3,0 mil), e.g. 0.02
The membrane is 1-2 mils (54-0.0508 m).
The photochromic substance migrates from the membrane and easily penetrates or diffuses into the interior of the plastic host material, thereby exhibiting a photochromic response, i.e., a change in transmittance when exposed to ultraviolet light, and the change in transmittance is visible. It must be thin enough so that plastic articles can be manufactured that can be used. If the film is too thick, the temperature and time required to transfer the photochromic amount of the photochromic material may be excessive, causing decomposition of the photochromic material. Additionally, a relatively significant amount of photochromic material remains in the thick membrane, either due to loss of photochromic material or due to the added expense of recovering photochromic material from spent membranes.
This would impose an adverse economic burden on the method.

The amount of photochromic material or amount of photochromic material required to achieve a visible photochromic response in the plastic host can vary and generally depends on the intensity of color change desired upon UV irradiation of the treated plastic article and the amount used. Depends on photochromic substances. The greater the intensity of the desired color change, the greater the amount of photochromic material required. Typically, the amount of photochromic material dispersed within the plastic host is 6.45CIII (1in”) for one flat surface.
A photochromic response can be obtained when about 0.2-1 μm/cm. In general, photochromic substances are
Varying the 0 representation present in the resin solution in an amount of about 1.0-5% by weight, more usually about 1.5-3.5% by weight, 1
In one preferred embodiment, the photochromic substance is
It constitutes about 25-40%, more preferably 30-35% by weight of the dry solid resin film. Also, different surfaces or even different parts or parts of the same surface can have different film thicknesses and/or different photochromic substance concentrations, thereby changing the intensity of discoloration of different parts of the plastic host. It is also intended that

The polymeric resin used to form the film on the surface of the plastic host material acts as a solvent for the photochromic material, e.g. spiro(indoline) type photochromic material such as spiro(indoline) naphthoxazine. The affinity between the photochromic substance, i.e. the solubility of the photochromic compound in the carrier resin, should preferably not be high but should be sufficient to form a homogeneous solution at the concentrations mentioned above. That is, the photochromic compound must be only slightly to moderately soluble in the resin so that the photochromic compound can be easily removed from the resin film.For example, if the photochromic substance is If it is infinitely or highly soluble, the driving force required to transfer the photochromic material to the plastic host is much higher than if the photochromic material is sparingly to moderately soluble in the resin. It will be.

Furthermore, the efficiency of migration, i.e. the amount of photochromic material transferred (based on the total amount in the resin), will be much lower; moreover, increasing the temperature of transfer to obtain a higher transfer efficiency May accelerate thermal decomposition of chromic substances. However, in order to obtain a photochromic compound concentration of, for example, 25-40% by weight in the dry resin film without crystallization or separation of the photochromic compound in the dry resin film, the resin is Must have sufficient affinity.

If the photochromic compound is too insoluble in the resin, the photochromic compound will crystallize out of the resin and form local concentrations or islands in the solid resin film. That is, a non-uniform coating is formed. When this occurs, a patchy film results, resulting in uneven migration of the photochromic compound into the plastic article, resulting in an article exhibiting uneven color density, an undesirable result. Similarly, the resin must not adhere strongly to the synthetic plastic host material so that it can be easily removed from the surface without leaving any marks on the surface of the synthetic plastic host material on which it is applied, and the resin must not adhere strongly to the synthetic plastic host material on which it is applied. At the temperature at which the material is transferred, the resin must remain solid and not liquid.

Examples of suitable polymeric resins that can be used to form the membranes described above are polyvinyl chloride, polyvinyl acetate, polyurethane, polyvinyl butyral, copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride and vinylidene chloride. Lower alkyl acrylic and methacrylic acids (c,'-C
4) Polymers of esters, such as methyl esters, ethyl esters, n-butyl esters, and isobutyl esters;
and mixtures of polyvinyl chloride and the polyacrylates described above, such as from about 90 parts polyvinyl chloride and about 10 parts polymethyl methacrylate to about 10 parts polyvinyl chloride and about 90 parts polymethyl methacrylate.

The photochromisomaterial-containing resin is applied to the surface of the plastic host in a manner that provides a substantially dry coating to obtain a substantially mottled coating. The photochromic substance-containing resin carrier medium is
Generally, it consists of a solution of a photochromic material-containing resin in a readily volatile organic solvent(s) at ambient temperatures, such as room temperature (20-22°C). Preferably the solvent is colorless. The solution generally contains about 1-5% by weight of photochromic material, about 2-10% by weight of resin, and about 85-97% by weight of photochromic material.
% by weight of solvent. Preferably, the solution is about 1.5
- Consisting of about 3.5% by weight of photochromic material, about 3-7% by weight of resin and about 89.5-95.5% by weight of solvent.

Examples of readily volatile or easily evaporated solvents include toluene, benzene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl chloroform, acetonitrile, tetrahydrofuran, dioxane, cyclohexanone, ethyl acetate, propyl acetate, isopropyl acetate, isobutyl acetate, butyl acetate. , methyl alcohol, ethyl alcohol, butanol, isopropanol, 2-methoxyethanol, acetone, and mixtures of such solvents. Preferably, the solvent is selected from toluene, methyl ethyl ketone, methyl isobutyl ketone and mixtures of such solvents.

A solution of photochromic substance, resin, and solvent can be prepared by any suitable method, for example, by independently dissolving the resin and photochromic substance in a suitable solvent.

The two resulting solutions are then mixed to obtain a solution of photochromic material-containing resin that is used to apply a coating to a plastic host surface.

A photochromic material-containing resin solution as described above is applied to at least one of the film-receiving surfaces of the plastic host in any manner known in the art suitable for producing a substantially spotless coating or film of substantially uniform thickness. Apply to one major surface, for example a substantially flat surface. Preferably, the method is such that as soon as the film is formed, the resulting film is substantially dry, i.e. the readily volatile solvent is substantially volatilized when the resin is applied to the receptor surface of the plastic host; The solution is applied in a manner that leaves a substantially dry film. Application methods that can be used include spraying, brushing, spinning, dipping, and draw-down blading (
This includes the use of a draw-down blade or wire bar. Among the above methods, spraying is preferred. Spraying allows for good solvent release from the atomized droplets of the solution having a viscosity of about 1-20 centipoise, such as 5 centipoise, in one preferred manner.

The viscosity of a spraying solution depends on its components and the amount of each component used. More preferably, the viscosity of the solution is in the lower part of the above range, for example 1-10 centipoise.

Spraying also allows for the controlled application of thin coatings of substantially uniform thickness. The thickness and uniformity of the film can be controlled by the number of sprays applied to the surface and the shape of the spray exiting the spray gun. Preferably,
Two to six sprays of the solution are applied onto the receptor surface in the production of relatively thin or homogeneous films of substantially uniform thickness and composition. In the spraying method, the membrane is substantially dry upon application to the plastic host surface because the sprayed solution has a high surface area and the solvent evaporates easily. This prevents the formation of droplets, spots, spots, spots or other defects when the coating remains in liquid form.

Prior to applying a solution of photochromic material-containing resin to a plastic host, it is preferred to clean the surface of the plastic to which the resin is applied.

Cleaning consists of washing the surface with an aqueous medium, e.g. soapy water, to remove dirt and grime, and/or with an organic solvent such as methyl chloroform or methyl ethyl ketone to remove any organic films present on the surface. This is done by washing the surface and/or removing the static charge present on the plastic material surface.

Static charge removal can be accomplished with commercially available devices that ionize the air above a surface to create a conductive path to absorb or neutralize the static charge.

The surface of the plastic material to which the resin is applied must be receptive to the imbibition of photochromic substances during the heating process. If the receptor surface is not susceptible to imbibition, it can be treated to improve the diffusion of the photochromic material into the plastic host surface, for example by physically or chemically etching the surface. monomeric substance(s) used to slightly undercure the plastic during plastic production or to produce an organic plastic host;
A receptive surface can usually be obtained by adding plasticizers to the material. Such methods are common in polymerization technology.

After applying the photochromic substance-containing resin film to the surface(s) of the plastic host material, the substantially dry film is allowed to completely dry. Drying is usually carried out in air at room temperature, although other drying conditions that prevent crystallization of the photochromic compound within the resin film can be used when opportunities permit. The coated plastic article is then substantially uniformly heated at a temperature below the melting temperature of the photochromic compound used. Heating can be accomplished by any method that provides substantially uniform heating of the membrane and plastic host. Preferably, the heating is
It is carried out in a conventional hot air circulation system which allows uniform heating and thus a constant driving force for the migration of the photochromic compound into the plastic host. Heating can also be performed in vacuum or using an inert atmosphere, such as a nitrogen atmosphere.

The temperature to which the coated plastic article is heated depends on the melting temperature and vapor pressure of the particular photochromic compound used and the softening temperature of the synthetic plastic host. Such temperature should preferably be close to but below the melting temperature of the photochromic compound and below the softening temperature of the synthetic plastic article. Furthermore, such temperature, ie, the photochromic material transfer or incorporation temperature, must be such that decomposition (thermal decomposition) of the photochromic compound is minimized. Therefore, the transition temperature chosen is to raise the vapor pressure of the photochromic compound sufficiently to allow migration of the photochromic compound into the plastic host without significant decomposition of the photochromic compound and softening of the plastic host. temperature is sufficient. Photochromic compounds, such as spiro (
The melting temperature and vapor pressure of indoline-type photochromic compounds vary depending on the nature of the compound and its substituents, so it can be applied to any photochromic substance.
It is not possible to indicate one temperature range. However, given the above requirements, one skilled in the art can easily determine the appropriate temperature for heating the coated plastic article. Approximately 5-
A transition temperature of about 50<0>C, preferably 5-10<0>C lower, is contemplated unless significant decomposition of the photochromic compound is observed at such temperatures. Generally, the temperature contemplated for use with spiro(indoline) naphthoxazine photochromic compounds and spiro(indoline) pyridobenzoxazine photochromic compounds is from about 145 to about 160<0>C. In particular, photochromic compounds: l, 3.3° 5.6-bentamethyl-9'-methoxyspiro [indolino-2,3' (3H) -naphtho [2° 1-b) (1,4) oxazine], 1 ,3.
5゜6-tetramethyl-3-ethylspiro[indoline-2,3' (3,H)pyrido(3,2-f)(1,
4) Benzoxazine), 1,3,3.4°5-(or 1.3,3.5.6-)pentamethylspiro[indoline-2,3' (3H) pyrido(3,2-f) (
1,4) benzoxazines], temperatures of about 145 to about 155°C, e.g. 150-155', are contemplated.

The coated plastic article is held at the transition temperature for a time sufficient to cause a substantial amount of the photochromic compound to diffuse into and subsurface the surface of the plastic article. Typically, the heating time is about 15 to about 60 minutes at the transition temperature, usually about 20 to about 45 minutes. For the above photochromic benzoxazine compound, heating for 25 to 30 minutes is appropriate.

The mechanism by which photochromic compounds migrate from the resin film attached to the surface of the plastic host material into the plastic host material is not precisely understood. It is hypothesized that migration can be accomplished by thermal diffusion, sublimation, condensation, or a combination of these mechanisms. What special mechanism (1
Even if more than one), the photochromic compound penetrates into the interior of the plastic substrate, usually into its surface regions, and becomes permanently and firmly incorporated within the plastic host material. In this manner, a photochromic amount of photochromic material is transferred substantially uniformly into and across the flat surface of the plastic host.

After transfer of the photochromic compound into the plastic article, the coated plastic is cooled, eg, to room temperature, and the residual resin film, which has a reduced concentration of photochromic material, is then removed from the surface of the plastic host. Removal of the photochromic compound consumable film can be carried out in any suitable manner, preferably in a manner that does not impair the optical quality of the surface of the plastic host. Typically, consumable membranes are prepared by contacting the membrane with a suitable organic solvent such as methyl chloroform, trichloroethylene, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketone-toluene mixtures, or other solvents such as acetone, ethylene dichloride, chloroform, chlorobenzenes. It is peeled off from the plastic substrate by letting it slide. The same solvent used to prepare the photochromic material-containing resin solution can be used to remove the residual resin film.

A suitable method of contacting the membrane with an organic solvent involves exposing the membrane to vapors of the selected solvent(s) and allowing the vapors to condense and flow down onto the surface of the plastic material, thereby forming a photochromic material depleted resin membrane. This is done using a vapor degreasing device that cleans the surface from the surface. Alternatively, the resin film can be removed by dipping the plastic substrate in a solvent bath, spraying the film with solvent, or physically peeling the film from the substrate.

After the photochromic compound consumable or used film is removed from the surface of the plastic article, the surface can be washed with water or other suitable aqueous medium, such as a soap or detergent solution, and dried. If desired, the plastic article can be colored by methods known in the art, such as conventional disperse and soluble dyes used in the coloring of organic plastic materials using conventional dye baths. Thereafter, the colored plastic article is washed, for example with soapy water, and dried. Coloring of the plastic material can be carried out immediately after removal of the used resin film and before cleaning with an aqueous medium.

Alternatively, the coloring can be done before applying the photochromic compound.

Synthetic plastic host materials that can be used in the method of the invention are solid, transparent, polymeric organic materials. Preferably, the host material is an optically transparent material, ie, a material suitable for ophthalmic or optical devices, such as ophthalmic lenses, or useful for applications such as windows, windshields, etc.

Examples of transparent host materials used with the photochromic compounds of the present invention include polyols (allyl carbonate)
Polymers and copolymers of monomers, such as polyacrylates, poly(alkyl acrylates), cellulose acetate, cellulose propionate, cellulose butyrate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), Includes poly(vinyl alcohol), polyurethane, polyethylene terephthalate, polystyrene, poly(styrene-methyl methacrylate) copolymer, poly(styrene-acrylonitrile) copolymer, polyvinylpyrrolidone, polyvinyl chloride, polyvinyl butyrate, and polyvinyl butyral. Transparent polymers and transparent blends of copolymers are also suitable as host materials. Preferably, the host material is LEXA
Poly (4,4'-
polycarbonates such as dioxydiphenol-2,2-propane); polyols (allyl carbonate);
Polymers of diethylene glycol bis(allyl carbonate) sold in particular under the trademark CR-39 and their copolymers, e.g. with vinyl acetate, such as copolymers of 80-90% diethylene glycol bis(allyl carbonate) with 1°-20% vinyl acetate. , especially bis(allyl carbonate) 80-85% and vinyl acetate 15-2
Copolymer with 0% cellulose acetate, cellulose propionate, cellulose butyrate; polystyrene and its copolymer with methyl methacrylate, vinyl acetate, acrylonitrile; optically transparent polymeric organic material made from cellulose acetate butyrate. Plexiglas (PLH)
Polymethyl methacrylate, such as materials sold under the trademark XIGLAS), can also be used with photochromic materials having melting points below about 140°C.

Polyol (allyl carbonate) monomers that can be polymerized to produce transparent host materials include allyl carbonates of linear or branched aliphatic liquid polyols or aromatic liquid polyols, such as aliphatic glycol bis(allyl carbonate) compounds. or an alkylidene bisphenol bis(allyl carbonate) compound. These monomers can be described as unsaturated polycarbonates of polyols such as glycols.

These honeycombs can be prepared by methods known in the art, such as U.S. Pat.
Manufactured by the method of No.

The polyol (allyl carbonate) monomer has the formula ■ (in the above formula ■, R is a group derived from an unsaturated alcohol, usually an allyl or substituted allyl group, R' is a group derived from a polyol, n is an integer from 2 to 5, preferably 2). Allyl group (R
) may be substituted in the 2-position by a halogen, especially chlorine or bromine, or an alkyl group containing 1-4 carbon atoms, generally a methyl or ethyl group. The R group has the formula ■ HtC=CCHz U (In the above formula ■, Ro is hydrogen, halogen, or C+
is a Ca alkyl group). Particular examples of R include allyl group, 2-chloroallyl group, 2-bromoallyl group, 2-fluoroallyl group, 2-methallyl group, 2-ethylaryl group, 2-isopropylaryl group, 2-n- Includes propylallyl group and 2-n-butylallyl group. Most commonly, R is an allyl group,)
lzc=clI Hz-.

R' is a polyvalent group derived from a polyol, which can be an aliphatic polyol or an aromatic polyol, containing 2 or 3 or 4 or 5 hydroxy groups, typically Typically, the polyol contains two hydroxy groups, ie, a glycol or a bisphenol.

Aliphatic polyols can be linear or branched and contain 2-10 carbon atoms. Usually, aliphatic polyols are alkylene glycols or poly(c! be.

Aromatic polyols are 2) (in the above 2), A is a divalent group derived from an acyclic aliphatic hydrocarbon, such as an alkylene or alkylidene group having 1 to 4 carbon atoms, such as methylene, ethylene,
Dimethylmethylene (isopropylidene), R1 represents a lower alkyl substituent of 1-3 carbon atoms, and p is an integer of 0 or 1 or 2 or 3. Preferably, the hydroxyl group is in the ortho or para position.

Particular examples of radicals R' include ethylene (-CL-CHg-), trimethylene, methylethylene, tetramethylene, ethylethylene, pentamethylene,
Alkylene groups H-C1 (x-0-CHg-1-CH
gCHt-0-CHtCHx-, -CHg-0-CHt
-CHz-1-CHgCHxCHz-0-CHgCHx
Alkylene ether group i -CH-C such as CHz-
Ht-0-CHzCHz-0-CHgCHg-1-CH
gCHgCTo-0-CHgCtlgCHt-0-CH
an alkylene polyether group such as gCToCII□-; -CHgCHg-0-CO-0-CHgCHg-1
-CHzCIIz-0-CHxCHt-0-CO-0-
Included are alkylene carbonate groups and alkylene ether carbonate groups such as CIIzCHz-0-CHzCllg-; and isopropylidene bis(para-phenyl). Most commonly, R' is -CH,CH,a- or -CHgCHz-0-CToCHx- or -CHx
CHt-0-CHgCHt-0-CHgC)It-.

Specific examples of polyol (allyl carbonate) monomers include ethylene glycol bis(2-chloroallyl carbonate), ethylene glycol bis(allyl carbonate), diethylene glycol bis(2-methallyl carbonate), diethylene glycol bis(allyl carbonate), triethylene glycol bis(allyl carbonate), Ethylene glycol bis(allyl carbonate), propylene glycol bis(2-ethylallyl carbonate)), 1,3-propanediol bis(
allyl carbonate), 1,3-butanediol bis(
allyl carbonate), 1,4-butanediol bis(
2-bromoallyl carbonate), dipropylene glycol bis(allyl carbonate), trimethylene glycol bis(2-ethyl allyl carbonate), pentamethylene glycol bis(allyl carbonate), isopropylidene bisphenol bis(allyl carbonate)
is included.

Industrially important polyol bis(allyl carbonate) that can be used in the invention contemplated herein
The monomer is C1l Yukiko CHHz, V
Diethylene glycol bis (A IJ J recarbonate), which is ethylene glycol bis (allyl carbonate), is preferred.

Method for producing polyol (allyl carbonate) monomers, namely phosgenation of polyols (allyl alcohol)
) and the subsequent allyl alcohol production method,
The monomer product may include related species in which the allyl carbonate group attachment moiety contains one or more carbonate groups. These related species are represented by the formula (1) (in the above formula (2), R is as defined above;

is a divalent group derived from a diol, for example f alkylene or phenylene, and S is an integer from 2 to 5). Related species of diethylene glycol bis(allyl carbonate) have the formula ■C) I! = C1,IX (In the above formula (1), S is an integer from 2 to 5).

The polyol (allyl carbonate) monomer may typically contain 2-20% by weight of related species, such related species as a mixture, i.e., the related species denoted by S equal to 2.3.4 etc. Can exist as a mixture.

Photochromic substances contemplated for use in the method of the invention are compounds containing spiro(indoline) type compounds that give a visible photochromic response, are moderately soluble in the resins mentioned above, and are soluble in plastic hosts. A compound that is molten and, as mentioned above, can be readily transferred from a film on the surface of the plastic host to the plastic host by application of heat without significant decomposition at temperatures close to but below its melting temperature. It is. Particularly contemplated photochromic materials are less than 600, such as about 250-
Spiro(indoline)pyridobenzoxazine, spiro(indoline)naphthoxazine, spiro(indoline)benzopyran, spiro(indoline)naphthopyran, spiro(indoline)quinopyran, spiro(indoline)benzoxazine, spiro(indoline) with a molecular weight of 450.
Spiro(indoline)pyridoxazine and spiro(indoline)pyridoxazine. Preferred photochromic materials are the pyridobenzoxazines and naphthoxazines mentioned above.

Spiro(indoline)pyridobenzoxazines contemplated in the present invention can be represented by the following formula X.

In the above formula The phenyl substituent is selected from the group consisting of substituted phenyl selected from C, -C, alkyl and CICs alkoxy, such as ethoxy, propoxy, butoxy, pentoxy. Preferably R, is hydrogen or C+-C4 alkyl or phenyl or benzyl group.

R2 and R5 of formula
- form a cyclic ring selected from the group consisting of alicyclic rings containing 8 carbon atoms (including spiro carbon atoms), norbornyl, adamantyl; Phenyl substituents can be chosen from C,-C4 alkyl and CI Cs alkoxy groups. Preferably, R2 and R1 are each selected from C, -C, alkyl such as methyl, ethyl. When one of R2 and R8 is a tertiary alkyl group such as tert-butyl or tert-amyl, the other is preferably an alkyl group other than a tertiary alkyl group.

R4 and R2 in formula X are each hydrogen, C, -C
selected from S alkyl, halogen, C+ Cs alkoxy, nitro, cyano, C1-C4 haloalkyl, C, -C, polyhaloalkyl, C, -C, alkoxycarbonyl. R4 and R2 can be present on any two available carbon atoms of the indoline portion of the compound, ie the 4th or 5th or 6th or 7th position carbon atoms. Preferably, when the substituents are other than hydrogen, the substituents are present in the 4 and 5 positions, or the 5 and 6 positions, or the 4 and 7 positions, or the 6 and 7 positions.

Regarding halogen or haloalkyl substituents, any halogen can be used, ie chlorine, bromine, iodine, fluorine, with chlorine, bromine, trifluoromethyl being preferred. Preferably R4 and R3 are hydrogen, C, -Ct
A, Ruxy, such as methyl, ethyl, chlorine, bromine, C,
-CS alkoxy, such as methoxy, ethoxy.

Photochromic substances of particular interest include R, methyl;
C, -C4 such as ethyl, n-propyl, isopropyl, n-butyl, nibutyl, isobutyl, tert-butyl
alkyl, and each of R1 and R1 is methyl, ethyl, or phenyl, and R4 and Rs
A photochromic compound of formula X, each of which is hydrogen or methyl or methoxy or chloro.

The spiro(indoline)pyridobenzoxazines mentioned above can be synthesized by reacting the corresponding nitroso-hydroxyquinoline compound with the corresponding free indoline (Finscher's base) or indolium salt, such as the chloride salt. Both precursor materials are refluxed in a suitable solvent such as toluene or isopropanol until the reaction is complete. If an indolium salt is used as a reaction component, a base such as triethylamine is present in the reaction medium. I want to be

Examples of suitable spiro(indoline)pyridobenzoxazines include compounds where R, %Rz, Rs, R4, Rs are as in the table below.

l-Compound Rt Rt Rx R4RsI
C113C113C11, HH2C11s
CH,I CHs C1(I
CH33CH3CHs CH20CI12 I
I4 CI(, I' C11s C
H2Cl1 C11s'5 CH3Cl3
CJS II II6
CHs CH3C'tHs CH3Cl0s
7 CH3cgos C, H5HH8n
-CJ* CHs CtHs HH9
CH3Cll3 phenyl Hl110
Cl1z phenyl phenyl
HIflll Czlls CH3C
tHSClhCl.

12 n-Ca11g CH3CtHs
Ctll CH.

Compound 2 on the front page is 1. 3. 3. 4. 5-
(or 1.3,3.5.6-)pentamethylspiro [
indoline-2,3' (3dan) pyrido[3,2-f
)(1,4)benzoxazine]. Similarly, compound 6 on the front page is 1°3.5.6-tetramethyl-3-ethylspiro(indoline-2,3'
Other compounds in Table i that can be named (3)pyrido[3,2-f)(1,4)benzoxazine] can be named similarly taking into account the different substituents. can.

Spiro(indoline)naphthoxazines contemplated in the present invention are represented by Formula XI below.

Spiro(indoline)naphthoxazines and their synthesis are described, for example, in U.S. Pat.
No. 78.602, No. 4.215,010.

In formula XI, R'1 is hydrogen and C, -C, alkyl,
For example, it can be selected from methyl, R+2, R'3,
each hydrogen, C, -C, alkyl, phenyl, typically C1Ct alkyl such as methyl, ethyl, R/4, R1, each hydrogen C, -0
% alkyl, halogen such as chlorine or bromine, nitro, cyano, CICs alkoxy, C+ Cs alkoxycarbonyl, R' b , R'
7 is hydrogen, halogen, such as chlorine, bromine, 0
It can be selected from 1Ca alkoxy.

Particular examples of spiro(indoline)naphthoxazines contemplated in the present invention include compounds in which the substituents R/1-R' are as shown in Table 1 below.

~ E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E
D. Section cIc: Compound 2 in Table ■ is 1.3.3.5.6-bentamethyl-9'-methoxyspiro(indoline-2,3'
(3H)-naphtho(2,1-b)(1゜4]oxazine].Similarly, compound 6 in Table ■
is 1.3.5.6-tetramethyl-3-ethyl-9'
-methoxyspiro[indoline-2,3' (3H)
Other compounds in Table 0, which can be named -naphtho[2°1-b)(1,4)oxazine], can be named similarly, taking into account different substituents.

Spiro(indoline) contemplated for use in the present invention
Benzopyran includes a compound represented by the following formula Xll.

Spiro(indoline) benzopyrans are known in the art. These benzopyrans and their synthesis are described in U.S. Pat. No. 3,100,778. , No. 3.212.898, No. 3
．． 346.385 and British Patent No. 1.418.0
It is described in No. 89.

In 2XH, Ra1 can be hydrogen or CI C4furkyl, R'! , RZ are each hydrogen,
C, -c, alkyl, phenyl, such as methyl, ethyl, CI-C! can be alkyl, R”4
, R'S is hydrogen, halogen such as chlorine or bromine, C3-c, alkyl, nitro, cyano, cl
-04 alkoxy, and R'&R' can each be selected from hydrogen, CI-Ca alkoxy, nitro, phenyl, halogen, such as chlorine or bromine.

Examples of spiro(indoline)benzopyrans include 1.3.
3-) Dimethyl-6'-nitro-spiro (2H-1-benzopyran-2,2'-indoline);1.3.3-trimethyl-6'-nitro-8'-methoxy-spiro (2
H-1-benzopyran-2,2'-indoline); 1,
3.3-Trimethyl-6'-bromo8'-promospiro(2H-1-benzopyran-2,2'-indoline);1.3.3-)samethyl-5'-bromo6'-nitro8 '-Methoxy-spiro(2H-1-benzopyran-2,2'-indoline);1°3.3-)dimethyl-5-chloro-6'-nitrosespiro(2H-1-benzopyran-2,2'-indoline); l-phenyl-3
, 3-dimethyl-6'-nitro-spiro (2H-1-benzopyran-2,2'-indoline).

Spiro(indoline)naphthopyran and spiro(indoline)quinopyran are represented by the following formula X1ll.

In the above formula X1ll, R+, Rt, Rs, Ra,
Rs is as explained in relation to formula X, and Ra, Ra
are each hydrogen, Cr Ca alkyl, CI -C
It can be chosen from 4-alkoxy, nitro, halogen, such as chlorine or bromine, and Y is carbon or nitrogen, respectively.

Examples of spiro(indoline)naphthopyran include 1.3.
3-) Limethylspiro(indoline-2゜2'-(2H
)-naphtho(1,2-b) biran]: 1.3.3, 5.
6-pentamethyl-spiro(indoline-2,2'-(
2H)-naphtho[1,2-b)bilane); 1.3.3-
) dimethyl-5-methoxy-spiro(indoline-2,
2'-(2H]-naphtho(1,2-b,)pyran); 1
．． 3゜3-Trimethyl-6'-chloro-spiro(indoline-2,2'-(2H)-naphtho(1,2-b)pyran);1.3.3-trimethyl-6'-nitro-spiro(Indoline-2,2' (2H)-naphtho(1,
2-b) Biran] is included.

Examples of spiro(indoline)quinopyran include spiro(2
H-indole-2,3'-(3H)pyrano (3,
2-f) Quinoline, 1.3.3-trinotylspiro(2
H-indole-2,3'-[3H]pyrano(3,2-
f) Quinoline; 1,3°3.5.6-pentamethylspiro(2H-indole-2,3'-(3H)pyrano
(3,2-f)quinoline: 1. 3. 5. 6-tetramethyl-3-ethylspiro (2H-indole-2,
3'-[3H]pyrano (3,2-f)quinoline, 1.
3゜3-trimethyl-5-methoxyspiro(2H-indole-2,3'-(3H)pyrano (3,2-f)quinoline; 5-chloro-1,3,3,6'-tetramethylspiro( Includes 2H-indole-2,3'-(3H)pyrano(3,2-f)quinoline.

Spiro(indoline)-benzoxazine, -pyridopyran, -pyridoxazine is represented by the following formula XIV.

In the above formula XIV, RISRl, R1, R4, R3 are of the formula
As explained above, 2 and Y are nitrogen and carbon, carbon and nitrogen, and nitrogen and nitrogen, respectively, and R6 and R9
is as explained in relation to formula X1ll.

According to the present invention, a polymer of diethylene glycol bis(allyl carbonate) or a copolymer of diethylene glycol bis(allyl carbonate) and 10-20% vinyl acetate or a polymer of an organic plastic host material such as polycarbonate is applied to a clean surface. Degreasing with an organic solvent such as methyl ethyl ketone to give

Remove the static charge from the cleaned surface by passing a high voltage discharge brush over this cleaned surface. Spiro(indoline), such as spiro(indoline)pyridobenzoxazine, in a readily volatile organic solvent. A solution of photochromic material and polyvinyl chloride resin is applied to a cleaned and substantially static charge-free plastic, host surface (1
(one or more), such as by spraying the solution onto the surface (one or more), whereby about 30-35
A very thin polymer resin containing % photochromic material, e.g. a thickness of about 0.0127-0.0762 tsuru (0,
5-3 mils) to form a substantially dry coating or film. The surface-coated plastic host is then treated in a heating zone for about 10-60 minutes at a temperature below the melting temperature of the photochromic material;
Thereby, the phototochromic material is transferred from the polymeric resin coating into the subsurface regions of the plastic host.

After cooling, the film is removed by contacting the photochromically depleted polymer resin film with an organic solvent such as methyl ethyl ketone. The photochromic treated plastic host is optionally colored with a conventional dye that is complementary to the color of the photochromic material. Thereafter, the surface is washed with soapy water to remove dye and organic solvent residues, and the article is dried. This photochromic (and optionally colored) plastic is then molded into a lens-like shape by known molding methods, such as thermoforming.

Thermoforming is a heat treatment of the lens in which a lens, for example a flat lens, is placed on a female mold whose geometry corresponds, for example, to a small circular segment of a sphere with a radius of 9 am, the lens is heated and pressed against the female mold for several minutes. This method transforms a flat lens into a concave shape.

The present invention will be explained in more detail with reference to Examples below.

These examples are for illustrative purposes only, as numerous modifications and changes in the examples will be apparent to those skilled in the art.

The implementation team applied a sprayable photochromic substance-containing solution to 1
1 in 7 parts methyl ethyl ketone and 17 parts toluene
It was prepared by dissolving a portion of a photochromic compound. 2 parts polyvinyl chloride resin (3M Company, (
Strip Coat 2253, available from 3M Company, was mixed with an approximately 80/20 toluene-methyl isobutyl ketone mixture.
It was dissolved in parts. Both resulting solutions were mixed and 2,54 am (fin) made from diethylene glycol bis(allyl carbonate) was mixed with a conventional air atomizing spray gun.
X5.08cm (2in)Xo, 32cm (0,1
25 inch) solid plastic coupons.

Application of the solution to the coupon was done using four consecutive coats. The entire surface area of the coupon was coated multiple times to obtain the highest film uniformity. The resulting film was substantially dry upon application to the coupon. Allow the membrane to dry completely;
The coated coupons were heated in a circulating air oven at 160° C. for 20 minutes. After cooling, the photochromic substance depletion film was removed with acetone or methyl ethyl ketone.

This coupon in which the photochromic compound was imbibed was heated at 3.0 mW/- with a xenon high-pressure arc lamp.
irradiated at ultraviolet energy levels of At the end of the light,
A 0X-1 filter was installed. The optical density change (ΔOD) at 30 seconds illumination and 4 minutes (saturated) illumination was measured using a radiometer (radiometer).

(meter). 347nm (λ11mg
) was also measured using a spectrophotometer.

These data are shown in Table ■.

Table ■ 1” 2 1.35 1 3 1.72 1 6 1.18 1 11 0.85 1 12 0.79 m 2 1.63 u 3 1.80 II 6 1.76 II 7 1.94 m 9 1.88 rllll 0.60 If 12 0.87 [131,20 *Uses 2.5 parts of polyvinyl chloride.

Δ0D 30 seconds Saturation 0.46 0.73 0.77 1.43 0.71 1.37 0.79 1.52 0.47 0.86 0°57 0.96 0.36 0.70 0.36 0 .71 0.43 0.91 0.29 0.63 0.32 0.64 0.13 0.38 0.35 0.65 0.36 0.72 The data in Table Incorporating hephotochromic compounds into plastic host materials
oraLing).

Above, the present invention has been described in particular with respect to spiro(indoline)pyridobenzoxacin and spiro(indoline)naphthoxadiphotochromic substances and a polymer of diethylene glycol bis(allyl carbonate) as a plastic host. Substituting the indoline-type photochromic material with other photochromic substances described herein and substituting the polymer of diethylene glycol bis(allyl carbonate) with other plastic host materials described herein. It is expected that substantially similar results will be obtained by doing so.

Although the invention has been described with respect to specific details of some embodiments thereof, such details are not to be construed as limitations on the scope of the invention other than as contained in the claims.

Claims (33)

[Claims] (1) (a) applying a substantially mottled, substantially uniform film of a polymeric resin having a photochromic substance dissolved therein onto at least one major surface of a plastic article; b) a membrane-supported plastic article;
A photochromic amount of the photochromic material is incorporated into the subsurface of the plastic article at a temperature near but below the melting temperature of the photochromic material.
(rate);
c) removing a photochromic material-depleted film from the surface of the plastic article. A method for imparting photochromic responsiveness to a synthetic plastic article. (2) The thickness of the film is approximately 0.0127 to 0.0762 mm (
0.5-3 mil). 3. The method of claim 2, wherein the photochromic material comprises about 25-40% by weight of the dry film applied to the surface of the plastic article. 4. The method of claim 1, wherein the film is applied by spraying a solution of the photochromic material and polymer resin in a readily volatile solvent onto the major surface(s) of the plastic article. (5) The method of claim (4), wherein the film is substantially dry as soon as it is applied. (6) The method of claim (1), wherein the viscosity of the solution is about 1-20 centipoise. (7) The method according to claim (1), wherein the main surface (at least one) is cleaned and substantially free of static charge. (8) The method of claim 1, wherein the temperature at which the membrane-supported plastic article is heated is about 5°C to 50°C lower than the melting temperature of the photochromic material. (9) The method according to claim (1), wherein the heating time is about 15 minutes to 60 minutes. (10) Claim No.
The method described in section 1). (11) The method according to claim (1), wherein the photochromic substance is a spiro (indoline) type photochromic compound. (12) The method according to claim (11), wherein the photochromic substance is spiro(indoline)pyridobenzoxazine or spiro(indoline)naphthoxazine. (13) Plastic articles include polymers and copolymers of polyol (allyl carbonate) monomers, polyacrylates, poly(alkyl acrylate) cellulose acetate, triacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(
vinyl alcohol), polyurethane, polycarbonate, polyethylene terephthalate, polystyrene, poly(
12. The method according to claim 11, wherein the method is selected from poly(styrene-methyl methacrylate), poly(styrene-acrylonitrile) and polyvinyl butyral. (14) The plastic article is a polymer of diethylene glycol bis(allyl carbonate), a copolymer of diethylene glycol bis(allyl carbonate) and vinyl acetate, polycarbonate, polyvinyl butyral, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene, styrene. and methyl methacrylate or vinyl acetate or acrylonitrile.
The method described in section 1). (15) The method according to claim (14), wherein the photochromic substance is spiro(indoline)pyridobenzoxazine or spiro(indoline)naphthoxazine. (16) Film thickness is approximately 0.0127-0.0762mm
(0.5-3 mil). 17. The method of claim 16, wherein the photochromic material comprises about 25-40% by weight of the dry film applied to the surface of the plastic article. (18) A solution of a photochromic substance and a polymer resin in an easily volatile solvent is applied to the main surface (at least one surface) of a plastic article.
17. A method according to claim 16, wherein the film is applied by spraying onto a single layer. (19) The method of claim (18), wherein the temperature at which the membrane-supported plastic article is heated is about 5°C to 50°C lower than the melting temperature of the photochromic material. (20) The method according to claim (19), wherein the heating time is about 15 minutes to 60 minutes. (21) The temperature at which the membrane-supported article is heated is approximately 145°C to 16°C.
The method according to claim (19), wherein the temperature is 0°C. (22) The method according to claim (20), further comprising the step of coloring the plastic article with a complementary color dye after removing the photochromic substance-deficient film from the surface of the plastic article. (23) The method according to claim (20), wherein the plastic article is colored with a complementary color dye before the photochromic substance-containing film is applied to the surface of the article. (24) (a) Applying a substantially mottled, substantially uniform film of a polymeric resin having a spiro(indoline) type photochromic substance dissolved therein over at least one major surface of a synthetic plastic article. wherein the film has a substantially uniform thickness over a portion of the surface of the plastic article to which it is applied and is substantially dry once applied, and the polymeric resin is the solvent for the photochromic substance and the inco
(b) coating the film-bearing plastic article in the surface of the plastic article at a temperature near but below the melting temperature of the photochromic material; (c) thereafter removing the photochromic material-depleted film from the surface of the plastic article. A method for imparting photochromic responsiveness. (25) Film thickness is approximately 0.0127-0.0762mm
(0.5-3 mil). (26) Membrane thickness is approximately 0.0254-0.0508mm
(1-2 mil). (27) Applying a film by spraying a solution of a photochromic substance and a polymeric resin in a readily volatile solvent onto the surface (at least one) of the plastic article and wherein the solution contains 25-40% by weight of the photochromic substance. 26. The method of claim 25, comprising sufficient photochromic material to produce a dry film containing the photochromic material. (28) 5℃ to 50℃ higher than the melting temperature of the photochromic substance
The method according to claim (27), wherein the heating time at a low temperature is 15 to 60 minutes. (29) (a) the plastic article is a polymer and copolymer of polyol (allyl carbonate) monomer;
Polyacrylate, poly(alkyl acrylate), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate) poly(vinyl alcohol), polyurethane, polycarbonate, polyethylene terephthalate, polystyrene, poly(styrene) (b) the photochromic substance is selected from spiro(indoline) pyridobenzoxazine, spiro(indoline) naphthoxazine, spiro(indoline) benzopyran, spiro(
(c) the polymer resin is polyvinyl chloride, polyvinyl acetate, polyurethane; and (c) the polymer resin is polyvinyl chloride, polyvinyl acetate, polyurethane. , polyvinyl butyral, copolymer of vinyl chloride and vinyl acetate, copolymer of vinyl chloride and vinylidene chloride, vinyl propionate, cellulose acetate butyrate, C_1- of acrylic acid or methacrylic acid
C_4 ester polymer, a mixture of polyvinyl chloride and the acrylic ester polymer, and a mixture containing 10 to 90 parts of polyvinyl chloride and 90 to 10 parts of the acrylic ester polymer. A method according to claim (25). (30) (a) The plastic article is a polymer of diethylene glycol bis(allyl carbonate), a copolymer of diethylene glycol bis(allyl carbonate) and vinyl acetate, polycarbonate, polyvinyl butyral, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene. , a copolymer of styrene and methyl methacrylate or vinyl acetate or acrylonitrile, and (b) the photochromic substance is selected from spiro(indoline)pyridobenzoxazine, spiro(indoline)naphthoxazine, and (c) the polymer The resin is polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, copolymer of vinyl chloride and vinyl acetate, polyvinyl propionate, cellulose acetate butyrate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride and the acrylic ester polymerization. a mixture of 10 to 90 parts of polyvinyl chloride and 90 to 90 parts of polyvinyl chloride;
10 parts of an acrylic acid ester polymer. (31) applying a film by spraying a solution of a photochromic material and a polymeric resin in a readily volatile organic solvent onto the surface(s) of a plastic article, and wherein the solution contains 25-40% by weight of the photochromic material; 31. The method of claim 30, comprising sufficient photochromic material to produce a dry film containing the material. (32) Claim (31), wherein the temperature at which the film-supported plastic article is heated is about 5°C to 50°C lower than the melting temperature of the photochromic substance, and the heating time is about 15 to 60 minutes. Method described. (33) The temperature and time for heating the membrane-supported plastic article are 145°C to 160°C and 20 minutes to 45°C, respectively.
The method according to claim (32), wherein the method is: