JPH07502345A - Photochromic polymer membrane - 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] I. Romic person The present invention relates to photochromic materials, and more particularly to photochromic polymers. This application is filed June 20, 1988, co-pending U.S. Application No. 209.414 is a continuation-in-part application.

As used herein, the term "photochromic" refers to ambient, actinic, visible radiation. reversible changes in optical transmission depending on the intensity of near-visible or near-visible radiant energy. It is used for the light transmitting material shown. Photochromic compounds are known Currently, most of the useful materials are silver halides, typically glass. silver halide dispersed in a matrix of Example of photochromic glass U.S. Pat. No. 3.208.860, U.S. Pat. No. 4.550.087 and U.S. Pat. No. 076.542 and the references cited therein. Other hotoku ROMIC materials are known, but many have a limited useful life.

This is the amount of radiation-responsive material that helps absorb light, especially in organic photomix materials. This is due to the fact that irreversible deterioration that reduces the

The main disadvantages of using glass as a matrix for photochromic glasses are , due to its weight and high manufacturing cost. Lighter and cheaper to manufacture than glass , window glass made from a transparent polymeric material similar to the properties of photochromic glass, Adding the photochromic properties of silver halide thread to eyeglass lenses and other articles There have been attempts to do so. However, such attempts have not been particularly successful in terms of industrial success. Not yet reached.

If silver halide is to be incorporated into a polymeric matrix, the chemical effects, e.g. chemical effects of catalysts and initiators that have a deactivating effect on the photosensitive particles. This deactivation effect must be avoided by shielding the silver halide grains and protecting the silver halide grains. Silver halogenide can be reduced, for example by peroxides used as initiators in the casting process ( It is believed that this is a result of some being easily oxidized. U.S. Patent No. 4.046. 586 and 4.596.673. Attempts have been made to solve the problem, but with no apparent industrial success. It was.

We have developed a behavior comparable to that of silver halide grains in a glass matrix. A number of interesting techniques have been developed to attempt to impart 0 to romic polymers. Some of these techniques, which are considered material for the present invention, are described in the U.S. patents listed below. and the references cited therein: U.S. Pat. No. 4,046.586. No. 4.049.567: No. 4.106.861: No. 4.110. No. 24: No. 4.556.605: No. 4.578.305: No. 4.58 1.283: 4.596.673: 4.489.108 and 4.489.108 No. 4.367.170, but no commercially available materials from any of these materials are available. It seems that the product is no longer manufactured. Transmittance of these materials without significant failure or these materials cannot be circulated with sufficient change in permeability. This may be due to the inability to show rapid or reverse changes.

Therefore, the main object of the present invention is to develop novel photochromic products containing polymeric matrices. The aim is to provide products.

Yet another object of the present invention is to produce substantial and reversible changes within an interval as short as a few minutes. Our goal is to provide products that demonstrate our uniqueness.

Another object of the invention is to provide a product for coating light-transmitting materials and The desired lifetime is such that it is not subject to irreversible deterioration that reduces chromic activity. In order to provide products and obtain photochromic lenses that weigh less under illumination. Our mission is to provide products for coating light-transparent synthetic resin materials. It also coats glass and plastic sheets or plates for a wide range of applications. It is an object of the present invention to provide a polymer which may be used in a polymer.

Accordingly, the present invention provides a method and several types of steps and one or more of such steps. and its relationship to other stages, as well as its characteristics as embodied in the detailed description below. Products and compositions having the characteristics, properties and relationships of the elements, as well as the claims. This includes a wide range of uses such as:

In general, to accomplish the foregoing and other objects, the present invention consists essentially of Provides a quantifiable material containing silver halide, the material is preferably applied as a coating on light-transmitting and/or light-reflecting materials. It is something that will be done. This material is approximately 50 to 800 angstroms in size. contains photochromic silver halide in the range of It is dispersed in a protective colloid that is capable of binding genes.

The primary intended uses for the material of the present invention are ophthalmic lenses, window glass, skylight glass, etc. laths, overhang glass, automobile windshields, camera filters, telescopes uvJ3, etc. on light-transmitting materials, including but not limited to, binoculars, greenhouses, etc. Forming a photochromic polymer film to suppress visible light emission and glare It is for the purpose of

For a better understanding of the nature and purpose of the invention, please refer to the accompanying drawings. Mentioned in the detailed description below.

Figure 1 shows a polymer film prepared according to the principles of the present invention exposed to bright sunlight. on a general axis representing transmission versus wavelength at several different times before and during exposure. A plot of several curves.

Figure 2 shows another polymeric membrane prepared according to the principles of the invention exposed to bright sunlight. A general axis representing transmission versus wavelength at several different times before and during each exposure. Here is a plot of some other curves above.

FIG. 3 shows a bright, thick structure of yet another polymeric membrane prepared in accordance with the principles of the present invention. Represents transmission versus wavelength at several different times before and during exposure to sunlight. Figure 2 is a plot of several other curves on the general axis.

FIG. 4 shows a second diagram of yet another polymer membrane prepared according to the principles of the present invention Another plot of the type shown in the figure.

FIG. 5 shows a second diagram of yet another polymer membrane prepared according to the principles of the present invention. Figure 2 is yet another plot of the type shown in the figure.

FIG. 6 shows a second diagram of yet another polymeric membrane prepared in accordance with the principles of the present invention. Figure 2 is yet another plot of the type shown in the figure.

FIG. 7 is a schematic cross-sectional view of an ophthalmic lens incorporating a membrane of the present invention. and FIG. 8 is a schematic cross-sectional view of a window glass incorporating the membrane of the present invention.

The present invention consists of photochromic silver halide grains in a polymeric matrix. Particularly useful in forming polymeric films for use with materials and optically transparent materials. Certain equivalents are particularly expressed in methods of manufacturing such materials. emulsion is preferably initially approximately 50 angstroms to 800 angstroms. prepared from surface-doped silver halide grains having diameters in the range of irreversibly removes the halogens generated during the subsequent photolysis of silver halide grains. Suspended in a non-binding polymer solution. Silver halide grains are typically AgCl , AgBr and AgI and mixtures thereof, first surface doped or Cu+ or Cu÷+ ions and if desired sulfur-bearing activated by compounds.

Reagents that will confer electrical conductivity on the polymeric mixture are added later; Such reagents may preferably be or exist in several different oxidation states. ions, but some single oxidation-stable cations may be used. The claimed reagent is the matrix formed after the polymer is formed into the membrane. In this case, both electron mobility and some ionic mobility must be provided.

Preferably, the polymeric mixture is also used in the previous reaction, i.e., the phototransmission of silver halide to silver. Including accelerators (selected from a number of different polyvalent cations) for decomposition. Should. Finally, the membrane is cast indoors under yellow or red light conditions. It is produced from a polymer mixture by

The details of the method of the present invention include imparting photochromic properties in a polymerizable matrix. The silver halide grains that will be produced are synthesized by a continuous crystal nucleation method. this purpose Therefore, solutions of silver ions can be prepared in either aqueous or mostly non-aqueous solvents. 0 particles are manufactured for use in non-aqueous solvent based systems. If so, then remove the water. Silver cations can be mixed with water, methanol, or acetonate. silver acetate, silver trifluoroacetate, silver nitrate in a suitable protic solvent such as tolyl, etc. It can be given by dissolving a soluble silver salt such as. silver in solution The initial concentration of the ions varies over a wide range, from concentrations as low as 0.001 to At concentrations as high as 0 molar, and even higher concentrations, however, the formation of silver halide grains Silver ions or halide ions, low concentrations are preferred for use in A water-soluble polymer that does not irreversibly bind to any polyvinyl alcohol, polycarboxylic acid, polysulfonic acid, polyether, and their copolymers, etc.) are added at low concentrations, preferably 10% by weight or less. , providing a protective environment for controlled silver halide grain growth. growth control Additives and monomeric or polymeric surfactants may optionally be added.

A second solution containing a halide salt is also prepared. Halide salts include ammonium, quaternary ammonium monium, alkali metals (e.g. lithium, sodium or potassium), or alkaline earth metal (e.g. magnesium or calcium) halides. Typically provided as an aqueous salt solution of soluble halide salts such as It can be one or more halides such as halides, iodides and chlorides. Hara The initial concentration of the ide salt solution can vary widely from o,oot to 7.0 molar or more. However, for use it should be reduced to about 0.1 mole or less. silver solution smell of a water-soluble protective polymer that does not irreversibly bind to silver ions or halide ions. Less than 10% by weight may be added, and the polymer is conveniently present in the silver solution. It does not have to be the same as used in

The silver ion solution and halide ion solution preferably adjusted to 0.1 mol or less are , - mixed together, preferably in stoichiometric amounts or formed halogenated would provide a net negative charge that would help maintain the stability of the silver. mixture with excess halide ions. Mixing is for photochromic use accelerate the reaction that will form silver halide grains of the most favorable size and shape. In order to Therefore, it should be carried out while controlling parameters such as temperature, ion concentration, and pH1 stirring. Ru. Silver halide grains are produced by continuous crystal nucleation, triple or double jet precipitation techniques. Synthesized preferably using techniques. The size of the particles formed is approximately 800 oz. 0 particle shape and size of less than 100 angstroms, preferably less than 500 angstroms. Accurate control of the This is easily achieved using a well-established manufacturing method.

After mixing the first and second solutions to form silver halide grains, a crystal growth inhibitor is added. It is added to this emulsion to slow down the growth of silver halide grains and increase the size of these grains. 0 to 800 angstrom units or less. Commercially available silver halide growth inhibitors include IH-purin-6-amine (Ease commercially available as Adenine from Toman Kodak Company, Rochinister, New York), Anine and l-phenyl-5-mercaptotetrazole (Fairmount Chemical Growth A list of modifiers and stabilizers is given in U.S. Patent No. 4.400.463. There is. Alternatively, the silver halide grains may be subjected to Ostold ripening prior to stabilization. Preferably, in both cases the particle size distribution is uniform in particle size. It would be very narrow.

In a preferred embodiment, the silver halide grains formed are It is relatively homogeneous and is formed as a mixed halide. However, during The grains vary so that the core region can have a different silver halide composition than the surrounding region. It can be thought of as a vine.

For example, a particle has an AgI core surrounded by an AgCI B r shell. Thus the vines are formed. Alternatively, the particles are surrounded by an AgI shell Vine formed by AgClBr.

As an alternative to mixing silver and halogen salts from an aqueous solution, silver and halogen salts are initially , or of fine grains of silver halide suspended in a dispersion medium during the grain growth stage. Once introduced into the reaction vessel all at once, the particles can be introduced in the form of After Ostwald ripening, the grain size becomes such that large grain nuclei form.

The silver halide grains are then washed and concentrated using conventional washing techniques to remove excess salts. and other soluble materials that are detrimental to the desired photochromic performance of the silver halide. Ultrafiltration (for example, cutting particles with a molecular weight of about 10,000) (through a Millipore filter) is the preferred method for cleaning silver halide grains. It is. This is because this method does not have undesirable salts dissolved in it. In addition to removing excess water from the Therefore, protection for the formation of silver halide grains is used as a preferred separation technique. Because it removes a significant portion of the water-soluble polymers used to provide the environment It is. Additionally, silver halide grains can be agglomerated and/or decanted, or or other techniques known in the art to provide photochromic activity. Do not react adversely with the polyvalent cations that are then used in the process of the invention to provide It can also be washed as long as no anionically charged substance is introduced.

This material contains photochromically inert silver halide grains that are washed and concentrated. After washing, the protective polymer removed during the cleaning process is treated with a high molecular weight polymer or It is possible to irreversibly replace the halogen with other non-binding protective polymers. can. The substituted polymer is a water-dispersible, film-forming polymer that can be used as an emulsion. mixed with silver halide in the form of silver. Polymer substitution provides superior mechanical strength. predetermined qualities such as Differentialization with selected polymers by predetermined use of species such as Instances such as scu"tCu+ or combinations thereof that can form scatterings on, S-, R-3-.

Sulfur-containing ions such as those selected from s203- or combinations thereof (wherein , R is alkyl, alkylidene, alkene, alkadiene, aryl, alkyl, 102 to 10105pp emulsions with organic groups such as lucaryl etc. silver halide particles are added to the emulsion at a concentration of Doped onto the surface and serves as a photoactivator, or alternatively sulfur-containing as an activator In place of or with the yellow ion, a thiol such as 2.2'-thiogentanol can be used. Ethers and/or redundancy lower than about 235 mv at pH 6.5. Mild reducing agents such as ascorbic acid, which has a Does not harm the quality of the particles, especially the grain size of silver halide grains in emulsions can be used as long as possible.

Such reducing agents may be present in amounts of 0.01 to 50 mole percent based on the weight of silver. added.

In a preferred embodiment of the present invention, in conventional conventional photographic systems, l - Phenyl-5-mercaptotetrazole (PMT) is a potential inhibitor of photosensitivity Surprisingly, it was thought to be an agent for inhibiting the growth of silver halide grains. is initially used for the purpose of cleaning and remains on the particles even after washing and concentration. mercapto-containing compounds such as residual PMT, or Na2S2O3, Na The combination of sulfur-containing compounds such as 2S and halogenated steel allows photoactivation of particles. It is done. Sulfur is believed to improve the quantum efficiency of photochromic reactions. Ru. Doping the surface of silver halide grains with activating ions improves their photosensitivity and The important things that maximize tochromic properties are cobalt, magnesium, and manga. foreign ionic substances such as carbon, chromium, and especially cerium, europium, and samarium. Rare earth metals such as aluminum (typically derived from their halides) In the present invention, the intervention of ions into the final emulsion promotes the aforementioned reaction. can serve as an agent.

The concentration of copper ions added to the emulsion is at least partially controlled by the inversion reaction (from silver to silver chloride). However, the final form disclosed in the present invention is For example, about 1 x 10-'o hm-'/cm-' at 3°C is applied to the formed film. Adding a drug that imparts greater specific conductivity to the latter controls the inversion reaction in the latter. It has been found to be very effective. Phosphorus, a well-known polyelectrolyte Acids (typically of the orthophosphoric acid type) are the materials that provide the desired electrical conductivity. others Agents useful for imparting conductivity to materials include methanesulfonic acid and base chloride. Quaternary ammonium salts such as dimethyltrimethylammonium and trimethylammonium chloride Monium chloride, even in high concentrations (up to 3 moles per mole of silver in the emulsion) Metal salts, either already present in the form of copper salts or added as promoters of forward reactions Glycerol containing salt, etc. In the presence of such drugs, ion gives mobility within the membrane, especially the conversion of copper ions from reduced form to oxidized form and silver chloride can accelerate electron transport during reduction reactions, including the conversion to silver.

A suitable point for reversibly re-donating halogen to hydrolyzed silver when irradiation is discontinued. Remer is a compound that loosely binds halide ions and re-supplies the ions when irradiation is stopped. It is something that can be given. The reverse reaction is performed so that the polymer has more than 50% halogenated groups. This is facilitated by Non-limiting examples of useful polymers include: Poly-4-vinylpyridine, poly-2-vinylpyridine, polyvinylpyridine chloride Lysine, polyvinylimidazole and its chloride, polylysine, polyvinyl alcohol polyvinyl pyrrolidone, polyvinylidine chloride, polyvinyl chloride, polyether esters, polycarboxylic acids, polysulfonic acids, polyvinylbenzyltrimethylane Quaternary ammonium halide such as monium halide and polyvinylpyridium halide Ride polymer, cellulose carboxylate, cellulose sulfate, Includes ethers of cellulose, and copolymers and mixtures thereof.

Surfactants are added to the emulsion to promote wetting of the polymer substrate during coating. You can also add lauroamphodibrobionate (milano) as a surfactant. Milanol 82M-S F jersey for Milanol commercially available from Brunswick, B.C.), sodium dioctyl sulfonate Succinate (Aerosol) to American Cinnamide Company (commercially available from Uniin, Jersey), and octylphenox. Cypolyethoxyethanol (from Rohm and Haas Co., Ltd. as Triton x-too) commercially available from Philadelphia, Pennsylvania). .

obtained by suspending surface-activated silver chloride with a suitable polymer as mentioned above. The emulsion is preferably maintained at a final pH of about 6.5 or less, preferably at pH 1.5. and 4.5. This emulsion can be used as a film on glass or other non-contact surfaces. Spread on an adhesive substrate and dry to remove substantially all moisture, solvent, and suspended phase. Thereafter, the dried emulsion is peeled off from the substrate to form a support-free film. Alternatively, apply an emulsion coated onto a clear polymeric substrate film and dried. photochromic breasts The agent can be applied to the substrate by dip coating, spray coating, spin code, flow coating, etc. method to form a continuous polymeric film 1-30 microns thick on the surface. be able to. Membranes or films can be prepared with or without solvents or adhesives. , e.g. as a plastic laminate, as well as eyeglass lens materials (e.g. poly Carbonate Cellulose acetate butyrate, polyester, polyvinyl chloride (lens materials made of RORIDO, CR-39 stock, etc.) Can be bonded onto glass, polymeric panes, or other light-transmitting materials. % light transmission when photochemically irradiating the final laminate can be adjusted by changing the thickness, amount of activation, and concentration of phytochromic materials. .

The invention will be further illustrated by the following examples, which illustrate the invention. It is not limited to.

Actual JL example.”

The first solution was mixed with a 1% W/V polyoxybrobylene-polyoxyethylene block copolymer. Bolimar (BASF Wyandote, Parspany, Newshire) Commercially available as Pluronic 31 R1 from: CAS Registered. Record #9003-11-6) 0.185 liters and 179 liters of deionized water. Prepared by mixing together and adding 3 g of AgNO3807. Mix well After combining, deionized water was added to bring the solution to 180 liters.

A second solution was mixed with the same 1% w/v polyoxybromine in 163 liters of deionized water. Birene-polyoxyethylene block copolymer 0.185’J ivy-1KBr 226g, 1154.4g of NaC, 39.4g of NaC and aerosol (^er By mixing together 6.3 liters of osoll OT (1% w/v) It was prepared using This mixture was mixed with polyvinylpyrrolidone (PVP) while being continuously stirred. K-15, 5% W/v, average molecular weight 10.000), mixed in 9.5 liters and desorbed. Added to 180 liters of ionized water.

The first and second solutions were then introduced into a continuous nucleation reactor with a residence time of 0.23 milliseconds. They squirted at the same time to the mouth side. Fill the mixing container and reactor with 10 liters of water each. Washed with tar. The predetermined scale reading is the average particle size of 100 angstroms. The particle size was monitored at 5 minute intervals using a turbidity meter until the primary , 0.05M 1-phenyl-5-mercaptotetrazole (PMT) 7.5 The litter was squirted into the stirred mixture for 3 minutes.

The dispersion was transferred to an aluminum oxide film equipped with 40 square feet of membrane with a molecular weight cutoff of 30.000. One volume ultrafiltered using an Amicon ultrafiltration unit is 40 liters. 5% W mixed with 29.5 liters of deionized water / V polyvinylpyrrolidone (PVP K-90, average molecular weight approximately 360.000) Repeat ultrafiltration until the zero volume with 10.5'J 9- is reduced to 40 liters. Add another 40 liters of deionized water until the conductivity of the filtrate is 70 micromonitors. The ultrafiltration step was repeated again until 0.2 cm/cm. The area of the ultrafiltration membrane is 10 square A final reduction in volume is made by reducing the volume to approximately 0.0 feet for silver. 3 mo The silver recovered was more than 95% of the silver initially put in.

1 seed fl The film-forming dispersion was mixed with 8.50ml of water 1.3% w/v octylphenoxypolyethyl Oxyethanol (Roh-K, Haas, Philadelphia, Pennsylvania) Commercially available as Triton X-100 from , Inc. CAS registration #9 002-93-1) Surfactant in the form of 0.50ml, 0.50M CuCl2 and Mixture of multiple surface doping sensitizers made from 0.50M thioglycerol and 5.0 ml of silver chloride emulsion prepared as in Example 1 and 0.33 ml of silver chloride emulsion prepared as in Example 1 It was made by mixing 6.0 ml of 4M (2 mmol).

Spread this dispersion uniformly to obtain 75 mg Ag/ft2 on cellulose acetate base Murakami. , and dried. This dry coating was treated with cellulose acetate using methanol. The sheet was laminated, dried in an oven at 50° C. for an additional 2 hours, and then cooled.

After exposing a portion of the resulting laminate to sunlight for one hour, the sample was Le 3410 Spectrophotometer (H1tachi Model 341 0 spectra-photometer) and set it at 380 or 670 on. Scanning was performed until fog was reached at a scanning speed of 1200 nm/sec. for the following times Curve numbers 1 to 12, each representing the transmittance, are shown in FIG.

1 Unexposed 2 After 1 hour exposure 3 After 1 minute in the dark 4 After 2 minutes in the dark 5 After 3 minutes in the dark 6 After 4 minutes in the dark 7 After 5 minutes in the dark 8 After 10 minutes in the dark 9 After 15 minutes in the dark 10 After 20 minutes in the dark 11 After 3 minutes in the dark 12 After 30 minutes in the dark Shigo Yuyu A laminate made as in Example 2 was exposed to sunlight for 2 hours and then exposed to the same strip. Figure 2 was placed in a pectro-photometer and scanned as described in Example 2. , the curve number representing the permeability measured for the same time as shown in the table of Example 2. No. 1-12 is shown. However, curve #2 is, of course, 2 hours after exposure. It is something that was given.

Sogokoshi A Laminated thin films were prepared as described in Example 2. However, each of Ag in the emulsion Additional PvP was added to the mmol number for a total of 3.0 mmol. . Instead of CuCl2, 0.5 mmol copper acetate was added to 1.0 mmol methane. The reverse reaction was controlled by addition of sulfonic acid and 2.5 mmol of glycerin. Furthermore , 1.0 mmol of 2.2°-dithiogetanol (HO-CH2CH2S- CH2CH20H) and 0.3 mmol (::eC13 as forward reaction promoter) added. This film was tested as described in Example 3. Obtained sensitometer The readings are shown in FIG. 3 by curves numbered with the same meaning as in FIG. 2.

Wataru Mitate 5 Thin films were prepared as described in Example 2. However, each millimeter of Ag in the emulsion For the number of moles, (, instead of uc12, 0.5 mmol of acetic acid steel is 1.0 It was used with mmol of methanesulfonic acid and 6 mmol of glycerin. Furthermore , 0.5 mmol of CeCl3 for each mmol of Ag in the emulsion. was added as a forward reaction accelerator. This film was tested as described in Example 3. Obtained The sensitometer readings obtained are shown in the curve with numbers having the same meaning in Figure 2. Shown in Figure 4.

1 ball of mitate Thin films were prepared as described in Example 2. However, each millimeter of Ag in the emulsion Based on the number of moles, 0.75 mmol of CLIC12 is mixed with 6.0 mmol of orthophosphorus. Used with acids to control reverse reactions.

For each mmol of Ag in the emulsion, 0.25 mmol of GaCl2 and 0.25 mmol MgCl2 were added as forward reaction promoters. This thin film is Tested as described in Example 3. The obtained sensitometer readings are the same as in Figure 2. The curves are shown in FIG. 5 with meaningful numbers.

11 children A thin film was prepared as described in Example 6. However, +CuCl2 with the following changes was 0.5 mmol and no GaCl2 or orthophosphoric acid was used. This thin The membrane was tested as described in Example 3. The obtained densitometer readings are shown in Figure 2. FIG. 6 shows curves with numbers having the same meaning.

As is comprehensively clear from Examples 1 to 7, the rate of the reverse reaction shown in Figure 1 is This can be significantly increased by adding an agent that imparts electrical conductivity to the thin film. Especially examples As shown in Figure 7, the reverse reaction occurs even in the absence of agents such as phosphoric acid and methanesulfonic acid. Rarely occurs (especially when forward reaction accelerators are included).

As mentioned above, one preferred use of photochromic emulsions is to Lens elements used to produce eyeglass lenses that are clear and transparent against As shown in the cross-sectional view of FIG. The lenses 20 are made of polyester coated with a film 26 of each of the emulsions of the present invention. comprising a laminate 22 made from a pair of sheets 2 of substrate material of different types, the laminate comprising two It is created by bringing the emulsion surfaces of sheets into face-to-face contact with each other. dry The double layer of emulsion is thus protected in the outer layer made of sheet 2. . The laminate 22 is then formed into a suitable known polymeric ophthalmic lens material by known techniques. Or polycarbonates, acrylic resins, CR-39 resins, polystyrene Incorporated into transparent resins such as polyesters, cellulose acetate butyrates, etc. It can be done.

Similarly, the laminate 22 can be placed between flat window panes or between plastic or glass sheets. 28 to create a photochromic window as shown in Figure 8. can be done.

Advantages and features of the invention are described below, together with details of its structure and function. However, it should be understood that this disclosure is merely illustrative. It is indicated by a general predicate with a broad meaning.

The scope of the claims is thereby expressed.

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Claims (19)

[Claims] 1. A photochromic emulsion for depositing a light-transmissive material, the emulsion containing about 5 Photosensitivity having a size within the range of 0 angstroms to 800 angstroms Photosensitive silver halide grains in which the core silver halide has been surface sensitized. Polymerizable colloidal suspension to protect the core silver halide grains. A clouding agent that irreversibly reacts with halogens generated during photolysis of core silver halide grains. A suspending agent selected to avoid binding: and to impart electrical conductivity to the core emulsion. A photochromic emulsion characterized by containing an agent. 2. The above agent is phosphoric acid, methanesulfonic acid, benzyltrimethylammonium chloride. , trimethylammonium chloride, and glycerin containing high concentrations of metal salts. The photochromic emulsion according to claim 1, which is selected from the group consisting of: 3. A photochromic emulsion according to claim 1, wherein said agent is phosphoric acid. 4. The photochromic emulsion according to claim 1, wherein the agent is methanesulfonic acid. hmm. 5. The photoreceptor according to claim 1, wherein the agent is benzyltrimethylammonium chloride. Romic emulsion. 6. 2. The hot drug according to claim 1, wherein the agent is glycerin containing a high concentration of metal salts. Romic emulsion. 7. The photochromic product according to claim 1, which contains a promoter for forward photochromic reaction. Quemulsion. 8. The accelerator is cobalt ion, chromium ion, manganese ion, magnesium ion. selected from the group consisting of rare earth metal ions, rare earth metal ions, and combinations thereof. 8. The photochromic emulsion according to claim 7. 9. The silver halide grains include AgCl, AgBr, AgI, and combinations thereof. The photochromic emulsion according to claim 1, wherein the photochromic emulsion is selected from the group consisting of: 10. The silver halide grains are composed of Cu++, Cu+, and combinations thereof. ions selected from the group, and (1) a thioether, (2) the emulsion a mild reducing agent chosen so as not to affect the colloidal properties of (3) R-S-; from S2O3=, S=, or a combination thereof (where R is an organic radical) and (4) a combination thereof. The photochromic emulsion according to claim 1, which is surface doped with a sensitizer. 11. The silver halide grains are composed of Cu++, Cu+, and combinations thereof. Claim 1 wherein the surface is doped with an ion selected from the group and a thioether. Photochromic emulsion as described. 12. 12. The thioether of claim 11, wherein said thioether comprises 2,2'thiodiethanol. Photochromic emulsion. 13. The silver halide grains are composed of Cu++, Cu+, and combinations thereof. Claim 1, wherein the surface is doped with an ion selected from the group and a mild reducing agent. Photochromic emulsion. 14. The photochromic emitter according to claim 13, wherein the reducing agent is ascorbic acid. Lujon. 15. The ions have an effect on the amount of silver in the emulsion with respect to the emulsion. 11. The concentration range of about 102 to 105 ppm. photochromic emulsion. 16. The R-S-, S2O3=, and S= ions are Na2S2O3, Na2S , 1-phenyl-5-mercaptotetrazole and mixtures thereof. 11. The photochromic compound according to claim 10, which is provided by one or more compounds selected from emulsion. 17. The colloid is poly-4-vinylpyridine, poly-2-vinylpyridine, Halogenated polyvinyl pyridine, polyvinylimixole, polylysine, polyvinyl pyridine vinyl alcohol, polyvinylpyrrolidone, polyvinylidene chloride, polyvinyl chloride , polyether, polycarboxylic acid, polysulfonic acid, polyvinylbenzyl chloride Halogenated polymerized quaternary containing trimethylammonium and polyvinylpyridium chloride grade ammonium, cellulose carboxylate ester, cellulose sulfate ester, selected from the group consisting of lulose esters, copolymers and mixtures thereof The photochromic emulsion according to claim 1, comprising a polymer. 18. The size ranges from approximately 50 angstroms to 800 angstroms. A step of forming photosensitive silver halide grains having a surface of a process in which the grains are sensitized; a polymerizable colloidal suspending agent during subsequent photolysis of the silver halide grains; The suspension is mixed with a suspending agent selected so as not to irreversibly bind to the halogens formed in the The method further comprises a step of mixing the mixture with an agent for imparting conductivity. A method for producing a photochromic emulsion. 19. further separating a substantial portion of the first suspending agent from the remainder of the mixture; Step: and adding a second, relatively high molecular weight suspending agent to the remainder, followed by a second, relatively high molecular weight suspending agent. to prevent irreversible binding to the halogen generated during photolysis of the silver halide grains. said first polymerization, characterized in that said first polymerization comprises a step of adding a suspending agent selected as 19. The colloidal suspension of claim 18, wherein the colloidal suspension has a relatively low molecular weight. Method for producing photochromic emulsion.