JPS5835214B2 - General polymer latex material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel composition containing both (a) a hydrophobic material and (b) a polymeric latex material, in which the hydrophobic compound is incorporated into a discontinuous phase of the latex. or absorbed into the particles that make up the dispersed phase.

The present invention further relates to polymer latex/hydrophobe compositions (sometimes referred to herein as loaded latex compositions) produced from the coating composition manufacturing method.

) and products coated with polymer latex/hydrophobe compositions.

The present invention consists of a photographic substrate coated with at least one layer comprising a hydrophilic colloid, such as gelatin, into which is distributed one or more hydrophobic compounds in the form of a filled latex composition. Particularly useful in the manufacture of photographic products.

'Traditionally, in the manufacture of photographic products, several methods have been used in which hydrophobic compounds, especially non-polymeric compounds such as dye-forming color formers, UV-absorbing substances, etc., are fairly evenly distributed in a layer of gelatin or other hydrophilic colloids. The method has been successfully used commercially.

One of the simplest of these methods involves first mixing a solid or liquid hydrophobic compound mi) with a suitable hydrophilic colloid solution or emulsion (11) and then mixing the resulting mixture. mechanically dispersing ([) in (11) by passing it several times through a high energy mill such as a colloid mill.

This method produces poor dispersion (compared to other conventional dispersion methods), and this defect dispersion is often unstable.

This method also consumes a large amount of energy to achieve the desired degree of particle comminution and dispersion.

This high consumption of energy is often accompanied by heat build-up or undesired local heating and causes undesired chemical deterioration of some of the ingredients contained.

Another method involves distributing the hydrophobic compound in a hydrophilic colloid solution or dispersion, which is subsequently coated and dried to produce a solid hydrophilic colloid layer in which the hydrophobic compound is dispersed.

) is U.S. Patent No. 2304940 and U.S. Patent No. 232202
It is stated in No. 7.

The method involves first dissolving the hydrophobic compound in an oil or high boiling solvent to form a solution and then dispersing the resulting oily solution into a hydrophilic colloid solution or dispersion.

Variations on this general method are, for example, U.S. Pat.
1171, including the use of low molecular weight co-solvents such as ethyl acetate or low molecular weight ketones to aid in dissolving the hydrophobe in the oily solvent.

Processes involving the use of such oily, high-boiling solvents, so-called color former solvents, are commercially widespread for the production of color photographic elements that incorporate and include ballasted dye-forming color former compounds. ing.

However, such methods of dispersing color former solutions require high-energy milling steps (to obtain the desired degree of dispersion and particle size) and typically involve undesirable effects in some of the components of the milled product. cause deterioration.

Furthermore, such a milling process is time consuming and expensive.

Thus, for many years there has been a need for improved methods for uniformly dispersing hydrophobic compounds, such as ballasted dye-forming color formers, in photographic emulsions and other hydrophilic colloid-containing dispersions and solutions. .

Such improved methods should at least eliminate the need for high energy mills to prepare useful dispersions of hydrophobic materials dispersed in hydrophilic colloid-containing materials and layers.

Although the present invention consists of using certain polymeric latexes with hydrophobic materials dispersed in coatings or layers such as those found in photographic elements, this use of latex is substantially different from conventional uses of latex. It's different.

Traditional uses of latex, for example, have included the use of latex simply as one source of the polymeric component of the coating layer.

Conventional latexes were often simply mixed into photographic emulsions, which usually contained zerotine, silver halide, and common photographic additives.

Traditionally, when hydrophobic compounds such as organic solvents and dye-forming color formers are used with synthetic polymers in the preparation of coating compositions, the hydrophobe and polymer are often combined with the other components of the coating composition. Dissolve in a solvent in advance (US Pat. No. 3,518,088, US Pat. No. 2,2691)
No. 58 and No. 3619195).

Tong, U.S. Pat. No. 2,772,163 describes certain latexes, and U.S. Pat.
In conjunction with an alkali-soluble, ballasted, dye-forming color former of the type described by John C. Schneider.

Such color formers can be dissolved in an alkaline solution and precipitated from the solution by neutralization of the alkali.

The latex used by the tongs differs from the latex of the present invention in that it is not a loadable latex as described below.

Moreover, the present invention is also much more broadly useful with respect to hydrophobes than Tong's hydrophobes, and the process
Compared to Tong's process, it allows for the incorporation of significantly higher amounts of hydrophobic substances into the polymer latex particles.

The present invention provides a novel and valuable process for producing hydrophilic colloid layers (typically on a substrate) containing one or more hydrophobic substances homogeneously dispersed therein, and a method useful for producing such hydrophilic colloid layers. , a process for making improved polymer latex compositions, and improved polymer latex compositions and products that can be made therefrom.

The process for manufacturing a filled polymer latex according to the present invention is a method for manufacturing a filled polymer latex composition having a dispersed phase consisting essentially of a filled polymeric material filled with a hydrophobic material distributed in a fillable polymeric material. to the hydrophobic substance solution dissolved in a water-miscible organic solvent,
It consists of gradually adding a fillable aqueous latex and at least enough water to make the hydrophobic substance insoluble in the solution.

The novel polymer latex compositions (filled latex compositions) of the present invention are characterized in that the dispersed or discontinuous phase is substantially particles of a synthetic polymer, and a solution of a hydrophobic compound dissolved in a water-miscible solvent. A polymeric latex consisting of particles of a synthetic polymer having one or more hydrophobic compounds distributed throughout said particles by a process consisting of mixing together fillable latexes.

As used herein, the term "distribution" means to interact with the polymer particles both on the surface and within the polymer particles.

One article of the invention is a support coated with at least one layer in which particles of filled latex as described above are distributed.

Preferred polymeric latex compositions of the present invention, hereinafter referred to as photographically useful filled latex compositions.

) can be produced by a process consisting of gradually mixing a fillable aqueous polymer latex into a solution of a hydrophobic compound dissolved in a water-miscible organic solvent (the expression "fillable" polymer latex). (clarified below).

The order of addition is very important for the successful implementation of this invention in order to prevent coagulation of the latex or accumulation of excessive amounts of hydrophobic material outside the latex particles.

A number of valuable results obtained by practicing the present invention include:
Directly from the unique physicochemical changes (with respect to the hydrophobe and polymeric latex particles) that occur in the novel step of the inventive process of mixing the fillable aqueous latex into the hydrophobe solution (dissolved in a water-miscible solvent). I think it's something that will affect you.

That is, as the aqueous latex is gradually introduced into a solution of a hydrophobic substance (e.g., a solution of acetone), the acetone solution becomes more hydrophilic or water-like in nature due to the further incorporation of water into the acetone solution. gradually becomes

At some point (depending on the particular type and amount of hydrophobe and the particular type of water-miscible organic solvent used), the acetone solution becomes so hydrophilic that the hydrophobe can no longer be dissolved in acetone. It can no longer be hydrated and begins to change to an insoluble state (in acetone).

Up to this point, a number of fillable polymer latex particles are introduced into an acetone solution along with water (in latex form).

These particles apparently swell at least to some extent in the presence of acetone, thereby making them very receptive to hydrophobes, so that they are forced out of the acetone solution (becoming insoluble). ), the hydrophobic substances are preferentially absorbed into the fillable polymer latex particles in a still unexplained manner.

Thus, the method of the present invention reduces the hydrophilicity of a solution of a hydrophobe in a water-miscible solvent in the presence of non-coagulating, insoluble, fillable polymeric latex particles. It involves gradually increasing the amount until it is not dissolved in the phase.

This increase in hydrophilicity is achieved by adding water into a solution of a hydrophobic substance in a water-miscible solvent in the form of a fillable aqueous polymer latex.

As long as the water content is kept below a level that interferes with the desired mechanism described above, preferably below a level that causes a cloudy appearance to the solution of the hydrophobe dissolved in the water-miscible solvent.
It should be noted that some water can be present in the hydrophobe solution dissolved in a water-miscible solvent, if desired, before the start of the process described above.

Benefits derived from practicing the invention include the following.

(a) Hydrophobic dye-forming color formers, preferably hydrophobic ballasted dye-forming color formers, hydrophobic UV absorbers, hydrophobic filter dyes (particularly for visible light), hydrophobic sensitizing dyes, etc. Hydrophobic dyes, hydrophobic dye developers, hydrophobic silver developers, hydrophobic redox dye releasing agents, hydrophobic brighteners, hydrophobic antioxidants, hydrophobic silver halide solvents, and mixtures of , soluble in - or more water-miscible organic solvents described below) can be uniformly distributed in a hydrophilic colloid-containing layer without the use of a high-energy mill.

As a result, the process of the present invention allows obtaining sufficient dispersions with substantially less undesirable material degradation and at lower cost than conventional dispersion methods requiring high-energy milling. can.

(b) Some of the filled latex compositions of the present invention have unique properties, such as the hydrophobic moieties being more effective.

For example, the particle size of a dye color former in a photographic element is
Smaller than those of conventional photographic elements.

In such cases, the reaction between color former and developer is improved.

Some of the hydrophobic portions of these filled latex compositions are more effective.

For example, UV absorbers have increased UV absorption when used in accordance with the present invention than when used in conventional methods.

(c) Generally, when a hydrophobic compound that is highly susceptible to air oxidation is distributed into the fillable polymer latex according to the present invention, the hydrophobic compound will be primarily incorporated into the fillable polymer particles; , can apparently impart them with remarkable oxidation resistance.

The present process thus provides, as a practical matter, a means of distributing substances into the hydrophilic colloid layer within a very short period of time without excessive degradation.

Examples of such substances susceptible to air oxidation include p-
Included are organic aromatic amine dye developers such as phenylene diamine, p-aminophenol, and certain pesticides.

(d) In many cases, the process allows for the incorporation of significantly higher amounts of hydrophobic material into the insoluble polymer particles than was previously possible.

(e) The use of the filled latex compositions of the present invention may result in the use of hydrophobic substances that were previously incompatible or too reactive (e.g., hydrophobic substances with other components in the layer). It is possible to incorporate hydrophobic substances into a given layer (due to their general reactivity with substances).

In such cases, the use of the present invention allows the use of materials containing materials that are too reactive to be included in a single layer.
The need for more than one layer on the substrate can be eliminated.

Water-miscible organic solvents useful in the practice of this invention include (a) 80
2 parts by volume of water to at least about 20 parts by volume of solvent.
(b) has a boiling point (at atmospheric pressure) greater than about -10°C; and (c) is useful in the practice of this invention. and (d) does not dissolve more than about 5 cm by weight of such fillable polymer latex at 20°C.

Regarding requirement (c) above for solvents useful in the practice of this invention, reaction of the solvent with the polymer may occur under certain circumstances, but is considered undesirable.

Typical examples of useful water-miscible organic solvents include acetone, ethyl alcohol, methyl alcohol, isopropyl alcohol, methyl ethyl ketone, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, and mixtures thereof. It is not limited to.

Among these, acetone, dimethylformamide and/or
or tetrahydrofuran are preferred when the hydrophobic substances in question are soluble therein.

The term "fillable polymeric latex" as used herein refers to the following latex compositions:

(a) polymer particles that are compatible with a water-miscible solvent (i.e., the polymer particles do not coagulate or precipitate when the latex is gradually mixed into a solution of a hydrophobic substance dissolved in a water-miscible organic solvent); (b) When the latex is used in a photographic element, it is preferably compatible with an aqueous gelatin solution (at 25° C.) containing about 5% by weight of each gelatin and latex solids.

(C) A gelatin aqueous solution containing equal weights of gelatin and latex polymer is coated to preferably form a compatible (transparent) film when dried.

(d) having a discontinuous or dispersed phase consisting essentially of fillable polymer particles and an aqueous continuous phase.

(e) Passes the fillable polymer latex test described below.

A fillable polymer latex is a polymer polymerized from (1) at least two ethene monomers, of which from about 2 to about 25 weight units contain carboxylic acid, carboxylate, sulfonic acid, or sulfonate groups; (11) an aqueous continuous phase in which the polymer latex does not coagulate or precipitate when the following tests are performed: Obviously including (
However, fillable latexes are not limited to these polymer latexes).

Fillable Polymer Latex Test 250 rnl of polymer latex containing about 12-20 weight cups of dispersed phase are gradually stirred into an equal volume of acetone at 25°C.

This addition should be done at a steady, uniform rate over a period of one minute, and the acetone should be stirred moderately during this addition.

Stirring is discontinued and the resulting mixture is left at approximately 25° C. for 10 minutes.

After 10 minutes, the mixture is left at about 25° C. for 10 minutes.

Observe the mixture after 10 minutes. A "fillable polymeric latex" is one that exhibits substantially no coagulation or precipitation under these test conditions.

Preferred polymer latexes for the practice of this invention are fillable latexes in which the dispersed phase consists essentially of polymers made from:

(a) from about 75 to about 98% by weight, derived from one or more aqueous ester monomers having the structure:
Preferably about 80 to about 95 units by weight, (in the above formula, R is hydrogen or an alkyl group having 1 to 5 carbon atoms, R' is hydrogen or a methyl group, and R'' is an aliphatic group having 1 to 6 carbon atoms. show.

)(b) about 2 containing carboxylic or sulfonic acid groups or ammonium or alkali metal salts thereof;
~25 parts by weight, preferably from about 2 to about 10 parts by weight, hydrophilic ethene monomers, preferably the ethene monomers having a molecular weight of at most about 300; and (c) for photographic applications of the invention. hardening materials by reaction with photographically acceptable hardening agents such as formaldehyde or aldehyde substances such as succinic aldehyde or mucohalic acid, triazine chloride, vinyl sulfones such as bisvinylsulfonyl methyl ether, aziridine, etc. generate.

from about 0.2 to about 10% by weight of one or more curable or crosslinked ethene monomers containing one or more crosslinkable groups.

It should be noted that the seven-mer ratios mentioned herein are based on the relative proportions of the various monomers charged into the polymerization reactor in conventional free radical polymerization processes.

The products from such reactions will vary to some extent in proportions derived from the monomer charges for a variety of reasons well known to those skilled in the art of making synthetic polymer latexes.

Although fillable polymer latexes can be made from two, three, four, or more different types of polymers, the latices preferred for use in the practice of this invention generally include the present invention. It consists of three or four different types of monomers depending on the desired properties of the final coated product of the invention.

It is generally believed that polymer latexes containing relatively soft particles as a dispersed phase are capable of dispersing relatively more hydrophobic substances into the particles in the latex.

On the other hand, if the best physical protection of the hydrophobe content (eg from abrasion) is desired, relatively hard filled polymer latex particles should be used.

Those skilled in the art of making polymers by free radical polymerization methods are familiar with the types and amounts of monomers used to make relatively soft or hard filled polymer latices according to the guidelines described herein.

Such a person skilled in the art would also know how to produce latex by the process described above.

It is therefore pointed out that the preferred fillable polymer latices described above are generally prepared by such free-radical initiated reaction of a 7-mer dispersed in an aqueous medium containing one or more suitable surfactants. Otherwise, details of such manufacturing methods need not be described herein.

For example, US Patent No. 2914499, US Patent No. 3033
No. 833, No. 3547899 and Canadian Patent No. 7
See No. 04778.

Still other polymers preferred for use in the preparation of fillable polymer latexes include (i) acrylic ester monomers selected from the group consisting of methyl, ethyl, propyl and butyl acrylates and methacrylates; (11) for example: a sulfonic acid (or a water-soluble salt thereof) preferably attached to the terminal carbon atom, having the structure
A hydrophilic ethene monomer selected from a group of monomers having groups (alkali metal cations instead of H, preferably N
a or K or ammonium ions can be replaced.

) The general formula of a preferred subclass of hydrophilic ethene monomers is where R1 is methyl or hydrogen, R2 is methylene, ethylene, 2-methylethylene, trimethylene, tetramethylene or 2,2-dimethylethylene, and M is an ammonium, hydrogen or alkali metal cation.

) and (1[D is a curable or crosslinkable ethene monomer containing an active methylene curable group.

Examples of such preferred crosslinkable ethene monomers include: (12) N-allyl cyanoacetamide 03) Ethyl methacryloyl acetoacetate (14) N-cyanoacetyl-N-methacryloyl hydrazine 05) 2-acetoacetoxyethyl methacrylate (16) N-(3-methylacryloyloxypropyl)cyanoacetamide α7) 2-cyanoacetoxyethyl methacrylate (18) N-(2-methacryloyloxymethyl)cyanoacetamide (1gl Ethyl α-acetoacetoxymethacrylate (20) 2-acetoacetoxypropyl Methacrylate (21) 3-acetoacetoxy-2,2-dimethylpropyl methacrylate (22) N-(methacryloyloxymethyl)acetoacetamide (23) N-t-butyl-N-methacryloyloxyethylacetoacetamide (202-acetoacetoxyethyl Acrylate (42
-acetoacetoxy 2-methylpropyl methacrylate and other similar crosslinkable ethene monomers.

Some of these materials are described in U.S. Patent No. 3,459,790.
No. 3488708, No. 2808331, and No. 2940956.

The term "curable group" refers to a crosslinking reaction as indicated by an increase in the melting point of a hydrophilic colloid layer incorporating said latex upon reaction with formaldehyde or other photographic hardeners such as vinyl sulfone hardeners. means a group that can be raised.

Typical "curable groups" well known to those skilled in the art of photographic element manufacture are primary amines and active methylene groups.

Typical examples of fillable polymeric latices include, but are not limited to, latexes having a solids content of at least about 2 wt φ to about 20 wt.

The relative weight ratios of the monomers listed below are the amount ratios of the monomers charged to the reactor during latex production.

Ag3: 5ec-butyl acrylate 10: Sodium 3-methacryloyl oxypropane-1
-Methyl-1-sulfonate 5: 2-acetoacetoxyethyl methacrylate B 85: n-butyl methacrylate 10: Sodium 3-methacryloyloxypropane-
1-Methyl-1-sulfonate 5: 2-acetoacetoxyethyl methacrylate C70: n-butyl methacrylate 15: Sodium 3-methacryloyloxypropane-
1-Methyl-1-sulfonate 10: Methyl methacrylate 5: 2-acetoacetoxyethyl methacrylate D 85: n-butyl acrylate 10: Sodium 3-methylacryloyloxypropane-1-methyl-1-sulfonate 5: 2-acetoacetoxyethyl Methacrylate E 85: n-butyl acrylate 10: Sodium 2-acrylamido-2-methylpropanesulfonate 5: 2-acetoacetoxyethyl methacrylate F 75: n-butyl methacrylate 10: Methyl methacrylate 10: Sodium 2-acrylamido-2-methylpropane Sulfonate 5: 2-acetoacetoxyethyl methacrylate G85: n-butyl methacrylate 10: sodium 2-acrylamido-2-methylpropanesulfonate 5: 2-acetoacetoxyethyl methacrylate H80: n-butyl methacrylate 10: sodium 2-acrylamide-2- Methylpropanesulfonate 10 Niacrylic acid I 50: n-Butyl methacrylate 40: Styrene 10: Sodium 2-acrylamide-2-methylpropanesulfonate J 40: n-Butyl acrylate 50: 2-acetoacetoxyethyl methacrylate 10: Sodium 2-acrylamide- 2-Methylpropanesulfonate K 60: 2-acetoacetoxyethyl methacrylate 30: n-butyl acrylate 10: sodium 2-acrylamido-2-methylpropanesulfonate L 50: N-butyl acrylate 40: 2-acetoacetoxyethyl methacrylate 10: sodium 2-Acrylamido-2-methylpropanesulfonate Other useful fillable latex polymers include:

H80: n-butyl acrylate 20: sodium 2-acrylamide-2-methylpropanesulfonate N95: n-butyl acrylate 5: sodium 2-acrylamide-2-methylpropanesulfonate 0 90: styrene 10: sodium 2-acrylamide 2-methylpropane Sulfonate P 85: Ethyl acrylate 10: 3-methacryloyloxypropane-1-sulfonic acid, sodium salt 5: 2-acetoacetoxyethyl methacrylate 85: Methyl acrylate 10: 3-methacryloyloxypropane-1-sulfonic acid, sodium salt 5: 2-acetoacetoxyethyl methacrylate 85: n-butyl acrylate 15: 3-methacryloyloxypropane-1-sulfonic acid sodium salt 70: n-butyl acrylate 20: sodium 3-methacryloyloxypropane 1
-Sulfonate 10: 2-acrylamido-2-methylpropanesulfonic acid, sodium salt 85: Ethyl acrylate 10: Sodium 2-acrylamido-2-methylpropanesulfonate 5: 2-acetoacetoxyethyl methacrylate 50: n-butyl methacrylate 40: Styrene 10: Sodium 2-acrylamido-2-methylpropanesulfonate 70: n-butyl acrylate 25 Niacrylamide 5: 2-acetoacetoxyethyl methacrylate 85: Methyl acrylate 10: Sodium 2-acrylamido-2-methylpropanesulfonate 5: 2-aceto Acetoxyethyl methacrylate 85: n-butyl methacrylate 10: 2-(methacryloyloxy)ethyltrimethylammonium methosulfate 5: Sodium 2-acrylamido-2-methylpropanesulfonate 85: ethyl acrylate 10: 2-(methacryloyloxy)ethyltrimethylammonium Methosulfate 5: Sodium 2-acrylamido-2-methylpro/
Gunsulfonate 85: n-butyl acrylate 10: 2-(methacryloyloxy)ethyltrimethylammonium metsulfunate 5: sodium 2-acrylamido-2-methylpropanesulfonate A 95: n-butyl acrylate 5: p-styrene Sulfonic acid sodium salt BB 90
: n-butyl methacrylate 10: -styrene sulfonic acid sodium salt From the above description it is clear that a large number of heptad combinations can be used in the preparation of the fillable synthetic polymer latex according to the present invention. .

However, it must be pointed out that there are many polymer latexes that are not fillable latexes as described above.

For this reason, before assuming that a given latex is "fillable," it is desirable to test the latex using the "Fillable Polymer Latex Test" method described above.

The use of this test is also desirable as a control procedure since industrial production of polymers and latexes can sometimes result in relatively low batch-to-batch reproducibility.

A preferred method of making a fillable latex is described below prior to the examples.

Hydrophobic compounds that can be advantageously used in the practice of this invention are those that are useful in photographic elements when mixed or dispersed in a layer of at least about 20 weight φ of hydrophilic colloids such as gelatin, and that have a certain solubility. Contains all hydrophobic compounds that meet the criteria.

Such hydrophobic compounds are hydrophobic compounds that (a) are substantially insoluble (preferably no more than about 0.5 wt. soluble) in distilled water at 25°C; (b) require a special alkali or acid. soluble in at least one of the water-miscible organic solvents or mixtures thereof which may be advantageously used in the practice of the invention described above, and preferably, as a practical matter, at least about 5 wt. (c) must be a hydrophobic compound that precipitates from solution in a water-miscible solvent on addition of water up to a specific volume.

In this way, "hydrophobic compound" or "
The term "hydrophobe" means any useful compound that meets the above solubility criteria.

The specific identity of any hydrophobe that fits this definition is not critical to the successful implementation of the general process aspects of the invention, but is not anticipated by the use of any class or type of hydrophobe. It has been found that a product with valuable utility can be obtained.

The resulting uniform distribution of these particular classes of hydrophobes into fillable polymeric latex particles, which can be produced by the present process, represents a preferred embodiment of the present invention.

Such a uniform distribution is often referred to herein as a "photographically useful filled latex composition."

Preferred hydrophobic compounds useful in this aspect of the invention are pallasted dye-forming color formers, filter dyes, ultraviolet absorbing compounds, dye release agents, developers, and sensitizing dyes.

All of these materials are hydrophobic according to the solubility tests described above and are useful in photographic elements.

Such materials are well known to photochemists and need not be described in detail in this application.

Photographic materials for which the process of the present invention is particularly useful are listed under the Product Licensing Index (Pr.
Product Licensing Index)
, Vol. 92, (December 1971), pp. 107-11
These include, for example, image transfer materials, physical development materials, radiographic materials, dry development systems, dye-forming materials, etc., as described on page 0 and in British Patent No. 923,045.

Although this preferred embodiment is useful in the photographic industry, the invention is not limited to photographic materials and processes, but is useful wherever it may be desirable to distribute hydrophobic materials into polymeric materials.

Although the layer of hydrophobic material distributed in the polymeric material is preferably present and ultimately used on the substrate, the substrate may not be necessary in some cases.

For example, useful hydrophobic substances include hydrophobic pesticides, herbicides, acaricides, hormones, vitamins, enzymes, etc., which meet the above requirements.

It will be appreciated that the ultimate use of such material-filled polymer latexes will not include a substrate.

For example, the process is useful for producing latex-type surface coating compositions such as latex paints, e.g.
In latex coatings, hydrophobic UV absorbers or chemical stabilizers (antioxidants) are incorporated into the coating composition by simply mixing with a sufficient amount of one suitably selected filled polymeric latex composition prepared according to the present invention. be able to.

Other uses of the filled latex compositions of the present invention are discussed in the examples herein.

Still other uses will become apparent from the present disclosure.

Examples of photographically useful filled latex compositions as described above include compositions comprising preferred fillable polymer latexes as described above, the latex particles comprising one or more hydrophobic materials as described above. evenly distributed within).

Generally, the amount of hydrophobic material that may be present in association with the latex particles ranges from a minimum amount of less than about 2 parts by weight or more to about 200 parts by weight or more per 100 parts by weight of solid fillable polymer in the fillable polymer latex. It can be within the range of

The weight ratio of hydrophobe to polymer in such filled latex compositions is from about 1:40 to about 3:1, preferably from about 1:20 to about 1:1, respectively.

When it comes to the photographic industry, particularly preferred hydrophobic materials are:
Contains a hydrophobic pallastized dye-forming color former capable of reacting with an oxidized organic aromatic primary amine 7 dye developer to form a dye.

Examples of such color formers, classified as ketomethylene, pyrazolone, phenol or naphthol compounds, are well known to the ordinary photographic chemist and can be found in Product Licensing Index, Volume 92.

It is described in detail on page 110 (December 1971).

Optional hydrophobic pallasted color formers that may be used in the practice of this invention include U.S. Pat.
No. 4, No. 3311476, No. 3277550,
Same No. 3277155, Same No. 2778658, Same No. 3
No. 253924, No. 3447928, No. 3408
No. 194, No. 3476563, No. 3253294
No. 3458315, No. 2423730, No. 3277554, and No. 3703375.

Other classes of hydrophobic materials useful in the practice of this invention are described in Product Licensing Index, Volume 92, Page 109 (1971), and U.S. Pat. No. 3,687,671;
Same No. 3706700, Same No. 2739888, Same No. 3
No. 652284, No. 3468897, No. 3004
896 and 3,253,921.

Hydrophobic dyes that can be used in the practice of the present invention are disclosed in U.S. Pat.
No. 06443 and Progect Licensing Index Vol. 92, pp. 108-109 (December 1971).

Dye image-forming materials useful in the practice of the present invention include Canadian Patent No. 602,607; US Pat. No. 3,443,939;
No. 25062, No. 3415644, No. 34156
No. 45, No. 3415646, No. 3647437 and No. 3635707, and Belgian Patent No. 757
No. 959, No. 757960, No. 810195, and No. 788268.

Many hydrophobic developers that can be used in the practice of this invention are described in Product Licensing Index, Volume 92, 11
0 (1971) and in U.S. Pat. No. 3,801,321, U.S. Pat. No. 3,672,896, U.S. Pat.

Valuable film products containing filled latex compositions that can be produced by the process of the present invention exhibit the identity of the polymer particles of the film product that are clearly derived from the latex even after drying the latex-containing layer. can be easily identified and distinguished from conventional film products containing physical mixtures of polymers and hydrophobic substances.

Thus, the hydrophobic material is almost completely uniformly distributed among the polymer particles in the compositions of the present invention, even if the filled latex particles contain one or more hydrophilic materials, including other materials such as silver halide, etc. Even if it is dispersed in a colloidal layer,
Appearance remains distributed in such particles.

Thus, the solid particles of the filled latex compositions of the present invention retain the identity of being latex-derived particles even after the latex-containing aqueous coating composition has been conventionally coated onto a substrate or support and dried. clearly held.

This makes it easy and reliable to distinguish and identify the compositions of the invention.

Identification of the product prepared according to the invention is that (a) the F2 molecules are clearly obtained from the latex and (b) the hydrophobe is analyzed (possibly a solid solution of the hydrophobe in the polymer). (as) to maintain physical association with the polymer particles (distribution within the polymer particles) in the coated article.

Isolating the particles, determining the identity of the polymer, confirming that the polymer is derived from the latex, and determining the identity, presence, and amount of hydrophobes in the particles is within the capabilities of a skilled analytical chemist. It is.

In this regard, at sufficient levels in the filled latex compositions of the present invention (relative concentrations of fillable polymers and hydrophobes and their respective glass transition temperatures (T
g).

) When hydrophobic materials are present, it is of particular interest that certain hydrophobic materials can alter the Tg of fillable polymeric materials.

The ability of certain hydrophobic substances to influence or change the original or expected Tg of the discontinuous phase of some of the fillable polymer latices useful in the practice of the present invention is important for the photographic applications of the present invention. In filled latex compositions useful as a chemical agent, there is evidence of a distribution of hydrophobic materials among the polymer particles that make up the dispersed phase of such compositions.

Indeed, measuring the Tg of dry-filled latex compositions represents one method of identifying preferred filled polymer latex compositions of the present invention.

A number of such preferred compositions have a Tg that differs by at least about 5°C from the initial or original Tg of the fillable latex polymer.

The reason that the Tg of some of such preferred filled latex compositions differs by no more than 5°C from the native Tg of the latex polymer is that certain hydrophobes are very close to the glass transition temperature (Tg) of the particular latex polymer. This is because they have similar Tg's or the relative amount of hydrophobe in the filled latex particles is much lower.

The Tg of a uniformly mixed substance is the Tg of a pure substance, respectively.
Not all of the filled latex compositions produced according to the process of the present invention must be between -
It does not exhibit a Tg that differs by at least about 5° C. from the original Tg of the fillable latex polymer.

However, because of the large proportion of the preferred filled polymer latex compositions of the present invention, the original Tg
Deviations from the formula can be used as one means of identifying a composition made in accordance with the present invention.

Methods for measuring the Tg of various substances are well known.

A preferred method involves continuously measuring the temperature of the test sample in a conventional differential thermal analyzer (relative to the symmetric temperature of the blank) while gradually applying heat to the sample container.

The temperature corresponding to the midpoint of the baseline shift characteristic of the change in specific heat associated with the glass transition is the Tg of the test sample.

The accompanying drawings illustrate this interesting feature.

Curve A is a 40 gravimetric cyan dye-forming color former (+39
Figure 2 shows the Tg curve of a filled polymer latex (with an original Tg of -42°C) that has been incorporated by the present process (with an original Tg of -42°C).

Note that in Curve A, the Tg of the fillable poly insect repellent rug 3 dye-forming color former composition is about -15°C.

Curve B, shown for comparison, is a differential thermal analysis curve of a heterogeneous (physical) mixture sample in which the latex and color former (used in curve A) were simply mixed together and then dried.

The melting endotherm (at about 135° C.) of the crystalline color former is evident from curve B, indicating the presence of a heterogeneous latex/color former composition.

The filled latex compositions of the present invention are shown in curves A and B of the drawings.
Note that it is usually detectable even in the presence of gelatin, as evidenced by the small Tg (for gelatin) of about +60°C in both curves and the pronounced gel-sol transition at about +93°C.

Gelatin was present in both test samples used to generate the data for curves A and B in the figure.

The valuable results from the practice of the present invention are believed to be due to the very small particle size of the resulting filled latex dispersion of hydrophobic substances dispersed in a hydrophilic colloid layer, such as a gelatin-containing photographic emulsion. .

The color former dispersed particles in conventional photographic emulsions (the dye-forming color former is dissolved in a high boiling solvent and dispersed into the emulsion by a high energy colloid mill) typically range in size from about 0.3 to about Particles of the photographically useful filled polymer latex compositions of the present invention may be 0.9 microns or larger, even if the latex particles have been swollen to some extent by incorporating a relatively large proportion of hydrophobic material. Even if the diameter is on the small order of magnitude, it is within the range of about 0.02 to about 0.2 microns, preferably about 0.02 to about 0.08 microns.

In one experiment involving a fillable latex, such as that described in Example 3 below, the average diameter of the filled latex particles contained an equal weight of cyan dye-forming color former to the dry weight of polymer in the latex. Incorporation swelled to approximately 0.186 microns (from an initial average diameter o, ii of 7 microns).

Such very small particle sizes indicate that the use of the fillable polydye-forming color former composition of the present invention produces photographic hydrophilic colloid layers with a much more uniform dye distribution than previously observed. This may be at least a partial reason for the observation that

The specific physicochemical state of the dye-forming color former material in such color former filled polymeric latex compositions contributes to an unexplained extent in producing such valuable results.

For example, a photographic element containing an emulsion layer containing a color former-filled polymer latex composition (and essentially a conventional, non-high boiling color former solvent) may be used in a color developing composition that does not contain an organic solvent such as benzyl alcohol. I think it is a great thing to be able to develop images using .

This is of great concern since it was previously believed that the use of organic solvents was necessary to effectively develop photographic elements containing dye-forming color formers in the absence of high boiling color former solvents. be.

Another valuable aspect of the process of the present invention relates to reducing or reducing the pressure and/or stress sensitivity of certain photographic products.

This type of problem has been addressed by J. Soc. Phot, (Journal of the Photographic Society of Japan), Japan, Vol. 22, March issue, pp. 135-138 (
(1959), J.

Phot, Sci, Vol. 21, pp. 32-38 (
(1973), J. Phot, Sci., Vol. 21, pp. 221-226 (1973) and Re5ea-
rch Disclosures Volume 116, Volume 135
137 (1973).

By replacing conventional hydrophobe solutions with hydrophobe-filled latex compositions in the manufacture of photographic products where such problems exist, such problems can be reduced or even eliminated.

For example, dyes incorporated as latex dispersions do not readily migrate along break lines in photographic elements subjected to pressure and/or stress.

Another valuable aspect of the process of the present invention relates to its ability to incorporate surprisingly large amounts of hydrophobes into polymeric latex particles.

Methods have previously existed for producing latexes with hydrophobic materials such as plasticizers, developer materials, and alkali-soluble dye-forming color formers that work together with the latex; The relative amount of hydrophobe incorporated was very small compared to the amount that can be incorporated into fillable polymer latex particles by the process of the present invention.

The time required to incorporate hydrophobes into the latex is also greatly reduced by the process of the present invention (U.S. Pat. Nos. 3,518,088, 3,438,920 and 2
No. 772163).

For example, liquid plasticizers have traditionally been incorporated into polymeric latex particles by mixing the latex and oily plasticizer together over many hours (US Pat. No. 3,438,920).

According to this method, a relatively small amount of plasticizer was incorporated in a very long process.

In contrast, the present process allows for the incorporation of hydrophobic substances (into latex particles) in amounts exceeding the weight of the polymer latex, if desired, and in very short operating times. .

Preferred filled polymer latex compositions of the present invention contain from about 25 to about 60 more weight hydrophobic materials (eg, dye-forming color formers) per dry weight of the filled latex composition.

In such preferred compositions, the hydrophobic material is uniformly incorporated into the filled polymer latex particles, resulting in many valuable results from the practice of this invention.

Yet another prior art technique for mixing hydrophobes and polymeric hydrosils is exemplified by the Tong process (US Pat. No. 2,772,163) referenced earlier herein.

Tongs intended for dispersing alkali-soluble dye-forming color formers (i.e., color formers that must first be dissolved in a solution containing a strong alkali, such as IJum) into photographic emulsions (i.e., hydroxylated to disperse them). The method required that the color former be dissolved in an alkaline mixture of water and ethyl alcohol before mixing with the resulting solution of polymeric hydrosil.

The alcohol used by Tong was to completely wet out the particular alkali-soluble color former in order to speed up the dissolution of the color former in the aqueous alkali.

The tongs then neutralized the mixture of latex, color former, and solvent just before or after mixing into the photographic emulsion.

Tong's method clearly depends on (a) the type of hydrophobic color former material he was able to use (it must be alkali soluble) and (b) the amount of color former with which the latex particles were able to associate. were limited in both respects.

And, of course, Tong's method of incorporating an alkali-soluble color former material into hydrosil particles is not part of the process of the present invention.
significantly different.

The polymer latex used by Tong is not a fillable polymer latex according to the description and testing described above.

Tong's method is further limited to color former materials that can be initially dissolved in highly alkaline solvents.

In contrast, this process is almost universal for hydrophobic materials useful in photographic emulsions, since all of the hydrophobic materials are virtually soluble in one or more water-miscible solvents without the need for further addition of alkali. useful.

In the method of the invention, the order of addition of the fillable polymer latex into the solution of the hydrophobe dissolved in the water-miscible solvent is very important.

If the order is reversed, either coagulation and precipitation will occur from the latex unless some critical limit is found, or a large proportion of the hydrophobic material will escape from the latex particles, a condition that is highly undesirable or of little use. Accumulate.

In making the filled latex compositions of the present invention, the relative volumes of (a) the fillable polymer latex and (b) the solution of the hydrophobic substance (dissolved in a water-miscible solvent), mixed in the required manner, are: In general, it is not considered to be critical as far as the successful implementation of the invention is concerned.

Thus, as long as some fillable latex particles are present in the solution while the hydrophobe is extruded from the solution (due to the increasing hydrophilicity of the solution, as discussed above), the filled latex particles generate.

For example, one aspect of the general process of the present invention comprises stepwise: (a) an amount necessary to separate the hydrophobe from the solution, but not sufficient to affect the hydrophilicity of the hydrophobe solution; and (b) into the mixture obtained in (a) an amount of water sufficient to affect the desired transfer of the hydrophobic substance from the water-miscible solvent into the latex particles. Including adding.

In this way, filled latex compositions containing a relatively large proportion of hydrophobe to particles can be produced using a relatively dilute solution of hydrophobe.

Thus, the necessary increase in the hydrophilicity of the hydrophobe solution (during which the hydrophobe becomes insoluble in such a solution)
It turns out that there are more than two ways to obtain .

For this reason, when the expression "at least enough water to render a hydrophobic substance insoluble in solution" (with respect to the basic steps of the process) is used in this application, the word "water" used in that expression refers not only to water, but also to water in the form of a solution, such as the "water part" of the fillable aqueous polymer latices previously mentioned herein as well as dissolved salts.

However, when the dispersed phase polymer solids content of a fillable polymer latex exceeds 10 parts by weight, the relative amount of hydrophobe solution mixed with such latex may range from about 50 to about 100 parts per 100 parts of fillable polymer latex. 200 parts by volume is generally preferred, and about 1 part by volume of hydrophobic material is mixed per part of fillable polymer latex, especially when the latex contains polymer particles of about 12 to about 20 weight φ. It is even more preferable.

The actual optimum time required to gradually mix (i) the latex and (11) hydrophobe solution according to this process depends on (a) the type of polymer latex, hydrophobe and water-miscible solvent; ) the relative concentrations of the polymer dispersed phase and the hydrophobic substance in each substance to be mixed, as well as (C
) Gradual mixing of the fillable polymer latex into the hydrophobe solution may vary in any case, depending on factors such as the relative amounts of latex and hydrophobe, but in particular the fillable In those cases where the polymer solids content of the polymer latex is greater than about 12 by weight, it is generally preferred to run for at least about 10 seconds.

Mixing too quickly can create a second solid phase in the system and/or cause coagulation or settling of latex particles.

It was discovered that Slow mixing for at least 20 seconds is more preferred.

Generally, after the initial preparation of a filled latex composition for photographic use, as previously described herein, some or all of the water-miscible organic solvent is added to determine the usefulness of such filled latex compositions. It can be optionally removed from the composition without harm.

Removal of the water-miscible organic solvent is conveniently accomplished by evaporation under any widely varying conditions (eg, temperatures below about 40° C.), preferably under reduced pressure.

Preferably, at least about half of the water-miscible solvent is removed from the initial compatible mixture (fillable polymer latex/hydrophobe/water-miscible solvent mixture) to form preferred useful filled latex compositions of the present invention. generate one of the following.

The amount of hydrophobe after removal of the water-miscible solvent is at least about 2 weight φ of the dispersed phase of the filled latex composition.

Such preferred photographically useful filled latex compositions retain their latex properties.

That is, they include an aqueous continuous phase optionally comprising a water-miscible organic solvent (although preferably the amount of water-miscible organic solvent is not more than about 30% by weight of said continuous phase).

), a dispersed phase consisting of filled latex particles in which the hydrophobic substance is virtually completely incorporated into the polymer particles of the dispersed phase.

As previously discussed herein, the organic solvent and/or some water can optionally be removed from the initial mixture of filled latex + water-miscible solvent to form a filled latex composition with a high solids content. can get.

If it is desired to improve the stability of the filled latex composition and prevent the tendency of the latex to gradually settle upon prolonged storage, the composition can be mixed with an aqueous solution of a hydrophilic colloid such as gelatin.

The preferred minimum amount of hydrophilic colloid in the product mixture is about 1 weight per weight of filled latex composition, although larger amounts of hydrophilic colloid can be used to produce a stable latex product if desired. can.

For example, the weight ratio of gelatin to latex polymer in a gelatin/filled latex coating composition, based on dry weight, can be from about 1:20 to about 20=1.

If desired, stable filled latex products such as those described above can be coated directly onto a suitable support by conventional means.

then removing a substantial amount of the water (generally at least about half, but preferably at least about 80% more by weight) of the resulting wet coating layer from the wet coating layer, preferably by evaporation;
Produce the desired coated substrate product.

In addition to hydrophilic colloids and photographically useful filled latex particles, many other materials can be present in the coating compositions of this invention.

For example, photosensitive silver halide grains, sensitizing dyes, antifoggants, and coating aids may be mixed with any of the photographically useful filled latex compositions described above to produce a final coated substrate product, depending on the desired composition of the coating. Coating compositions useful for certain purposes can be prepared.

Generally, to prepare useful coating compositions containing such adduct materials, an aqueous dispersion and/or solution of the adduct material is
Preferably, the resulting coating composition or photographic emulsion can be simply mixed in appropriate proportions with one of the photographically useful filler latex compositions briefly before being coated onto the substrate.

Any coating technique that can be used to coat conventional photographic emulsions onto conventional photographic supports, including the use of coating hoppers and/or other equipment, can be used to coat one or more layers of the coating compositions of the present invention. It can be used to apply to a support.

Useful coating techniques and supports are described in Product Licensing (Intex) Vol. 92, p. 109, (1971).
(December 2016).

The induction step of the process of the invention generally takes about 25
Although preferably carried out at temperatures of 0.degree. It may be carried out at temperatures in the range above 100 to 100 ml, with only the discretion being necessary to prevent or encourage precipitation or gelling of the coating composition, if desired or necessary. be.

Under some circumstances, when the fillable polymer latex includes relatively hard polymer particles (i.e., fillable latex particles having a relatively high Tg), relatively high temperatures, such as about 30° C. or higher, may be used in the present process. The latex particles can be made more receptive to hydrophobic substances if used during the impivision step.

Although the following examples illustrate only some fillable polymer latexes, hydrophobic compounds, and water-miscible organic solvents, the methods and materials described below are useful for making and using the compositions of the present invention. It should also be noted that the present invention process is merely illustrative.

Where appropriate, the hydrophobic compounds described herein above can be used in a manner similar to that described below.

One method of making the preferred fillable latex of the present invention is illustrated below.

In a polymerization flask, 11 g of Triton 770 (alkylaryl polyether sulfate sodium salt surfactant available from Rohm and Haas), 0.5 S' potassium peroxydisulfate and 0.11 g 95 with dissolved sodium pyrosulfite
At the same time, a mixture of 85 g of 5ec-butyl acrylate with 5 g of 2-acetoacetoxyethyl methacrylate, 10 f of 3-methacryloyloxypropane-1-sulfonic acid, sodium salt, and 0.15 P of pyrosulfite were added in a solution at mixture with sodium and water at 95°C 100
rnl were simultaneously mixed with continuous stirring for 20 minutes.

After the addition was complete, stirring was continued for 70 minutes while maintaining the reaction at a temperature of 95°C.

The resulting latex product was cooled and then dialyzed against a stream of distilled water in a conventional dialyzer for about 16 hours.

The solid content of the produced polymer latex was 9.5 or more.

This latex was "fillable" according to the Fillable Polymer Latex Test described above.

By varying the relative amounts of monomer reactants and water, fillable latexes of varying solids content can be produced.

The following test was conducted to determine whether the latex used by Tong, US Pat. No. 2,772,163, was "fillable" according to the test described above.

58.8% n-butyl acrylate, 25.2 liters of styrene, and 16 liters of styrene as in Example 1 of U.S. Pat. The particles in the dispersed phase prepared by emulsion polymerization of a mixture of methacrylamide were gradually mixed into an aqueous latex for about 20 seconds.

The solids content of the latex was 11.8%.

Within a few minutes most of the latex flocculated and settled out of suspension.

This indicates that the tong example latex is not a fillable polymeric latex according to the present invention.

Example 1 102 yellow dye-forming color former, α-4-(4-benzyloxyphenylsulfonyl)phenoxy-α-pivalyl-2-chloro-5-, dissolved in 160 ml of acetone.
(r-(2,4-di-tert-amylphenoxy)
Add the fillable polymer latex of 90% as described above to the butylamide to acetanilide solution for about 1 minute, except that the solid content of the latex was 11.3φ (the solid content was the residue after drying at 110°C). The mixture was gradually added with stirring.

After mixing the fillable latex with the color former solution, most of the acetone was removed by evaporation (in a rotary evaporator at 40° C.).

The resulting color former filled latex composition did not solidify on storage and produced a transparent layer after coating and drying on a transparent photographic support.

This color former filled latex composition was also compatible with gelatin.

Example 2 The color former compound of this example was used as α-pivalyl α-(4-carboxy-phenoxy)-2-chloro-5-Cf-(2
, 4-di-tert-amylphenoxy)butyramide]acetanilide was used.

Virtually identical results were obtained.

Example 3 The color former compound was converted into a cyan dye-forming color former, 2-[α-(2
, 4-di-tert-amylphenoxy)butyramide) -4,6-di-chloro-5-methylphenol was used, and Example 1 was repeated with virtually identical results.

Using the color former filled latex compositions from Examples 1.2 and 3 above, photographs were taken by simply mixing each said color former filled latex composition with the appropriate sensitized silver halide emulsion as follows. A milky lotion was prepared.

A The filled latex composition prepared in Example 3 was mixed into another conventional red-sensitive gelatin silver halide emulsion.

The resulting emulsion was coated onto a conventional photographic polymer film support to yield a clear dry layer containing the following ingredients:

Color former - 8.5 m9/dm2 Silver = 3.7 ■/dm2 Gelatin - 32,1"i'/dm2 B The color former filled latex composition prepared in Example 1 above was halogenated with other conventional blue-sensitive gelatin. Mixed into silver emulsion.

The resulting emulsion was coated as in A above to produce a clear dry layer containing the following ingredients:

Coloring agent = 7.1772? / d772,2 silver = 3.8
■/dm2 Sera f = 11.7'? /dB2C An emulsion was prepared as in B above using another conventional green-sensitive gelatin silver halide emulsion and the color former filled latex composition of Example 2.

D Each of the photographic elements described above was exposed and developed in conventional manner to determine the relative speed, D gamma, and D gamma of the element.

Also in each case were "control elements" prepared by coating and drying an emulsion containing the same amount of the same color former dissolved in an equal volume of a conventional color former solvent but not containing a color former filled latex composition. evaluated.

The exposed elements were developed in the following order at 24°C and the results are listed in Table 1 below.

Table 1 Sample” Relative D℃ Kasoma D Kabura speed A-Coloring agent filling latex products B pair comparison B-Coloring agent filling latex products B pair comparison C-Coloring agent filling latex products C pair comparison 57 82 9 6 0 6 2.84 2.97 1.42 1.15 1.77 1.67 3.16 3.13 2.33 1.13 3.13 2.93 0.05 0.05 0.05 0.05 0.05 0.05 *The color development order and the solutions used are as follows.

Color development sequence Pretreatment bath 10 seconds rinse 10 seconds developing bath 8 minutes rinse 10 seconds fixing 2 minutes washing 1 minute bleaching 6 minutes washing 2 minutes Color development solution preparation Pretreatment bath Water Borax (Na2 B407 ・10 H20) Dry sulfuric acid Sodium Sodium hydroxide (%10φ solution water Total amount 1.0 pH (70 below), 9.3 of 0.1 Specific gravity (70”F), 1.096±0.00 Color developing bath water, approx. 70- 75'''F (21-24°C) Sodium Hexametallate Dry Sodium Sulfite 800.0ml 20.0r 100.0r 10.0ml Amount to make 800.0rrl1 2, (H' 4.0? 2-Amino5- Diethylamino- 3,01 Toluene monohydrochloride Sodium carbonate (-water salt) 20.0? Potassium bromide or 2.0? Sodium bromide 1.7f with water
The total amount is 1. pH for OL (70'F)
10.63±0.05 specific gravity (70”F), 1.023±
0.003 fixing bath water, approx. 125'F (50°C) 600.0ml
Sodium thiosulfate (hypo) 240.0P Dry sodium sulfite 15.0'? glacial acetic acid
13.4r/11 crystal boric acid 7.5g potassium alum 15.0P with water
The total amount is 1. pH to Ot (70'F), 4.25
0.25 Specific gravity (under 70), 1.150±0.005 Bleach bath water, approximately 70°F (21°C) 800.0yd
Potassium bromide 20.0 g or sodium bromide 17.02 Potassium dichromate 5.01 Potassium alum 40. Of water
Bring the total volume to 1.0 oz (Adjust the pH to 31 ± 0.20 (below 70) with 10% sodium hydroxide or 7N sulfuric acid) Specific gravity (below 70), 1° 036 ± 0.003E Travis A cobalt hexamine amplified developer (amp) according to the disclosure of U.S. Pat.
The results from the development of another sample of the same element tested above, processed by the use of a lif 1er-developer), are listed in Table 2 below.

Table 2 Test Samples Relative I) g Gamma D Diction Speed A - Color former filled latex product A vs. Color former filled latex product B vs. Color former filled latex product B vs. Control C - Color former filled latex product C vs. 525 3.46 4. 56 0.08 562 3.56 4.43 0.11 795 1.47 1,63 0.08 32 1.33 1.30 0.08 107 123 1.80 1,50 0.08 1.74 1, 90 0.08 In these examples, the color former loaded latex compositions of the present invention were milled without the aid of high energy milling.
Moreover, the optional color former-filled latex composition of the present invention was dispersed in the photographic emulsion described above without requiring a long time for incorporation and dispersion, but the results shown in Tables 1 and 2 were obtained. It should be noted that the products made in accordance with the present invention have been shown to be accepted in the art and to be comparable to conventional dye photographic products.

One distinct characteristic observed with respect to embodiments of the color former filled latex compositions of the present invention is with respect to the outstanding utility of the color former to react with oxidized dye developer in developing the dye.

For some reasons as yet unidentified, the dye-forming color formers may be used in certain solvents (such as color former solvents, i.e., benzyl alcohol) when the color formers are incorporated into photographic elements in the form of filled latex compositions in accordance with the present invention. It is highly reactive with dye developers without requiring any solvents.

When the present invention is practiced with a color former as described above, a much more uniform distribution of color former in the gelatin layer is also obtained than is generally obtainable using conventional color former dispersion methods. It will be done.

Therefore, after color development, the resulting dyes are more uniformly distributed in each layer of the final color photographic element.

In the following few examples, the present invention will be described with reference to RDR-filled latex (
(RDR refers to one or more redox dye releasing agents).

Redox dye releasing agents are known to be compounds that can be oxidized by oxidized developers.

For example, they are cross-oxidized
tion) to provide a chemical species that releases a diffusible dye as an oxidative action, such as by alkaline hydrolysis.

Such redox dye releasing agents were introduced on April 3, 1973.
U.S. Patent No. 3,725,062 (Anderson and Lamb), issued October 17, 1972;
No. 698897 (Rubber and Ram), December 2, 1971
U.S. Patent No. 3,628,952 (Busiel et al.), issued on the 1st.
and Belgian Patent No. 788.268, Belgian Patent No. 7960
No. 41, No. 796042, No. 796040, and No. 810195.

RDR-filled latex compositions are prepared by combining the specific hydrophobic RDR compound of choice in a suitable water-miscible organic solvent medium;
Using specific solvents (usually for incorporation into hydrophilic colloid layers during the manufacture of photographic elements) depending on their solubility properties,
It can be manufactured using the operating method described in Example I.

Example 4 This example illustrates a hydrophobic RDR-filled latex composition and its use in manufacturing photographic elements.

Elements prepared using RDR-filled latex compositions were compared to identical elements prepared using RDR compounds conventionally incorporated into the elements by conventional color former solvent methods.

A. RDR - Preparation of Filled Latex Composition 12fRDR
The compound was dissolved in 240 ml of tetrahydrofuran at room temperature with stirring.

150 r of fillable polymer latex was then slowly mixed into the resulting solution while continuing to gently stir.

The resulting filled polymer latex composition of solvent and RDR filled latex was then charged into a rotary evaporator.

All but about 1 weight part of tetrahydrofuran was then removed under vacuum at 50°C.

The resulting composition was graded as Ree Angel grade (Ree
veAngel Grade) 230 copies of paper.

The P solution (RDR--dispersion of filled latex particles) had a total weight of 2001, and the 35-layer latin solution (5
00G) 34f was mixed into it.

The resulting stabilized filled latex composition was then cooled and frozen until used as a component of a coating composition.

B. Photographic Element Details regarding the amounts of materials in each layer and other aspects of photographic elements having the following layer structure are described in U.S. Patent Application Nos. 351,673 and 351,700, filed April 16, 1973.

The layers are arranged in the following order (a) to (h): a) transparent emulsion cover sheet b) gelatin overcoat layer C) red-sensitive emulsion d) RT) R-filled latex composition e) carbon + gelatin f) TlO2+gelatin (-mordant+gelatin) (h) A clear Napoli (ethylene terephthalate) support layer (d) was coated with a stabilized RDR-filled composition prepared according to A of this example.

In this composition, the RDR compound is a cyan dye-releasing redox compound, N-C4-(2,4-di-tert-
pentylphenoxy)butyl-1-hydroxy-4(
3-(5-hydroxy-6-(2-methylsulfonyl-
The amount of fillable latex was 85 parts.

-butyl acrylate, 10 parts of sodium 3-methacryloyloxypropane-1-sulfonate, and 5 parts of 2-acetoacetoxyethyl methacrylate by free radical emulsion polymerization.

In the stabilized RDR-filled latex composition coated to form layer (d) of said element, the weight ratio of RDR compound to latex polymer to gelatin is such that the resulting layer is 0.51' RDR compound per square meter. ,0.
The amounts were such that it contained 54r latex copolymer and 1.08f gelatin.

Preparation of C0 Control Elements as described in B of this Example were combined with the same gel and RDR levels as described in B of this Example, using a conventional organic solvent/gelatin dispersion in place of the RDR-filled latex composition. The preparation was substantially identical to the above preparation except that it was prepared using

The solvent was 1,4-cyclohexylene dimethylene bis(2
-ethylhexanoate) was used at a level of 0.279 per layer rrl.

D. Comparative Test Each element from Examples B and C was exposed (-seconds) to a tungsten light source through a transparent cover sheet and a graduated density test object filtered against red light.

A conventional viscous alkaline treatment composition containing carbon is passed through a diffusion transfer sand inch between a pair of juxtaposed rollers such that the layer of liquid treatment is 0.005 inch thick. This caused a pod to spread between the transparent cover sheet and the photosensitive element at about 22°C.

Upon development, the resulting cyan test image in the mordant (layer f?) gave the following sensitometric measurements:

Relative* Speed: ″Trough Dmin Dma・Example 4 110 1.39 0.20 1.91 Control
100 1.42 0.221.96*Measured at 1 and 0 exceeding Dmin.

Note that almost identical sensitometric results were obtained.

Example 5 In addition to being more easily and more uniformly dispersed in the hydrophilic colloid coating layer in the form of a hydrophobic filled latex,
Some hydrophobic materials have shown unexpected performance when incorporated into the layer in this form.

An example of such unexpected performance is illustrated here with respect to the Shiba-gai absorbing compounds.

In this case, the use of the UV absorber-filled latex composition according to the invention shows a very high optical density, and
An unexpected and valuable sharp cutoff at about 415 nm (cot
-off) is obtained.

A. The UV absorber-filled latex composition was prepared by first adding 40f of 3-dimoxylamino-2-noarylidene malononitrile to 4
00 CC of acetone and then the total solids content was 9.
Part 5 of the aqueous latex, poly(n-butyl methacrylate-2-acrylamide-2-methylpropane carbonate acetoacetoxyethyl methacrylate (85:10:5), 1320r) was gradually added to the resulting solution with stirring. Added.

Acetone is then extracted from the product mixture at 50°C under vacuum for approximately 2
It was removed by processing for 4 minutes.

The resulting latex composition was then mixed into an aqueous gelatin solution, coated onto a clear photographic support, and dried.

The coating amount of gelatin and UV absorber in the produced coating is as follows.
Listed in the table.

B. For comparison, an equal amount of the UV absorber used in A of this example was dispersed into a gelatin solution using a colloid mill.

This UV absorber is liquid at room temperature.

The amount of gel and UV absorber was 1, an amount used that would give the same coverage as the coating layer prepared according to A of this example.

This comparison is labeled "No solvent/gelatin" in Table 3 below.

C0 In yet another comparative experiment, the same UV-absorbing compound used in Examples A and B was first added to an equal volume of di-n.
-Butyl phthalate dissolved in a high boiling point solvent.

The resulting solution was then dispersed into an aqueous gelatin solution in a conventional manner using a colloid mill.

The resulting dispersion was coated onto a transparent photographic support to produce coatings with the dry coverage listed in Table 3 below.

Table 3 gelatin UV absorber optical Test number 17m 17m” 3□.

One control 0.54 0 0.08B*
0.54 0.20 1.16C**0.54
0.20 1.60A***0.54 0.20
3.00 concentration 15 mno, 05 0.55 0.42 0.11 * Coating from B of this example, no high boiling solvent, no filled latex composition.

**Coating from C of this example, UV absorber dissolved in high boiling point solvent.

***Coating from A of this example, UV absorber filled latex composition.

Filled latex compositions loaded with UV absorbers have been shown to be able to produce unexpected and valuable results, including very high levels of extraneous light absorption and very sharp cut-offs of absorption in the visible part of the spectrum. As shown by this data.

EXAMPLES The examples in the following illustrate the production of photographic elements incorporating filter dies according to the process of the present invention.

UK Patent No. 923045 and US Patent No. 304612
No. 9 (Graham and Sagal), a color photographic element was prepared in which there was a "filter compound" dispersed in a gelatin layer between a blue-sensitive layer and a solid green-sensitized layer. .

The dye-forming layers of these elements incorporated and contained conventional color formers.

Without the filter layer, all test elements in this example are substantially equal.

The first contrast is Carey 'J-(Carey-
Les) Colloidal silver was dispersed.

A conventional mordant filter dye was dispersed in the second element.

The third element contains a filter dye-filled latex (35
The antifilter dye composition was dispersed.

Data regarding the amount of material coated in one layer of the filter are shown in the table below.

Identification of the various materials used in the filter layer is given after the table.

Dye 1: 4-((3-ethyl-2-penzoxazolylidene)ethylidene-3-methyl-1-(p-sulfophenyl)-2-pyrazolin-5-one monosulfonate-
US Pat. No. 3,282,699 Dye 2: p-diethylamino-2-(4-hexenesulfonylaminobenzoyl)
- Cinnamate nitrile mordant: Poly(α-methylallyl-N-guanidylketimine) - U.S. Patent No. 3,282,699 Latex: Poly(n-butyl methacrylate 2-acrylamide-2-methyl-propanesulfonic acid) -2
-acetoacetoxyethyl mecrylate (85:10
:5) The filter dye-filled latex composition used in this test was prepared by (a) diluting 9.5f latex (15,2 multi-part) with 55ml of water, (b) then diluting the diluted latex, into a solution of 0.48 S' filter dye in 50 ml of tetrahydrofuran, (C) remove the tetrahydrofuran at 40'C in a rotary evaporator, and (
d) In the finally obtained filled latex composition, 2.5
It was prepared by mixing 267 ml of a gelatin aqueous solution and 5.3 ml of saponin (a 15% aqueous solution).

3 drying elements to obtain the previous relative blue speed value.
Exposure was performed for □ seconds to a 500 watt tungsten lamp adjusted to a temperature of 2000°C.

This exposed element was then processed in a conventional color reversal process such as that described in US Pat. No. 3,046,149.

The results of this example demonstrate that a filter dye-filled latex composition prepared according to one aspect of the process of the present invention can be suitably used as a replacement for flat silver as a blue light filter in photographic elements. It was done.

Note that when the filled latex compositions of the present invention are used, the reduction in photosensitivity of the blue-sensitive emulsion layer is significantly lower than when using conventional mordant filter dyes.

Example 7 This example illustrates the use of a filled latex composition in which the latex particles are filled with photographic sensitizing dye.

A control dye for an A8 dispersion, dissolved in methanol, of a photographic material suitable for alkaline vapor processing was deposited on a polyethylene terephthalate film support in layers consisting of (a) to (g) at 2.981n9 silver/am"Ei. and 96.84 μg of gelatin/dd.

(a) A conventional sulfur, gold and reduction sensitized silver bromide emulsion, (
b) Spectral sensitizing dye, anhydro-3,9-diethyl-5,5'-dimethoxy-3'- dissolved in methanol
3-(3-sulfopropyl)thiocarbocyanine hydroxide, (c) ascorbic acid (d) antifoggant, 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene, (e) image stabilizer Precursor, 3-8-thiuronium-1-methylpropanesulfonate, (f) incorporated developer, 1,2,3,4-tetrahydro-1,4-methanonaphthalene-5,8-diol, and (g) curing agent, bis(vinylsulfonylmethyl) ether.

This material was exposed to a tungsten light (500W) for 30 seconds.

3000°K), applied with methylamine vapor for 30 seconds and washed with distilled water for 5 minutes.

Sensitometric results are shown below.

B. Sensitizing dye dispersed by filled latex composition ■ Preparation of dye-filled latex composition The following ingredients were used in this part of this example: (a) 350
(b) 350 ml of methyl alcohol; (c) the same sensitizing dye used in A of this example;
17 rul water (d) 175'1111 copoly(n-butylac I)
A fillable latex with a solids content of over 10.3 consisting of (85/1015) Heavy layer latin aqueous solution.

First, the mixture of (d)t(b)-+-(c) was gradually added to the solution of (a) dissolved therein with stirring.

After adding (e) into the resulting compatible mixture with stirring, to the resulting stabilized filled latex composition:
Vacuum Sl-IJ soaping was performed on a conventional laboratory scale rotary evaporator to remove substantially all of the methyl alcohol.

The vacuum stripped product was then silked into an emulsion that was otherwise the same as A in this example except for the composition.

The resulting emulsion was coated onto a polyester film support as in Example A and dried in conventional manner to form a photographic light-sensitive element.

This element was subjected to the same test as A in this example.

C0 Test Data and Results Elements A and B of this example were exposed, processed and cleaned as in A above.

The sensitometric properties of the treated film are as follows.

Sample Relative Speed Gamma DminA - Control 100 6.80 0.068 - Filling 97゛7
□.

. 6,4□. ,. These results show that the latex compositions of the present invention loaded with sensitizing dyes can work well in photographic elements.
Moreover, it has been proven that the alcohol solution of the sensitizing dye can be used as an effective means for dispersing the sensitizing dye in the photographic halide emulsion layer, before dispersing the sensitizing dye in the photographic emulsion layer. This is an advantage of this method, as it is possible to remove the alcohol in the following manner.

For some sensitizing dyes, this advantage will be more pronounced than others depending on the relative solubility of the dye in the alcohol.

Example 8 This example illustrates the use of the present process to prepare a pesticide loaded latex composition.

A.

151 commercially available methyl)L///rathion (20% methyl parathion + 80% xylene)
Dissolved in 50 rILl of acetone.

Fillable polymer latex 66' with a solids content of 18.25% is added into this solution at room temperature. 20 Of dilute latex, prepared by diluting with sufficient water, was gradually mixed with continuous stirring.

A fillable polymer latex was prepared by polymerizing a mixture of 50 parts by weight n-butyl methacrylate, 40 parts by weight styrene and 10 parts by weight 2-acrylamido-2-methylpropanesulfonic acid according to the method described above. .

The resulting filled latex/solvent mixture was then poured into 200 m
The mixture was placed in a No. 1 flask, and acetone was removed by vacuum suction at 50° C. for 15 minutes.

The resulting methyl parathion-loaded latex composition was then filtered (no afterflame was observed) to produce a homogeneous dispersion that was stable for many weeks (on storage at room temperature) without visible spontaneous precipitation.

The product contained particles apparently containing pesticide and polymer in a weight ratio of approximately 1:1.

B. Nono Lathion The above operation A was repeated using the following substances.

Nono Rathion 71 Guacetone 150TL1 18 Multi-solid latex 451 Water (for latex) 108ml The fried filled latex had a weight ratio of polymer to pesticide of about 8 to 7, respectively.

The parathion content of the filled latex product was in the 5.5 weight range.

This product could be easily diluted with water for conventional spray application to agricultural plants.

Example 9 This example illustrates the use of the present process to prepare a fiuor-filled latex composition.

This "phosphor" is used for scintillation counting (
It is a mixture of two hydrophobic substances that act together as an aid for scintillation counting.

Scintillation counting is useful for detecting and measuring relatively low levels of radioactivity and has found application in the field of radiotracing.

In this example, the phosphor composition is a mixture of 2,5-diphenyloxazole (PPO) and 2,2'-P-phenylenebis(5-phenyloxazole) (POPOP).

Both of these substances are hydrophobic.

3g of POP phosphor and 15g of POP OP phosphor were dissolved in 90TLl of tetrahydrofuran.

Next, a polymer containing 92 poly(n-butyl methacrylate-co-styrene-co-acrylamide 2-
Methylpropanesulfonic acid) (50:40:10) aqueous latex 90L? was slowly mixed into a solution of phosphor dissolved in THF at room temperature.

The solvent was then removed by evaporation on a conventional rotor 11-evaporator.

After filtration, 25? A 10-layer gelatin solution was mixed into the phosphor-filled Latinx composition.

The final stable gel composition has a PP of 3, 1.5
X10-2 POPOP, 9φ polymer and 25φ
Contains gelatin.

This composition was deposited on a conventional clear primed poly(ethylene terephthalate) photographic support at 10TLl/100Cr.
? It was coated with a coverage of L and then dried.

Dry scintillation 2 yielding three strips (2”×−)
“Cut from the counting element and (a) 0.0
1 mA' benzoic acid-3H aqueous solution, (b) 0.01
ml of benzoic acid-3H P-dioxane and (e) 0
．． Each sample was treated with 0.01 ml of benzoic acid-14C aqueous solution.

(Each solution was equal to approximately 22,000 collapses per minute.

) The strips were dried, fixed in 20 ml glass counting vials, and placed in a vasocurd tricarb (Pa
ckard Tri-carb) was measured using a liquid scintillation counter model 3380.

The strips were aligned perpendicular to the axes of the two photomultiplier tubes.

Counting efficiency was measured by comparing the detected radiation to the theoretical decay within a given time period.

The results of these tests are listed in Table 5 below.

Table 5 Sample Measurement Substance Counting Efficiency a
"H-benzoic acid 31.8% (water) b 3H-benzoic acid 25.6 poly(P-dioxane) c 14C-benzoic acid 89.5% (H2O) These counting efficiencies are based on solid scintillation counting compositions or It is usually considered high for the elements.

The high counting efficiency appears to be at least partially due to the fact that the phosphor is uniformly distributed in the form of a filled latex.

According to another aspect of the invention, a hydrophobic ballasted dye-forming color former is incorporated and comprises gelatin.
A method of making a support coated with at least one layer is provided, the method comprising: (a) (a layer of about 5
A fillable synthetic polymer latex comprising ~20 parts by weight of fillable polymer particles (11) in about 4 to about 50 parts by weight of a water-miscible organic solvent without the need for an alkali;
Hydrophobe-filled latex particles (containing the dye-forming color former homogeneously associated with the polymer in the particles) are prepared by gradually mixing into a solution in which 1 part by weight of the dye-forming color former is dissolved.
(b) then removing at least about half of the water-miscible organic solvent from said compatible mixture; and (c) mixing the compatible mixture with an aqueous solution of gelatin. (d) further coating a layer of the stabilized latex coating composition on a support; and (e) removing water from the layer. As a result, the formation of a solid layer on this support is preempted.

Preferably, the fillable polymer essentially consists of a terpolymer having the following structure.

In the above formula, n is about 60 to about 90, and m is about 2
to about 30, and p is about 2 to about 20, n,
The sum of m and p is 100, and M represents hydrogen, ammonia, or an alkali metal cation.

In the above method, the amount of dye-forming color former in the color former filled latex composition is from about 25 to about 60 by weight based on the weight of color former filled latex in the composition.

According to another aspect of the invention, there is provided a method of making a photographic element comprising dispersing a photographically useful hydrophobic material in a hydrophilic colloid layer on a photographic support, the method comprising: (a) ) Hydrophilicity of a solution of a photographically useful hydrophobic substance dissolved in a water-miscible organic solvent by mixing a fillable polymer latex into the solution until the substance is insoluble in the solvent. (b) removing at least half of the water-miscible organic solvent from the compatible mixture; (c) forming an aqueous solution of hydrophilic colloid in step (b); (d) applying the wetting properties of the mixture obtained in step (c) to a photographic support; and (e) drying the wetting layer.

In accordance with yet another aspect of the invention, there is provided a silver halide containing photographic element comprising at least one layer comprising photographically useful filled polymer particles derived from a latex. , the polymer particles consist essentially of a mixture of a photographically useful hydrophobe and a fillable synthetic polymer, and the ratio of hydrophobe to polymer in the particles is from 1:3 to 3:1. The particles have an average diameter of about 0.02-0.2μ.

The above photographic element according to yet another aspect of the present invention is a hydrophobic outside light absorbing compound of the following formula 1.\, -6□-6H-CH=C/CN R2'\CN (wherein R1 and R2 are hydrogen , alkyl, substituted alkyl, aryl, substituted aryl and cyclic alkyl, and at most one of R1 and R2 can be hydrogen, or R1 and R2 together form a piperazino, morpholino, pyrrolidino or piperazino group. Indicates the elements necessary to

) can be included.

The photographic element described above can further be prepared using a hydrophobic outside light absorbing compound of the following formula (
bis compounds).

In accordance with yet another aspect of the invention, an improved process for producing a hydrophilic colloid layer comprising a hydrophobic substance uniformly dispersed in the hydrophobic colloid layer is provided, the process comprising: (a) a hydrophilic colloid dispersed in the hydrophilic colloid; forming an aqueous dispersion of said hydrophobic substance; (b) forming a wetting layer by coating said aqueous dispersion on a suitable support surface; and (c) drying said wetting layer; Moreover,
In step (a), the solution is gradually made more hydrophilic by gradually mixing a fillable aqueous polymer latex into a solution of the hydrophobic substance dissolved in a water-miscible organic solvent, while the hydrophobic substance is dissolved in a water-miscible organic solvent. insoluble in the solution and associated with dispersed particles of the latex without coagulating the latex.

Although the invention has been described in detail with particular reference to preferred embodiments thereof, it will be understood that various modifications and changes can be made without departing from the spirit and scope of the invention.

[Brief explanation of drawings]

Figure 1 shows the Tg curve of the test sample. Curve A: 40 weight width weight ton dye-forming color former (+39°C
The filled polymer latex (with an original Tg of -42°C) is incorporated by this process (with an original Tg of
g) is a differential thermal analysis curve. Curve B is a differential thermal analysis curve of a heterogeneous (physical) mixture sample in which Nilatex and color former (used in Curve A) were simply mixed together and then dried.

Claims (1)

[Claims] 1. A method for making a filled polymer latex composition having a dispersed phase consisting essentially of a hydrophobic material distributed in a fillable polymeric material, the said polymeric material being dissolved in a water-miscible organic solvent. A polymer prepared from at least two ethene monomers and having about 2 to 25 weight percent of the polymer having carboxylic acid groups, carboxylate groups, sulfonic acid groups, or sulfonate groups is added to the hydrophobe solution. A process for making a filled polymeric latex composition comprising gradually adding a fillable aqueous latex comprising: and at least sufficient water to render the hydrophobic substance insoluble in the solution.