JPS6160099B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for impregnating a hydrophobic substance into polymer dispersion particles in an aqueous polymer latex, and more particularly to a method for producing a polymer latex composition impregnated with a photographic hydrophobic additive. It is. Conventionally, in the manufacturing process of silver halide photographic materials, various hydrophobic compounds, especially dye forming agents,
Several methods have been used to uniformly distribute compounds such as ultraviolet absorbing materials into gelatin or other hydrophilic colloid liquids. One of these methods is to mix a solid or liquid hydrophobic compound () with a hydrophobic colloid solution () and pass the resulting mixture several times through a high-energy mill such as a colloid mill. Therefore, there is a method of mechanically dispersing () in () to form a dispersion liquid, and dispersing this dispersion liquid in a hydrophilic colloid liquid. However, this method tends to result in poor dispersions, and these poor dispersions are often unstable. Furthermore, this method allows () to the desired extent
A large amount of energy is required to make the particles fine and disperse them. Such high consumption of energy is often accompanied by heat build-up or undesired localized heating, leading to undesired chemical changes in the contained ingredients. Other methods for dispersing hydrophobic compounds in hydrophilic colloid liquids are disclosed in U.S. Pat.
It is described in the specification of No. 2322027. That is,
In this method, a hydrophobic compound is first dissolved in oil or a high boiling point solvent to create a solution, and the resulting oily solution is dispersed in a hydrophilic colloid liquid. A variation of this method is, for example, the method described in US Pat. No. 2,801,171. Low molecular weight co-solvents such as ethyl acetate or low molecular weight ketones may be used in this method to assist in dissolving the hydrophobe in the oily solvent. In producing a silver halide color photographic emulsion containing a ballasted dye-forming agent (hereinafter referred to as coupler),
A widely used method is to dissolve a ballasted coupler in an oily, high-boiling solvent called a coupler solvent, and to disperse this solution in a hydrophilic colloid liquid such as a silver halide gelatin emulsion.
However, even in such a dispersion method,
To obtain the desired degree of dispersion and particle size,
A high-energy milling process is required and usually causes undesirable degradation, such as thermal decomposition, of some of the components of the milled composition. Furthermore, such a pulverization process is time consuming and costly. Therefore, there has been a need for an improved method for uniformly dispersing hydrophobic compounds such as ballasted couplers into photographic emulsions and other hydrophilic colloid liquids. In such an improved process, the use of high energy mills that have been used to disperse hydrophobic substances into hydrophilic colloid liquids must be eliminated. On the other hand, in Japanese Patent Publication No. 48-30494, a water-insoluble but organic solvent-soluble polymer is used for dispersing a hydrophobic coupler in order to improve photographic properties (e.g. image storage stability). ,
For emulsification of coupler-containing polymers,
Again, it was necessary to use a high-energy mill.
Japanese Patent Application Laid-Open No. 51-1970 developed a technology aimed at avoiding the use of high-energy mills that cause various disadvantages, and further adding advantages to various photographic emulsions.
It was published in No. 59942 and Japanese Patent Application Laid-Open No. 51-59943. In other words, a polymer latex with a hydrophobic substance impregnated into the polymer dispersion particles is used here, and the hydrophobic substance is made hydrophilic by impregnating the hydrophobic substance into the polymer dispersion particles. A method of dispersing it in a colloidal liquid is used. The use of a polymer latex imparts several desirable properties to the resulting silver halide photographic emulsion. That is,
Compared to photographic emulsions obtained by applying previous methods,
The particle size of the coupler-containing dispersion is reduced, thereby improving the sharpness of the resulting image,
The reactivity between developer and coupler is also improved.
In addition, hydrophobic compounds that were desired to be incorporated but could not be incorporated because they are susceptible to air oxidation,
By incorporating it in this way, it was possible to impart remarkable oxidation resistance and it became possible to introduce it into a hydrophilic colloid liquid. Furthermore, by using polymer latex, the reactivity of hydrophobic substances that are too highly reactive and may react with other components in the layer can be suppressed.
Now it is possible to incorporate it. In this way, the use of polymer latex as a dispersion carrier for photographic hydrophobic additives is a technique that can provide the above-mentioned excellent photographic properties without using a high-energy mill. It can be pointed out that this method has some problems that need to be solved. First, in the method of the invention, the amount of hydrophobic substance that could be impregnated into the dispersion particles in the polymer latex was insufficient. That is, when a coupler, which is a typical hydrophobic additive for photography, is impregnated into dispersion particles in a polymer latex by this method, when the amount is equal to or more than the coupler by weight, the amount of the dispersion is more than twice as much. For this reason, photosensitive materials made using these particles have a large film thickness, resulting in deterioration in developability and resolution. Furthermore, in the conventional method, since the concentration of the dispersion in the polymer latex used is low, a large amount of polymer latex must be used, which has the disadvantage of increasing the drying load. Furthermore, when a hydrophobic substance is impregnated into dispersion particles, it is necessary to use a relatively large amount of water-miscible organic solvent, which requires a large-scale equipment for removal, which has the drawback of requiring a long time for removal. be. Other disadvantages include that the types of polymer latex that can be used are quite limited and that the stability of the obtained impregnated polymer latex composition is not necessarily sufficient. As mentioned above, many conventionally known methods do not give satisfactory results. The present invention has been made to solve these problems, and the first object is to provide a method for producing an impregnated polymer latex composition impregnated with a hydrophobic substance without the above-mentioned disadvantages without using high energy. It is on offer. A second object is to provide a method for producing an impregnated polymer latex composition in which the dispersion particles are impregnated with a large amount of a hydrophobic substance. A third object is to provide a method for making an impregnated polymer latex composition using a polymer latex containing a high concentration of dispersion particles. A fourth object is to provide a method for producing an impregnated polymer latex composition, which allows easy impregnation of a hydrophobic substance into dispersion particles and also facilitates solvent removal treatment after impregnation. A fifth object is to provide a method for producing an impregnated polymer latex composition in which the type of polymer latex used is not too limited. In order to achieve the above-mentioned object, the present inventors conducted research and found that by impregnating a hydrophobic substance into polymer dispersion particles while dissolving it in a water-based polymer latex with a water-miscible organic solvent and water. Therefore, the inventors found that the above-mentioned problems could be solved, and completed the present invention. When using the method for producing an impregnated polymer composition of the present invention, the following excellent effects can be obtained. (1) Since a high-energy dispersion device is not required, the composition does not deteriorate due to the action of generated heat. (2) Since a large amount of hydrophobic substance can be impregnated into the polymer dispersion particles, the film thickness of the photosensitive material can be reduced;
Both developability and resolution improve. (3) Since it is possible to use an aqueous polymer latex with a high dispersion concentration, the drying load can be reduced. (4) Since the amount of organic solvent used during impregnation is small, removal is easy and takes a short time, and large-scale equipment is not required. (5) There are no restrictions on the type of aqueous polymer latex that can be used, and therefore hydrophobic substances that could not be impregnated heretofore can be impregnated, and the impregnated composition obtained is also extremely stable. When impregnating a hydrophobic substance into polymer dispersion particles in the method of the present invention, there are three methods for blending and mixing an aqueous polymer latex, a hydrophobic substance, and a water-miscible organic solvent. . That is, in the first method, a hydrophobic substance is added and suspended in an aqueous polymer latex, and a small amount of a water-miscible organic solvent is mixed therein. The second method involves simultaneously adding and mixing the hydrophobic substance and the water-miscible organic solvent into the aqueous polymer latex from separate hoppers. A third method is to simultaneously add and mix the aqueous polymer latex, hydrophobic substance, and water-miscible organic solvent in the same container. Although any of the above three mixing methods can equally achieve the object of the invention, the first method is preferable because it is easier to operate. The water-miscible organic solvent used in the present invention is most preferably one that mixes with water in any proportion, but any solvent that can be miscible with water in an amount of 10% by weight or more is suitable for the purpose of the present invention. Can be used. Examples of such things include, but are not limited to, the following:
Moreover, there is no harm in using two or more types in combination. moreover,
Since these solvents need to be removed in a later step, their boiling point is not very high and is preferably 150°C or lower, preferably 100°C or lower. Examples include acetone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, and dimethylsulfoxide. In addition, the mixing ratio of these organic solvents to water is
In the polymer latex dispersion, the weight ratio of water to organic solvent is 1:0.1 to 10, preferably 1:
It is preferably about 0.7 to 3. In the present invention, the hydrophobic substance includes substances that dissolve in water up to about 1%. There are many other examples of such additives in agriculture, medicine, dyes, etc., and hydrophobic additives for photography are one example. Typical photographic hydrophobic additives that can be impregnated using the present invention include couplers, ultraviolet absorbers, development inhibitor releasing substances, cross-oxidation dye releasing agents, and photographic dyes. A fluorescent brightener, an antihalation or irradiation inhibitor, a developing agent, etc. can also be impregnated. More specifically, examples of hydrophobic couplers include open-chain methylene yellow couplers,
Examples include 5-pyrazolone magenta couplers, phenolic or naphthol cyan couplers, and the like. These couplers may be so-called 2-equivalent type or 4-equivalent type couplers, and in combination with these couplers, azo-type colored couplers, osazone-type compounds, diffusible dye-releasing couplers, etc. for automatic masking can be used. It is also possible to use In order to further improve the photographic properties, so-called competing couplers, DIR couplers (Development
It can also include couplers called BAR couplers (Bleach Accelerator Releasing Coupler) and BAR couplers (Bleach Accelerator Releasing Coupler). Open-chain ketomethylene compounds have traditionally been used as yellow couplers; for example, a pivalyl acetanilide type yellow coupler is described in US Pat. No. 3,265,506, and a benzoylacetanilide type yellow coupler is described in British Patent No. 1,240,600. No. 2,875,051
The one described in the specification of No.
No. 3,408,194 for allyl substitution, active point -O
- US Patent No. 3447928 for amyl substitution; British Patent No. 1351424 for active point hydantoin compound substitution; British Patent No. 1331179 for active point urazole compound substitution; and British Patent No. 1331179 for active point substitution with a succinimide compound.
No. 1, monooxoimide compound substituted at the active site,
British Patent No. 94490 for active point fluorine substitution, British Patent No. 780507 for active point chlorine or bromine substitution, British Patent No. 1092506 for active point -O-sulfonyl substitution.
Those described in the specifications of No. 1, etc. can be used as effective yellow couplers. Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. U.S. Patent No. for pyrazolone magenta coupler
3127269, 2600788, 3519429, 3419391, 3062653 British Patent No. 1342553
No. 1,399,306, and U.S. Pat. No. 3,684,514, pyrazolotriazole magenta couplers are described in British Patent No.
1247493, pyrazolinobenzimidazole magenta couplers as described in U.S. Patent No. 3061432, and indazolone magenta couplers as described in British Patent No. 1335603. The one listed will be used. Magenta couplers particularly suitable for the method of the invention include those described in US Pat. No. 3,684,514 and US Pat. No. 3,127,269. Furthermore, cyan couplers useful in the present invention include, for example, US Pat. No. 2,423,730
Phenol compounds described in the specifications of No. 2801171 and No. 2895826, U.S. Patent No. 2474293,
Active site -O described in British Patent No. 1084480
-Aryl-substituted naphthol compounds, Canadian patent no.
Examples include phenol and naphthol compounds described in the specifications of No. 913082 and US Pat. No. 3,737,316. As the colored magenta coupler, a compound in which the active site of a colorless magenta coupler is arylazo-substituted or heteroarylazo-substituted is used, such as U.S. Pat. No. 3005712 and U.S. Pat. No. 2983608.
Examples include compounds described in the specifications of No. 2801171, British Patent No. 937621, and US Patent No. 3684514. Colored cyan couplers include U.S. Patent No. 3034892, U.S. Patent No. 2521908, British Patent No. 1255111, and U.S. Patent No.
3811892, British Patent No.
A masking coupler of the type described in No. 1084480, which reacts with the oxidized developer and causes the dye to flow out into the processing solution, can also be used. Further, as a competing coupler, those described in US Pat. No. 2,742,832, such as citradinic acid, etc. can be used, and as a Weiss coupler, those described in US Pat. No. 2,998,314 can be used. . Furthermore, a development inhibitor releasing substance (DIR substance)
As for U.S. Patent No. 3632345, U.S. Patent No. 3928041,
Those described in the specifications of the same No. 3958993 and the same No. 3961959 can be preferably used. As a UV absorber, U.S. Patent No. 3004896
No. 3253921, No. 3533794, No. 3533794, No. 3253921, No. 3533794, No.
Triazoles, triazines or Compounds such as benzophenones can be used. In addition, US Patent Nos. 3052636 and 3707535
It is also possible to use an acrylonitrile compound described in the specification of No. As a UV absorber, Tinuvin is available from Ciba Geigy in Switzerland.
It is also preferable to use those sold under the names PS (trade name), PS 320, PS 326, PS 327, and PS 328, either alone or in combination. Further U.S. Patent No. 2537877
No. 2739971, No. 2739888, No. 2739971, No. 2739888, No.
Azoles described in the specifications of US Pat. No. 2,784,087 and US Pat. No. 3,250,687, or polymeric triazine compounds described in US Pat. No. 3,512,984 and US Pat. No. 3,549,374 can also be used. Other photographic hydrophobic additives include photographic dyes shown in US Pat. No. 2,751,298 and US Pat. No. 3,506,443; US Pat.
DDR couplers (Diffusible Dye
Releasing Coupler), indicator dyes shown in U.S. Pat. No. 3,647,437, U.S. Pat.
Sulfonamide reducing agents shown in specification No. 3810321, US Patent No. 3672896, reductone reducing agents shown in US Patent No. 3679426, US Patent No.
The bisnaphthol reducing agent shown in US Pat. No. 3,672,904 and US Pat. No. 3,751,249;
3672904, 3679426, 3751249, and U.S. Pat.
Belgian Patent No. 3628952, Belgian Patent No. 3698897, Belgian Patent No. 3725062, Belgian Patent No. 788268, Belgian Patent No. 796040, Belgian Patent No.
No. 796041 and No. 796042
A so-called cross-oxidation dye releasing agent called DRR material (Dye Releasing Redox Material) can also be easily impregnated according to the method of the present invention. When a water-miscible organic solvent is added to the aqueous polymer latex containing polymer dispersion particles used in the present invention, the dispersion particles do not aggregate or precipitate, and the dispersion particles are stably dispersed. Must be. In addition, it is preferable that when mixed in a hydrophilic colloid liquid such as gelatin, the dispersion particles do not aggregate or precipitate, and when this liquid is coated on a support and dried, a transparent film is formed. . Such aqueous polymer latexes can be made by emulsion copolymerization of radically polymerizable ethene monomers, and include hydrophilic groups such as sulfo groups, sulfonate groups, carboxy groups, carboxylate groups, and hydroxy groups in the polymer. It contains at least one type of compound. The amount of compounds with hydrophilic groups contained in the polymer is usually 50
% or less, but if the monomer has a hydroxyl group as a hydrophilic group, it can be contained up to 70%. Further, according to the present invention, it is possible to use an aqueous polymer latex having a high concentration of dispersion particles, and a dispersion concentration of up to 60% by weight can be used. The aqueous polymer latex used in the present invention is produced by emulsion copolymerization of radically polymerizable ethene monomers, and examples of usable monomers are shown below, but the invention is not limited thereto. (1) Acrylic acid ester compounds Methyl acrylate, ethyl acrylate,
Butyl acrylate, dodecyl acrylate,
Glycidyl acrylate, 2-acetoacetoxyethyl acrylate, etc. (2) Methacrylic acid ester compounds Methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, glycidyl methacrylate, 2-acetoacetoxyethyl methacrylate, etc. (3) Acrylamides Butylacrylamide, N. N-diethylacrylamide, N/N-diisopropylacrylamide, dodecyl acrylamide, etc. (4) Methacrylamide Butyl methacrylamide, N/N-diethylacrylamide, dodecyl acrylamide,
N・N-diisopropylacrylamide, etc. (5) Vinyl ester compounds Vinyl acetate, vinyl butyrate, etc. (6) Vinyl halide compounds Vinyl chloride, etc. (7) Vinylidene halide compounds Vinylidene chloride, etc. (8) Vinyl ether compounds Vinyl methyl ether, vinyl ethyl Ether, vinylhexyl ether, vinyl glycidyl ether, etc. (9) Styrene compounds Styrene, α-methylstyrene, hydroxystyrene, chlorstyrene, methylstyrene, etc. (10) Other compounds Ethylene, propylene, butylene, butadiene, isoprene, acrylonitrile, etc. (11) Compounds with hydrophilic groups etc. (wherein, R represents a hydrogen atom or a lower alkyl group, and M represents an alkali metal, a hydrogen atom, or _-NH4
) Examples of the composition of the copolymer contained in the aqueous polymer latex used in the present invention are listed below, but the composition is not limited thereto. The aqueous polymer latex used in the present invention can be synthesized by known emulsion copolymerization. For example, add an emulsifier to degassed distilled water as needed.
Synthesis by adding a polymerization initiator, a polymerization initiation accelerator, a polymerization regulator, etc., then adding 10 to 60% by weight of the required monomer, heating to 40 to 90°C, and stirring for several hours. I can do it. Examples of emulsifiers include anionic surfactants such as sodium alkylbenzene sulfonate and sodium polyethylene oxide alkyl ether sulfate, nonionic surfactants such as polyethylene oxide alkyl ether, and amphoteric surfactants such as betaine type or sulfobetaine type. ,
Cationic surfactants such as quaternary ammonium salts can be used. These various surfactants can be used alone or in combination of two or more. As a polymerization initiator, ammonium persulfate,
Potassium persulfate, hydrogen peroxide, etc. are used, and acidic sodium sulfite, acidic soda carbonate, etc. are used as the polymerization initiation accelerator. As a polymerization regulator,
Mercaptan compounds, isopropanol, tertiary butanol, etc. can be used. Other additives that bring about favorable results in terms of synthesis may also be added as necessary. The particle size of the polymer dispersion particles in the aqueous polymer latex obtained by the above method depends on the type and amount of the emulsifier added, the type and amount of the monomer used,
It varies depending on the type and amount of polymerization initiator and synthesis conditions (e.g. temperature, time, stirring speed, etc.), but approximately 0.01
It is preferable to set it to 1 micron. The concentration of the polymer in the aqueous polymer latex used in the present invention is preferably 5% to 60% by weight.
A range of 5% by weight is more preferred. Next, a method for synthesizing a typical aqueous polymer latex used in the present invention will be shown below. Synthesis Example 1 (Aqueous dispersion containing exemplified copolymer 1) 2 four-headed colben (each head equipped with a thermometer, reflux condenser, 300 ml dropping funnel (A), 300 ml dropping funnel (B), Add 2 g of the anionic surfactant Nurex R (trade name, sodium dodecylbenzenesulfonate manufactured by Nissan Chemical) and 600 g of distilled water to a container (with a stirring device attached), and add 30 g of nitrogen gas.
for a minute and bring the temperature to 80°C. Next, add 0.5 g of ammonium persulfate and 0.2 g of acidic sodium sulfite, and immediately add 161.7 g of ethyl acrylate through the funnel.
From (A), 200 ml of an aqueous solution of 38.7 g of sodium 3-acroyloxypropane 1-sulfonate was simultaneously added dropwise from funnel (B) over 30 minutes. After finishing dropping 1
Continue stirring for an hour. Next, the temperature was returned to room temperature and the reaction was terminated. The polymer concentration of the resulting aqueous dispersion was 20% by weight, and the particle size of the polymer particles was about 0.07μ. The molecular weight was measured and was 120,000. Synthesis Example 2 (Aqueous dispersion containing exemplified copolymer 6) 1. Four-headed Kolben (each head has a thermometer, a reflux condenser, a 300 ml dropping funnel (A), a 300 ml dropping funnel (B), and (Attach a stirring device) to Syntrex L-100, an anionic surfactant.
(Product name, NOF manufactured by Sodium Lauryl Sulfate) 2
g and 266 g of distilled water were introduced, nitrogen gas was introduced for 30 minutes, and the temperature was raised to 80°C. Next, add 0.5g of azobiscyanovaleric acid and immediately add n-butyl acrylate.
A mixture of 169.1 g of sodium 1-sulfopropyl 3-acrylamide and 8.8 g of 2-acetoacetoxyethyl acrylate was added to the funnel (A).
200 ml of aqueous solution is simultaneously added dropwise from the funnel (B) over 30 minutes. Stirring was continued for 1 hour after the completion of the dropwise addition. Next, the temperature was returned to room temperature and the reaction was terminated. The polymer concentration of the resulting aqueous dispersion was 30% by weight, and the particle size of the polymer particles was about 0.09μ. The molecular weight was measured and found to be 68,000. Synthesis Example 3 (Aqueous dispersion containing exemplified copolymer 14) Anionic surfactant was added to a 4-headed colben (equipped with a thermometer, reflux condenser, 300 ml dropping funnel, and stirring device to each head). Add 10 g of Syntrex L-100 (trade name, sodium lauryl sulfate manufactured by Nippon Oil & Fats Co., Ltd.) and 600 g of distilled water, and introduce nitrogen gas for 30 minutes to bring the temperature to 85°C. Next, add 0.5g of potassium persulfate and acidic sodium sulfite.
0.2 g of P-toluenesulfonic acid and 0.5 g of P-toluenesulfonic acid were added, and immediately a mixed solution of 160 g of isobutyl acrylate and 40 g of glycidyl acrylate was added dropwise from the dropping funnel over 30 minutes. Continue stirring for 15 hours after completion of the dropwise addition. Next, the temperature was returned to room temperature to terminate the reaction. The polymer concentration of the resulting aqueous dispersion was 20% by weight, and the particle size of the polymer particles was about 0.1 μ. The polymer composition was found to be Exemplified Compound 14 as a result of NMR and elemental analysis, and the molecular weight measurement results were
It was 140,000. Synthesis Example 4 (Aqueous dispersion containing exemplified copolymer 15) 2 four-headed colben (each head equipped with a thermometer, reflux condenser, 300 ml dropping funnel (A), 200 ml dropping funnel (B), Add 2 g of sodium triisopropylnaphthalene sulfonate, an anionic surfactant, and 200 g of distilled water into a container (equipped with a stirring device), introduce nitrogen gas for 30 minutes, and bring the temperature to 75°C. Next, add 0.5 g of ammonium persulfate and 0.1 g of acidic sodium sulfite, and immediately add 173.5 g of methyl acrylate from the funnel (A) to a 100 ml aqueous solution of 26.5 g of sodium 3-acroyloxyphenyl 1-sulfonate and 0.2 g of acidic sodium sulfite. were simultaneously added dropwise from the funnel (B) over a period of 30 minutes, and stirring was continued for 1 hour after the addition was completed. Next, the temperature was returned to room temperature to complete the reaction. The polymer concentration of the resulting aqueous dispersion was 40% by weight, and the particle size of the polymer particles was approximately 0.08μ.
It was hot. The molecular weight was 84,000. Synthesis Example 5 (Aqueous dispersion containing exemplified copolymer 20) 2 four-headed colben (each head equipped with a thermometer, reflux condenser, 300 ml dropping funnel (A), 300 ml dropping funnel (B), Add 1 g of the anionic surfactant Nurex R (trade name, sodium dodecylbenzenesulfonate manufactured by Nissan Chemical) and 271 g of distilled water to a container (with a stirring device attached), and add 30 g of nitrogen gas.
for a minute and bring the temperature to 80°C. Next, add 0.5 g of azobiscyanovaleric acid, immediately add 159 g of ethyl acrylate from the funnel (A), and simultaneously add 100 ml of an aqueous solution of 41 g of sodium 3-acroyloxypropane 2-hydroxy 1-sulfonate from the funnel (B).
Drop in 30 minutes. Stirring was continued for 1 hour after the completion of the dropwise addition. Next, the temperature was returned to room temperature to complete the reaction. The polymer concentration of the resulting aqueous dispersion was 35% by weight.
The particle size of the polymer particles was approximately 0.09μ.
The molecular weight was measured and found to be 117,000. According to the above synthesis example, an aqueous polymer latex containing the copolymer exemplified above can be easily synthesized. A polymer latex composition impregnated with a photographic hydrophobic additive by the method of the present invention can be applied to all objects to which polymer latex compositions obtained by known methods can be applied. In addition, according to the method of the present invention, the above object can be achieved, and since the particle size of the polymer latex impregnated with a hydrophobic substance by the method of the present invention is extremely uniform, it can be applied to couplers and used for color photography. When used as a material, the color development properties in color development are better than those obtained by conventional methods, and the color purity and fastness of the obtained color images are also good. Furthermore, as a result of the wider selection of polymers than in conventional methods, the range of substances that can be impregnated has been expanded, including, for example, substances that could not be impregnated heretofore. The present invention will be explained in more detail below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 Take 100 ml of an aqueous polymer latex (polymer material concentration of 10% by weight) containing Exemplary Copolymer 1 synthesized according to Synthesis Example 1, and add 5 g of yellow dye-forming coupler α-( 3-
Benzyl-2,4-dioxo-imidazolidine-
3-yl)-α-vivaroyl-5-[α′-(2.4
-di-tert-amylphenoxy)butyramide]
The -2-chloroacetanilide was added all at once while stirring in crystalline form to suspend the coupler in the aqueous polymer latex. A small amount of 100 ml of acetone was then added to this, and the suspended coupler was rapidly impregnated into the dissolved polymer dispersion particles. Acetone was removed under reduced pressure using a rotary evaporator to obtain a dispersion (sample 1). For comparison, 5 g of the yellow dye-forming coupler was dissolved in 100 ml of acetone, and 100 ml of the aqueous polymer latex was added dropwise over 1 minute while stirring. When stirring was continued for about 1 minute after the completion of the dropwise addition, all of the coupler was impregnated into the dissolved polymer dispersion particles. Acetone was removed using a rotary evaporator to obtain a dispersion liquid (comparative sample 1). Comparative Sample 2 was prepared by thoroughly mixing a solution of a yellow dye-forming coupler in acetone and an aqueous polymer latex solution, and separating the acetone. For these samples, the spectral transmittance of green light (530 mm), stability, and time required for impregnation were measured as characteristics that substituted for the particle size of the polymer dispersion, and the results are shown in Table 1.

【table】

[Table] The amount of acetone used is 50ml and 35ml.
(Thus, the polymer substance concentration at the time of impregnation is 6.6% and 7.5%, respectively) and was tested in the same manner as above. However, in the comparative method, when the acetone amount was 50 ml and 35 ml, precipitates clearly detected with the naked eye were deposited. The obtained Sample 1 and Comparative Sample 1 do not solidify upon storage and are also compatible with gelatin solution, and when coated and dried on a transparent photographic support after being mixed with gelatin solution, both become uniform. A transparent layer was obtained. Example 2 Copolymerized copolymer illustrating aqueous polymer latex
A polymer latex composition impregnated with a stable coupler was obtained by carrying out the same experiment as in Example 1 except that the acetone contained 28 and tetrahydrofuran was used instead of acetone. Example 3 In 20 ml of an aqueous polymer latex (polymer substance concentration 25% by weight) containing Exemplary Copolymer 1,
5 g of cyan dye-forming coupler 2-[α-(2.4
-di-t-amylphenoxy)butyramide]-
4,6-dichloro-5-methylphenol was added directly and stirred into suspension in the aqueous polymer latex. Add 15ml of tetrahydrofuran (below)
When adding a small amount of THF) while stirring, 1 to 2
After a few minutes, the coupler was completely impregnated into the polymer dispersion particles, resulting in a homogeneous dispersion. Aqueous polymer latexes with different concentrations of polymeric material were then used to impregnate couplers according to the method of the present invention. That is, in 17 ml of aqueous polymer latex (polymer material concentration 30% by weight)
g of the cyan coupler was added and stirred to suspend it in the aqueous polymer latex. Add 15ml to this
A small amount of THF was added with stirring, and after 1 to 2 minutes, the coupler was completely impregnated into the polymer dispersion particles to form a uniform dispersion. After adding 30 ml and 33 ml of pure water to each, and removing THF under reduced pressure using a rotary evaporator, there was no coagulation or precipitation of crystals, and stable coupler-impregnated polymer latex compositions were obtained. This shows that according to the method of the present invention, a stable coupler-impregnated polymer latex composition can be obtained even when using a concentrated aqueous polymer latex (polymer substance concentration of 20% by weight or more). Example 4 The coupler is a magenta dye-forming coupler, 1-
(2,4,6-trichlorophenyl)-3-(2
-chloro-5-octadecylsuccinimideanilino)-pyrazolin-5-one, the water-miscible organic solvent was acetone:THF=1:1, 30 ml, and the aqueous polymer latex was exemplified copolymer 6.
The same experiment as in Example 2 was conducted, except that the polymer material concentration was 20% by weight, and similar good results were obtained. Example 5 100 ml of the aqueous polymer latex (polymer substance concentration 10% by weight) containing Exemplified Copolymer 1 used in Example 1 was placed in a container, and while stirring, 30 ml of acetone:THF = 1:1 was added from one side. from the other hand to the yellow dye-forming coupler α-(3-benzyl-2,4-dioxo-imidazolidin-3-yl)-α-pivaloyl-5-[α'-(2,4 5 g of -di-tert-amylphenoxy)butyramide]-2-chloroacetanilide were added separately and simultaneously to the aqueous polymer latex over a period of 1 minute each. By continuing to stir for 1 minute after addition, all the couplers were impregnated into the polymer dispersion particles, and a homogeneous liquid was obtained. The solvent was removed under reduced pressure on a rotary evaporator to obtain a stable impregnated polymer latex composition. Example 6 100 ml of the aqueous polymer latex used in the previous example, 5 g of the yellow dye-forming coupler, and 100 ml of acetone as a water-miscible organic solvent were each added simultaneously and separately into a 500 ml beaker for 10 seconds. After the addition, the three components were thoroughly mixed by stirring, and after about 1 minute, all the couplers were impregnated into the polymer dispersion particles, and a homogeneous liquid was obtained.
Removal of the acetone under reduced pressure using a rotary evaporator resulted in a stable impregnated polymer latex composition with no coagulation or precipitates. Example 7 Cyan dye-forming coupler, 2-[α-(2.4-
di-tert-amylphenoxy)butyramide]-
Dissolve 5 g of 4,6-dichloro-5-methylphenol in 5 g of dibutyl phthalate and 15 ml of ethyl acetate to make a 3.5% gelatin solution [Alkanol XC (trade name).
(alkylnaphthalene sulfonic acid (manufactured by Dupont) as a dispersant) was mixed and then subjected to ultrasonic dispersion according to a conventional method, and the resulting dispersion was designated as A. Next, 5 g of the cyan dye-forming coupler was directly added to 50 ml of the aqueous polymer latex (polymer concentration 20% by weight) containing the exemplified copolymer 6 obtained in Synthesis Example 2, and the mixture was stirred and suspended. When a small amount of 30 ml of THF is added to this, the coupler is impregnated into the dissolved polymer dispersion particles in 1 to 2 minutes.
A uniform dispersion will result. After adding 50 ml of pure water, THF was removed under reduced pressure using a rotary evaporator, and the resulting dispersion was designated as C. Next, 100 ml of the same aqueous polymer latex diluted to a polymer substance concentration of 10% by weight was added dropwise over about 2 minutes to 160 ml of THF in which 5 g of the cyan coupler was dissolved.Then, the THF was depressurized in the same manner. The dispersion obtained by removal was designated as B. Coupler dispersion A produced in this way,
B and C were each mixed with a silver chlorobromide emulsion for red-sensitive paper and coated on a photographic polymer film coated paper support as described below.

[Table] Each of the above samples was wedge exposed and developed with the following developer for 4 minutes at 25° C. according to conventional processing. Developer 2-Methyl-4-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline 3/2
Sulfate 4.5g Sodium carbonate (monohydrate) 20g Potassium bromide 2.0g Sodium sulfite 3.0g Hydroxylamine sulfate 2.0g Sodium hexametaphosphate 2.0g Benzyl alcohol 10ml In water 1 PH10.1 The results are shown in Table 2.

[Table]
From these results, it has become clear that the method of the present invention does not require the use of a large amount of solvent as in known methods, and can provide equivalent photographic properties. Example 8 Comparative Sample 2, Comparative Sample 3 and Sample 2 of Example 7
After processing in the same manner as in Example 7, each sample was left to stand for two weeks under forced deterioration conditions of 80% relative humidity and 50° C. After that, the percentage of residual dye in the D _nax portion of the coloring dye was compared. The results are shown in Table 3.

[Table] As is clear from Table 3, sample 2 of the method of the present invention
has superior image storage stability compared to comparative sample 2,
It can also be seen that it has almost the same performance as Comparative Sample 3. Example 9 Magenta dye-forming coupler 4,4'-bis{1-
(2,4,6-trichlorophenyl)-3-[3-
(2,4-di-tert-amylphenoxyacetamide)benzamide]-pyrazolin 5-one}10
g and the DIR substance 2-(1-phenyltetrazolyl-5-thio)-4-octadecylsuccinimide)
After dissolving 1.2 g of indanone in 10 g of tricresyl phosphate and 30 ml of ethyl acetate, the mixture was added to 75 ml of a 3.5% gelatin solution containing Alkanol Protection distributed. (Dispersion D). Then, 10 g of the magenta dye-forming coupler and 1.2 g of the DIR material were added to 50 ml of an aqueous polymer latex containing the exemplified copolymer according to Synthesis Example 5 and having a polymer material concentration of 20% by weight and stirred. Suspend. Next, when 30 ml of acetone:THF=1:1 mixed solvent was added to this liquid, the coupler and DIR substance were completely impregnated into the dissolved polymer dispersion particles in 1 to 2 minutes, resulting in a homogeneous liquid (dispersion). Liquid E). Both dispersions were mixed with a green sensitive color negative silver iodobromide emulsion and coated onto a triacetate base to prepare samples as described below.

[Table] Table 4 shows the results of developing the obtained sample according to the Sakura Color development process after wedge exposure.

[Table] As is clear from Table 4, the method of the present invention
It also showed excellent properties for material dispersion, comparable to conventional methods. Furthermore, in terms of characteristics such as graininess, even better results were shown. The relative sensitivity here indicates the sensitivity when the comparative sample is set as 100. Example 10 DRR substance 4-[3-{5-hydroxy-
6-(2'-methylsulfonyl4'-nitrophenylazo)-1-tert-butylaminosulfonyl}benzenesulfonamide]-1-hydroxy-2-
[Δ-(2,4-di-tert-amylphenoxy)-
When 12 g of n-butyl naphthamide was added to 75 ml of an aqueous polymer latex (polymer concentration 20%) containing Exemplary Copolymer 6 and 50 ml of THF was added with stirring, the DRR substance was dissolved in 1 to 2 minutes. It was impregnated into the polymer dispersion particles and became a uniform liquid. Using a rotary evaporator,
THF was removed under reduced pressure to obtain a homogeneous dispersion of DRR material. On the other hand, for comparison, a dispersion liquid for a comparative example was prepared using diethyl laurylamide as a high boiling point solvent by a commonly used protect dispersion method. Next, by the method disclosed in JP-A-47-126331, both of the above dispersions were mixed with a negative silver bromide emulsion, a hardener and a spreading agent were added, and then a polyester film base was prepared. A photographic light-sensitive element was prepared by coating as follows. DRR substance 1.1・10 ^-5 mol/dm ² Silver 10 mg/dm ² Gelatin 33 mg/dm ² Next, as a mordant, poly(styrene-2-vinylbenzyl chloride-2-N-benzyl-
A mordant layer consisting of 25 mg/dm ² of N.N-dimethyl-N-vinylbenzylammonium chloride-2-di-vinylbenzene (molar ratio 4.90:0.49:4.41:0.2) and 13 mg/dm ² of gelatin was coated with a polyester film. An image-receiving element was created by coating it on a base. After wedge exposure, the photographic light-sensitive element was placed on an image-receiving element, and the sanderch structure was passed between a pair of pressing rollers to introduce the following viscous processing liquid between the sanderch structures. Sodium hydroxide 40g 4-oxymethyl-4-methyl-1-phenyl 5-pyrazolidone 4g 5-methylbenzyltriazole 0.1g Potassium bromide 0.1g Hydroxyethyl cellulose 25g Distilled water 1000ml After 90 seconds, peel off the image receiving element and check the pH. I washed it with water to make it 7. A good cyan transfer image was obtained on the receiving element. The results are shown below.

[Table] When the method of the present invention was used, results superior to the conventional method in both sensitivity and D _nax were obtained. Example 11 2-benztriazole, an ultraviolet absorber
2.0 g of 4-tert-butylphenol, 1.5 g of 2-benztriazolyl-4,6-di-tert-butylphenol, 2-(5-chlorobenztriazolyl)-4,6-di-tert-butyl Phenol 2.5
g, 2-(5-chlorobenztriazolyl)-4-
6g of 2.5g of methyl 6-tert-butylphenol
of dibutyl phthalate was dissolved in 20 ml of ethyl acetate, and using a colloid mill according to a conventional method, this was protected and dispersed in an aqueous gelatin solution to form dispersion F.
I got it. Next, in 30 ml of the aqueous polymer latex used in Example 4, the same amount of the mixture of the ultraviolet absorbers was added and suspended, and when 20 ml of THF was added while stirring, all the ultraviolet absorbers were removed in 1 to 2 minutes. The dissolved polymer dispersion was impregnated into particles and became a homogeneous liquid. The organic solvent was removed under reduced pressure using a rotary evaporator to obtain a dispersion H. Furthermore, add 8.5 g of the UV absorber mixture to 100 ml.
of the aqueous polymer latex, and then the polymer substance concentration of the aqueous polymer latex was adjusted to 10%.60
ml was added dropwise over 1 minute with stirring, and after the dropwise addition, acetone was removed under reduced pressure using a rotary evaporator to obtain a dispersion liquid G. The above dispersions F, G, and H were each mixed with an aqueous photographic gelatin solution and coated on a photographic triacetate film base so that the coating amounts of gelatin and ultraviolet absorber were the same. The optical density at 370 nm and 415 nm of the sample thus obtained was measured using a spectrophotometer, and the following results were obtained.

[Table] As is clear from the above results, the ultraviolet absorber impregnated and dispersed by the method of the present invention has a higher level of ultraviolet optical density and visible It can be seen that there is a sharp cut-off characteristic towards the end. Furthermore, compared to the aqueous polymer latex dispersion method disclosed in JP-A No. 51-59943, the effect is almost the same, but the amount of organic solvent used in the dispersion process is 1/5. The solvent removal step was therefore significantly shortened. Preferred embodiments of the present invention described in detail above will be described below. (1) A method for producing an impregnated polymer latex composition, which comprises adding and mixing a water-miscible organic solvent into a mixture of an aqueous polymer latex and a hydrophobic substance. (2) A method for producing an impregnated polymer latex composition, in which a hydrophobic substance and a water-miscible organic solvent are separately and simultaneously added and mixed into an aqueous polymer latex. (3) A method for producing an impregnated polymer latex composition by simultaneously mixing three components: an aqueous polymer latex, a hydrophobic substance, and a water-miscible organic solvent. (4) The aqueous polymer latex is made by emulsion copolymerization of radically polymerizable ethene monomers, and the polymer contains sulfo groups, sulfonate groups,
At least one selected from the group consisting of a carboxy group, a carboxylate group, and a hydroxy group.
1. A method for producing an impregnated polymer latex composition containing at least one compound having a hydrophilic group. (5) The polymer in the aqueous polymer latex contains carboxy groups, carboxylate groups, sulfo groups,
A method for producing an impregnated polymer latex composition containing 1 to 50% by weight of monomer units selected from the group consisting of sulfonate groups. (6) A method for producing an impregnated polymer latex composition, wherein the polymer in the aqueous polymer latex contains 10 to 70% by weight of monomer units having hydroxy groups. (7) The polymer in the aqueous polymer latex contains carboxy groups, carboxylate groups, sulfo groups,
A method for producing an impregnated polymer latex composition comprising 2 to 50% by weight of monomers selected from the group consisting of sulfonate groups and 0.2 to 10% by weight of monomer units having active methylene groups. (8) A method for producing an impregnated polymer latex composition in which the concentration of polymer substance in the aqueous polymer latex is 60% by weight or less. (9) A method for producing an impregnated polymer latex composition in which the hydrophobic substance is a photographic hydrophobic additive. (10) A method for producing an impregnated polymer latex composition in which the photographic hydrophobic additives include a dye forming agent, an ultraviolet absorber, a development inhibitor-releasing substance, a cross-oxidation dye-releasing agent, and a photographic dye. (11) A method for producing an impregnated polymer latex composition, wherein the water-miscible organic solvent is miscible with water in an amount of 10% by weight or more.

Claims (1)

[Scope of Claims] 1 A copolymer of one or more compounds selected from acrylic esters, methacrylic esters, acrylamides and methacrylamides,
and in polymer dispersed particles in an aqueous polymer latex solution (hereinafter referred to as latex) containing one or more types of polymers having a hydrophilic group selected from sulfo groups, sulfonate groups, carboxy groups, and hydroxy groups in the polymer. In a method of manufacturing an impregnated polymer latex composition by impregnating a hydrophobic substance, (1) a method of adding a hydrophobic substance to a latex and then adding and mixing a water-miscible organic solvent; (2) a method of adding and mixing a water-miscible organic solvent to a latex; and a water-miscible organic solvent separately and simultaneously, or (3) a method in which a latex, a hydrophobic substance, and a water-miscible organic solvent are simultaneously added and mixed. Method for producing a tuxu composition.