JPS59218438A - Photographic element - Google Patents

Abstract

PURPOSE:To improve both of physical properties and photographic characteristics of a film by incorporating a latex consisting of the polymer particles having different phase structures, consisting of the outside polymer being noncationic and higher in swellability than the inside polymer. CONSTITUTION:A latex having different phase structures is good in compatibility with gelatin and forms no coarse particles in gelatin. The inside core polymer on the outside of which a noncationic polymer is formed may be also cationic. As the monomer compsn. of the polymer of both cores and shells, the cores are made from hydrophobic monomer units, and the outside shells are made from a combination of hydrophobic and hydrophilic monomer units in a prescribed proportion. Both polymers may be same in compsn., but they must be different in the monomer compsn. proportion. When a water-soluble monomer is used, the polymer to be formed is however made hardly soluble in water. Seed polymn. is carried out by using a water-soluble or hydrophobic polymn. initiator. A preferable particle diameter is <=0.7mum, and a preferable mol.wt. of the polymer is 5,000-500,000.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to photographic elements, and more particularly to film transparency,
The present invention relates to a photographic element with improved dimensional stability and film adhesion properties and with good photographic properties.

BACKGROUND OF THE INVENTION It has been known for various purposes to use latexes containing polymer particles as photographic coating compositions for photographic light-sensitive materials. For example, regarding a photographic light-sensitive material in which the above-mentioned latex is mixed with a hydrophilic colloid solution such as gelatin and coated as a photographic constituent layer, for example, US Pat.
6.005, same No. 2.763,625, same No. 2,7
No. 72,166, No. 2.852,386, No. 2.
8F13,457, 3.062,674, 3,142,568, 3,220,844, 3,325,286, 3,397,988,
Same No. 3,556,795, Same No. 3,904,413, Same No. 3,929,482, Same No. 4,197,127
No.-Each, British Patent No. 1. ．． No. 030.001, No. 1
, No. 121,357, No. 1,1115,979, No. 1.222,714 - each - 1 West German Patent No. 2゜204
．． No. 056, No. 2,218,218, No. 2゜21
No. 9.004, No. 2.421.859 - each, East German Patent No. 152. tJIO, Belgium IF'4, vr
' No. 686.

No. 439, No. 688,882, No. 691.360
No. 708.347, No. 1711.248, No. 711.928, No. 712.823, No. 723.690, No. 748,266, No. 768
゜558 Winter 1 European Patent No. 1 (No. 1, 335,
No. 18.601 Specifications, Special Publication No. 41-16721
No. 45-3832-1 No. 45-5331, No. 4
No. 5-18415, No. 45-22186, No. 47-1
No. 0196, +0147-26899, No. 48-43
No. 125, No. 49-20532, No. 49-25499
No. 49-32344, JP-A No. 50-56227,
No. 50-73625, No. 51-138217, No. 5
No. 1-146826, No. 53-112732, No. 53
-126060, 55-502 = 10, 57
It is disclosed in No. 84454, No. 57-200031, etc.

Further, regarding a photographic coating liquid that is used by adding a photographic hydrophobic substance to latex and impregnating the monomer particles in the latex with the photographic hydrophobic substance, US Pat. No. 2,772,163 No. 3, 554.

No. 987, No. 4,199.363, No. 4, 20
3.

No. 716, each specification J, JP-A No. 48-30494, 5
1-59942 Specification Publication and Research Disclosure w - (Re5earch Disclosure
) No. 15.129, No. 15,930, No. 19,52
It is disclosed in No. 9 etc.

However, the latexes used in the photographic and photographic coatings described in the above publications, for example, can improve the dimensional stability of the coating layer, but have drawbacks in film adhesion, or have poor dimensional stability. Although it has excellent properties and film adhesion, it is
At present, there is no latex that is necessarily excellent in terms of improving physical properties and satisfies -C in terms of AtJ performance, even though the properties may deteriorate.

On the other hand, regarding photographic materials in recent years, especially silver halide photographic materials (hereinafter simply referred to as "photosensitive materials"),
There is a growing demand for improved performance, such as improved film adhesion of photographic coating layers, improved dimensional stability, and even improved optical properties.
In particular, there is a strong demand for improved transparency, and there is also a need to develop a latex that has excellent performance without deteriorating its photographic properties.

OBJECTS OF THE INVENTION An object of the present invention is to provide a latex that has excellent film adhesion, dimensional stability, and film transparency, and does not cause deterioration of photographic properties. The object of the present invention is to provide a photographic A'A element containing excellent latex and having improved film properties and photographic properties.

Structure of the Invention As a result of extensive studies, the inventors of the present invention have found that the above-mentioned objective is to provide a Photo J14 element having at least one photographic constituent layer on a support, and to provide at least one of the photographic constituent layers.
We have discovered that this can be achieved by a photographic element in which the polymer on the outside of the particle has a greater swelling property than the polymer on the inside of the particle, and the polymer on the outside of the particle is non-cationic. .

Hereinafter, the present invention will be explained in more detail.

In the latex with a different phase structure according to the present invention, the polymer forming the outside of the particle has greater wettability to C water than the polymer forming the inside of the particle, and at the same time, the polymer outside the particle is non-cationic. It is characterized by

According to the invention, the polymer forming the particle exterior has a pH of
2 to 7. It is preferable that the monomer is composed of monomers whose degree of swelling in water at 20° C. is greater than 1% by volume, and more preferably whose degree of nuclear swelling is greater than 5% or whose degree of swelling is 5%. It is particularly preferable to have a heterophase structure, such as a monomer that is smaller than % and is liquid at a temperature lower than 100°C.

The latex having a different phase structure as described above according to the present invention has better compatibility with gelatin than conventional latex, does not form coarse particles in gelatin, and can be used as a latex such as -Ii, A, The photographic element of the present invention, which is contained in the constituent layers and coated on the support, not only has excellent film adhesion and dimensional stability, but also has good film transparency and does not inhibit photographic properties or cause staining. There's nothing to do.

An example of a latex having such a heterophasic structure is described, for example, in JP-A-56-17352. The heterophasic latex disclosed herein has a cationic vinyl monomer as a shell, and water other than the monomer. It has a structure having an insoluble monomer as a core, and this seed polymerized cationic polymer latex is used by being included in the mordant layer of a diffusion transfer photographic element. However, when this extremely cationic latex is added to an emulsion layer, for example, it reacts with anionic surfactants such as saponin, which are used as distribution aids, causing aggregation. The emulsion layer on the support becomes difficult to fabricate.Also, residual cationic monomers or oligomers increase emulsion fog.

Further, when the above-mentioned cationic latex is used in a constituent layer other than the emulsion layer, emulsion fogging occurs due to diffusion during aging or storage.

Furthermore, polymerization of cationic monomers is difficult, resulting in coarse particles and gelation. Therefore, if such coarse-grained latex is used in the photographic constituent layer, the transparency of the film will be lost, and if it is contained in the coating solution, it will increase the viscosity of the coating solution and cause coating failures, so it should not be used. Have difficulty.

As mentioned above, the heterophase structure latex according to the present invention does not cause the above-mentioned non-ZIS combination because the polymer outside the particles is non-cationic.

In the latex having a different phase structure according to the present invention, the polymer inside the particles may be cationic for the above reasons.

Regarding the monomer composition forming the outside of the particle (hereinafter referred to as the shell part in the present invention) and the inside of the particle (hereinafter referred to as the core part in the present invention) having a different phase structure as described above, in the present invention, the core part is hydrophobic. A hydrophobic monomer is used in combination with a water-based monomer, and a hydrophobic monomer and a water-based monomer are used in the shell portion, respectively.

Examples of monomers used in the core or shell part include acrylic esters (specifically methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, tert-phthyl acrylate, stearyl acrylate, benzyl acrylate, 2- Large methacrylic esters such as hydroxyethyl acrylate and fringyl acrylate (specifically 4':
L1 methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroquinoethyl methacrylate, cricidyl methacrylate, etc., styrenes (specifically, styrene, α-methylstyrene, p-chlorostyrene, m-chlorostyrene, etc.), Diene compounds (specifically butadiene, chloroprene, isoprene, etc.), acrylonitrile, vinyl acetate, acetic acid Wilanil, methylene diethyl malonate, dimethyl itaconate, noethyl itaconate, dibutyl itaconate, vinylidene sulfate, divinylbenzene, ethylene glycol dimethacrylate,
Triethylene glycolone resin acrylate, (meth)
Acrylic acid, (meth)acrylamide, itaconic acid, N
-Hydoxymethylacrylamide, N-butoxy7methylacrylamide, sodium 2-acrylamido-2-methylpropanesulfonate, sodium vinylbenzenesulfonate, etc., which are described in Research Disclosure (RD) No. 39551. Monomers are listed as commonly used monomers.

Among the various monomers mentioned above, photographically active monomers such as N-vinylbenzyltrihexylammonium chloride, N-vinylbenzyltrioctylammonium chloride, N-vinylbenzyl-N, N-J7
-/lz horse chestnut/ruammonium chloride Quaternary cationic monomers such as 5-ide and monomers that develop color with developing agents, such as hydroquinone, generate capri in photographic elements, so shell polymers are obtained. It cannot be used in cases.

The monomers forming the shell part spanning the core part, which can be exemplified above, contain at least one type of monomer according to the example, and may have the same seven-mer composition as the core part and the shell part, but the monomer composition It is necessary that the ratios are different. When using a water-bathable nanatsumer as a nanatsumer, it is sufficient that the polymer constituting the core or shell part exhibits compatibility with water; for example, the bath solubility in water is generally Specifically, it is preferable that F is 30% or less.

In addition, in the present invention, the "'" Mjk ratio ti of the core part and the shell part, core/shell='/99 to 90
/(O degree is preferable, but in order to maintain transparency in the photographic material, the range of 2(1780 to 8()/2o is particularly preferable). Although typical specific examples of monomer compositions forming the compound will be described as examples of compounds, the present invention is not limited thereto.The numbers represent weight %.

(Compound example) (]) Core group; Methyl methacrylate (100)/L part; Methyl acrylate/Acrylic M (90/10
) Core part/Shell part = 60/40 (2) Core part; Styrene (10θ) Shell part; Ethyl acrylate (loo no Core part/Shell part = 20780 +31 Core part; Phthanene/Styrene → ('r1 product)
Synthesized and described in 12 Shell part: Ethyl acrylate/acrylic acid (90/1
0) Core part/Shell part=80/2LJ (4) Core part; Ethyl acrylate/Ethylene glycol dimethacrylate (93/7) Shell part; Ethyl acrylate/Acrylic If (90
/10) Core part/Shell part - 5015t+51 Core part; Butyl acrylate/Styrene (50
15o) Shell part; terj-butyl acrylate/
2-Hydroxyethyl methacrylate (70/3f recoa part/shell part = 6U/4 (J (6) core part; ethyl acrylate/itako; '1
1 & (99/1) shell part; bunal acrylate/2-
Sodium acrylamide-2-methylpropanesulfonate (75/2b) Core part/Shell part = 80/20 Core part; Butyl acrylate (100) Shell part; Ethyl acrylate (loo) Core part/Shell part = 7
0/3tJ (8) Core part; Butyl acrylate/glycidyl methacrylate/styrene (50/2JJ/additional) Shell part; Ethyl acrylate/glycidyl methacrylate (3
0/70) Core part/shell part = 70/additional (91 core part; ethyl acrylate/styrene (5
015 (1) Shell part; Ethyl acrylate/acrylamide (70/30) Core part/Shell part = 80/2t1 Synthesis is carried out using a seed polymerization method to obtain a latex with a different phase structure according to the present invention. Regarding the synthesis of latex by
Vol. 1, No. 9, pp. 576-586, (1974), Vol. 33, No. 10, pp. 575-583, (1976)
), Volume 33, No. 11, pp. 663-672 (1
976), Volume 36, No. 7, 459-464 members (1979), and 1. Physical properties and applications of synthetic resin emulsions (I*J Molecular Publishing Association, Sakae Ogata et al., 1978)
, etc., and can be carried out by a conventional method using a water-soluble polymerization initiator or a hydrophobic polymerization initiator.

The latex forming the core portion is not limited to the emulsion polymerization method, and may be an emulsion dispersion of a water-insoluble polymer synthesized by, for example, a solution polymerization method, a radiation polymerization method, or the like.

The combination initiators used in the synthesis of the latex that will become the core part or in the seed polymerization include water-temperature polymerization initiators, such as persulfates, redox systems of persulfate and bisulfite, hydrogen peroxide and iron (11 ), sodium azobiscyanovalerate, 2,2'-azobis-(2-amidinopropane) dihydrochloric acid, and hydrophobic polymerization initiators such as azo-sisobutyronitrile, lauroyl bicarbonate, etc. zide, acetyl peroxide, ter
t-butyl peroxide, cyclohexanone peroxide, 2,4-dichlorobenzoyl peroxide,
Examples include benzoyl peroxide, pensoyl peroxide and dimethylaniline.

How much cholera initiator should be used in the shell? - 0. (l l-10.0% by weight, particularly preferably from 0.05 to 3.0% by weight).

In the operation of the seed polymerization method, for example, as described in "Chemistry of Polymer Latex" (by Bo Muroi, 1976, pp. 151-54), - "temporal charging method, delayed monomer addition method," A monomer division addition method or the like can be used.

Further, when seed polymerization is carried out, a new emulsifier may be added if necessary, and in this case at least one of anionic activators and nonionic activators can be used.

Additionally, protective colloids such as gelatin, polyvinyl alcohol, eh, methyl cellulose, dipotassium phosphate, etc. or chain transfer agents such as tert-dodecyl mercaptan may also be added.

The average particle diameter of the different phase structure latex in the present invention is 0
．． It is preferably 7μ or less, particularly preferably 0.02 to 03μ. That is, if the particle size is larger than the above, the transparency of the coating film will be poor, and if the particle size is too small, the viscosity of the coating liquid will increase significantly, making coating difficult.

Regarding the seed polymerization temperature (°C), it is necessary to arbitrarily select the polymerization temperature, reaction time, resin concentration, method of supplying the monomer to the reaction system, etc., depending on the monomer composition forming the core or shell part. be. Preferred conditions include a polymerization temperature of 50'-95°C, a reaction time of 2 hours to 4 hours, a resin concentration in the core and shell parts of 5 to 20% by weight, and a method of supplying the monomer to the reaction system. Examples include a monomer one-time charging method and a seven-piece continuous dropping method. And the molecular weight of the polymer according to the present invention is 1.000 to I,0
00,000, preferably 5,000 to 500.
00 (J.

The method for synthesizing a latex with a different phase structure according to the present invention will be described below using typical examples thereof, but the present invention is not limited thereto. Furthermore, all monomers used in the following synthesis method were purified by distillation.

Synthesis Example 1 (Synthesis of Sheet Polymerized Latex of Exemplary Compound (1) 9 Distilled water 3 (10 ml and stirred for 2 hours at an internal temperature of 80°±2°C under a stream of nitrogen gas, then added 2 g of sodium dodecylbenzenesulfonate and 0.2 g of ammonium persulfate.
Then, at an internal temperature of 80'±2°C, 40 g of methyl methacrylate was added dropwise over 1 hour, and the reaction was carried out at lnJ temperature for 1 hour.
4I and 3 g of acrylic acid were added at once, then 30 ml of a 1% aqueous solution of ammonium persulfate was added dropwise over 1 hour, and the reaction was continued for an additional 3 hours. After the reaction was completed, the latex was a milky white substance with a resin component content of 17%, and the amount of aggregates was 0.3p. The average particle size of the obtained latex was measured using a microscope and was 0.0°9μ.
Met.

Synthesis Example 2 (Synthesis of Sheet Polymerization Latex of Exemplary Compound (3)) Using the same equipment as described in Synthesis Example 1 above, butadiene-styrene cobolymer latex (Sumitomo Norcatak Co., Ltd., SN-304, resin) was used as the core latex. Turn i
48%）'AH1b- and distilled water 180-,
Under a nitrogen stream, the internal temperature was raised to 60°C, 1 tnl of a 1% aqueous solution of potassium persulfate was added, and ethyl acrylate 2.
A mixed solution of 2 g of acrylic acid and 0.2 fl of acrylic acid was subjected to a simple F over a period of time. After the dropwise addition was completed, a 1% aqueous solution of potassium persulfate (la) was further added, and the mixture was reacted for 3 hours. The latex after the reaction was a milky white homogeneous bath liquid with a resin component content of 5.6N%,
Aggregates were collected at 0.2 g. The average particle size of the obtained latex was 0.3 μm as measured using an electron microscope.

Synthesis Example 3 (Synthesis of sheet compound latex of exemplified compound (7)) Using the apparatus described in Synthesis Example 1 above, 250 d of steamed water
and stirred for 2 hours at an internal temperature of 700±2°C under a nitrogen stream.
and 0.5 g of Azobiscyano Valerian sodium salt were added, and at an internal temperature of 70° ± 2° C., butyl acrylate (35 jj) was added dropwise over 1 hour, and then azobiscyanovaleric sodium JnO, 2,! Add i' and ethyl acrylate l! 1 was added dropwise over a period of minutes.

After the dropwise addition was completed, the reaction was carried out for 2 hours at the same temperature. After the reaction, the latex contains a resin component of -1fi: 16.6% by weight.
It was a milky white homogeneous solution, and no aggregates were observed. The average particle size of the obtained latex was measured using an electron microscope and was found to be 0.06 μm.

In accordance with the above synthesis example, the exemplified appendages f2J and f are respectively
41.

(5), (6), (sl and (9)) were also synthesized, and the resulting latexes are listed in the table below.

Comparative threat example 1 (Comparative synthesis of exemplified compound (1)) @
'Using the same equipment as in Example 1, add 300 ynl of steamed water and stir in a room under a stream of purple air at an internal temperature of 800±2°C for 2 hours, then add 2.9 ml of sodium dodecylbenzenesulfonate and 0.211 ml of ammonium persulfate. Methyl methacrylate 40y and methyl acrylate Ou I at an internal temperature of 80°±2°C
and 3I acrylic acid in a mixed bath solution for 1 hour.
The reaction was continued for an additional 3 hours. After the reaction is completed, the latex contains a resin component of 18% milky white lily liquid,
The aggregate size was 0.5.9. Comparative Synthesis Example 2 A latex of Example Fukaite (2) was synthesized in exactly the same manner as in Comparative Synthesis Example 1 above.

Comparative Threat Example 3 -gr&I was added to the latex of Exemplary Compound (4) in exactly the same manner as the synthesis method of the above-mentioned Comparative Synthesis flJl.

Comparative Synthesis Example 4 A latex of Exemplified Compound (7) was synthesized using the same method as in Synthesis Example 1 for Preparation of I Synthesis.

Comparative Synthesis Example 5 In the present invention, the latex of exemplified compound (9) was synthesized by the same method as the synthesis method of Comparative Synthesis Example 1 above. In the present invention, the photographic constituent layer refers to a photographic layer containing a hydrophilic colloid as a binder, such as a photosensitive silver halide emulsion layer, an intermediate layer, a film-retaining layer, a filter layer,
Examples include an antihalation layer or a backing layer, and the photographic element of the present invention means a light-sensitive material obtained by coating the above-mentioned photographic S layered support.

The latex with a different phase structure of the present invention is used by being included in at least one of the above-mentioned photographic constituent layers, and is particularly compatible with gelatin and has excellent coating properties. It not only improves the physical properties, such as film adhesion and dimensional stability, but also has good photographic properties, eliminates concerns about desensitization and capri, and suppresses stain.

When the latex with a different phase structure according to the present invention is contained in the layer forming the base layer, one type or two or more of the above-mentioned latexes may be added in an amount of 5 to 100 parts by weight of the latex based on 100 parts by weight of the hydrophilic colloid layer. % and can be applied as a layer by the method of Koga I.

The silver halide emulsions used in the photographic elements of this invention and 1-
Then, for example, silver halide grains such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. are mixed with hydrophilic polymer bis:・
What is dispersed in the goo is violet. Examples of the binder include gelatin, gelatin IF form, colloidal albumin, zelkova, gum arabic, alginic acid,
Contains acetyl Jjj-.

Cellulose U4 such as cellulose acetate hydrolyzed to 19-26%, acrylamide, imidized polyacrylamide, casein, urethane carboxylic acid groups or cyanoacetyl groups such as vinyl-alcohol, vinyl cyanoacetate copolymers. Vinyl alcohol polymers, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by tonopolymerization of proteins or saturated acylated proteins and monomers having vinyl groups, etc. can be used.

Further, the silver halide emulsion can be sensitized using an appropriate chemical sensitizer. Chemical sensitizers to be used include, for example, sulfur sensitizers such as allylthiocarbamide, thiourinol, allyl isothiocyanate, sodium thiosulfate, and cystine, active and inactive selenium sensitizers, and potassium sensitizers. Gold compounds such as chloroaurate, auric trichloride, potassium auric thiocyanate, 2-aurothiabenzothiazole methyl chloride, palladium compounds such as ammonium chloroparadate, sodium chloropalladite, platinum compounds such as potassium chloroaurate, and Examples include sheet metal sensitizers such as ruthenium compounds, ronram compounds, and iridium compounds.

This chemical sensitizer can be used once a month, even if it is used in one glaze or in a mixture of two or more types.

Furthermore, the silver halide emulsion can be sensitized using an appropriate reduction sensitizer. Examples of the reduction sensitizer used include triazoles, imidazoles, azaindenes, benzothiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof, or thioether type or quaternary ammonium salts. sensitizing compounds of type or polyalkylene oxide type. Further, the silver halide emulsion includes:
For example, wetting agents such as glycerin, hydroxyalkanes such as 1,5-bentanediol, esters such as ethylene bisglycol, bisethoxydiethylene glycol saczonate, and water-separable polymeric polymer compounds obtained by emulsion polymerization. , plasticizers and the like. Furthermore, hardening agents such as ethyleneimine, lTh compounds, vinyl sulfone compounds, dioxane rods, dicartanyl saccharide, dicartanyl chloride, methanesulfonic acid vinylester, saponin, sulfosuccinates, etc. Photographic additives such as auxiliaries, fluorescent whitening agents, interfacial gamma aging agents, and antistaining agents can be contained. In addition, this halogenated milk j1 may be optically sensitized using a 7-anine dye, a merocyania dye, a composite 7-anine dye, or the like. However, a unique coupler such as a colorless coupler or a colored coupler may be included.

Supports used in the photographic elements of this invention include hydrophobic films or sheets such as cellulose triacetate films, polyester films such as polyethylene terephthalate, polycarbonate films, polystyrene films, polyolefin films, polyethylene laminate papers, and the like.

In the photographic element 9 of the present invention, a silver halide photographic light-sensitive material using a hydrophobic film or sheet as a support is effectively used.
μ for i. These photosensitive materials include various intermediate and finished products such as general black and white photosensitive materials, special black and white photosensitive materials, color photosensitive materials, printing photosensitive materials, and X@ photosensitive materials. It will be done. Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 50g of alkali-treated gelatin for photography and 66g of ion-exchanged water
After adding 00M and carving, the mixture was heated to 40°C and dissolved.

Add 2ON of 10% saline to this solution and make the total 900ml.
I finished it in j. 50 TLl of the above gelatin solution (gelatin 2
．． 09) at 40℃ under stirring at ゛C, resin component content i
, o g were added to each latex listed in Table 1, and the compatibility with seratin, that is, the presence or absence of aggregates, and the transparency of the gelatin solution were visually determined. Regarding the transparency of the gelatin solution, its quality was judged by dividing it into the following four stages.

(1) Almost the same transparency as heavy gelatin solution...
◎(2) It's a little cloudy...
・Q(3) The light is cloudy...
...△(4) Resin components are separated "°゛°°゛×Table 1 As is clear from the results in the above table, the monomer composition of the core part and shell part according to the present invention is different from the seeded 7F method. It has been found that the heterophasic latex of the present invention obtained by polymerization has excellent gelatin compatibility without forming aggregates in gelatin or deteriorating the transparency of gelatin. ).On the other hand, the latex according to the comparative synthesis example lacked gelatin compatibility.

Example 2 A silver iodobromide gelatin high-sensitivity emulsion containing 2 mol% of silver iodide was
After chemical sensitization using a gold sensitizer and a sulfur sensitizer during the second ripening, 4-hydro-? C6-methyl-1+3+3a, 7-titrazaindene compound and mucohalogenic acid as a hardening agent, saponin as a coating aid and the following compound as a sensitizing dye were added.
01n9/7? After addition, the exemplified compounds (11, (41, (61) and (9
) was added to 5 so that the latex resin component was 20 M 1% with respect to gelatin to prepare an emulsion solution, and to the remaining two, Comparative Synthesis Examples (11 and (31k 7JO Then, emulsions were prepared in the same manner, and the resulting six emulsions were dropped onto a subbing-treated polyethylene terephthalate film support.
The film was dried to a dry film thickness of 8 microns.

(Sensitizing dye) C, H.

Next, on the silver iodobromide emulsion layer prepared above, 2% gelatin liquid containing a hardening agent and a coating aid in the following composition ratio is applied so that the dry film thickness is 1.5 microns. Like a fallen cloth,
After drying and applying a protective layer, C photographic elements were obtained, designated as Samples 1-6.

(Composition of Retentive Layer) After exposing Samples 1 to 6, they were developed using a dust image solution having the composition F for 3 minutes at a temperature of 0.degree. C., fixed, washed with water, and dried.

(4) 1-I1 νV ML Formation,) Looking at the residual color of the photographic element processed in the above manner, the # degree of the last exposed area was defined with green light using a cherry density needle. ,
The results obtained are shown in Table 2.

Table 2 In the test method according to this example, it is said that there is no problem with residual color if the green light density is 0.02 or more. )
, +41, +61 and (9) showed good results with no residual color, but compared to
It was found that the comparative latex according to the example exhibited color retention. Furthermore, each of the above samples was exposed and developed in accordance with JIS standards, and the sensitivity and fog were measured. Is latex made up of U-indicated compounds? When used, good photographic properties were exhibited without a decrease in sensitivity or the generation of capri, but with the comparative latex, desensitization or generation of capri was observed.

Example: The anti-halation coating solution and the silver chlorobromide emulsion were divided into 6 parts, and exemplified compounds according to the present invention +21, (31.

(5) The latex obtained by seed polymerization from (8) and the latex obtained from Comparative Synthesis Example (4) were each prepared so that the latex resin component was % of the gelatin. , coated on a subbed polyethylene terephthalate film support,
After drying, an antihalation layer and a silver halogen emulsion layer were provided.

Next, add 30% of each latex resin component to gelatin.
Samples 7 to 12 were obtained by providing a protective layer so that the weight ratio and the dye content were 2 oomy/rrt.

(The above-mentioned samples containing dyes were tested for degree of curl and performance against dry film formation as described above.

(Curling degree test) Each of the above samples was made into a circular sample with a diameter of 100 mm.
After standing for 3 hours in an atmosphere of 20% RH, the degree of curl was measured. Curl degree is the radius of curvature of the curve expressed in meters.

(Test with dry membrane) The above sample was kept in an air-conditioned room at 23°C and 80% aH for 1 it per day.
After h', the emulsion surface of the sample was cut at 45 degrees with a razor, and a cellophane adhesive tape was pressed onto it. If the residual rate is 80% or more, it is judged as good adhesion.

The results of each of the above tests are shown in Table 3 below.

From the results in the table above, samples 7 to 11 in which the latex according to the present invention was contained in the photographic constituent layer all had a small degree of curl and had good dimensional stability. It can be seen that it has excellent properties and also has good dry film adhesion. On the other hand, it is clear that those using C-ratio soft latex are inferior in dimensional stability and dry resetting. Furthermore, the transparency of the coating solutions used for the antihalation layer, silver halide emulsion layer, and protective layer containing the latex according to the present invention was significantly superior to that using the comparative latex.

Next, after exposing the above samples 7 to 12, CDL-27
1 (Konishi Roku Photo Industry Co., Ltd.) developer was used for 1 minute and 30 seconds at a heated temperature.In order to reduce the residual color of each sample obtained by washing with W, washing with water, and drying. The density of the unexposed area was measured with the blue light of Sakura #Keikei (1-).The results are shown in Table 4 below.

In the measurement method in the fourth example, the blue light density is 0.02.
If it is below, there is no practical problem, so all the samples according to the present invention showed good results in terms of residual color. However, it was also found that the samples using the comparative latex had residual color and were not good quality.

In addition, the above samples are based on JIS standards/[! The 61M measurements also revealed that all the samples according to the invention were photographically customizable, especially with respect to sensitivity and fog, with no bad f#.

Effects of the Elderly The latex with a different phase structure obtained by the undobo method according to the present invention has improved film transparency, dimensionality, dry film adhesion, and Photographic properties and residual colors tI, S are significantly improved.

Agent Yoshimi Awahara

Claims (1)

[Claims] In a photographic element having at least one photographic constituent layer on a support, in at least IN of the photographic constituent layer, a polymer outside the particles has a greater swelling property than a polymer inside the particles, and A photographic element characterized in that the polymer contains a non-cationic heterophasic latex.