JP3464326B2 - Silver halide emulsion, method for producing the same, and silver halide photographic material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver chloride-containing tabular emulsion having a {100} plane as a principal plane and a method for producing the same. The present invention also relates to a silver halide photographic light-sensitive material using these emulsions, particularly a medical X-ray photographic light-sensitive material.

[0002]

2. Description of the Related Art It is widely known in the art that a high aspect ratio tabular emulsion has a high covering power (concentration of developed silver / amount of coated silver), and there is a need for higher aspect ratio. Is high. Further, in view of speeding up processing and reducing replenishment, a silver halide photographic light-sensitive material containing an emulsion having a high silver chloride content is required.

A method for forming tabular grains having the {100} plane as the principal plane is described in, for example, JP-A-5-204073.
U.S. Pat. No. 4,063,9.
No. 51, No. 4,386,156, No. 5,275.
930, 5,264,337, 5,29
No. 2,632. In these patents, particularly in the formation of silver chlorobromide-based {100} tabular grains, the formation of {100} tabular nuclei is described, for example, in the presence of Cl ions and a trace amount of I ions with Ag ions and Cl ions or Cl ions. A method of performing double jet addition of I ions (trace amount), or by forming AgCl microcrystal nuclei in advance and then immediately adding Ag ions and Br or Br and Cl ions to create a gap in the halogen composition to achieve anisotropic growth. A method of forming the {100} flat plate nuclei is described. Further, in the usual particle forming method, following the formation of such a nucleus,
The steps such as physical ripening and further growth are taken. In these growth processes, the temperature is usually raised to increase the growth rate.

[0004]

The problem to be solved by the present invention is to provide a high silver chloride {100} tabular emulsion having a high aspect ratio and excellent monodispersity. Another problem to be solved by the present invention is to use a silver halide photographic light-sensitive material excellent in rapid processing property and low replenishment resistance at the time of processing by using the above-mentioned emulsion, especially medical X-Ray.
To provide a photographic light-sensitive material.

[0005]

In order to attain a high aspect ratio and monodispersion in the formation of silver chlorobromide-based {100} tabular grains, the present inventors are very important as follows. I found a thing. That is, (1) following the introduction of a halogen gap (formation of heterogeneous halogen nuclei), physical ripening-before the growth process, a step of depositing a silver halide that is more soluble than the silver halide that has been formed up to that point, Stabilization of {100} plate nuclei, resulting in a large number of uniform nuclei. (That is, nucleation including this stabilization step should be performed.) (2) In the growth, low supersaturated growth promotes anisotropic growth, and for that purpose, growth at a high temperature is preferable. (3) Further, at the time of growth, growth in the presence of fine particles promotes anisotropic growth, but if the particle size distribution of the fine particles is large, the anisotropic growth decreases. Etc.

JP-A-5-204073 and JP-A-6-5
936, US Pat. Nos. 5,275,930 and 5,5
Nos. 264,337 and 5,292,632 relate to {100} tabular grains having a high silver chloride content, but the deposition of silver halide before ripening is a monodispersion of {100} tabular nuclei. It was completely unexpected that it was important for the stabilization of nuclei, the stabilization of nuclei, and the formation of high aspect ratio {100} flat plate nuclei. It was also unexpected that it was important to carry out the deposition within 10 'after the formation of the nucleus having a halogen gap (that is, before the aging progressed). Further, Japanese Patent Application Laid-Open No. 6-5936 describes grain growth by adding fine grains. In the process of growing a {100} silver chlorobromide flat plate, the degree of monodispersion of fine grains is to promote anisotropic growth or to form monodisperse grains. What's important to me is that it is totally unexpected. That is, the present inventors have found that the above-mentioned problems can be solved by the following method. (1) The main plane with a silver chloride content of 10 mol% or more is {10
In a tabular silver halide emulsion having an average aspect ratio of 2 or more consisting of 0} planes, it corresponds to 1 mol% or more of the total silver amount during the grain formation process, after the introduction of a halogen gap during nucleation and before the growth process. A silver halide emulsion characterized in that a certain amount of silver ion is added. (2) The silver halide emulsion according to the above (1), wherein the silver ions are added within 10 minutes after the introduction of the halogen gap during the nucleation. (3) The silver halide emulsion according to the above (1) or (2), wherein the temperature during nucleation and the temperature during grain growth are different by 20 ° C. or more. (4) The main plane with a silver chloride content of 10 mol% or more is {100}
In a tabular silver halide emulsion having an average aspect ratio of 2 or more, the tabular silver halide emulsion has a coefficient of variation of grain size of 1 in the growth process after nucleation during grain formation.
A silver halide emulsion characterized by being grown in the presence of a fine grain emulsion of 5% or less. (5) The main plane with a silver chloride content of 10 mol% or more is {100}
In the grain formation process of a tabular silver halide emulsion having an average aspect ratio of 2 or more consisting of planes, an amount of 1 mol% or more of the total amount of silver is introduced after the introduction of the halogen gap during nucleation and before the growth process. A method for producing a silver halide emulsion, which comprises adding silver ions. (6) The method for producing a silver halide emulsion according to (5), characterized in that the silver ions are added within 10 minutes after the introduction of the halogen gap during nucleation. (7) The method for producing a silver halide emulsion according to (5) or (6), wherein the temperature during nucleation and the temperature during grain growth are different by 20 ° C. or more. (8) The main plane with a silver chloride content of 10 mol% or more is {100}
In the grain formation process of a tabular silver halide emulsion having an average aspect ratio of 2 or more, the tabular silver halide emulsion is a fine grain emulsion having a grain diameter variation coefficient of 15% or less in the growth process after nucleation. A method for producing a silver halide emulsion, which comprises growing in the presence of (9) A silver halide photographic light-sensitive material having a layer containing the silver halide emulsion described in any one of (5) to (8) on at least one side of a support. (10) A silver halide photographic light-sensitive material having a layer containing the silver halide emulsion described in (1) to (4) on both sides of a support.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION A tabular silver halide emulsion of the present invention having a silver chloride content of 10 mol% or more and a main plane of {100} planes and an average aspect ratio of 2 or more (hereinafter referred to as {100 of the present invention. } The tabular emulsion containing silver chloride) and its preparation method will be described in more detail below. {100} of the present invention
The grain preparation process of silver chloride-containing tabular emulsion is roughly classified as follows.
It consists of a) nucleation step, b) ripening step and c) grain growth step. The nucleation step is a step of forming fine silver halide grains (nuclei) by adding silver ions and halogen ions, and the nucleation step of the present invention is further subdivided into a-1) a nucleation step, a- 2) Halogen gap introduction step and a-3) Stabilization step. (2) The step of introducing a halogen gap is the addition of a halogen (for example, Br) different from the halogen (for example, Cl) that constitutes the nucleus generated in (-1), so that a heterogeneous mixed crystal of silver halide is obtained. Is a step of forming. Although a halogen gap is introduced into the nucleus by forming a heterogeneous mixed crystal in the steps a-1) and a-2), a-1) and a-2)
In addition to the method of performing the steps in this order, a-1) and a-
It is also possible to simultaneously form the step 2) as one step to form a heterogeneous mixed crystal. For example, a water-soluble solution containing silver ions and an aqueous solution containing two kinds of halogen ions are rapidly added and mixed in a short time to form a heterogeneous mixed crystal of silver halide. Here, the heterogeneous mixed crystal of silver halide refers to a mixed crystal of silver halide having uneven distribution of two kinds of halogen ions in the grain.

A technique relating to tabular grains having a high silver chloride content and having a {100} plane as a main plane is disclosed in JP-A-5-2040.
73, JP-A-6-5936, US Pat. No. 5,27.
No. 5,930, No. 5,264,337, No. 5,2
92,632 and the like. As the nucleation method in the present invention, the nucleation method described in these patent documents or the like can be arbitrarily used. Incidentally, these patent documents disclose methods for forming mixed crystals or gaps of different halogens during nucleation in the form of AgCl / AgI, AgCl / AgBr, etc. Are formed.

In the present invention, silver ions are added after the introduction of the halogen gap and before the growth process. Silver ion is 1 mol% or more, preferably 1 mol% or more and 10 mol% or less, more preferably 2 mol% or more and 8 mol% of the total silver amount.
It is the following. In the present invention, the addition time of silver ions is preferably 1 second or more and 10 minutes or less, more preferably 5 seconds or more and 5 minutes or less, particularly preferably 15 seconds after the introduction of the halogen gap.
It is preferably not less than 2 seconds and not more than 3 minutes. A-3) Stabilization process The nucleus is formed by introducing a halogen gap into the nucleus in the previous step and then adding silver ions and halogen ions to deposit silver halide on the nucleus into which the halogen gap has been introduced. Is a step of stabilizing. The most preferred embodiment of the present invention is that the amount of silver ions added in the stabilizing step (3-3) is 1 mol% or more of the total silver amount. Especially, the amount of silver ions added in this stabilizing step is 1 mol% of the total amount of silver.
10 mol% or more is preferable and 2 mol% or more is 8 more
It is preferably not more than mol%. In this stabilization process, silver ions or silver ions and halogen ions are added so that a layer having higher solubility (that is, higher Cl content) than the already formed nuclei is deposited. be able to. This stabilization step is preferably within 10 minutes after the introduction of the halogen gap, and particularly preferably within 10 seconds to 5 minutes. Particularly preferred is 10 seconds or more and 3 minutes or less. Further, after this stabilizing step, the growth is started after ripening, but the time until the start of growth is preferably within 30 minutes.

After completion of the nucleation step (a), the temperature of the emulsion of the present invention is raised. The temperature rise depends on the temperature of the emulsion in the reaction vessel. The degree of temperature rise is preferably 10 ° to 45 ° C., 20 ° C. or higher,
It is particularly preferably 20 to 40 ° C. Regarding temperature, the nucleation step is preferably 20 ° to 80 ° C, and 20 to 60 ° C.
Is more preferable, and 25 ° C to 50 ° C is particularly preferable.

Next, b) the aging step will be described. The ripening step is a step of performing physical ripening by raising the temperature after the completion of the nucleation step of b). In a preferred embodiment, no new silver ion is added in this step. This aging step is not essential in the present invention, and it is also possible to immediately raise the temperature after completion of the above-mentioned (a) nucleation step and immediately enter the (c) grain growth step described later. However, in the present invention, it is preferable that b) the aging step be present between the nucleation step of b) and the grain growth step of c). The aging step is preferably performed at 50 ° to 90 ° C, more preferably 55 ° to 85 ° C, and 65 ° to 8 ° C.
0 ° C. is particularly preferred.

Next, the c) grain growth step will be described.
In the step (a), after the completion of the nucleation step, the temperature is raised, and if necessary, (b) the ripening step, and then silver and halogen are newly added to grow silver halide grains. The grain growth step is preferably performed at 50-90 ° C., 55
-85 degreeC is more preferable, and 65 to 80 degreeC is especially preferable. The temperature of the grain growth step of the present invention is preferably 10 ° to 45 ° C. higher than the temperature of the nucleation step of b), 2
It is preferably 0 ° C. or higher, particularly 20 to 40 ° C. high temperature.
In the present invention, this grain growth step is preferably carried out in the presence of fine silver halide grains.

The method of crystal growth (hereinafter referred to as a fine grain emulsion addition method) of the present invention by physical ripening in the presence of fine silver halide grains (fine grains are dissolved and substrate grains grow) will be described below. 0.20μ in this fine grain emulsion addition method
mX diameter or less, preferably 0.15 μm diameter or less, more preferably 0.15 to 0.01 μm diameter AgX fine grain emulsion is added, and substrate particles are grown by Ostwald ripening.
The fine grain emulsion can be added continuously or continuously. The fine grain emulsion can be continuously prepared by supplying the AgNO ₃ solution and the X ^- salt solution in a mixer provided in the vicinity of the reaction vessel, and immediately added to the reaction vessel immediately, or in advance in another vessel. It is also possible to add it continuously or continuously after preparing it in a batch manner. The fine grain emulsion can be added in a liquid form or as a dry powder. It is also possible to mix the dry powder with water immediately before addition to liquefy it and add it. Further, even when the AgNO ₃ solution and the X ^- salt solution are continuously supplied to the reaction solution by the double jet method or the like to grow, the solubility of the system is controlled to constantly form fine particles (re-nucleation), By melting it, {100} tabular grains of the substrate can be grown. However, the coefficient of variation of the average spherical equivalent diameter of the fine particles that coexist with {100} tabular grains during growth is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less.

Regarding the monodispersity of the emulsion of the present invention, considering the monodispersity based on the variation coefficient defined by the method described in JP-A-59-745481, it is preferably 30% or less and 5% or more. It is preferably 25% or less. Particularly when used for a sensitive material having a high contrast, it is preferably 5% or more and 15% or less.
The aspect ratio of the particles of the present invention will be described below. The aspect ratio is a value obtained by dividing the circle equivalent diameter of the projected area by the thickness. The average aspect ratio is a statistical average of aspect ratios of all particles. The number is preferably 2 or more, particularly preferably 5 or more, and further preferably 8 or more 20
It is the following. The particle thickness is defined by the side length of the shortest side of the particle, but the average thickness is 0.5
μm or less is preferable, and 0.3 μm or less is more preferable. Particularly preferably, it is 0.03 μm or more and 0.2 μm or less. When the thickness is small, a high aspect ratio can be achieved in small-sized grains, and thus the covering power (developed silver concentration / developed silver amount of grains) can be easily designed to be high.

The ratio of the lengths of the adjacent sides of the main plane of the particles of the present invention is preferably 1: 3 to 1: 1 on average. This is because if one of the adjacent sides of the main plane is too short (for example, if it is close to the thickness), the aspect ratio does not increase and the covering power also decreases. In the particles of the present invention, the ratio of adjacent side lengths of the main planes is particularly preferably on the average of 1: 2 to 1: 1.

The preferred halogen composition of the emulsion grains of the present invention is that the silver iodide content is 1 mol% or less.
It is particularly preferably 0.5 mol% or less. Further, the silver bromide content is preferably 1 mol% or more and 90 mol% or less,
Particularly preferably, it is 1 mol% or more and 60 mol% or less.

In the silver halide emulsion of the present invention containing at least a dispersion medium and silver halide grains, the total projected area of the silver halide grains is 50% or more, preferably 60% to 9%.
9%, more preferably 70-99%, Cl ^- content 10
It is a tabular grain having a mol% or more, preferably 20 mol% to 99%, more preferably 30 to 90 mol%, still more preferably 40 to 80 mol% and a main plane of {100} plane.

As described above, the emulsion of the present invention is a) after the nucleation step, heated, and if necessary, b) ripened and c).
After the grain growth step, it is washed with water and chemically sensitized.
The emulsion of the present invention is preferably selenium and / or tellurium sensitized. The sensitization of selenium and tellurium will be described. These may be used alone or in combination. Particularly, preferred examples of these compounds and examples of compounds are described in, for example, JP-A-3-116132 and JP-A-5-113635,
5-165136, 5-165137, 5-
This is as described in detail in No. 134345 and the like.
Particularly preferred selenium sensitizers include, for example, compounds represented by the general formula (I) or (II) of JP-A-5-165137 and compound examples I-1 described therein.
To I-20 and II-1 to II-19 can be mentioned. Regarding the tellurium sensitizer, the compounds represented by the general formulas (IV) and (V) of JP-A-5-134345 and the compound examples IV-1 to IV-22 and V-1 to V-16 described therein.
Can be mentioned.

The photosensitive material of the present invention is not particularly limited, but PEN (polyethylene naphthalate) can be preferably used. Polyethylene as PEN
2,6-naphthalate is preferred. The polyethylene-2,6-naphthalate referred to in the present invention may be any polyethylene-2,6-naphthalene dicarboxylate whose repeating structural unit is substantially composed of ethylene-2,6-naphthalenedicarboxylate units, and polyethylene-2, which is not copolymerized, Not only 6-naphthalenedicarboxylate but also 10% or less of the number of repeating structural units,
Preferably, 5% or less includes a copolymer modified with other components, and a mixture or composition with other polymers. Polyethylene-2,6-naphthalate is synthesized by combining naphthalene-2,6-dicarboxylic acid or a functional derivative thereof, and ethylene glycol or a functional derivative thereof in the presence of a catalyst under appropriate reaction conditions. The polyethylene-2,6-naphthalate referred to in the present invention includes polyethylene-2,6-naphthalate.
Before the completion of the polymerization of 6-naphthalate, one or more appropriate third component (modifying agent) is added.

It may be a copolymer or a mixed polyester. Suitable third component is a compound having a divalent ester-forming functional group such as oxalic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,7-dicarboxylic acid, succinic acid, diphenyl ether dicarboxylic acid. Such as dicarboxylic acids, or lower alkyl esters thereof, oxycarboxylic acids such as p-oxybenzoic acid, p-oxyethoxybenzoic acid, or lower alkyl esters thereof, or dihydric alcohols such as propylene glycol and trimethylene glycol. Compounds. Polyethylene-2,6-naphthalate or a modified polymer thereof is obtained by blocking the terminal hydroxyl group and / or carboxyl group with a monofunctional compound such as benzoic acid, benzoylbenzoic acid, benzyloxybenzoic acid or methoxypolyalkylene glycol. Or a compound modified with a trifunctional or tetrafunctional ester-forming compound such as glycerin or pentaerythritol in an extremely small amount within a range where a substantially linear copolymer is obtained.

The photosensitive material of the present invention is particularly effective when it has at least one silver halide emulsion layer on each side of the support. When the present invention is applied to a light-sensitive material having an emulsion on both sides of such a support, in addition to the effects described above, it is characterized in that an image having high image quality and high sharpness can be obtained. It also has the unexpected effect of not contaminating the tank or rollers. As the chemical sensitization method, a gold sensitization method using a so-called gold compound, a sensitization method using a metal such as iridium, platinum, rhodium or palladium, a sulfur sensitization method using a sulfur-containing compound, or a reduction sensitization method using a tin salt, polyamine or the like is used. Method, a sensitization method with a selenium compound, a sensitization method with a tellurium compound, or a combination of two or more of these. The silver amount of the light-sensitive material of the present invention is preferably 0.5 g / m ^{2 to} 5 g / m ² (on one side), more preferably 1 g / m ^{2 to} 3.4 g / m ² (on one side). For proper rapid processing, it is preferable not to exceed 5 g / m ² .

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, for example, JP-A-2-6853.
It is possible to use those described in the following relevant portions of Japanese Patent Publication No. Item This section 1. Silver halide emulsion and JP-A-2-68539, page 8, lower right column, lower column, 6 from its manufacturing line, to page 10, upper right column, 12th column. 2. Chemical sensitization method, page 10, upper right column, line 13 to lower left column, line 16 3. Antifoggant / stabilization, page 10, lower left column, line 17 to page 11, upper left column, line 7 agent, and page 3, lower left column, line 2 to page 4, lower left column. 4. Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column. 5. Surfactant / antistatic, page 11, upper left column, line 14 to page 12, upper left column, line 9 antistatic agent. 6. Matting agent / slip agent ・ From page 12, upper left column, line 10 to upper right column, line 10 Plasticizer, page 14, lower left column, line 10 to lower right column, line 1 7. Hydrophilic colloid, page 12, upper right column, line 11 to lower left column, line 16 8. Hardener, page 12, lower left column, line 17 to page 13, upper right column, line 6 9. Support, page 13, upper right column, lines 7 to 20. 10. Dyes / mordanting agents, page 13, lower left column, line 1 to page 14, lower left column, line 9

As a method of forming an image using the light-sensitive material of the present invention, there is a method of forming an image in combination with a phosphor having a main peak at 400 nm or less. More preferably, a method of forming an image by combining with a phosphor having a main peak at 380 nm or less is preferable. A screen having a main emission peak at 400 nm or less is disclosed in JP-A-6-11804,
The screen described in WO93 / 01521 is used, but the screen is not limited to this. The emission wavelength of the phosphor preferably used in the present invention is 400 nm or less, more preferably 370 nm or less. As a typical phosphor,
M'phase YTaO ₄ alone or Gd, Bi, Pb, C
e, Se, Al, Rb, Ca, Cr, Cd, Nb, etc. added compounds, LaOBr added with Gd, Tm, Gd and Tm, Gd and Ce, Tb compounds, HfZ
r oxide alone or a compound to which Ge, Ti alkali metal or the like is added, Y ₂ O ₃ alone or a compound to which Gd or Eu is added, a compound to which Gd is added to Y ₂ O ₂ S, or a matrix of various phosphors Gd , Tl, and Ce as activators. Particularly preferred compounds include
M ′ phase YTaO ₄ alone or a compound added with Gd, Sr, a compound added with Gd, Tm, Gd and Tm to LaOBr, a compound added with an oxide of HfZr or an alkali metal such as Ge, Ti. The particle size of the phosphor is preferably 1 μm or more and 20 μm or less, but can be changed depending on the required sensitivity and manufacturing problems. The coating amount is preferably 400 g / m ² or more and 2000 g / m ² or less, but it cannot be unequivocally determined depending on the required sensitivity and image quality. A single intensifying screen may be used to provide a particle size distribution from the vicinity of the support to the surface. In this case, it is generally known to increase the size of particles on the surface. Space filling of phosphor is 40%
Or more, preferably 60% or more.

When the phosphor layers are provided on both sides of the photosensitive material for photographing, the phosphor coating amount on the X-ray incident side and the opposite side can be changed. It is generally known to reduce the coating amount of the intensifying screen on the X-ray incident side, especially when a high-sensitivity system is required because of shielding by the intensifying screen on the X-ray incident side. The support used for the screen used in the present invention includes paper, metal plate, polymer sheet, and the like.
Generally, a flexible sheet such as polyethylene terephthalate is used. The support may be added with a reflecting agent or a light absorbing agent, or may be provided as a separate layer on the surface, if necessary. If necessary, the surface of the support may be slightly uneven, or an adhesive layer for increasing the adhesion to the phosphor layer or a conductive layer may be provided as an undercoat. As the reflecting agent, zinc oxide, titanium oxide,
Examples thereof include barium sulfate, but titanium oxide and barium sulfate are preferable because the emission wavelength of the phosphor is short. The reflecting agent may be present not only in the support or between the support and the phosphor layer, but also in the phosphor layer. When it is made to exist in the phosphor layer, it is preferably unevenly distributed near the support. Examples of the binder used in the screen of the present invention include proteins such as gelatin, polysaccharides such as dextran and corn starch, and natural polymer substances such as gum arabic; polyvinyl butyral, polyvinyl acetate, polyurethane, polyalkyl acrylate, vinylidene chloride, nitro. Examples thereof include synthetic polymeric substances such as cellulose, fluorine-containing polymers, polyesters, and mixtures and copolymers thereof. As a preferable binder, the basic performance is that it has high transmittance for light emitted from the phosphor. In this respect, gelatin, corn starch, an acrylic polymer, a fluorine-containing olefin polymer, a polymer containing a fluorine-containing olefin as a copolymer component, a styrene / acrylonitrile copolymer and the like can be mentioned. These binders may have functional groups that are crosslinked by the crosslinking agent. Further, depending on the required image quality performance, an absorber for the light emitted from the phosphor may be added to the binder, or a binder having a low transmittance may be used. Examples of the absorber include pigments, dyes, and ultraviolet absorbing compounds. The ratio of the phosphor to the binder is generally 1: 5 to 5 in volume ratio.
It is 0: 1, preferably 1: 1 to 5: 1. The ratio of the phosphor to the binder may be uniform or non-uniform in the thickness direction. The phosphor layer is usually formed by a coating method using a coating liquid in which the phosphor is dispersed in a binder solution. Examples of the solvent for the coating liquid include water or alcohols, chlorine-containing hydrocarbons, organic solvents such as ketones, esters and ether aromatic compounds, and mixtures thereof. In the coating liquid, a dispersion stabilizer such as phthalic acid, stearic acid, caproic acid and a surfactant for phosphor particles, phosphoric acid ester, phthalic acid ester, glycolic acid ester,
A plasticizer such as polyester or polyethylene glycol may be added.

The screen used in the present invention may be provided with a protective layer on the phosphor layer. As the protective layer, a method of coating on the phosphor layer, or a method of separately preparing and laminating a protective layer film is generally used. In the coating method, the phosphor layer may be coated at the same time, or the phosphor layer may be coated and dried before coating. The protective layer may be the same substance as the binder of the phosphor layer, or may be a different substance. Examples of the substance used for the protective layer include the substances listed as the binder for the phosphor layer, as well as cellulose derivatives, polyvinyl chloride, melamine, phenol resins and epoxy resins.
Preferred materials include gelatin, corn starch, acrylic polymers, fluorine-containing olefin polymers, polymers containing fluorine-containing olefins as copolymer components, and styrene / acrylonitrile copolymers. The thickness of the protective layer is generally 1 μm or more 2
It is preferably 0 μm or less and 2 μm or more and 10 μm or less, and 2
More preferably, it is not less than μm and not more than 6 μm. It is preferable to emboss the surface of the protective layer of the present invention. Further, a matting agent may be present in the protective layer, or a substance having a light-scattering property for light emission depending on the image to be obtained, such as titanium oxide may be present. A surface slipperiness may be imparted to the protective layer of the screen used in the present invention. Examples of preferable slip agents include polysiloxane skeleton-containing oligomers and perfluoroalkyl group-containing oligomers. You may give electroconductivity to the protective layer of this invention. Examples of the conductivity imparting agent include white and transparent inorganic conductive substances and organic antistatic agents. Preferred inorganic conductive materials include ZnO powder, whiskers, and Sn.
Examples include O ₂ and ITO.

The photographic material of the present invention can be preferably developed with a developing solution containing ascorbic acid and its derivative as a developing agent. The replenishment amount of the processing solution is preferably 10 cc / 4 or less, more preferably 5 cc / 4.
It is less than or equal to off, and the effect is significant. Examples of ascorbic acid or a derivative thereof used in such a developing solution include compounds represented by the general formula (I) of JP-A-5-165161 and compound examples I-1 to I-8 described therein.
II-9 to II-12 are particularly preferable. The ascorbic acids used in the developer used for the development processing of the light-sensitive material of the present invention include endiol type (Endiol) and enaminol type (En
aminol), enediamine type (Endiamin), thiol enol type (Thiol-Enol) and enamine-thiol type (Enam
on-Thiol) is generally known as a compound. Examples of these compounds are described in U.S. Pat. No. 2,688,549 and JP-A-62-237443. Methods for synthesizing these ascorbic acids are also well known, and are described in, for example, Tsujio Nomura and Hirohisa Omura, "Chemistry of Reductone" (Uchida Lao Tsurugai Shinsha 1969). Ascorbic acids can also be used in the form of alkali metal salts such as lithium salt, sodium salt and potassium salt. These ascorbic acids are contained in an amount of 1 to 100 per liter of the developing solution.
It is preferable to use g, preferably 5 to 80 g.

Particularly, it is preferable to use 1-phenyl-3-pyrazolidones or p-aminophenols together with ascorbic acid as an auxiliary developing agent. As 3-pyrazolidone-based auxiliary developing agents, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1 -Phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Trilyl-4,4-dimethyl-3-pyrazolidone, 1-p
-Tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. As the p-aminophenol-based auxiliary developing agent, N-methyl-p-aminophenol,
p-aminophenol, N- (β-hydroxyethyl)
-P-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p
-Benzylaminophenol, etc., but among them N-
Methyl-p-aminophenol is preferred. The auxiliary developing agent is usually preferably used in an amount of 0.001 mol / liter to 1.2 mol / liter.

Alkali agents used for setting the pH of the developer include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate. Be done. As a preservative of sulfite used in the developer, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite,
Examples include sodium bisulfite and potassium metabisulfite. The sulfite content is 0.01 mol / liter or more, and particularly 0.1.
02 mol / liter or more is preferable. The upper limit is 2.
It is preferably up to 5 mol / liter. For other developers, LFA Mason "Photographic Processing Chemistry", published by Focal Press (19
66), pages 226-229, US Pat. No. 2,193,
015, 2,592,364, JP-A-48-64.
You may use what is described in No. 933 grade.

Generally, a boric acid compound (for example, boric acid, borax) is often used as a pH buffering agent in a developing solution, but a boric acid compound is substantially contained in a developing solution containing ascorbic acid. It is preferable not to contain it.

As a method for preparing a processing agent used for processing the light-sensitive material of the present invention, the methods described in JP-A-61-177132, JP-A-3-134666 and JP-A-3-67258 can be used. . As a method for replenishing the developing solution, the method described in JP-A-5-216180 can be used. When developing in dry to dry for 100 seconds or less, a roller made of a rubber material as described in JP-A-63-151943 is used at the outlet of the developing tank in order to prevent development unevenness peculiar to rapid processing. It is applied to a roller, and as described in JP-A-63-151944, the discharge flow rate for stirring the developing solution in the developing solution tank is set to 10 m / min or more. As described in the specification of Sho 63-264758,
It is more preferable to stir more strongly than during standby at least during the development process.

The photosensitive material of the present invention is not particularly limited as a photographic photosensitive material, and general black and white photosensitive materials and color photographic photosensitive materials are mainly used. In particular, photographic materials for laser light sources, general photographic paper sensitive materials, printing sensitive materials, direct medical X-ray sensitive materials, indirect medical X-ray sensitive materials, CRTs.
It can also be used as an image recording light-sensitive material, a microfilm, a general photographing light-sensitive material (including a reversal light-sensitive material), and the like.

[0032]

【Example】

Example 1 Preparation of (100) tabular emulsion 1-1 1582 ml of gelatin aqueous solution (gelatin-1) was placed in a reaction vessel.
(Deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) 19.5 g, HNO ₃ 1N liquid 7.
Containing 8 ml, pH 4.3, NaCl-1 solution (100 ml)
13 ml of NaCl (containing 10 g) was added and the temperature was adjusted to 4
While keeping the temperature at 0 ° C, Ag-1 solution (100 mL of AgNO
₃ including 20 g) and X-1 solution (NaCl in 100ml
(Including 7.05 g) was simultaneously mixed and added at 62.4 ml / min in 15.6 ml portions. After stirring for 3 minutes, Ag-2 solution (1
AgNO ₃ containing 2g) and X-2 solution in 100 ml (100
1.4g of KBr in ml) 80.6ml / min 2
Simultaneous mixing of 8.2 ml each. After stirring for 3 minutes, Ag-
Solution 1 and solution X-1 were simultaneously mixed and added at a rate of 62.4 ml / minute and 46.8 ml each. After stirring for 2 minutes, gelatin aqueous solution 20
3 ml (gelatin-113 g, NaCl 1.3 g, pH
NaOH 1N solution is included in order to adjust to 6.5), and p
After setting Cl to 1.8, the temperature is raised to 75 ° C. and pCl
And then aged for 42 minutes. An AgCl fine grain emulsion (average particle diameter 0.1 μm) was added for 20 minutes at an addition rate of AgCl of 2.68 × 10 ⁻² mol / min. After addition 1
After aging for 0 minutes, a precipitating agent was added, the temperature was lowered to 35 ° C., and the precipitate was washed with water. Add gelatin aqueous solution and p at 60 ℃
Adjusted to H6.0. A transmission electron micrograph image (hereinafter referred to as TEM) of the particle replica was observed. The resulting emulsion was silver chlorobromide (100) tabular grains containing 0.44 mol% of AgBr based on silver. The shape characteristic values of the particles were as follows. (Total projected area of tabular grains having an aspect ratio larger than 2 / sum of projected areas of all AgX grains) × 100 = a ₁ = 90% (average aspect ratio (average diameter / average thickness) of tabular grains) = a ₂ = 9.3 (average diameter of the tabular grains) = a ₃ = 1.67 .mu.m (average thickness) = a ₄ = variation of 0.18 .mu.m a ₃ factor =
a ₅ = 25%

For this tabular emulsion preparation method, Ag-2
The emulsions 1-2 to 1-6 were prepared by changing the stirring time after simultaneous mixing of the solution and the solution X-2 as shown in Table 1, and the shape characteristic values were similarly obtained. .

[0034]

[Table 1]

[0035]

[Table 2]

After forming the halogen gap (that is, after mixing the Ag-2 solution and the X-2 solution) as in the present invention, Ag-
By adding the 1st solution within 10 minutes,
A tabular emulsion having a high aspect ratio was obtained.

Example 2 Exactly the same as Emulsion 1-1 of Example 1, except that A
Emulsions 2-1 to 2-6 were prepared by changing the addition amounts of Ag-1 solution and X-1 solution after the addition of g-2 / X-2 solution as shown in Table 3. The time required for the addition was changed by changing the addition rate.

[0038]

[Table 3]

The shape characteristic values of the emulsion thus prepared were determined in the same manner as in Example 1. This is shown in Table 4.

[0040]

[Table 4]

As is apparent from Table 4, it is understood that a {100} tabular emulsion having a high aspect ratio can be obtained by adding 1 mol% or more of silver ion to the final silver amount after introducing the halogen gap.

Example 3 Emulsions 3-1 to 3-4 were prepared in exactly the same manner as the emulsion 1-1 of Example 1, except that the temperature after nucleation was changed from 75 ° C. to that shown in Table 5. .

[0043]

[Table 5]

The shape characteristic values of the emulsion thus obtained were determined in the same manner as in Example 1 to obtain the crystals shown in Table 6.

[0045]

[Table 6]

As is apparent from Table 6, the aspect ratio is remarkably increased when the temperature during growth is higher than the temperature during nucleation by 20 ° C. or more.

Example 4 In the grain formation of the emulsion 1-1 of Example 1, the variation coefficient of the average equivalent spherical diameter of the AgCl fine grain emulsion added in the course of growth after ripening for 20 minutes was changed as shown in Table 7. I used the one. The average equivalent spherical diameter (average particle diameter) is approximately 0.1 μm
Met. Emulsions 4-1 to 4-5 were prepared in the same manner as in Example 1 except for the other conditions. Emulsion 2 of Example 2
However, the coefficient of variation of the average equivalent spherical diameter of the added fine grain emulsion during the growth process was changed as shown in Table 7. Also in this case, the average equivalent spherical diameter (average particle diameter) is approximately 0.1 μm.
Met. Emulsions 4-6 to 4-10 were thus prepared.
When the shape characteristic values of the emulsions 4-1 to 4-10 were obtained in the same manner as in Example 1, the results shown in Table 8 were obtained. As shown in Table 8, it can be seen that the smaller the variation coefficient of the average spherical equivalent diameter of the added fine grain emulsion is, the finally obtained {100} tabular grains have a high aspect ratio and a high monodispersity.

[0048]

[Table 7]

[0049]

[Table 8]

Example 5 The emulsions of the present invention prepared in Examples 1 to 4 were mixed with stirring.
Chemical sensitization was performed while the temperature was kept at 0 ° C. First, 10 ⁻⁴ mol of thiosulfonic acid compound-I was added per 1 mol of silver halide, then 1.0 mol% of AgBr fine particles having a diameter of 0.10 μm was added, and thiourea dioxide was further added. 1 × 10 ⁻⁶ mol / mol Ag was added, and the mixture was kept for 22 minutes for reduction sensitization. Next, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added at 3 × 10 ⁻⁴ mol / mol Ag, and sensitizing dye-1 and sensitizing dye-2, respectively. Further calcium chloride was added. Then sodium thiosulfate (6 × 10 ^-6 mol /
Mol Ag) and selenium compound-I (4 × 10 ⁻⁶ mol / mol Ag) were added. Chloroauric acid 1 × 10 ^-5 mol /
Mol Ag and potassium thiocyanate 3.0 × 10 ⁻³ mol / mol Ag were added and after 40 minutes cooled to 35 ° C.
Thus, preparation of the emulsion (chemical ripening) was completed.

[0051]

[Chemical 1]

(Preparation of Emulsion Coating Layer) The following chemicals were added to the chemically sensitized emulsion per mol of silver halide to prepare an emulsion coating solution.・ Gelatin (including gelatin in emulsion) 111 g ・ Dextran (average molecular weight 39,000) 21.5 g ・ Sodium polyacrylate (average molecular weight 400,000) 5.1 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.2 g-Hardener 1,2-bis (vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling rate is 230% -Compound-I 42.1 mg-Compound-II 10.3 g-Compound-III 0.11 g- Compound-IV 8.5 mg-Compound-V 0.43 g-Compound-VI 0.004 g-Compound-VII 0.1 g-Compound-VIII 0.1 g pH adjusted to 6.1 with NaOH

[0053]

[Chemical 2]

[0054]

[Chemical 3]

For the above coating solution, the following UV absorbing dye-
A sample to which the dye emulsion A was added and a sample to which the dye emulsion A was not added so that each of I to III was 10 mg / m ² per side were prepared.

[0056]

[Chemical 4]

(Preparation of Dye Emulsion A) 20 g of each of the above ultraviolet absorbing dyes I to III and the following high boiling point organic solvent
62.8 g of I, 62.8 g of high boiling organic solvent-II and 333 g of ethyl acetate were dissolved at 60 ° C. Next, 65 cc of 5% aqueous solution of sodium dodecyl sulfonate, 94 g of gelatin, and 581 cc of water were added, and the mixture was mixed with a dissolver to 60
Emulsified and dispersed at 30 ° C. for 30 minutes. Next, 2 of the following compound-IX
g and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, using Asahi Kasei's ultrafiltration laboratory module ACP1050, the total amount was concentrated to 2 kg, and 1 g of the compound-IX was added to obtain a dye emulsion A.

[0058]

[Chemical 5]

(Preparation of Coating Solution for Surface Protective Layer) A coating solution for surface protective layer was prepared so that each component had the following coating amount. Gelatin 0.780 g / m ² · Sodium polyacrylate (average molecular weight 400,000) 0.035 g / m ² · Sodium polystyrenesulfonate (average molecular weight 600,000) 0.0012 g / m ² · polymethylmethacrylate (average particle size 3.7μm ) 0.072g / m ² · coating aids -I 0.020g / m ² · coating aids -II 0.037g / m ² · coating aids -III 0.0080 g / m ² · coating aids -IV 0.0032 g / m ²・ Coating aid-V 0.0025 g / m ²・ Compound-X 0.0022 g / m ²・ Proxel (manufactured by ICI Corporation) 0.0010 g / m ² (adjusted to pH 6.8 with NaOH)

[0060]

[Chemical 6]

(Preparation of Support A) Biaxially Stretched Thickness 1
A 75 μm polyethylene terephthalate film was subjected to corona discharge, a first undercoating liquid having the following composition was applied by a wire bar coater so that the applied amount was 4.9 cc / m ^2, and dried at 185 ° C. for 1 minute. . Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene-terephthalate used contained 0.06 wt% of Dye-IV,
A dye-V containing 0.06 wt% was used.

[0062]

[Chemical 7]

* Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158 cc * 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41 cc・ Distilled water 801 cc * The latex solution contains 0.4 wt% of the following compounds as an emulsifying dispersant based on the latex solids.

[0064]

[Chemical 8]

(Preparation of Support B) Support B was prepared in the same manner as Support A, except that Dye-V was not contained.

(Preparation of photographic material) The above emulsion layer and the surface protective layer were combined on the support prepared as described above and coated on both sides by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² . A sample was prepared in this way.

(Evaluation of Photographic Properties) Ultra Vision First Detail (UV screen) made by Du Pont and GRENEX Ortho Screen HR-4 made by Fuji Film Co., Ltd. were used to adhere to both sides, and from both sides,
X-ray sensitometry was carried out by giving an exposure of 0.05 seconds. The exposure amount was adjusted by changing the distance between the X-ray tube and the cassette. After the exposure, automatic developing machine processing was performed with the following developing solution and fixing solution.

(Processing) Automatic processor: CEPROS manufactured by FUJIFILM Corporation
-30 Preparation of concentrate <Developer concentrate> Part agent A Potassium hydroxide 330 g Potassium sulfite 630 g Sodium sulfite 255 g Potassium carbonate 90 g Boric acid 45 g Diethylene glycol 180 g Diethylenetriaminepentaacetic acid 30 g 1- (N, N -Diethylamine) ethyl-5-mercaptotetrazole 0.75 g Hydroquinone 450 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 60 g Water was added to give 4125 ml.

[0069]   Parts agent B     Diethylene glycol 525 g     3,3 'dithiobishydrocinnamic acid 3 g     Glacial acetic acid 102.6g     2-nitroindazole 3.75g     1-phenyl-3-pyrazolidone 34.5 g     750 ml with water

[0070]   Parts agent C     Glutaraldehyde (50wt / wt%) 150 g     Potassium bromide 15 g     Potassium metabisulfite 105 g     750 ml with water

[0071] <Fixer concentrate>     3000 ml ammonium thiosulfate (70 wt / vol%)     Ethylenediaminetetraacetic acid / disodium / dihydrate 0.45 g     Sodium sulfite 225 g     Boric acid 60 g     1- (N, N-diethylamine) -ethyl-5-mercap       Totetrazole 15 g     Tartaric acid 48 g     Glacial acetic acid 675 g     Sodium hydroxide 225 g     Sulfuric acid (36N) 58.5 g     Aluminum sulfate 150 g     6000 ml with water       pH 4.68

(Preparation of Processing Solution) The developer concentrate was filled in a replenishing container for each parts agent. In this replenishing container, the partial containers of the parts agents A, B, and C are connected together by the container itself. Further, the above-mentioned fixing solution concentrate was also filled in the same kind of container. First, 300 ml of an aqueous solution containing 54 g of acetic acid and 55.5 g of potassium bromide was added as a starter in the developing tank. Insert the above treatment agent container upside down and insert it into the perforation blade of the treatment solution stock tank mounted on the side of the automatic processing machine to break the sealing film of the cap and transfer each treatment agent in the container to the stock tank. Filled. These processing agents were filled in the developing tank and fixing tank of the developing machine at the following ratios by operating the pumps installed in the developing machine. Also, every time 8 sheets of the photosensitive material were processed in terms of 4-cut size, the processing agent stock solution and water were mixed at this ratio and replenished in the processing tank of the automatic developing machine.

Developer Parts liquid A 51 ml Parts liquid B 10 ml Parts liquid C 10 ml 125 ml water pH 10.50 Fixer Concentrated liquid 80 ml 120 ml water pH 4.62 The wash tank was filled with tap water.

As a water stain preventive agent, 0.4 g of actinomycetes supported on perlite having an average particle size of 100 μm and an average pore size of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300-mesh nylon cloth. Prepare three pieces filled with water and fungi from the cloth), two of them at the bottom of the washing tank, and one at the bottom of the stock tank for washing water (liquid volume 0.2 liters). I sunk each. Image of processing speed and processing temperature 35 ° C 8.8 seconds Fixing 32 ° C 7.7 seconds Water washing 17 ° C 3.8 seconds Squeeze 4.4 seconds Dry 58 ° C 5.3 seconds Total 30 seconds Replenishing amount Developer 25ml / 10 × 12 inch fixer 25 ml / 10 × 12 inch In the evaluation of sensitometry, the light-sensitive material of the present invention showed good results.

Example 6 The photographic light-sensitive material prepared in Example 5 was processed with the following developer. [Automatic processor processing] The automatic processor was "Fuji X Ray Processor CEPROS-30" manufactured by Fuji Photo Film Co., Ltd., and the total processing time was 30 seconds. The dry blowing temperature was set to 55 ° C. Development Replenisher Solution Part A Potassium hydroxide 18.0 g Potassium sulfite 30.0 g Sodium carbonate 30.0 g Diethylene glycol 10.0 g Diethylenetriamine pentaacetic acid 2.0 g 1- (N, N-diethylamino) ethyl-5-mercaptotetrazole 0.1 g L-ascorbic acid 43.2 g 4 -Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.0 g Water was added to 300 ml.

[0076]   PartB     Triethylene glycol 45.0 g     3,3'-dithiobishydrocinnamic acid 0.2 g     Glacial acetic acid 5.0 g     5. Nitroindazole 0.3 g     1-phenyl-3-pyrazolidone 3.5 g     60 ml with water

PartC Glutaraldehyde (50%) 10.0 g Potassium bromide 4.0 g Potassium metabisulfite 10.0 g Water was added to 50 ml PartA 300 ml, PartB 60 ml and PartC 50 m.
Add water to 1 to make 1 liter and adjust to pH 10.90. Development Starter Solution Acetic acid was added to the above-mentioned development replenisher solution to adjust the pH to 10.20, which was used as a development starter solution.

As the fixing solution, CE-F1 manufactured by Fuji Photo Film Co., Ltd. was used. Development temperature: 35 ° C Fixing temperature: 35 ° C Drying temperature: 55 ° C Replenishment amount (both developer and fixer) 25 ml / 10 x 21 inches (325 ml / m ² ) Each sample 10 x 12 inches size Good performance was obtained by running 600 sheets of the film. It was found that the combination of the light-sensitive material of the present invention and the developing solution was good with no change in sensitivity at the start and in the running solution.

[0079]

Industrial Applicability According to the present invention, it is possible to provide a {100} principal plane high silver chloride tabular emulsion having a high aspect ratio and a high monodispersity.

Continuation of front page (51) Int.Cl. ⁷ identification code FI G03C 1/07 G03C 1/07 1/46 1/46 (56) References JP-A-5-80448 (JP, A) JP-A-5- 204079 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 1/015 G03C 1/035 G03C 1/07

Claims (10)

(57) [Claims] 1. In a tabular silver halide emulsion having a silver chloride content of 10 mol% or more and an average aspect ratio of 2 or more with a major plane of {100} planes, a halogen gap is introduced during nucleus formation during grain formation. A silver halide emulsion characterized in that an amount of silver ion corresponding to 1 mol% or more of the total amount of silver is added before the growth process. 2. 10 after introduction of a halogen gap during nucleation
The silver halide emulsion according to claim 1, wherein the silver ion is added within minutes. 3. The temperature during nucleation and the temperature during grain growth are 2
The silver halide emulsion according to claim 1 or 2, which is different by 0 ° C or more. 4. In a tabular silver halide emulsion having a silver chloride content of 10 mol% or more and a main plane of {100} planes and an average aspect ratio of 2 or more, during the growth process after nucleation during the grain formation process. And the tabular silver halide emulsion is grown in the presence of a fine grain emulsion having a grain diameter variation coefficient of 15% or less. 5. In a grain forming process of a tabular silver halide emulsion having a silver chloride content of 10 mol% or more and a main plane of {100} planes and an average aspect ratio of 2 or more, growth is performed after introducing a halogen gap during nucleation. A method for producing a silver halide emulsion, characterized by adding silver ions in an amount corresponding to 1 mol% or more of the total silver amount before the step. 6. After introducing a halogen gap during nucleation, 10
The method for producing a silver halide emulsion according to claim 5, wherein the silver ion is added within minutes. 7. The temperature during nucleation and the temperature during grain growth are 2
The method for producing a silver halide emulsion according to claim 5, wherein the difference is 0 ° C. or more. 8. In a grain formation process of a tabular silver halide emulsion having a silver chloride content of 10 mol% or more and a main plane of {100} planes and an average aspect ratio of 2 or more, in a growth process after nucleation thereof. A method for producing a silver halide emulsion, characterized in that the tabular silver halide emulsion is grown in the presence of a fine grain emulsion having a variation coefficient of grain diameter of 15% or less. 9. A silver halide photographic light-sensitive material having a layer containing the silver halide emulsion according to claim 1 on at least one surface of a support. 10. A silver halide photographic light-sensitive material having a layer containing the silver halide emulsion according to claim 1 on both sides of a support.