JP2002040596A - Photographic recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a graphic arts recording film having improved covering power at a low production cost. SOLUTION: A red-sensitive photographic recording material with an emulsion layer having a low sliver halide content and a low binder content is disclosed. This material includes a polyester base with an undercoat layer on each of both sides and an antihalation layer on the rear side.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The graphic arts prepress of the present invention (g
improved photographic recording materials for raphic arts prepress).

[0002]

BACKGROUND OF THE INVENTION Photosensitive materials based on silver halide chemistry are used in many applications, such as black and white or color photographic materials for general amateur and professional photography, recording and printing materials for the motion picture industry, and medical diagnostics. Used in materials for image recording and copying. Other specialty materials have been developed for micrographs, non-destructive testing and graphic arts prepress. In the graphic arts reproduction method, the original image, which appears to have a continuous color gradation, is reproduced in the screening method either by optical means in the case of camera film or electronic means in the case of recorder film by the accumulation of a large number of dots. You. Apart from camera and recorder films, there are also so-called contact films that can reproduce the screened image. In some photographic areas, especially in graphic arts prepress films, there is always a demand for lower manufacturing costs, higher covering power, sharper images, and reduced refill rates. This is especially the case for films with large turnovers, such as graphic arts recorder films designed for recording screened images, line drawings and text stored electronically in an image-setter or scanner. .

[0003]

OBJECTS OF THE INVENTION It is an object of the present invention to provide a graphic arts recording film having improved covering power.

[0004] It is another object of the present invention to provide a graphic arts recording film at low manufacturing costs.

[0005]

SUMMARY OF THE INVENTION The above object comprises a polyester support which is subbed with a latex subbing layer on both the front side and the backside, and on the front side, a gelatin subbing layer,
Total silver coverage of at most 3.6 g / m ² of Ag (equivalent to 5.5 g / m ² expressed as AgNO ₃ ) and the sum of at most 1.5 g / m ² of all other solid components This is achieved by providing a photographic recording material for graphic arts that further comprises one or more red-sensitive emulsion layers having a dry coverage, and one or more anti-scratch layers.

In a preferred embodiment, the photographic recording material further comprises on the back side an antihalation layer comprising at most 1.5 g / m ² of gelatin and an antihalation dye.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The various elements of the present invention will now be described in detail.
explain. -Emulsion layer The recording material of the present invention comprises silver halide grains, a binder and other
One or more emulsion layers containing the solid components of
contains. In the most preferred embodiment of the present invention, only one
There is an emulsion layer. Total silver coverage of at most 3.6 g / m^Twoof
Ag (AgNO _Three5.5 g / m^TwoEquivalent to
Is an essential feature of the present invention. All others
The total dry coverage of the solid components is at most 1.5 g / m^Twoso
Certain is another essential feature of the present invention.

The graphic arts recording material preferably contains a majority, preferably between 50 and 95 mol%, most preferably between 60 and 89 mol% of chloride and a small amount of iodide and the remaining An emulsion in which the halide is bromide is used.

One or more photographic emulsions are prepared from soluble silver salts and soluble halides, for example, by P. Glafkides in "Chimie et Physique Photographique", Paul Mon.
"Photograp" by GF Duffin in tel, Paris (1967)
hic Emulsion Chemistry ", The Focal Press, London (1
966), and by VL Zelikman et al "Making
and Coating Photographic Emulsion ", The Focal Pre
ss, London (1966). They can be made by mixing the halide and silver solutions under partially or completely controlled conditions of temperature, concentration, order of addition, and rate of addition. Silver halide can be precipitated according to the single-jet, double-jet, conversion or alternation of these various methods.

Various metal salts or complexes, such as rhodium and iridium additives, can be incorporated into the silver halide emulsion.

The emulsion is prepared in a conventional manner, for example by dialysis.
Desalting can be by flocculation and redispersion or by ultrafiltration.

The photosensitive silver halide emulsion is preferably
For example, see "Chimie et PhysiquePhotographique" above, P
by P. Glafkides in aul Montel, Paris (1967)
"Photographic Emulsion Chemistry" above, The Foca
l "Making and Coating Photographic Emulsion", GF Duffin, Press, London (1966)
VL Zelikman et al in Focal Press, London (1966)
And edited by H. Frieser and Ak
"Die Grundlagen der Photographischen Prozesse, published by ademische Verlagsgesellschaft (1968)
sensitized chemically as described in "Mit Silberhalogeniden". As described therein,
Chemical sensitization can be carried out by aging in the presence of small amounts of sulfur-containing compounds, such as thiosulfates, thiocyanates, thioureas, sulfites, mercapto compounds, and rhodamines. The emulsion may be prepared with a gold-sulfur ripener, a gold-selenium ripener or a reducing agent such as GB
789,823, tin compounds, amines,
Hydrazine derivatives, formamidine-sulfinic acids,
And sensitization with a silane compound. Chemical sensitization is performed with small amounts of Ir, Rh, Ru, Pb, Cd, H
It can also be performed using g, Tl, Pd, Pt, or Au. One or a combination of these chemical sensitization methods can be used.

Light-sensitive silver halide emulsions include, for example, FM
"The Cyanine Dyes and Related Compoun by Hamer
ds ", 1964, John Wiley & Sons. Suitable dyes such as those described in John Wiley & Sons. Dyes which can be used for the purpose of spectral sensitization are cyanine dyes, merocyanine dyes, complex cyanine dyes. , Composite merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes, and particularly valuable dyes are those belonging to cyanine dyes, merocyanine dyes and composite merocyanine dyes.
S4,717,650, FR2 058 405 and E
P427892.

One or more silver halide emulsions for use in accordance with the present invention contain compounds which prevent fogging or stabilize photographic properties during the manufacture or storage of the photographic element or during its photographic processing. Can comprise. Many known compounds can be added to a silver halide emulsion as fog-inhibitors or stabilizers. A good example is Research Disclosure Item 36544, September
1994, Chapter VII.

[0015] In addition to silver halide, another essential component of the photosensitive emulsion layer is a binder. The binder is a hydrophilic colloid, preferably gelatin. However, gelatin can be partially or totally replaced by synthetic, semi-synthetic, or natural polymers.

The binder of the photographic element can be any suitable hardener, for example of the epoxide type, of the ethyleneimine type, especially if the binder used is gelatin.
Of vinylsulfone type, for example 1,3-vinylsulfonyl-2-propanol, chromium salts such as chromium acetate and chromium alum, aldehydes such as formaldehyde, glyoxal and glutaraldehyde, N-methylol compounds such as dimethylolurea and Methylol dimethylhydantoin, dioxane derivative such as 2,3-dihydroxy-dioxane, active vinyl compound such as 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compound such as 2,4-dichloro-6-hydroxy It can be hardened with -s-triazine and mucohalic acids such as mucochloric acid and mucophenoxychloric acid. These hardeners can be used alone or in combination. Binders are fast-reacting hardeners, for example US4,
Hardening can also be carried out with carbamoylpyridinium salts as disclosed in U.S. Pat.

In a preferred embodiment of the present invention, the emulsion layer further contains a polymeric latex that functions as a plasticizer. A preferred latex is copoly (AMPS-butyl methacrylate), where AMPS means 2-acrylamido-2-methylpropanesulfonic acid sodium salt, a monomer from Lubrizol Co. In a most preferred embodiment, the latex is present in an amount of at least 15% by weight of all solids except silver halide grains.

The photographic emulsion layer may further comprise various types of surfactants and lubricants in the photographic emulsion layer or in another hydrophilic colloid layer. Suitable surfactants and lubricants are listed in Research Disclosure Item 36544,
September 1994, Chapter IX. One or more anti-scratch layers Generally, in a photographic material there is only one anti-scratch layer on top of the emulsion layer. However, in a preferred embodiment of the invention, there are two thin anti-scratch layers. In an even more preferred embodiment, the anti-scratch layer closest to the support contains a mixture of gelatin and latex. In the most preferred embodiment, this layer contains about 0.5 g / m ² gelatin and about 0.5 g / m ² latex. The latex used may be the same as the latex optionally present in the emulsion layer. The top antiscratch layer is preferably a gelatinous layer without latex. Preferably,
Its gelatin coverage is also about 0.5 g / m ² . The anti-scratch layer may further contain spacing agents, wetting agents and lubricants, such as polyethylene dispersions. -Latex undercoat layer The polyester support of the recorder film of the present invention is undercoated on both sides with a so-called latex undercoat layer. An essential component of the latex subbing layer is an adhesion promoting latex. A preferred type of latex polymer for this purpose is a vinylidene chloride-containing copolymer having a carboxyl functionality. Examples of such polymers are (1) copolymers of vinylidene chloride and an unsaturated carboxylic acid, such as acrylic acid or methacrylic acid; (2) half-esters of vinylidene chloride and an unsaturated carboxylic acid, such as monomethyl of itaconic acid. Copolymers of esters, (3) terpolymers of vinylidene chloride, itaconic acid and alkyl or alkyl methacrylate, for example ethyl acrylate or methyl methacrylate, and (4) vinylidene chloride, acrylonitrile or methacrylonitrile and Ternary copolymers of unsaturated carboxylic acids, for example acrylic acid or methacrylic acid.

In the most preferred embodiment, the latex polymer is co (vinylidene chloride-methyl acrylate-itaconic acid: 88% / 10% / 2%). This copolymer was used as an emulsifier in 0.5% MERSOLAT H (Bayer A).
G (trademark). It is necessary to add an additional surfactant, a so-called post-stabilizer, to the latex to ensure good stability on storage. Excellent storage stability is obtained when 4% of Ciba-Geigy's trademark ULTRAVON W or Dow's trademark Dowfax is used.

As another preferred component of the coating solution for the latex subbing layer, colloidal silica can be added as a binder. A preferred compound is KIESELSOL 100F having an average particle size of 25-30 nm.
(Trademark of Bayer AG). The ratio of the amount of latex to silica is preferably about 80/20.

The dry thickness of the latex subbing layer is preferably about 0.1 mm.

The back latex subbing layer is preferably of the same composition as the upper latex subbing layer. However, in a particularly preferred embodiment, the layer further contains a conductive polymer to render the layer antistatic. The properties of the conductive compound will be described in detail below.

Such compounds, typically polymers, can exhibit ionic or electronic conductivity.

However, the conductivity of the antistatic layer containing the ion-conductive polymer is water-dependent even after cross-linking. Accordingly, electron conductive conjugated polymers have been developed. A substance having electronic conductivity instead of ionic conductivity has a conductivity independent of moisture. They are particularly suitable for use in the manufacture of antistatic layers having permanent and reproducible conductivity.

Many of the known electron-conducting polymers are not well-suited for use in photographic materials because of their strong coloration, but some of them of the group of polyarenemethylidenes, such as polythiophenes and polyisophenes Tianaphthenic acid is not prohibitively colored and is transparent, at least when coated in a thin layer. As a result, polythiophene derivatives are a preferred type of conductive compound for use in the present invention.

The preparation of conductive polythiophenes is described in the manufacturing literature cited in the above book: "Science and Applications o.
f Conducting Polymers ", p. 92.

For morphological reasons, the coating of the antistatic layer should be carried out, where possible, by using as little organic solvent as possible from the aqueous solution. The preparation of antistatic coatings from aqueous coating compositions which are dispersions of polythiophenes in the presence of polyanions is described in EP 0 440 957. Due to the presence of the polyanion, the polythiophene compound is kept in the dispersion.

Preferably, the polythiophene has at least one alkoxy group or —O (CH ₂ CH ₂ O) _n C
H ₃ group [wherein, n is 1-4] thiophene nuclei substituted with or, most preferably, is closed by an alkylene group includes two form substituted on an oxygen atom alkylene group With a thiophene nucleus.

Preferred polythiophenes for use according to the invention have the general formula:

[0030]

Embedded image

Wherein each of R ¹ and R ² independently represents hydrogen or a C _1-4 alkyl group, or together with a optionally substituted C _1-4 alkylene group or cycloalkyl group; Alkylene group, preferably ethylene group, optionally alkyl-substituted methylene group, optionally C _1-12 alkyl- or phenyl-optionally substituted 1,2-ethylene group, 1,3-propylene Or a 1,2-cyclohexylene group].

The most preferred compounds have the formula:

[0033]

Embedded image

Poly (3,4-ethylenedioxy-thiophene), (PEDT).

The preparation of the polythiophene and the aqueous polythiophene-polymeric polyanion dispersion containing the polythiophene is described in EP 0 440 957 cited above.
It is described in.

Suitable polymeric polyanion compounds required to keep the polythiophenes in dispersion are provided by the free acid or neutralized form of the acidic polymer. The acidic polymer is preferably a polymeric sulfonic acid. Examples of such polymeric acids are polymers containing vinyl sulfonic acid and styrene sulfonic acid or mixtures thereof.

In order to ensure sufficient stability of the dispersion, the anionic acidic polymers used together with the dispersed polythiophene polymer preferably have more than 2% by weight of anionic groups with respect to the polymer compound. Having a content of
Suitable acidic polymers or corresponding salts are, for example, DE
-A-25 41 230, DE-A-25 41 27
4, DE-A-28 35 856, EP-A-149
21, EP-A-69 671, EP-A-130 11
5, US-P4,388,550, US-P4,388,4
03 and US-P 5,006,451.

The weight ratio of polythiophene polymer to one or more polymeric polyanion compounds may be, for example, about 5
0/50 to 15/85 can be widely changed.

The most preferred polymeric polyanion for use in combination with a polythiophene derivative, such as PEDT, is polystyrene sulfonate (PSS).

The conductive latex subbing layer (c) is preferred.
It has a dry thickness of about 0.1 mm. -Gelatin subbing layer The gelatin subbing layer is on the top of the latex subbing layer on the front side.
Coated. In addition to spacing agents, gelatin
The subbing layer is preferably gelatin and colloidal silica
A mixture of The preferred compound is again Kiese
Lusol 300F (trademark of Bayer AG). Drying
Cracking in dry layers due to excessive layer shrinkage
Plasticizing compounds can be used to avoid
Wear. Plasticizers are known in the art. Low molecular weight compounds
(Eg, acetamide, glycerin) and polymeric latices
Tex (eg polyethyl acrylate, polyacryl
N-butyl acid) can be used for this purpose.
You. In addition, one or more gelatin subbing layers
Surfactant can be contained. Useful surface activity
Agent is an aryl sulfonate from CIBA-GEIGY
Lafon^TMNonylphenylpolyethylene from W, HOECHST
ARKOPAL is a ren-glycol ^TMN06
0 (formerly HOSTAPAL)^TMW).

The thickness of the gelatin subbing layer is preferably 0.5.
It is between 1 and 1 μm. -Antihalation layer In the most preferred embodiment of the present invention, the antihalation layer is on the back side of the support on top of the latex subbing layer. The antihalation layer contains an antihalation dye and a binder. Antihalation dyes improve image sharpness by reducing the upward reflection of light by the support in the emulsion layer. Useful dyes that are absorptive in the visible spectrum are colored pigments of US 2,697,037, US 2,27
4,782 pyrazonol oxonol dyes, US 3,4
32,207 styryl and butadienyl dyes, US
2,956,879 diarylazo dyes, US 2,52
7,583 merocyanine dyes, US 3,486,89
7, US 3,652,284 and US 3,718,472
Merocyanine and oxonol dyes, and US
3,976,661 enamino hemioxonol dyes. Dyes, some of which are absorbing in the red spectral region of the di- or triphenylmethane type with electron-withdrawing groups, are described, for example, in US Pat. No. 2,282,890, DE 103.
8395, FR2,234,585, JP-A59-22
8250, US 2,252,052 and A. Guyot, Com
pt. Rend., Vol 114 (1970), p. Some of the disclosed compounds contain one or more water-soluble groups.

It may be advantageous for the antihalation dye to be non-diffusible under normal coating conditions and to become diffusible and / or discolor only under alkaline processing conditions. Such dyes can be added in dispersion or in the form of so-called microcrystalline solid particles. Non-diffusible or non-diffusible dyes of this type are described, for example, in US
4,092,168, EP274723, EP27656
6, EP294461, EP299435, GB156
3809, EP015601, US4,857,446,
JP-A02-259752, JP-A02-2642
47, EP582753 and EP587229.

At most 1.5 g / m ^{2 of the} antihalation layer
It is an essential feature of the present invention that the thin layer has a gelatin coverage. -Coating technique In a particularly preferred embodiment, the two latex subbing layers, the gelatin subbing layer and the antihalation layer are coated in a continuous "on-line" manner in a production array of the polyester itself. The molten polyester is extruded and stretched in the machine direction. Next, a first latex subbing layer is applied to the top side and a second latex subbing layer, which may be conductive, is applied to the backside.
The primed polyester is then stretched in the transverse direction.
A gelatin subbing layer is applied on top and finally an antihalation layer is applied on the backside.

The one or more emulsion layers and the anti-scratch layer are coated "off-line." Any known coating technique, such as immersion coating,
Air knife coating, slide hopper coating, and curtain coating can be used. In a preferred embodiment, the emulsion layer and the two anti-scratch layers are applied by curtain coating.

The invention will now be described by way of the following non-limiting examples.

[0046]

EXAMPLES Example 1 Comparative Example Preparation of Polyester Sample The polyester support in all examples was 100 μm.
Thickness of a polyethylene terephthalate (PET) support.

Composition of backing undercoat layer: 180 mg / m ²
Terpolymer of vinylidene chloride / methyl acrylate / itaconic acid (88% / 10% / 2%), 20 mg / m ²
Conductive subbing layer containing colloidal silica (100 m ² / g surface area) and 3.15 mg / m ² poly (3,4-ethylenedioxythiophene) / poly (styrene sulfonate) composite And then 0.2 g of gelatin /
m ² , 0.2 g / m ² colloidal silica and 1 mg / m ²
A gelatin backing layer with m ² of 3 μm PMMA (polymethyl methacrylate) matting agent was coated.

Composition of emulsion-side undercoat layer: 162 mg / m^Two
Of vinylidene chloride / methyl acrylate / itaconic acid
Original copolymer (88% / 10% / 2%), and 40 mg
/ M ^TwoLatex undercoat containing colloidal silica
Layer, then 0.2 g / m^TwoGelatin, 0.2 g / m^TwoRoller
Id-like silica, and 1 mg / m^Two3μm PMMA gloss
A gelatin subbing layer containing an eraser is coated
Was.

Both the backing layer and the emulsion-side subbing layer
Coated during ester production.Emulsion production Gelatin aqueous solution containing sodium chloride (23.3 g
Gelatin / mol silver), aqueous solution of silver nitrate, and bromide
Potassium, sodium chloride, 2.3 × 10^-7Mol / mol
Silver Na_ThreeRhCl₆And 3.0 × 10^-7Mol / mol silver
Na_TwoIrCl ₆Do not stir the aqueous halide solution containing
It was added according to the double jet method. Using physical aging
0.27μm average particle size (coefficient of variation: 19%)
Chlorobromide having a chloride content of 64 mol%
Particles formed. After physical ripening of the emulsion, KI is added
Crystal growth was stopped.

The emulsion was then washed using conventional flocculation techniques, and then 33.3 g / mole silver gelatin was redispersed. The resulting emulsion was adjusted to pH 5.3 and then chemically sensitized with gold / sulfur at 50 ° C by ripening for 3 hours. 8.4 × 10 ^-3 emulsion
Mol / mol silver of 4-hydroxy-6-methyl-1,3,3
Stabilized with a, 7-tetraazaindene and 2.9 × 10
Spectral sensitized with dye SD-1 in an amount of ^-4 mol / mol silver.

[0051]

Embedded image

The resulting emulsion had a gelatin / silver ratio of 0.51. Preparation of Emulsion-Coated Samples Two backing layers were simultaneously coated on the back side of a primed polyester support.

[0053] closest backing to the support 1m ² per 2.
44 g gelatin, 0.96 g polyethylene acrylate (PEA) latex, 0.5 g colloidal silica, 100 mg blue antihalation dye AHD-1:

[0054]

Embedded image

Was contained.

The second backing layer contained 0.6 g of gelatin per m ² , 50 mg of a 7 μm PMMA matting agent and a coating aid.

The emulsion layers were simultaneously coated on a polyethylene terephthalate film support using a two-layer arrangement such that the emulsion layers were closest to the support and the anti-halation layer was on top.

The emulsion layer was coated at a pH of 5 with a silver coverage of 3.88 g per square meter of silver. The pAg was adjusted by the addition of potassium bromide (3.6 mmol / mole silver). 300 to improve curling
mg / m ² of PEA latex was added. This emulsion layer was then coated with an anti-abrasion layer containing 1.5 g / m ² of gelatin and also formaldehyde as a hardener, hydroquinone and phenidone as stabilizers, a coating aid and a PMMA matting agent (3 μm). Overcoated. Example 2: Preparation of the inventive polyester sample Composition of the backing subbing layer: latex conductive subbing layer as in Example 1, and 1.2 g / m ² gelatin, 100
gelatin backing layer comprising mg / m ² of the anti-halation dye as the AHD-1 and 10 mg / m ² of PMMA matting agent (7 [mu] m) was coated.

Composition of undercoat layer on emulsion side: 162 mg / m^Two
Of vinylidene chloride / methyl acrylate / itaconic acid
Original copolymer (88% / 10% / 2%), and 40 mg
/ M ^TwoLatex undercoat containing colloidal silica
Layer, then 0.2 g / m^TwoGelatin, 0.2 g / m^TwoRoller
Id-like silica, and 1 mg / m^Two3μm PMMA gloss
Gelatin subbing layer with eraser.

Again, the backing subbing layer and the underside of the emulsion
Both coats are coated during polyester production
Was.Emulsion production Gelatin aqueous solution containing sodium chloride (23.3 g
Gelatin / mol silver), aqueous solution of silver nitrate, and bromide
Potassium, sodium chloride, 2.3 × 10^-7Mol / mol
Silver Na_ThreeRhCl₆And 3.0 × 10^-7Mol / mol silver
Na_TwoIrCl ₆Do not stir the aqueous halide solution containing
It was added according to the double jet method. Using physical aging
0.27μm average particle size (coefficient of variation: 19%)
Chlorobromide having a chloride content of 64 mol%
Particles formed. After physical ripening of the emulsion, KI is added
Crystal growth was stopped.

Thereafter, the emulsion was washed using conventional flocculation techniques and then 10 g of gelatin / mole silver were redispersed. The resulting emulsion was adjusted to pH 5.3 and then ripened for 3 hours at 50 ° C.
Chemically sensitized with sulfur. The emulsion was treated with 8.4 × 10 ^-3 mol / mol silver of 4-hydroxy-6-methyl-1,3.3a,
Stabilized with 7-tetraazaindene, 4.0 × 10 ^-4
Spectral sensitized with the dye SD-1 in the amount of mol / mol silver.

The emulsion obtained has a gelatin / silver ratio of 0.31. Preparation of Emulsion- Coated Samples The emulsion layers were simultaneously coated on a polyethylene terephthalate support using a three-layer arrangement such as an emulsion layer closest to the support, followed by an intermediate layer, and a top anti-scratch layer. , Coated.

The emulsion layer was coated at a pH of 5 with a silver coverage of 3.23 g per square meter of silver. The pAg was adjusted by the addition of potassium bromide (3.6 mmol / mole silver). This emulsion layer was overcoated with an interlayer containing 0.5 g / m ² gelatin and 0.5 g / m ² copoly (AMPS-butyl methacrylate) latex, and hydroquinone and phenidone as stabilizers.

The anti-scratch layer was coated on top with 0.5 g / m ² of gelatin containing divinyl sulfone hardener, a coating aid and a PMMA matting agent.

After coating, the film samples were dried. Example 3: The composition of production backing subbing layer of the present invention the polyester sample: Latex conductive subbing layer, and AH-1 and 10 mg / m ² as an anti-halation dye gelatin / m ^2, 100mg / m ² of 1.2g
A gelatin backing layer comprising 7 μm PMMA matting agent was coated.

Composition of emulsion side undercoat layer: 162 mg / m^Two
Of vinylidene chloride / methyl acrylate / itaconic acid
Original copolymer (88% / 10% / 2%), and 40 mg
/ M ^TwoLatex undercoat containing colloidal silica
Layer, then 0.2 g / m^TwoGelatin, 0.2 g / m^TwoRoller
Id-like silica, and 0.025 mg / m^Two1μmPM
Gelatin subbing layer with MA matting agent.

Again, the backing subbing layer and the emulsion side
Both coats are coated during polyester production
Was.Emulsion production Gelatin aqueous solution containing sodium chloride (16.7 g
Gelatin / mol silver), aqueous solution of silver nitrate, and bromide
Potassium, sodium chloride, 2.3 × 10^-7Mol / mol
Silver Na_ThreeRhCl₆And 3.0 × 10^-7Mol / mol silver
Na_TwoIrCl ₆Do not stir the aqueous halide solution containing
It was added according to the double jet method. Using physical aging
0.27μm average particle size (coefficient of variation: 19%)
Chlorobromide having a chloride content of 64 mol%
Particles formed. After physical ripening of the emulsion, KI is added
Crystal growth was stopped.

The emulsion was then washed using conventional flocculation techniques and then 6.7 g of gelatin / mole silver were redispersed. The resulting emulsion was adjusted to pH 5.3 and then chemically sensitized with gold / sulfur at 50 ° C by ripening for 3 hours. The emulsion was treated with 8.4 × 10 ^-3 mol / mol silver of 4-hydroxy-6-methyl-1,3,3.
a, stabilized with 7,7-tetraazaindene, 4.0 × 10
Spectral sensitized with dye SD-1 in an amount of ^-4 mol / mol silver.

The resulting emulsion has a gelatin / silver ratio of 0.22. Preparation of Coated Emulsion Samples Emulsion layers were simultaneously coated on a polyethylene terephthalate support using a three-layer arrangement such that the emulsion layer was closest to the support, followed by the middle layer, and finally by the anti-scratch top layer. , Coated.

The emulsion layer was coated at a pH of 5 with a silver coverage of 2.72 g per square meter of silver. The pAg was adjusted by the addition of potassium bromide (3.6 mmol / mole silver). 0.6 to improve curling
mg / m ² of copoly (AMPS-butyl methacrylate)
Latex was added.

The emulsion layer was overcoated with an interlayer comprising 0.5 g / m ² gelatin and 0.5 g / m ² copoly (AMPS-butyl methacrylate) latex, hydroquinone and phenidone as stabilizers. .

The anti-scratch layer is topped with 0.5 g gelatin / m ² containing divinyl sulfone hardener, 0.8 ml
/ M ² of a 20% polyethylene dispersion, a coating aid and a PMMA matting agent.

After coating, the film samples were dried. Example 4 The composition of the undercoat layer and the antihalation layer of the present invention and the preparation of an emulsion were the same as in Example 3. Preparation of Coated Emulsion Sample Simultaneously place the emulsion layer on a polyethylene terephthalate film support, the emulsion layer closest to the support, the middle layer next,
The last was coated using a three-layer arrangement such as a scratch-resistant top layer.

The emulsion layer was coated at a pH of 5 with a silver coverage of 2.72 g per square meter of silver. The pAg was adjusted by the addition of potassium bromide (3.6 mmol / mole silver).

The emulsion layer was overcoated with an interlayer comprising 0.5 g / m ² gelatin and 0.5 g / m ² copoly (AMPS-butyl methacrylate) latex, hydroquinone and phenidone as stabilizers. .

The anti-scratch layer was coated on top with 0.5 g of gelatin / m ² containing divinyl sulfone hardener, a coating aid and a PMMA matting agent, among others.

After coating, the film samples were dried. Example 5: The compositions of the undercoat layer and the antihalation layer according to the present invention and the preparation of the emulsion were the same as in Examples 3 and 4. Preparation of Coated Emulsion Sample Simultaneously place the emulsion layer on a polyethylene terephthalate film support, the emulsion layer closest to the support, the middle layer next,
The last was coated using a three-layer arrangement such as a scratch-resistant top layer.

The emulsion layer was coated at a pH of 5 with a silver coverage of 2.63 g per square meter of silver. Dextran was added in a volume of 0.675 ml / m ² of a 20% solution. Potassium bromide (3.6 mmol / mole silver)
Was added to adjust the pAg.

The emulsion layer was overcoated with an interlayer comprising 0.5 g / m ² gelatin and 0.5 g / m ² copoly (AMPS-butyl methacrylate) latex, hydroquinone and phenidone as stabilizers. .

The anti-scratch layer was coated on top with 0.5 g / m ² of gelatin which additionally contained a divinyl sulfone hardener, a coating aid and a PMMA matting agent.

After coating, the film samples were dried. Exposure and photographic processing of coated samples Each sample was exposed through a continuous wedge using a 670 nm laser diode in a laser sensitometer, and then developer A at 35 ° C. for 15 or 30 seconds.
Developed. Thereafter, each sample was subsequently subjected to fixing in a conventional fixing bath containing ammonium thiosulfate, and then subjected to washing and drying operations. Processing is performed using a Rapiline 66T3 processor (Agfa-Gevaert N.A.).
V. trademark). Composition of developer A Value Water 800 ml Potassium carbonate 29.5 g Potassium sulfite 34.1 Potassium bromide 2.4 Diethylene glycol 14 ml Hydroquinone 17 Sodium erythrobate 2.5 4-Hydroxymethyl-4-methyl-1-phenyl 0. 275-3-pyrazolidone methyl benzotriazole 0.06 Water to adjust volume to 1 liter Sodium hydroxide to adjust pH to 10.5 Evaluation of exposed samples Water-absorbing samples are rinsed in water for 2 minutes It is. Thereafter, the water remaining on the surface was removed. Water absorbency is the weight difference before and after. After exposure through a sensitivity wedge, the density was measured. Sensitivity was measured at a density higher than 3.0 than fog. Higher numbers mean lower sensitivity. Tone The tones were measured at densities between 0.1 and 0.5 above fog. The difference in sensitivity between development time of 30 seconds developing speed and 15 seconds is a measure related to the development rate. Lower numbers are better. After exposure with a 670 nm laser diode in a covering power laser sensitometer and development for 30 seconds, the maximum density (D _max ) was measured using a densitometer Macbeth TD904. Silver coverage was calculated by the following formula: Coverage = D _max / coated silver coverage (g silver / m ² ).

A summary of the composition is shown in Table 1.

The data obtained for the samples are contained in Table 2.

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[Table 1]

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[Table 2]

As is clear from the table, the gradation of the sample of the present invention is higher. This results in better image quality of the film on the laser recorder.

The embodiments of the present invention clearly show a significant improvement in water absorption, so that less replenishment is required. This material will also dry much faster in an automatic processor.

Since the developing speed is higher, the sample of the present invention can be processed at a higher speed than the comparative example.

Further, the covering power also increases. Thus, the price of the material can be significantly reduced.

Continued on the front page (72) Inventor Ciutefane Lingier Belgium B 2640 Malt Cell Septes Trat 27 Agfa-Gevert Na Mrose Fennout Japs (72) Inventor Etienne Van Teiro Belgium B 2640 Malt Cell Septes Trat 27, Agfa-Gevert Nahr, Mrose, Fennout, F-term (reference) 2H023 AA00 BA00 FB01 FB02 GA00

Claims (1)

[Claims] 1. A polyester support comprising a latex subbing layer subbed on both the front side and the backside, and a gelatin subbing layer on the front side, at most 3.6.
g / m ² silver total silver coverage and at most 1.5 g / m 2
A photographic recording material for graphic arts, further comprising one or more red-sensitive emulsion layers having a total dry coverage of all ^two other solid components, and one or more anti-scratch layers.