JPS619646A - Photographic material - Google Patents

Abstract

PURPOSE:To prevent cracking by drying and flawing under external force and to provide high resolving power by incorporating polymer latex into a pigment layer contg. a white pigment and a dye which is decolored or discharged in a photograhic process on a support. CONSTITUTION:A pigment layer consisting of a white pigment, a dye which is decolored or discharged in a photographic process and a hydrophilic binder is formed on at least one side of a photographic support, the pigment layer is coated with at least one photosensitive silver halide emulsion layer, and polymer latex is incorporated into the pigment layer. An intermediate layer may be formed on the pigment layer before the coating. The amount of the pigment in the pigment layer is >=50wt% (expressed in terms of solid matter) of the amount of the binder, gelatin is used as the binder, and the amount of the latex incorporated into the pigment layer is regulated to 10-150wt% (expressed in terms of solid matter) of the amount of the binder. Elasticity can be provided by incorporating the polymer latex into the pigment layer, and a photosensitive material protected from cracking by drying and from flawing under external force and having high resolving power can be obtd.

Description

[Detailed description of the invention] 〔Technical field〕 The present invention relates to photographic materials having a pigment layer.

[Prior art]

BACKGROUND ART Conventionally, so-called baryta paper, in which a baryque layer is coated on one side of a paper base using a hydrophilic colloid as a binder, has been used as a support for photographic printing paper. Baryta paper is perfect in terms of white discoloration and resolution, and is still used by many professional photographers. However, since the base material is paper, it has poor water resistance, and as a result, there are disadvantages such as dimensional changes in the aqueous photographic processing process and deterioration of the processing solution due to contamination of the processing solution. Water-resistant supports are often used.

That is, it is a paper base coated with polyolefin on both sides, and titanium white pigment is kneaded into the polyolefin on the photosensitive side to improve white discoloration and photographic resolution. Alternatively, there is also a support made by kneading a white pigment into a thermoplastic resin to form a film.

These supports are water-resistant silica and white melon, which are very satisfactory for general photography, but their resolution is not necessarily satisfactory for aerial survey photography, printing materials, and photographic materials for professional photographers. isn't it. The reason is that
With current synthetic resin processing technology, the amount of pigment that can be kneaded into the polymer is at most about 15 inches, but considering the economy of processing speed, about 10 inches is good; This is because the tunnel effect in which light is scattered within the film cannot be completely eliminated by increasing the amount of light scattered within the film.In order to improve this drawback, the present inventors have made several proposals (Japanese Patent Application Laid-open Nos. 55-69630 and 57 -642
No. 35). That is, by using the water-resistant support method described above, the resolution is considerably improved. In particular, the method described in JP-A No. 57-64325 proposed by the present inventor, that is, absorbing light in the sensitive wavelength range of a silver halide emulsion layer coated on a pigment layer containing a white pigment. The resolution can be significantly improved by a method in which dyes that are decolorized or washed out in the photographic processing step are incorporated into the pigment layer.

In the process of researching the above proposal, the present inventors found that when the applied amount per unit area of the white pigment in the pigment layer and the dye that disappears or flows out in the photographic processing process is the same, the smaller the amount of binder, the higher the resolution. We obtained the knowledge that the However, it has become clear that increasing the content ratio of pigment relative to the amount of banhku is accompanied by drawbacks from the viewpoint of film physical properties. That is, if the content ratio of white pigment to binder is high, the coating film may crack after drying, or even if no cracks occur, the dried film has poor elasticity and becomes brittle against external forces.

It is known that by incorporating a polymer latex into the constituent layers of a photographic material, photographic properties such as dimensional stability and flexibility can be improved, and surface gloss can be increased. For example, Japanese Patent Publication No. 49-37845 discloses that a polymer latex is contained in a silver halide emulsion layer, and Japanese Patent Application Publication No. 57-200031 discloses that methyl acrylate and ethyl acrylate are contained in the constituent layers of a photographic material. It is described that a copolymer is included.0 However, although it uses a polymer latex, it is not described that a white pigment is used together with a dye that disappears or flows out during the photographic processing process, and a polymer latex. do not have.

[Purpose of the invention]

An object of the present invention is to provide a photographic material with high resolution that does not cause cracks or cracks when dried and has a pigment layer that is highly elastic and is less likely to be damaged by external forces.

In order to achieve this objective, the present inventors conducted extensive research and found that a pigment layer containing a white pigment and a dye that disappears or flows out during the photographic processing process further contains a polymer latex to impart elasticity to the pigment layer. The present invention was accomplished by providing the following. That is, the object of the present invention is to provide, on at least one side of a photographic support, a pigment layer consisting of a white pigment, a dye that disappears or flows out during the photographic processing process, and a hydrophilic binder, and to provide a pigment layer on at least one side of a photographic support, and to apply a pigment layer to the pigment layer directly or intermediately. In a photographic material formed by coating at least one silver halide emulsion layer with layers interposed therebetween, 0 [Constitution of the Invention] Photographic support in the present invention is achieved by containing a polymer latex in the pigment layer. is mainly a water-resistant support, so-called resin-coated paper in which polyolefin is laminated on both sides of the paper base, and hardened paper in which both sides of a natural or synthetic resin film are roughened or a white pigment is kneaded. film(
(also called synthetic paper), "or transparent film, etc."
Resin-coated paper is a preferred support, and particularly resin-coated paper containing the following white pigments, such as titanium oxide, in the resin layer on the side of the emulsion layer is preferred. The surface of the thermoplastic resin is subjected to corona discharge treatment, ultraviolet irradiation treatment, electron impact treatment,
It is preferable to make it hydrophilic by flame treatment or potassium permancanate concentrated sulfuric acid treatment.

These supports are advantageously provided with an undercoat layer on one or both sides for adhering the pigment layer.

The white pigments contained in the pigment layer of the present invention include titanium dioxide, barium sulfate, lithopone, alumina white, carunium carbonate, nrica white, antimony trioxide, and titanium phosphate, which are generally used for photography. These are titanium dioxide and sulfuric acid/hium. Among them, titanium dioxide is particularly effective. Such titanium dioxide may be of the rutile type or the anatase type, and may also be produced by the sulfate method,
It may be manufactured by any of the chloride methods. In order to disperse these pigments in a hydrophilic binder, it is recommended to use an emulsifying device such as an ultrasonic homogenizer, colloid mill, xantmill, or whole mill. .

The dye used in the pigment layer of the present invention is disclosed in U.S. Pat.
7124 specification, British Patent No. 933466 specification,
Specification No. 1311884, JP-A-48-85130
oxonol dyes described in U.S. Pat. No. 2,298,337, U.S. Pat. 42668
Styryl dyes described in the above publication, cyanine dyes, melonanine dyes, heminanine dyes, hemioxonol dyes, anthraquinone dyes, etc. can be used, and two or more of the above dyes can also be used in combination. .

Specific examples of dyes that can be used in the present invention are listed below.
The present invention is not limited to these exemplified compounds.

(Oxonol dye) 1, HOOC-C-C=CH-CHHOH-CHHOH
-C-C-COOHII I
II II>LJ3
A 503KCI-■2COO
CH,, C00K3, CHl
-C-C=CH-C to 〇H-CI(=CI-1-C-C
-Cl-13II I
II 11N
HON6, HOOC-C-C=CH
-CHHOH-C--C-C00HII I
II 11SO3K
8 to SOl, C4H0OOC
CC,,F=CHCC(OOC,+l-111HII Q HON SO3 to 10, OH,,Cool-10HCH20001
-1C4H0C4H0 (ab dye) 11, 5o3Na 0-8O□Na
03 S' 13, OH03Na UCHs Na03S , 5O3Na (anthraquinone dye) -19, Nap3SCH2NHONHCH2803Na
0 NHCH25O3N, a The hydrophilic binder in the present invention includes, for example, natural polymer compounds such as seratin, gelatin derivatives, cellulose derivatives, textlan, gum arahia, etc., and water-soluble polyvinyl compounds such as polyhinyl alcohol,
Although various water-soluble polyhinyl compounds such as polyhinylpyrrolitone and polyacrylamide can be used, seratin is most preferred.

When using a white pigment in the pigment layer and a dye that discolors or flows out during the photographic processing process, if the solid weight ratio of the white pigment to the hydrophilic binder is 30% or more, the water content of the film must be 10% or less. If the coating is dried to a temperature of 50% or more, the coating will crack, and if the coating is dried to a temperature of 50% or higher, the dry state becomes brittle. This drawback is avoided by using a polymer latex.

The polymer latex used in the present invention has an average particle size of 2
An aqueous dispersion of a water-insoluble polymer with a diameter of 0 to 200 mμ, the preferred amount used is 10% as a solid content relative to the hydrophilic binder.
~150 weight.

Preferred examples of polymer latexes include those having an alkyl ester, hydroxyalkyl ester, or glycidyl ester of acrylic acid, or an alkyl ester, hydroxyalkyl ester, or glycidyl ester of methacrylic acid as a monomer unit, and having an average molecular weight of 100,000 or more. A particularly preferred polymer is 300,000 to 500,000, and a specific example is represented by the following formula.

Polymer 1 -(-CH2-CH+n COOC4H9 Polymer 2 (-CH2-CH element ■ C00C3■(7 polymer 3 +C1l2-CH9 " C00C2H.

Polymer 4 CH3 " To +CH2-C ■ C00C,H.

Polymer 5 CH3 ■ +cr-+2-LcH "1 child CH2-C edition)
I CooC,H,C00CH2CH-CH2N2 crystal In addition to the above polymer latex,
Publication No. 331, U.S. Patent No. 2852386, U.S. Patent No. 306
Polymer latexes described in the specifications of No. 2674, No. 3411911, and No. 3141912 can also be used. Most preferred polymer → Te.

The acrylic acid alkyl ester emulsion copolymer is particularly preferred, and an emulsion copolymer consisting of 40 to 10 parts of acrylic acid methyl ester and 60 to 90 parts of acrylic acid ethyl ester is particularly preferred.

The pigment layer of the present invention may contain a viscosity increasing agent, a so-called thickener. As the thickener, a polymer having repeating units represented by the following general formula is preferably used.

In the formula, p represents 50 to 500, q represents 0, 1 or 2,
M represents an alkali metal atom or an ammonium group. The preferred thickener may be a homopolymer or a copolymer of other monomers as long as it has the above-mentioned repeating unit, but the following homopolymers are particularly preferred.

The amount of the thickener added is preferably 5% by weight or less, particularly 1 to 3% by weight, based on the hydrophilic binder in the pigment layer.

Organic or inorganic hardeners can be used alone or in combination in the pigment layer of the present invention. For example, T, H
, James [The Theory of Photographic Process, 4th Edition J (1,977), and others.
U.S. Patent Nos. 3,316,095, 3,232,764, 3,288,775, 2,732,303, and 36,357
No. 18, No. 3232763, No. 2732316, No. 2586168, No. 31034-37, No. 3017
No. 280, No. 29836], No. 2725294,
No. 2725295, No. 3100704, No. 3091
No. 537, No. 3321313, No. 3543295,
No. 3125449, British Patent No. 994869, No. 1
Hardeners described in each specification of No. 167207 can be used. Typical examples include mucochloric acid, mucofuric acid,
Mucofenoxochloroic acid, mucofenoxybromic acid, formaldehyde, tumethylol urea, [・limethylol melamine, cryogysal, monomethyl cryogysal, 2,3-dihydroxy-1,4-7 oxane 1.2,
3-dihydroxy-5-methyl-1,4-shioki→)“
aldehyde compounds and derivatives thereof such as N, succinic aldehyde, 2,3-somethoxytetrahydrofuran, and curcuric aldehyde;

N'-ethylene his (vinylsulfonylacetamide),
1.3-His(vinylsulfonyl)-2-propatur, methylene bismaleimide, 5-acetyl-1,3-diacryloyl-hegizahydro-8-triazine, 1,3
．． Active vinyl compounds such as 5-1-rivinylsulfonyl-hexahythro-S-triazino, 2,4-fuchloro-6-methoxy-8-triazine, 2,4-7chloro-6-(2-sulfoethylamino)- 8-1-riazine,
Active halokene compounds such as N,N'-his(2-chloroethylcarbamyl)piperazino, his(2,3-evoquinpropyl)methylpropylammonium-P-toluenesulfonate, 1,4-bis(2 ', 3'-epoquinepropyluoquine)butane, 1,3.5-tricrinenorisocyanurate, 1,3-chrycine-5-
Epoquine-based compounds such as (7-acedoquine-β-oxinepropyl)incyanurenie 1.2,4.6-doriethylene-S-triazino, 1,6-hexamethylene-N
, N'-bisethyleneurea, ethyl-imino compounds such as his-β-ethyleneiminoethylthioether,
1,2-(methanesulfoneoxy)/IJ:/, 1
．． Methanesulfonic acid ester compounds such as 4-(methanesulfoneoxy)butane, 1,5-so(methanesulfoneokino)pentane, cyclohexyl lupodiimide, 1-cyclohexyl-3-' (3-1-limethylaminobutane) carbodiimide-based compounds such as carbodiimide/P-toluenesulfonate, 1-ethyl-3-(3-ethylaminoprobyl)carboimide,
2,5-7 methyl inoxazole perchlorate, 2-
Inoxanol compounds such as ethyl'-5-phenylisoxanol-3'-sulfonate, 's,s'-(paraphenylene)hisisoxanol, inorganic compounds such as chromium alum and chromium acetate, N - dehydrated network type peptide reagents such as carboethoxy-2-isopropoquine-1,2-dihydroquinoline, N-(,1-morpholinosulfoxo)-4-methylpyridium chloride;
N, N'-Asoboirunokinjizakushinimito, N,
Examples include active ester compounds such as N'-terephthaloyl oxididisacunnimide, and isocyanates such as toluene-2,4-phyisocyanate and 1,6-hexamethylene soisocyanate.

Surfactants can be used alone or in combination in the pigment layer of the present invention. Surfactants are used as coating aids, but are also used, for example, for emulsification and dispersion, sensitization and other improvements in photographic properties, adjustment of charging voltage, and the like. This surfactant includes surfactants such as saponin, nonionic surfactants such as alkylene ookindo type, chrycerin type, and crindol type, higher alkylamines, quaternary ammonium salts, pilins and other heterocycles, Hoss□
Cationic surfactants such as honium or sulfoniums, carbonic acid, sulfonic acid, phosphoric acid, sulfuric acid ester,
They are divided into anionic surfactants containing acidic groups such as phosphoric acid esters, and amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols. These surfactants that can be used are described in U.S. Pat.
No. 271623, No. 2240472, No. 228822
No. 6, No. 2739891, No. 3068101, No. 3
No. 158484, No. 3201253, No. 321019
] No. 3294540, No. 3415649, No. 3
No. 441413, No. 3442654, No. 347517
No. 4, No. 3545974, No. 3666478, No. 3
507660, British Patent No. 1] 98450, Ryohei Oda et al., "Synthesis of Surfactants and Their Applications" (Maki Shoten 1964), and A. W. Helly, "Surface Active Eso-Enso" (Interscience
)＼Flication Incorporated 19 s
s), J. P. Sisley [Encyclopedia of Active Escensos, Volume 2] (Chemical Publishing Company, 1964).

The pigment layer of the present invention may contain various additives other than those mentioned above, if necessary.

The photographic material of the present invention has at least one light-sensitive silver halide emulsion layer on the pigment layer. As the photosensitive silver halide, various types of silver 10, such as silver bromide, silver iodide, silver chloride, silver chlorobromide, silver chloroiodide, silver bromoiodide, and silver chlorobromoiodide can be used. I can do it. Such photosensitive silver halide may be of the surface latent image type or of the internal latent image type as described in US Pat. No. 2,592,250. Further, as the photosensitive silver halide, a pre-fogged one described in British Patent No. 723019 can also be used. The photosensitive silver halide may be either a monospersed emulsion having a uniform and narrow particle size distribution, an alkaline emulsion, or a polyspersed emulsion that is not monospersed.

The silver halide emulsion may be chemically sensitized by various methods. For example, chemically sensitized by aging in the presence of destabilizing sulfur-containing compounds such as allyl thiocyanate, allyl thiourea, periosulfate, etc.
8687, the imino-aminomethanesulfinic acid compounds described in British Patent No. 789823, and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium, rhodium compounds. It may be sensitized by reducing agents such as.

Also, US Patent Nos. 2,531,822 and 2,533,990
British Patent No. 920637, British Patent No. 940041,
945340, Belgian Patent No. 991608, and Belgian Patent No. 648710, and amino-N-oxide onium compounds described in French Patent No. 1498724. It may be sensitized.

The photosensitive silver halide emulsion used in the present invention may be sensitized with an optical sensitizing dye. The sensitizing agents for this purpose include cyanines, merocyanines, complex (trinuclear or tetranuclear) merocyanines, complex, kusu (trinuclear or tetranuclear) '/heptamines, holoporacyanines, styryls, Hemicyanines, oxonols, hemioquinonols, etc. can be used.

The photographic material of the present invention can contain a yellow coupler, a Macenck coupler and a cyan coupler in the blue, green and red sensitive silver halide emulsions, respectively. α-acylacedoanilide compounds are well known as yellow couplers, pyrazolone compounds are well known as magenta couplers, and phenol or naphthol compounds are well known as cyan couplers. can be used. Typical yellow couplers include, for example, US Pat. No. 3,046,129, US Pat. No. 3,277,155, US Pat. No. 3,408]94, US Pat.
4B-29432, 48-66834, 48
-66835, 48-94432, 49-12
No. 29 and No. 49-1.0736. Masenck couplers are known, for example, from U.S. Pat. No. 368
No. 451.4, British Patent No. 1183515, Special Publication No. 4
No. 0-603], No. 40-6035, No. 44-157
No. 45, JP-A-49-29639, JP-A No. 49-5343
No. 7, No. 49-]'17034, No. 49-12303
No. 3, No. 50-108925, No. 50-159334
For example, the Noan coupler is disclosed in US Patent No. 2.
No. 423730, No. 2801171, Special Publication No. 1973-
It is described in various publications such as No. 16056.

The photosensitive silver halide emulsion layer further contains an antifoggant,
It can contain hardeners, surfactants, polymer latexes, wetting agents, thickeners, and the like.

〔Example〕

Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited to the Examples and can be applied within the scope of the claims.

Example] One side of a paper base was coated with a polyethylene layer containing no white pigment, and the other side was coated with one layer of anatase-type titanium white pigment.
A photographic material was prepared by using laminated l-paper coated with 0% polyethylene as a support and sequentially applying the following compositions to a white pigment-containing polyethylene layer.

Incidentally, the surface of the white pigment-containing polyethylene layer is made hydrophilic by performing a corona discharge treatment.

Sample A: On the above support, irradiate an undercoat liquid with the following formulation with ultrasonic waves,
After finely dispersing the titanium white pigment, the titanium white pigment was applied in an amount of 2.8 g per square meter.

Gelatin 90.9 Titanium white pigment 9o, p saponin (10%
Aqueous solution) 10-Formalin (20% aqueous solution) 3-Water
2300 m7 Next, the following silver halide emulsion composition was coated on top of the undercoat layer at a rate of 70 g per square meter to prepare Sample A, which was sensitive to the thickest wavelength of 635 nm.

Silver halide emulsion 'IKp (containing silver 32.9) sensitizing dye' (1:2000 methanol solution) 14
trLl.

Saponin (10% aqueous solution) 2O-formalin (20% aqueous solution) 3fnl Add water to make a total volume of 1.7 to 9 Rice silver halide consists of 85 moles of silver chloride and 15 moles of silver bromide, with an average grain size. It is a cubic, monodispersed emulsion with a diameter of 0.4 μm.

The following compound was used as the future sensitizing dye.

Sample B A sample B was prepared in exactly the same manner as Sample A except that an aqueous solution of Dye 7 (Exemplified Compound 60-1) was added to the undercoating solution.

Sample C Polymer latex (80% ethyl acrylate) in the undercoating liquid
Sample B was prepared in exactly the same manner as Sample B except that iooy (a 20% methyl acrylate copolymer containing 40% solids) was added.

In order to investigate the cracks in the three types of samples obtained in this way, each sample was left in a constant temperature and humidity chamber at a temperature of 25°C and a relative humidity of 55% for 12 hours, and then the radius of curvature was 2 in the same temperature and humidity chamber. The sample was folded to a size of .5 mm, and the occurrence of cracks was observed through a looper. In addition, in order to examine the resolution, three different types of samples were placed in close contact with a knife and xenon light was irradiated through the red filter of Eastman Kotak's Utten Flat 29.
The film was processed with a black and white developer containing phenyl-3-virapriton as a developing agent, followed by conventional fixing, water washing and drying processes to obtain a naifetsu image. Scanning and measuring the density of the obtained Naifetsu image with a microdensitometer,
From measurements, A. Jones.

G, C, Higgins, J, SMPTE', 58
．． Acutans barium was determined by the method described in 227 (1952).

The results are shown in Table-11.

Table 1 From the results in Table 1, it can be seen that cracks occur in Samples A and B, but no cracks occur in Sample C of the present invention.

Furthermore, it can be seen from the contrast between Sample B and Sample C that there is no decrease in sharpness due to the addition of polymer latex.

Claims (1)

[Claims] 1. A pigment layer consisting of a white pigment, a dye that disappears or flows out during the photographic processing process, and a hydrophilic binder is provided on at least one surface of a photographic support, and a pigment layer is provided on at least one surface of the photographic support, and the pigment layer is coated directly or intermediately. 1. A photographic material comprising at least one photosensitive silver halide emulsion layer coated via layers, characterized in that the pigment layer contains a polymer latex. 2. Claim 1, wherein the content of the pigment in the pigment layer is 50% or more by weight of the solid content relative to the hydrophilic binder.
Photographic materials listed in section. 3. The photographic material according to claim 1, wherein the hydrophilic binder of the pigment layer is gelatin. 4. The photographic material according to claim 1, wherein the content of the polymer latex in the pigment layer is 10% to 150% by weight of the solid content of the polymer latex relative to the hydrophilic binder.