JPH01224748A - Photosensitive material - Google Patents

Abstract

PURPOSE:To prevent delamination of a photographic emulsion layer in a photosensitive material from an undercoat layer and to improve sensitivity of the photosensitive material by incorporating dextran in the photosensitive material and a water-soluble ionic polymer in at least one layer which is nearer to a base body side than a layer contg. the dextran. CONSTITUTION:The title photosensitive material has at least one layer contg. substantially no dextran between a base body and a hydrophilic colloid layer (A) which is nearest to the base body among hydrophilic colloid layers contg. dextran, and a water-soluble ionic polymer is contained in the hydrophilic colloid layer (A). It is preferred that the layer (A) contains no photographic emulsion and that the layer (A) is adjacent to an undercoat layer. Preferred thickness of the layer (A) is 1.0-5.0, more pref. 1.0-3.0mu. If it is <1.0mu, the adhesion improving effect is insufficient resulting inferior adhesion to the undercoat layer. On one hand, if the mol.wt. of the dextran is too large, a sensitizing effect is indistinct.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a photosensitive material, and in particular to a high-sensitivity silver halide photographic material. This invention relates to a photosensitive material that has increased sensitivity without impairing adhesive properties.

(Prior Art) Increasing sensitivity is of great interest to photosensitive material manufacturers.

In order to increase the sensitivity, it is known that various types of I9-preparation agents are applied to photographic emulsions made of halides.

Examples of these Va additives include sugars and synthetic polymers. A typical example of a saccharide is dextran, described in US Patent No. J, 06J.

rJt No. 3,272.431, etc. However, if these are used in amounts sufficient to achieve the purpose, the following disadvantages will occur during development processing.

During the development process, the photographic emulsion layer peels off from the subbing layer (a layer provided to adhere the photographic emulsion layer to the support).

It is easy to see that the commercial value of photographic materials that suffer from these inconveniences is significantly impaired.

Japanese Patent Application Laid-open No. 61-620 as a method to prevent peeling during gen-ei processing
It has been found that simply changing the ratio of dextran (to binder) as described in No. 61 is insufficient to maintain the value of this product.

(Objective of the Invention) An object of the present invention is to provide a photographic material in which the photographic emulsion layer does not peel off from the undercoat layer and has improved sensitivity.

(Disclosure of the Invention) The above object of the present invention is to provide at least two
A silver halide photographic material having a hydrophilic colloid layer and containing dextran in at least one of the hydrophilic colloid layers.

Among the hydrophilic colloid layers containing dextran, there are at least seven layers between the hydrophilic colloid layer located closest to the support and the support and which do not substantially contain dextran; This was achieved using a photosensitive material characterized by having a water-soluble ionic polymer. Hereinafter, a layer containing such a water-soluble ion-containing mer will be referred to as an "adhesion improving layer".

In the present invention, it is preferable that the layer not containing a text run closest to the support does not contain a photographic emulsion.

A typical I-configuration of the photographic material of the present invention is as follows.

Embodiment 1 On one side of a support having two downward layers, from the support side (1) an adhesion improving layer not containing dextran;
A photographic material having a photosensitive emulsion layer containing 1 dextran, (3) a surface protective layer in this order, and a back layer on the other side.

Embodiment 2 On one side of a support having two sublayers, from the support side, (1) an adhesion improving layer not containing a text run;
1. A photographic light-sensitive material having a plurality of photosensitive emulsion layers containing 1-dextran, a skin-protecting layer consisting of a t3LZ layer in this order, and a back layer on the other side.

Embodiment 3: On one side of the support having the undercoat layer, from the support side, (1) an adhesion improving layer not containing dextran;
) a non-photosensitive hydrophilic colloid layer containing dextran;
(3) a photosensitive emulsion layer containing a text run, (
4) A photographic material having a surface protective layer in this order and a back layer on the other side.

Embodiment≠: (1) of Embodiment 1 on both sides of the support having an undercoat layer
A photographic material having a layer of (3).

Embodiment: On one side of the support with a subbing layer, (1) an adhesion-improved light-sensitive emulsion layer that does not contain dextran; (2)
A photosensitive material having a photosensitive emulsion layer containing dextran, (3) a surface protective layer in this order, and a back layer on the other side.

Typical supports used in the light-sensitive material of the present invention include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and other polyesters, as well as glass, paper, metal, wood, and the like.

In the present invention, dextran is preferably added to the photographic emulsion layer.

The dextran of the present invention has a weight average molecular weight t (MW) of j
,000 or more preferably from 70,000 to cooo,o
oo, particularly preferably from 20,000/IrO,00
0 is good. Although the amount of dextran to be added can be arbitrarily selected, the optimum amount of addition varies depending on the type of photographic emulsion.

In the present invention, the text run added to the photographic emulsion layer is
Dextran-producing bacteria such as Leuconostoc and Mesenteroides, or native dextran obtained by acting on a sucrose solution with textlan sucrase isolated from the culture broth of these bacteria, are subjected to partial decomposition polymerization using acids, alkalis, and enzymes to reduce the molecular weight. It has been lowered.

The amount of dextran added in the present invention is preferably 1% by weight of j-30 of the total binder in the layer to which it is added.

If dextran is added to the emulsion, it can be added at any time, but the second step is to add dextran to the emulsion. It is appropriate to add it after pS formation and before coating.

Dextran can be used as a powder to give 7IO, but 5 to 3
It is convenient to use it as a 0% water bath solution.

In the present invention, the dextran-free layer is preferably adjacent to the undercoat layer. At least /) - or more of the dextran-free layers are used as adhesion improving layers.

The thickness of such a layer not containing dextran is /
0-! , 0μ, particularly preferably /, 0 to 3.0μ. If it is less than 7.0μ, the effect of improving adhesion is small and the adhesion with the undercoat layer may be deteriorated.

On the other hand, if the molecular cage of dextran is too large, the sensitizing effect will not be significant, which is not preferable.

Examples of water-soluble polymers used in the invention include synthetic polymers containing repeating units of the following general formula [P], natural water-soluble polymers, and derivatives thereof.

General formula [P] In the formula, %R1 and R2 may be the same or different and each represents a hydrogen atom or an alkyl group, preferably the number of carbon atoms/~≠
an alkyl group (including those containing substituents, such as methyl, ethyl, propyl, butyl, etc.), a halogen atom (such as a chlorine atom), or -CH2C00M, and L is -CONH-1- NHCO-1-COO-
1-OCO-1-CO-1-8Q2-1-NH802-
1-802NH- or -0-, J is an alkylene group, preferably an alkylene group with the number of carbon atoms/~IO (
Those having direct substituents are also included. For example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc.), arylene group (including those with substituents, e.g., unicine group, etc.), aralkylene group [
/n group (substituent or +CH2CH2O-US Cl-I
2su", (-CH2CHCH20chi → CH2su, m H (m is an integer of O-≠O, n is an integer of 0-+.)
Representing wo, ma7'cQ is -COOM, -803M.

-o-Q-OM, -0M, and C00M0M is particularly preferred. M represents a hydrogen atom or a cationic group,
p and q each represent o- or /.

r is an integer, particularly preferably /. Y represents a hydrogen atom or a carboxyl group (or a salt thereof).

Additionally, the synthetic water-soluble heptamers of the present invention can be copolymerized with ethylenically unsaturated monomers.

Examples of copolymerizable ethylenically unsaturated monomers are styrene, alkylstyrenes, hydroxyalkylstyrenes (
Alkyl groups have a carbon number of up to 100%, such as methyl,
(ethyl, butyl, etc.), vinylbenzenesulfonic acid and its salts, α-methylstyrene, N-vinylpyrrolidone, monoethylenically unsaturated esters of fatty acids (e.g. vinyl acetate, vinyl propionate, etc.), ethylenically unsaturated Monocarboxylic or dicarboxylic acids and their salts (eg acrylic acid, methacrylic acid), maleia anhydride K1.
Esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate, dimethyl maleide), amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. acrylamide,
λ-acrylamide (sodium 2-methylpropanesulfonate), etc.

Next, specific examples of the synthetic water-soluble polymer of general formula [P] will be given.

P-/ CH3 OONa P-≠ P-z CH2COOH OOH -A P-? CH2COOH COOCH2CH20H -2 OONa m: n = 4' 0: / O
cH3P-// CH3 m: n=jO: jo 8
03Na, p-/2 P-/ Hirom:n=/j:rj P-/j fi:m:n=/j:2j:AO P-/4 The molecular weight of the synthetic water-soluble polymer of the present invention is 1, 000-/
,000,000, preferably λ,000-300
,000.

As the natural water-soluble ionic polymer, anionic polymers are preferred. For example, alginic acid, gum arabic, pectic acid, and gum tragacanth can be used.

Further, examples of derivatives of natural water layer ionic polymers include dextran acid ester, carboxyalkyl dextran, cellulose sulfate, carboxyalkyl cellulose, pullulan sulfate, and carboxyalkyl pullulan. The molecular weight of these natural water-soluble ionic polymer derivatives is preferably 1,000 to 1,000,000, and particularly preferably 2,000 to 3,000,000.

Tokuko Sho J! is involved in the production of these. ;-//Riri No. 3,76λ, 22tA, Special Publication Akihiro! -/2120
No. 447-/llA/! A method similar to the method described in No., Hiroj.

Next, other configurations of the halogenated thread-sensitive material of the present invention will be described.

The silver halide grains in the silver halide photographic emulsion used in the present invention have a regular structure such as a cube or an octahedron.
It may have a lar crystal, an irregular crystal shape such as a spherical shape, a plate shape, or a composite shape of these crystal shapes. It may also consist of a mixture of particles of various crystalline forms.

These photographic emulsions are published by P. Glafkidea in Chem.
tee Ph1sique Photography
que (published by Pau1Monte1, 1967),
Photographic by GJ', L)uffin
Emulsion Chemistry (The Fo
Cal Press, 1266), V.

Making by L. Zelikman et al.
andCoating Photographic E
mulsion (The Focal Press
It can be prepared using the method described in, for example, published by J.D. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

Proteins such as gelatin and casein can be used as binders for the photographic layer.

Gelatin referred to herein refers to so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin. As the gelatin, gelatin containing polymeric TG fraction described in JP-A-62-7-7-52 is preferred.

Further, the photograph W & source material of the present invention has US patent tube 3. in the photographic constituent layer. ≠II, ri No. 11, same 3. ≠ii.

72, Japanese Patent Publication No. J-133/, etc., may be included.

Although the silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, the Glafkide S'l or Zeli
Kman et al.'s book or H.
ndlagen der Photography
henProzesse mit 8i1berhal
ogeniden (Akademische Verl.
agsgese achaf t, / 91. ! ) can be used.

That is, a sulfur sensitization method using a sulfur compound or activated gelatin that can react with silver ions, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc., may be used alone or in combination. Can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rotanes, and other compounds can be used. Specific examples thereof are described in U.S. Pat. ,x,4cio,tr2,2.271,ri≠7,
λ, No. 721,441,! ,6jl,,ri! ! It is written in the number. As the reduction sensitizer, stannous salts, amines, hydrazine visiting conductors, formamidine sulfinic acid, silane compounds, etc. can be used. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used.

The light-sensitive material of the present invention may contain various compounds as antifoggants or stabilizers.

That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted compounds): heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazole mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially l-phenyl-!-mercaptotetrazole), mercaptopyridines: the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group : Thioketo compounds such as oxazolinthione; Azaindenes such as tetraazaindenes: (especially ≠-hydroxy device m(/+3.3a+7) tetraazaindenes): Benzenethiosulfonic acids: Benzenesulfine: etc. Many compounds known as agents or stabilizers can be used.

For more detailed examples of these and how to use them, see U.S. Patent No. 3. 31. ≠7≠ No. 3.
References can be made to the specifications of RI♂λ, RI≠7, Oλ/, 24#, and Ordinance Specification-21゜6to.

Hardeners include mucochloric acid, formaldehyde, dimethylol urea, glyoxal, succinaltehyde,
Aldehyde thread compounds such as glutaraldehyde, divinyl sulfone, methylene bismaleimide,! -acetyl,3-diacryloyl-hexahydro-8-toIJazine, /,3゜j-triacryloyl-hexahydro-
3-triazine, /, J, j-) IJ vinylsulfonyl-hexahytrose s-triazine bis(
vinylsulfonylmethyl)ether, l,3-bis(vinylsulfonylmethyl)propanol, bis(α-
Active vinyl compounds such as vinylsulfonylacetamido)ethane: 2. Hiro-dichloro o-6-hydroxy-5-
) Active halogenated compounds such as riazine sodium salt (2N-rubamoylviridinium tlil ((/-morpholinocarbonyl-3-pyridinio)methanesulfonate), haloamidinium salts (/-(/-chloro-
Examples include inorganic compounds such as pyrrolidinium/pyridinomethylene), λ-naphthalene sulfonate, etc.) and chromium aerobane.

The photographic emulsion layer or other constituent layers of the light-sensitive material of the present invention may contain a dimple auxiliary agent, antistatic property, slip property improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (for example, promoting blemish formation, m-toning, and sensitization). Surfactants other than those of the present invention may also be included for the purpose of woodcutter use.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols alkylamines or amides, polyethylene oxide adducts of silicones), dalicidol conductors (e.g. alkenylsuccinic polyglycerides).

Nonionic surfactants such as alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars: alkylsulfonates, alkylsulfonates, alkylbenzenesulfonates,
Alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate M, N-acyl-N-
Carboxy groups such as alkyl tauric acids, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., sulfo groups, phospho groups, sulfate ester groups, phosphoric ester groups, etc. Anionic surfactants containing acidic groups, diamino acids, aminoalkylsulfonic acids,
Ampholytic surfactants such as aminoalkyl@acids or phosphoric esters, alkyl betaines, and amine oxides; alkylamine salts, aliphatic or aromatic cylindrical ammonium salts, and heterocyclic bronchial ammoniums such as pyridinium and imidazolium. Salts, and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The photographic emulsions of this invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes,
Included are merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine color complexes can be used as the basic heterocyclic nucleus for these pigments. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.:
Nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is,
Indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole bale, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus.

Quinoline bales etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a bigrin-yone nucleus, a thiohydantoin nucleus, and a λ-thioxazolidine-1 nucleus having a ketomethylene structure.
．． J-4-membered heteroartic ring nuclei such as ≠-dione nucleus, thiazolidine-Kotsuhiro-dione nucleus, rhodanine nucleus, and thiobarbic acid nucleus can be applied.

(Examples) The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

(Example -/) +I+ Preparation of photosensitive silver halide emulsion Potassium bromide, potassium iodide, and silver nitrate were added to a gelatin bath solution with vigorous stirring. Silver iodobromide (71 DL) was added in the form of a thick plate with an average grain size of lμ. An average iodine content of 10 mol%) was prepared. Thereafter, it was washed with water using a conventional precipitation method to obtain % Dye-/, and then chemically sensitized using a gold/sulfuric acid sensitization method using chloroauric acid and sodium thiosulfate to form a photosensitive silver iodobromide emulsion A.
I got it. A 0.7μ thick plate-shaped silver halide emulsion B (average iodine content 6 mol%) was prepared in the same manner as silver halide emulsion A, except that the temperature of the potassium iodide was adjusted. .

(2) Preparation of coated sample On a triacetyl cellulose support containing m+n=j2/'me/m2 silicon oxide jη/rn2 in the top layer of a bag, each layer of the following formulation was simultaneously applied sequentially from the support side to prepare a sample. /~/≠ was created.

(Bottom layer) Binder: Gelatin - / 197m2 Cloth auxiliary agent: Poly p-styrene sulfone potassium salt 10.0 ~ / □2 (Binder layer) Surfactant: Binder: Gelatin -' /? /m2Fixing accelerator: o, /6y/m2E-/Dye-'-24'InQ/
rrL2 dye-27/! m9/rrt2 Dye-l Dye-27 (Intermediate layer) Binder: Gelatin-/0. Hiro W/m2 Coating aid: Poly p-styrene sulfonic acid potassium salt 3.3ma/rrt2 (emulsion layer -/) ω Fabric silver amount: Emulsion B/, 197m2 Hinder: Gelatin 72 21/m2 JIW sensitive dye:
Dye −/2, /IQ/Ag
/Saturating agent: C15HasOeCHzCHzOkaTHz, r■/Ag/r Coating aid: Polyp-cetininsulfonic acid potassium salt 10m9/m2 Hardener: /, 2-bis(vinylsulfonylacetamide)ethane ≠! m9/m2 (Emulsion layer - 2) Coated silver amount 2 Emulsion A ≠v/TrL2 Dextran: Listed in Table 7 Binder: Gelatin-2 Hiro, 2? /m2 sensitizing dye:
1)ye-/2. /Immediately/Ag/y'115
7JO agent: Cx5HasofCHzO(zO)-'
δ-H! , f1n9/Ag/Tatrimethylolbronoξn Hiroλ0rn9/m2 Coating aid: poly p-styrene sulfonic acid potassium salt 100~/, 2 Sensitizing dye: Dye −/ (surface protective layer) Binder: Gelatin − j O, 7t/m2 Slip agent: ≠3■/r! L2 3H7 C3F17802NCH2COOK 2
m9/m "10m9/m2 Matting agent: Polymethyl methacrylate fine particles (average particle size 3μ) 0./3■/m2 However, L/Proportion of high molecular weight component" Gelatin-
/ 13.7% -2≠, /% -j /J, 2% Result of measurement by the method described in Japanese Patent Publication No. 62-172J (3) Sensitometry These samples were heated at 30°C6j. It was stored for 1 day after application at a temperature and humidity of %RIH. Each sample was tested in the following manner.

(1) Wet adhesion test (peel test) Current practice, fixation,
At each stage of washing, scratches are made on the photographic emulsion side of the film in the processing solution using an iron brush, and the scratches are rubbed with the tip of a finger in a direction perpendicular to the line.

If the emulsion layer does not peel off on the scratch, it is grade A, and the maximum peeling width is 3.
When it is within 11I-IL, it is classified as B class, and when it is larger than this, it is classified as 0 class.

(11) Measurement of Sensitivity Each sample was exposed through an optical wedge to a 4too lux tungsten source for 1710 seconds, and then developed with the following developer at 20'C for 7 days.

Using the same method for each sample after fixing, washing, and drying, the fog density was calculated using a constant density (O).

- optical density) was measured.

These results are shown in Table 1.

Developer Metol Co-sodium sulfite 1009 Hydroquinone
j7 positive lux・10H20koV Calorie water /1 fixed nursing i
:Fuji Fix (Fuji Photo Film stock sample l≠ is,
When the adhesion improver was added to the binder layer at a rate of 0°219/m2, it agglomerated and was out of the practical range as a coated sample.

As can be seen from Table 1, samples in which the adhesion improver of the present invention was added to a layer closer to the support than the dextran-added layer showed improved adhesion when wet without impairing sensitivity.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Claims] In a photosensitive material comprising at least two constituent layers on at least one side of a support, the photosensitive material contains dextran, and at least one layer closer to the support than the dextran-containing layer contains a water-soluble ionic material. A photosensitive material characterized by containing a polymer.