JPS61117534A - Silver halid photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having a film strength after a film formation and less tendency for generating a reticulation after a developing treatment, when the material is rapidly dried at a high temp. in a production of the titled material by incorporating a gelatin obtd. by a lime - treatment of a pig skin to the titled material as a binder of a hydrophilic colloidal layer having a nonsensitive property. CONSTITUTION:The gelatin obtd. by the lime - treatment of the pig skin is incorporated to the titled material comprising at least one of the photosensi tive silver halide emulsion layer and at least one of the hydrophilic colloidal layer having a nonphotosensitive property provided on the substrate as the prescribed binder. The above described gelatin is preferably used to the most outer layer of the titled material or in a course of its production, such as a surface protective layer and the titled material having the good coating property in addition tot he prescribed characteristics is obtd.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic material (hereinafter referred to as a "sensitive material"), and particularly relates to a silver halide photographic material (hereinafter referred to as a "sensitive material"). Relating to a sensitive material in which reticulation does not occur.

(Prior art) Sensitive materials generally include a light-sensitive silver halide emulsion layer on a support,
It has an intermediate layer, a surface protective layer, etc., and a hydrophilic colloid is usually used as a binder for these layers.

The most commonly used hydrophilic colloid used as a binder is gelatin.

In recent years, the manufacturing process for photosensitive materials has become increasingly faster, and after coating a hydrophilic colloid layer on a support, the drying process requires increasingly high temperature and rapid drying. It has been done.

As the temperature in the drying process increases, wrinkles appear on the surface of the hydrophilic colloid layer after development.
``Reticulation'' becomes more likely to cause development.

When reticulation occurs, it has a serious effect on the photographic performance of the photosensitive material and significantly reduces its commercial value.

For this reason, research has continued for many years on photosensitive materials that do not cause reticulation after development even if they are rapidly dried at high temperatures during production.

For example, Tokko Akira! t-co J/47-A discloses a technique using acid-treated gelatin as a binder for a surface protective layer of a sensitive material.

Also, Tokukai Akira! /-12Jr Publication states that the intermediate layer and the surface protective layer have isoelectric points of t,! A technique using pigskin acid-treated gelatin of -2,j is disclosed.

Even more Tokko Akira! No. 3,777 discloses a technique of using acid-treated gelatin having a jelly strength of 2 or more in a photosensitive material having a paper support coated with polyolefin.

Japanese Patent Publication No. 54A-air 7 contains a combination of alkali-treated gelatin and acid-treated gelatin, contains a coupler emulsified with a high boiling point solvent and an anionic surfactant, and contains At", Cr" Sensitive materials containing such ions have been disclosed.

However, in general, as the gelatin used as a binder in the photosensitive silver halide emulsion layer, lime-treated (alkali-treated) gelatin is generally used due to limitations in its photographic performance; In the case of technology using gelatin, the second problem is that in the manufacturing process of a sensitive material in which multiple layers are coated simultaneously, a layer made of acid-treated gelatin and a layer made of lime-treated gelatin come into contact at the interface. However, coating properties may deteriorate.

On the other hand, Japanese Patent Publication No. Shojj-211λjJ discloses a technique for preventing reticulation by using lime-treated gelatin having a jelly strength of 5 oot or more as the top layer. The lime-treated gelatin mentioned in the publication is lime-treated gelatin with a jelly strength of 300 f or more made from cow bones, but it is difficult to produce lime-treated gelatin with such high jelly strength on an industrial scale. be.

On the other hand, Tokuko Sho J-Ko≠Ori No. 7, same JJ-Ko/441
No. 4,009,300 discloses a technique in which a synthetic polymer is used in place of gelatin for the surface protective layer.

The use of these synthetic polymers has drawbacks such as increased swelling of the surface protective layer, slow drying, and reduced film strength in the developer when developing the photosensitive material after manufacture. are doing.

(Objects of the Invention) Therefore, the first object of the present invention is to provide a photosensitive material that does not cause reticulation after development even if it is rapidly dried at high temperature during the production of the photosensitive material.

The first objective is to provide a sensitive material that has excellent coating properties and does not cause reticulation.

Third, it is a sensitive material that is easy to manufacture industrially, has slow drying during the manufacturing process, does not cause reticulation after development, and has a strong film after completion. Our goal is to provide the following.

(Means for Solving the Problems) These objects of the present invention provide a light-sensitive material having at least/often a light-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer on a support. This was achieved by using a light-sensitive material that uses lime-treated gelatin made from pig skin as a binder for the non-photosensitive layer.

There are no particular limitations on the method for producing lime-treated gelatin from pigskin used in the present invention. For example, collagen is partially hydrolyzed in advance by soaking pig skin in a suspension of slaked lime for 30 to 20 days (lime treatment), and then washed with water to remove lime and then neutralized with hydrochloric acid. Wash again with water and extrude at the specified pH! - Obtained by doing.

゛ Regarding the manufacturing method of gelatin, for example, T, ) I
.

James;The Theory of TheP
photographic Process Fth
, ed.

77 (Maamilan) j page 1, Scientific Photography Handbook (Part 1) pages 7-2 to 7j (Maruen), Fundamentals of Photographic Engineering - Silver Salt Photography Edition l/ri~l Cog Pages (Corona Publishing), etc. can be used as a reference.

Jelly strength (PAGI) of pork skin lime-treated gelatin of the present invention
(according to law) is 200~JOOf.

In particular, 2110-λrot is preferable.

Regarding the PAGI method, the photographic gelatin test method
You can refer to the description on page 1 of the photographic gelatin test method joint council waste stone).

In the present invention, the layer using pork skin lime-treated gelatin is at least one of the non-photosensitive layers such as a surface protective layer, an intermediate layer, and a filter layer, but especially a surface protective layer or an intermediate layer. The layer is preferably the outermost layer of the photosensitive material or a layer that becomes the outermost layer during the photosensitive material manufacturing process.

Particularly preferred is an embodiment in which pork skin lime-treated gelatin is used for the surface retention layer and the intermediate layer 1@.

In the present invention, the coating amount of pigskin lime-treated Seratin is 002 to 1097 m2 per 7 layers, especially 0, j to 3f.
/m2 is preferable. It is preferable to use pigskin lime-treated gelatin in an amount of 0 to ioo based on 10 to 100 weight of hydrocolloid in one layer.

As the hardening agent for the pork skin lime-treated gelatin of the present invention, a gelatin hardening agent having a vinylsulfonyl group is preferably used.

As a gelatin hardening agent having a vinylsulfonyl group,
Preferably, it is a compound represented by the following general formula.

(CH2=CH-802-CH2÷2-person formula chunin represents a divalent group, but it is not necessary.

Examples of compounds that can be used in the present invention include the following.

Compound example H0H V-j (Q(2=CH5O2CH2CONH+2
V-A (Q(2=OtSO2CH2CON)(+
2CH2V -7(Q(2=CH8O2CH2CONH
CH2-)-2V-1(CHz=CH8OzCHaC
ONHCH2÷2CH2r- V-/J CH2=CH(SO2CH2SO2CH=
CH2V-tp CH2=CH・5O2C)T2CH
2SO2CH=CH2V-it CH2=CH-80
2CH2CH2Q (2802CH=(?) f2V -i
y C2H3C(CH2SO2CH=Q(2) !I
V-#r CH2=CH3O2CH2CHCH2SO
2CH=CH25O2CH=CH2 (Q(2=Q(So 2CH2) B CQ(2SO2
Q(Q(2NHQ(2CH25o3NaV-2/ ■-23 CI(,=CH(SO20(2CH20CH2CH20
CI(2CH2SO2CH-CH2V-,2y CH
2=CH802CH20(?H2SO2CH-CH2V
-Jt Q(2-CH802(?H2Q(2(疋■r
2CB2802Q(=CH2■-24 CH2=CH802CH2Q(2CH2CH,0CH2
CH2CH2CH2SO2Q(=CH2V-27(Q(
2=CH-8O2CH2CH2CONH+2CH2V-
21(CH2=CH(5()2CH2CH2CONH-
(J12+z■-1? (CH=CH2) The amount of these gelatin hardening agents used in the present invention is 0.07 to 20% by weight relative to gelatin, preferably 0./
~10 weight class.

Of course, other hardeners such as λ-hydroxy-1,t-dichloro-8-)riazine can also be used in conjunction with the vinylsulfonyl group-containing gelatin hardener.

In addition to color films such as color negative film, color reversal film, color e, and e-, the photosensitive material of the present invention can include black and white films, but the effects of the present invention are particularly effective with color films. In case.

The surface protective layer or intermediate layer of the photosensitive material of the present invention includes a matting agent,
It can contain surfactants, slip agents, dyes, ultraviolet absorbers, colloidal silica, non-photosensitive silver halide particles, colloidal silver particles, and the like.

As matting agents, homopolymers or copolymers of polymethyl methacrylate, silicon dioxide, etc. with particle sizes of 1 to 10
μ particles can be used.

As a surfactant, for example, saponin (steroid type)
, 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 fIJ alcohol alkyl amines or amides nonionic surfactants such as polyethylene oxide adducts of silicone), cricidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylic acids salts, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates.

Carboxy groups, sulfo groups, such as alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as phospho groups, sulfuric acid ester groups, and phosphoric acid ester groups can be used.

More preferably used surfactants include fluorine-containing surfactants. As the fluorine-containing surfactant, Japanese Patent Publication No. Sho≠1r-113IJO, jj
Compounds described in -4!4!4c// and 4A7-ta 303 can be preferably used.

There are no particular restrictions on the various materials used in the light-sensitive silver halide emulsion or other layers of the sensitive material of the present invention, and research disclosure journals, Vol. 17, pp. 22-31 (L. month) can be referred to. For example, as a yellow coloring coupler, a known open-chain ketomethylene type coupler can be used. Among these, the penzoylacetanilide and piparoylacetanilide compounds are advantageous. As the magenta coloring coupler, pyrazolone compounds, pyrazolotrimazole compounds, indashilon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds and pyrazolotriazole compounds are particularly advantageous. As the cyan coloring coupler, phenol compounds, naphthol compounds, etc. can be used. In particular, it is preferable to use phenolic compounds having a lareido group or an acylamino group. In addition to this coupler, D
IR couplers, colored couplers, couplers that release fogging agents, etc. can be used.

In the sensitive material of the present invention, benzo-/J-triazole compounds, benzophenone compounds, butadiene compounds, benzoxidol compounds, and the like can be used as ultraviolet absorbers.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. mercaptotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptothiazoles (especially l-phenyl-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthione; azaindenes, For example, triazaindenes, tetraazaindenes
7 Hiro-types (%≠-hydroxy-substituted (/, J, ja, 7) tetraazaindenes), pentaazaindene groups; such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. A number of compounds known as antifoggants or stabilizers can be added. As the anti-fading agent, hydroquinone rust conductors, gallic acid derivatives, pL-r lucoxyphenols, and bisphenols can be used.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 A multilayer color photosensitive material sample Ioi was prepared by forming each layer having the composition shown below on a cellulose triacetate film support.

(Sample 10/) 1st layer: Antihalation layer (AHL) Gelatin layer containing black colloidal silver Ceratin 197m2 4th layer: Red-sensitive emulsion layer (RL) 1/j-/- Silver iodobromide emulsion (silver iodide :/θ,!Molar coefficient average particle size/, 2
Polydisperse emulsion of μ) ・・・・・・・・・・・・ Silver coating amount ≠, 7f/
m2 sensitizing color compound・・・・・・・・・・・・λ, jx10-' mol sensitizing dye for 1 mol of silver ■・・・・・・・・・・・・・・・...0 for 1 mole of silver, Axlo mole coupler C-/...O for 1 mole of silver
, oor mole coupler C-2...0 per mole of silver
．． 010 mole Kab7-B-,2...0.002 mole gelatin per mole of silver ≠t/m2 Third layer:
Intermediate layer (ML) Gelatin layer containing an emulsified dispersion of J-di-t-octylhydroquinone Gelatin /, 097 m2 μth layer: Green-sensitive emulsion layer (GL) Silver iodobromide emulsion (silver iodide ania, 0 mol. Average particle size -/!-
J- i, iμ polydisperse emulsion) ・・・・・・・・・・・・Amount of coated silver ≠, ot7m2 sensitizing dye■・・・・・・・・・・・・・・・1 mole of silver /, I × 10 mole sensitizing dye ■・・・・・・・・・・・・ Oob × lO mole coupler M−/・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・θ per mole of complex
, 0/j mole coupler E-4...0 per mole of silver
．． 003 Molgelatin J, Of/m2 jth layer;
Yellow Filter Single Layer (TEL) Emulsified dispersion of yellow colloidal silver and j-di-t-octylnohydroquinone in a gelatin aqueous solution gelatin
Of/mfl 4th layer; Blue-sensitive emulsion layer (BL) Silver iodobromide (polydispersed emulsion with a silver iodide nimolar average grain size of μ) ......Coated silver amount 0. 1t/m2 coupler Y
-/・・・・・・1/ 00033 mol gelatin 1.0 t/m2 7th layer for 1 mol of silver;
Protective layer (PL) Trimethylmethanoacrylate particles (diameter approx. l.

Apply a gelatin layer containing ja).

In addition to the above composition, antifoggant j-methyl-7-hydroxy-/7.4'-)riazaindolizine, gelatin hardening agent V-7, and surfactant are added to each gelatin/Of7m2 layer. did.

The sample prepared as described above was designated as sample 10/.

The type of gelatin used for sample ioi was bovine bone lime treated gelatin.

The drying conditions during the production of sample ioi were 440'C and 7 minutes. Sample 1 was prepared in the same manner by changing the gelatin and drying conditions of the first layer, third layer, j-th layer, and seventh layer as shown in Table 1.
02 to 104 were created. After each sample was prepared, it was developed, and the surface of each sample was observed with the naked eye and with a microscope to determine whether reticulation occurred.

The results are shown in Table 1.

As is clear from Table 1, the sample lop~i according to the present invention
It can be seen that ot is preferable because it does not cause reticulation after development even if it is quickly dried at high temperature.

Compound sensitizing color chart ■; Anhydro-!・j′-dichloro-3・3
'-di(r-sulfopropyl)-terethyl-thiacarbocyanine hydroxide pyridinium salt sensitized color chart■; 11-dibenzothiacarboxy, anine hydroxide/triethylamine salt sensitizing dye ■; Anthitroterethyl-1-! '-shipp
o o-j・J'-di(r-sulfoflovir)oxacarbocyanine/sodium salt sensitizing dye -[β-(r-sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt coupler E-2 coupler E-j r!-2/- coupler M-/α coupler Y-/ coupler C-/ coupler C −λ

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, the binder of the non-photosensitive hydrophilic colloid layer is pigskin lime-treated gelatin. A silver halide photographic material characterized by: