JPS61110133A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease the change of flatness with respect to temp. and humidity by providing a silver halide emulsion layer on one surface of a base and provid ing >=3 layers of hydrophilic colloid layers contg. a layer into which a lipophilic material is incorporated as the layer nearest the base to the other surface. CONSTITUTION:At least one silver halide emulsion layer is coated on one sur face of the base by a dip coating method, etc. The hydrophilic colloid layers made into at least three-layered construction are coated on the other surface of the base by a dip coating method, etc. The lipophilic material is incorporated into the layer nearest the base among the hydrophilic colloid layers to form the silver halide emulsion photographic sensitive material. There are diethyl azipate having >=110 deg.C b.p. and small solubility particularly with water, etc. as the lipophilic material to be compounded with the hydrophilic colloid layer. A cellulose deriv., polyester, etc. are suitable for photographic use as the base.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material having excellent film properties.

According to the present invention, curling of a silver halide photographic light-sensitive material coated with a hydrophilic colloid layer is significantly improved, and not only curling is prevented, but also adhesion resistance and blocking resistance are improved.

[Prior Art] Generally, a silver halide emulsion layer (hereinafter referred to as "
A halogen 7i photographic light-sensitive material (hereinafter referred to as "back layer") which has a backing (hereinafter referred to as "back layer") containing a hydrophilic colloid such as gelatin as a binder on the other side.
(hereinafter referred to as "sensitive materials") have flatness properties (non-curling properties) that do not change much with changes in temperature or humidity during handling from photography to development, printing, and storage, compared to sensitive materials that only have a photographic layer. ) is desired.

For example, if the flatness is poor, the distance between the photosensitive material and the lens will vary depending on the location, and if the photosensitive material is particularly large, the image will be unclear, and the photosensitive material may be easily scratched when printing. arise.

The flatness of such a photosensitive material varies depending on the characteristics of the photographic layer, back layer, undercoat layer, and support that constitute the photosensitive material.

For example, in the case of a support, depending on the drying conditions during film formation, the distribution of the added plasticizer may become uneven in the thickness direction, width direction, or width direction. tLWJ
During coating and drying, the solvent of the undercoating solution is introduced into the support at an early stage. The increase in crystallinity due to transparency causes expansion and a decrease in elastic modulus, and in the 911 stage, contraction occurs and the flatness is significantly impaired.

In addition, the lower m layer uses a monomer selected from vinyl chloride, vinylidene chloride, methacrylic acid, maleic anhydride, etc. as a starting material for the purpose of imparting adhesion to the support of the photographic layer and back layer. Cooperative combination, polyethyleneimine,
Epoxy ml? , Grafting - Nitrocellulose, etc. is used as an undercoat resin, and a solvent that swells or dissolves the support is used. However, these solvents are relatively volatile and are released during storage of the undercoat solution, resulting in the application of the undercoat resin. Fluctuations in the amount may result in loss of flatness.

On the other hand, in the case of the photographic layer and the back layer, gelatin, acylated gelatin such as phthalated gelatin, maleated gelatin, carboxymethyl cellulose, human oxygen, etc. are used as binders.
In a sensitive material in which a hydrophilic binder made of a cellulose derivative such as xyethylcellulose is used as a binder, and the binder is coated on a support, when the relative humidity is high, these layers expand more than the support. Conversely, at low relative humidity these layers shrink more than the support. As a result, the flatness of the sensitive material is significantly impaired by relative humidity.
Furthermore, when these hydrophilic binders contain silver halides, various additives, couplers, emulsion polymerized latex polymers, etc., each contained material exhibits a unique modulus of elasticity due to the physical properties of the contained materials, and at the same time Flatness is also impaired because the hydrophilic binder easily expands and contracts in response to changes in temperature and humidity.

As mentioned above, the flatness of sensitive materials can be broadly classified and fluctuates due to the reasons mentioned above, and in particular, the photographic layer consisting of a hydrophilic colloid layer and the back layer have a greater influence on flatness than the support and the lower layer. .

On the other hand, for photosensitive materials, it is necessary to firmly adhere a photographic layer and a back layer made of hydrophilic colloids such as gelatin to a support. 1) After surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, etc., apply a close-up layer and a backing layer to the surface and restore adhesion. Method.

(2) A method in which a subbing layer is provided on a support as described above, and a photographic layer and a backing layer are coated thereon.

However, it is difficult to obtain sufficient adhesive strength with method (1) alone, and even with method (2), the solvent that swells or dissolves the support in the liquid containing the undercoat resin is highly polar. Using an etching agent with a boiling point,
It is essential in most cases to use the basecoat resin's own solvent, and the etching power of these solvents is extremely temperature dependent, so that the adhesion itself is dependent on the temperature during coating and drying and other steps.

Therefore, in order to improve the flatness of the above-mentioned photosensitive material, a method is known in which a lipophilic substance is contained in the hydrophilic colloid layers of the photographic layer and the back layer to make the binder flexible. Furthermore, it is well known among those skilled in the art that a hydrophilic colloid layer may contain a lipophilic substance and be coated thereon in order to firmly adhere the above-mentioned photographic layer and back layer to a support.

Regarding such technology, for example,
No. 72, No. 39-177024, No. 43-13482, No. 45-5331, No. 5g-57732, U.S. Pat.
No. 2166, No. 2852386, No. 2853457, No. 3397988, No. 3411911, No. 341
No. 1912, No. 3488708, No. 3397988 [l:, etc.].

However, the method of adding a lipophilic substance to a hydrophilic colloid layer constituting a photographic layer has problems such as an increase in desensitization fog to silver halide, a delay in permeability during development, and an increase in air resistance. tend to cause problems, and
On the other hand, it has the disadvantage that it causes extreme filter clogging due to aggregation and coagulation caused by salts and organic solvents, and also causes coating defects in the coating process, which naturally limits its usage. Furthermore, varying (ie, decreasing) the thickness of the photographic layer also reduces photosensitivity and dye density, and can lead to undesirable co-coupling.

In addition, the photographic layer contains a hydrophilic binder such as gelatin, various additives such as silver halide, and couplers, and silver halide is also used as a silver halide emulsion layer with different color sensitivities and sensitivities. It is common to have a structure in which the layers are stacked, and in order to maintain the physical and photographic properties of the various photographic layers, the dry film thickness inevitably increases, and even the flatness is impaired.

A back layer that balances flatness with such a photographic layer is
Conventionally, it is composed of one layer or 21 m. Moreover, the lipophilic substance used for the purpose of adhesion to the support is added to the back layer composed of one layer or 21 layers. However, under storage conditions with severe changes in temperature and humidity, this lipophilic substance is no longer retained in the binder used for the back layer, which consists of one or two layers, and the surface of the back layer and the
In the case of 1HR composition, blocking tends to occur, in which the adhesive migrates to the adjacent backing layer, increases the adhesiveness of the surface of the backing layer, and easily adheres to other objects when it comes into contact with them. .

This phenomenon occurs between photosensitive materials or other objects that come into contact with them during manufacturing, image processing, or storage, and often causes various inconveniences. As a technique for preventing this, there is a method of adding a matting agent to the outermost layer to increase the surface roughness, thereby creating a so-called matte. However, if a large amount of matting agent is used, it may reduce the transparency of the image formed when the photosensitive material is developed, impair the graininess of the image, or worsen the smoothness of the surface, making it easier for images to stick. It happens. or,
It is also known that blocking can be improved by adding a certain type of organic fluoro compound to the outermost layer, but due to its high surface activity, it is easy to align to the outermost surface and is effective against blocking, but on the other hand, it has poor charging characteristics. The amount of use is naturally limited from the point of view of the peeler belt IEI adjustment.

Generally speaking, in conventional back layers composed of 11 or 2 layers, the lipophilic substance used for the purpose of adhesion of the back layer to the support has a negative effect on the blocking properties and further reduces the flexibility of the entire back layer. This increases the number of layers more than necessary, making it unsuitable as a back layer for adjusting the flatness of a photosensitive material having various photographic layers. Therefore, in order to compensate for the physical characteristics of the photographic layer, support, or undercoat layer, it is necessary to: ■ have little elasticity in response to fluctuations in temperature and humidity, maintain flatness with the photographic layer at all times, and ■ support There is a strong demand for a backing layer that has the following properties: (1) good transparency and excellent anti-blocking properties;

[Object of the Invention] The object of the present invention is to provide a photosensitive material having a photographic layer on one side of the support and a back layer on the other side, in which the back layer consisting of a hydrophilic colloid layer firmly adheres to the support. The object of the present invention is to provide a light-sensitive material in which the flatness of the light-sensitive material shows little change due to changes in temperature and humidity, has excellent blocking resistance, and has improved physical properties of a back layer.

[Structure of the Invention] The object of the present invention is to provide a silver halide comprising at least one silver halide emulsion layer on one side of a support and a hydrophilic colloid layer on the other side of the support. In the photographic light-sensitive material, the hydrophilic colloid layer has a structure of at least three layers, and this is achieved by a silver halide photographic light-sensitive material in which the layer closest to the support among the hydrophilic colloid layers contains at least a lipophilic substance. It was done.

The lipophilic substance used in the present invention plays a role in not only adhesion of the back layer to the support but also flexibility of the entire back layer. Lipophilic substances that diffuse or dry and completely disappear are undesirable. Specifically,
These lipophilic substances are those that can be emulsified and dispersed without being completely miscible with the hydrophilic coid liquid of the backing layer, and preferably have a boiling point of 110"CD or above, and are especially soluble in water. Specific examples include diethyl adipate, dibutyl adipate, diisobutyl adipate, di-n-hexyl adipate, dioctyl adipate, dicyclohexyl azelate, di-2
-ethylhexyl azelate, dioctyl sebacate,
Diisooctyl sebacate, dibutyl succinate, octyl stearate, dibenzyl phthalate, tri-cresyl phosphate, diphenyl-mono p-te
rt-butylphenyl phosphate, monophenyl-di-0-chlorophenyl phosphate, monobutyl-dioctyl phosphate, 2.4-di-n-amylphenol, 2.4-di-tert-amylphenol, 4-n
-nonylphenol, 2-methyl-4-n-octylphenol, N,N-diethylcapryl 7mide, N,N-
Dimethyl laurylamide, glycerol tripropionate, glycerol tributyrate, glycerol monolactate diacetate, tributyl citrate, acetyl triethyl citrate, di-2-ethylhexyl adipate, dioctyl sebacate, di-isooctyl azelate, Diethylene glycol dibenzoate, diethylene glycol dibenzoate, triethyl citrate, tri(2-ethylhexyl) citrate, acetyl tri-n-butyl citrate, di(isodecyl) 4.5
- Epoxytetrahydrophthalate, oligovinylethyl ether, dibutyl fumarate, polyethylene oxide (n>16), glycerol tributyrate, ethylene glycol dipropionate, di(2-ethylhexyl) isophthalate.

Butyl laurate, tri(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, silicone oil, dimethyl phthalate,
Diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisooctyl phthalate, cyamyl phthalate, di-n-octyl phthalate, cyamylnaphthalate, triamylnaphthalene, monocaprin, monolaurin, monomyristin, monovalmitin, monostearin, monoolein, Cicaprin, dilaurin, simiristin, civalmitin, distearin, diolein, 1-
stearo-2-valmitin, 1-palmito-3-stearin, 1-palmito-2-stearin, triacetin,
Tricaprin, trilaurin, trimyristin, tribalmitin, tristearin, triolein, tripetroserin, trierucin, trilicyruin, lyluodistearin, lyluozirirunine, oleogersin, lyluoziercin, palmitooleorilunine, paraffin, linseed oil, eno oil, tung Oil, flaxseed oil, kaya oil, walnut oil, soybean oil, camphor oil, poppy seed oil, sunflower oil, t! Drying oils such as I oil, quail oil, safflower oil, etc. : Cotton'fc oil 1. Semi-drying oils such as corn oil, sesame oil, rapeseed oil, rice bran oil, buzz oil, mustard oil, kaboku oil, dehydrated castor oil W4: peanut oil, olive oil, camellia oil, sasanquat oil,
There are chazuke oil, mustard oil, water-containing castor oil, almond oil, sesame oil, pen oil, and large egg oil.゛The lipophilic substances used in the present invention can be dissolved individually or in combination of two or more in a low boiling point solvent such as acetone or ethyl acetate, and then directly dispersed in an aqueous phase or a hydrophilic colloid solution. In the presence of a dispersant, it is fractionated into an aqueous phase or a hydrophilic colloid solution and added as so-called oil droplets to the preparation solution when coating a backing layer.

Here, as the dispersant, any of a 7-ionic surfactant, a nonionic surfactant, a cationic surfactant, or a mixture thereof can be used. However, from the viewpoint of photographic properties, anionic and nonionic activators are preferable.

The smaller the size of the oil droplets of the lipophilic substance added here, the better, considering the transparency of the back layer.

- If the oil droplets are large, the stability of the liquid itself over time may deteriorate, and the resulting coating film of the back layer may also become unclear. In particular, adhesion to a support is related to the ratio of the lipophilic substance added to the hydrophilic binder, and is not related to the size of the oil. Its size can be set arbitrarily from the viewpoint of stability of immersion in oil. In particular, the effective size for use is approximately 0.01 to 10 from the viewpoint of transparency and oil droplet stability.
Oil droplets with an average particle size of μ are preferred.

In the present invention, the back layer constituting the photosensitive material has a structure of at least three layers, and among the back layers, the layer closest to the support contains at least the lipophilic substance described above. As the amount of lipophilic substance used in the back layer increases, the adhesive strength will increase, but if the amount increases too much, the cohesive force of the back layer itself containing this substance will weaken and the strength will decrease. Depending on the film forming property and film strength of the binder itself in the back layer, it is possible to add about twice the amount of the binder in terms of weight ratio. Also, adhesion, film strength, transparency, am
Considering the setting properties of each back layer during coating and the flexibility of the back layer to maintain the flatness of the sensitive material, a particularly preferable amount of the lipophilic substance to be used is 1/1 of the binder in terms of the ta ratio of dry fiIIIt. ~1 times the amount. In addition, the layer adjacent to the back layer containing the lipophilic material closest to the support may also contain the lipophilic material, but the amount used should be lower than that of the layer closest to the support in terms of binder weight ratio. is preferred.

Therefore, in the back M configuration of the present invention, by using at least a lipophilic substance in the back layer closest to the support, not only adhesive properties but also 2! i
It is possible to achieve a good balance between the photogm and the i1 degree. On the other hand, when the total binder coating amount and i oily substance amount of the back layer are the same as those in the present invention, the i oily substance is uniformly distributed over the entire back layer, or the i oily substance is distributed sequentially outward from the support. In the conventional back II construction in which more lipophilic substances are used in the layers, the flatness of the photosensitive material tends to be pronounced in the photograph HfjA.

In addition, as mentioned above, if a large amount of lipophilic substance is used to further increase the adhesive strength of the back layer to the support,
The lipophilic substance that is no longer held in the binder moves to the outermost layer and deteriorates the blocking properties, but in the present invention, a plurality of lipophilic colloids are placed on the layer containing the lipophilic substance closest to the support. By providing a layer, it is possible to trap lipophilic substances and improve blocking properties.

In this way, in the back layer of the present invention, the layer containing a relatively small amount of lipophilic material, which is coated on the bottom layer containing a lipophilic material, plays an important role in terms of adhesive strength, blocking properties, and flatness. However, it is preferable that more binder is applied than the bottom layer.

In addition, for the layer farthest from the support among the back layers in the present invention, for example, a matting agent, a coating aid, a charge control agent, etc. are added. As already mentioned, the back layer of the present invention can be used most efficiently as a layer, so it can be designed with superior physical properties compared to the conventional IWJ or two-layer back layer. It is clear from this.

Supports used in the present invention include supports made of all polymeric materials, but supports particularly suitable for photocopying include those that have transparency, flexibility,
Due to other chemical properties, so-called cellulose derivatives such as cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose nitrate, polystyrene, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, Examples include styrenic polymers such as α-methylstyrene, polyesters and esters such as polyethylene terephthalate, polyhexamethylene terephthalate, polyethylene-2°6-naphthalate, and polycarbonate, polyolefins such as polyethylene and polypropylene, and paper. Furthermore, the support may be transparent, may contain a dye, may contain a pigment such as titanium difluoride, may be a laminate film made by laminating plastic on paper, or may be a laminate film as described in U.S. Pat. No. 3,515,567. It may also be a plastic film that has been surface treated as described above.

Next, the undercoat layer of the photographic layer coated on the support has carboxyl groups, carbonyl groups, hydroxy groups in its molecules,
Monomers containing sulfo groups, Amim L amide groups, epoxy groups, Wi anhydride mtg, so-called polar groups, such as acrylic acid, sodium acrylate, methacrylic acid, itaconic acid, crotonic acid, sorbic acid, itaconic anhydride, maleic anhydride Acid, cinnamic acid, methyl vinyl ketone, hydroxyethyl acrylate, hydroxyethyl methacrylate, human O-oxychloropropyl methacrylate, hydroxybutyl acrylate, vinyl sulfonic acid, potassium vinylbenzenesulfonate, acrylamide, N-methylacrylamide, acroylmorpholine, Polymers consisting of dimethyl methacrylic 7-mide, N-t-butyl-acrylamide, diacetone acrylamide, vinyl pyrrolidone, glycidyl 7-acrylate, glycidyl methacrylate, etc., or copolymers of these monomers with other co-containing monomers. Formed by coating.

For example, acrylic acid esters such as ethyl 7-acrylate and 1-ethyl 7-acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, acrylic acid, methacrylic acid, or one of them! Ethylenically unsaturated esters represented by derivatives, homopolymers consisting of ethylenically unsaturated acids, or copolymers of these with other vinyl monomers, itaconic acid, itaconic anhydride,
Polysalts such as maleic acid and maleic anhydride! 31 and styrene,
There are copolymers with vinyl monomers such as vinyl chloride, vinylidene chloride, and butadiene, or terpolymers of these monomers and other ethylenically unsaturated monomers. It is preferable to perform a surface activation treatment such as , electrodeless discharge, or flame treatment. Regarding the back layer, is it the same as the photo layer? i14! It is preferable to apply the coating on the undercoat layer.

In addition to gelatin, the binder for the gelatin-containing hydrophilic layer of the photographic layer and back layer in the present invention may include gelatin derivatives and cellulose E such as hydroxyethyl cellulose.
Synthetic hydrophilic polymers such as L1, starch, polyvinyl alcohol, polyN-vinylpyrrolidone, polystyrene sulfonic acid, and polyacrylic acid can also be used.

As the gelatin, acid-treated gelatin, alkali-treated gelatin, enzyme-treated gelatin, etc. can be used.

Furthermore, coating, auxiliary agent, antistatic, slippery improvement, emulsification dispersion,
Various surfactants may be contained for various purposes such as preventing adhesion and improving photographic properties.

For example, saponins (steroids), alkene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol furkyl ethers or polyethylene glycol alkylaryl ethers, poly,
Ethylene glycol esters, polyethylene glycol solmethane esters, polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol! ! ! Nonionic surfactants such as polyglycerol alkenylsuccinate, alkylphenol polyglyceride, fatty acid esters of polyhydric alcohols, and alkyl esters of sugars = furkyl carboxylates, alkyl sulfonates, and alkylbenzene sulfones. Acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphorus esters M, N-7silyl N-furkyl tauric acid, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl 7-ion surfactants containing acidic groups such as carboxy groups, sulfo groups, phosphor groups, sulfate ester groups, phosphoric ester groups, etc., such as phosphorous esters, aminoalkyl sulfones, aminoalkyl sulfones, and aminoalkyl sulfones! Or amphoteric surfactants such as fR1 esters, alkyl betaines, and amine oxides: alkylaminesIi% aliphatic or aromatic quaternary ammonium! ! Cationic surfactants such as heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, phosphonium or sulfonium salts containing aliphatic or heterocyclic rings, and fluorine-containing surfactants can be used.

For these compounds Belgian patent no. 74268
No. 0, British Patent gI 1496534, US Patent No. 3
．． 888, 678, etc. can be used as a meeting.

Further, in the photographic layer and back layer of the present invention, a microscopic or inorganic gelatin hardening agent may be added alone or in combination, such as C, E, and K.

Mees and T, H, Jaies W r The
Theory of the photography
ic Pr0CeSSJ No. 0CeSSJ 6th year) US Patent @ 3,316,095 Bow, j! ! 13,232,76
No. 4, 3.288,775@, 2,732,303
Month, 3,635,718jij.

No. 3,232,763, No. 2,732,316, j
5J 2,586,16 August, same No. 3,103,437, same No. 3,017,280, same No. 2,983.611 Bow, same No. 2,725,294, j! 02,725,295
Month, 3.100,704, 3,091,537, jQl 3,32L313, 3,543,292
No. 3,125,449, British Patent No. 994.869
Typical examples include mucochloric acid, mucobromic acid, mucophenoxychloric acid, mucophenoxybromic acid, formaldehyde, dimethylol urea, Such as trimethylolmelamine, glyoxal, monomethylglyoxal, 2,3-dihydroxy-1,4-dioxane, 2,3-dihydroxy-5-methyl-1,4-dioxane succinic aldehyde, 2,5-dimethoxytetrahydrofuran, glutaraldehyde. Aldehyde compounds and their TI4 conductors; divinyl sulfone N, N
--Ethylene bis(vinylsulfonylacetamide), 1
．． 3-bis(vinylsulfonyl)-2-propertool,
Methylene bismaleimide, 5-7 cetyl-1,3-diacryloyl-hexahydro-3-triazine, 1.3.
5-Triacryloyl-hexahydro-3-triazine, 1°3.5-trivinylsulfonyl-hexahydro-
Active vinyl compounds such as 3-triazine: 2.4-dichloro-6-hydroxy-3-triazine sodium salt, 2.4-dichloro-6-nodoxy-S-triazine,
2,4-dichloro-6-(4-sulfo7nilino>-s
-triazine sodium salt, 2,4-dichloro-6-
(2-sulfoethylamino)-s-triazine, N,N
Active halogen compounds such as -bis(2-chloroethylcarbamyl)piperazine: bis(2,3-epoxypropyl)methylpropylammonium p-toluenesulfonate, 1,4-bis(2').

3'-epoxypropyloxy)butane, 1.3°5-
Epoxy compounds such as triglycidyl isocyanurate, 1,3-diglycidyl-5-(γ-7cetoxyβ-oxypropyl)isocyanurate; 2,4.6-
Ethyleneimino compounds such as triethylene-s-triazine, 1,6-hexamethylene-N,N'-bisethyleneurea, and bis-β-ethyleneiminoethylthioether: 1°2-di(methanesulfonoxy)ethane,
1.4-di(methanesulfonoxy)butane, 1.5-
Methanesulfonic acid ester compounds such as di(methanesulfoneoxy)pentane, dicyclohexylcarbodiimide, 1-cyclohexyl-3-(3-trimethylaminopropyl)carbodiimide-p-toluenesulfone m
Salt, 1-ethyl-3-(3-dimethylaminopropyl)
Carbodiimide compounds such as carbodiimide salt
2.5-dimethylisoxazole/perchlorine number salt, 2-
Isoxazole compounds such as ethyl-5-7enyl isoxazole-3'-sulfonate and 5.5'-(paraphenylene)bisisoxazole; Non-visual compounds such as alum alum and chromium; N- Carboethoxy-2-isopropoxy-1,2-dihydroquinoline,
Dehydrated rice tai type peptide samples such as N-(1-morpholinocarboxy)-4-methylpyridinium chloride INN,N
' -Adiboyldioxydisuccinimide, N, N'
-Active ester compounds such as terephthaloyl dioxydisuccinimide; Isocyanates such as toluene-2,4-diisocyanate and 1,6-hexamethylene diisocyanate.

The back layer in the present invention may contain colloidal silica, and the colloidal silica has an average particle diameter of 7-μ.
~1201μ, the main component is bilayered silicon, and may contain alumina or sodium aluminium as a minor component.These colloidal silicas also contain sodium hydroxide, water-waved potassium, and hydroxide as stabilizers. Inorganic bases such as lithium, ammonium hydroxide, and organic salts such as tetramethylammonium ion may be included. In particular, as a stabilizer for colloidal silica, colloidal silica consisting of potassium hydroxide or ammonium hydroxide may be used. is preferred.

For these colloidal silicas, for example, E go
n M atijevic@, 5urface and
Co11oidS Cie! No. 61.3 of nCe
100 pages (1973, John Wiley &
5ons).

A specific example of colloidal silica is E.

1, du Pont de' Nemours &
Go, (・USA) to 1-udox AM, 1u
dox As, Ludox LS.

From Nissan Chemical Co., Ltd. (Tokyo, Japan) under trade names such as Ludox TM and Ludox HS,
Snowtex 20. Snowtex C, Snowtex N.

With product names such as Snowtex 0, Mon5anto C
o.

From (USA), 5yton C-30,5VtO
With product names such as n200, Na1co Chew
, Co.

From (LISA), N a+coagto3o, N
a+coaoioeo.

Examples include those commercially available under trade names such as Na1coaol D-21-64.

Furthermore, the back layer can contain a matting agent.

The matting agent used in the present invention has an average particle size of 1 to
It is a 5μ solid or organic fine powder, and inorganic matting agents include silica (silicon dioxide), magnesium oxide,
Organic matting agents such as titanium dioxide and calcium carbonate include polymethyl methacrylate, cellulose acetate propionate, and polystyrene, and silica and polymethyl methacrylate, particularly polymetal methacrylate, are preferably used.

In addition to the various additives mentioned above, the back layer in the present invention contains a silver halide photographic material with photographic performance and
Various additives can be added to improve the physical properties.1 For example, during manufacturing processes such as coating, drying, processing, photographing, developing, baking, etc., when the sensitive material is used, it can be used to remove lint, spring return, or transport. British Patent No. 14 was developed to prevent scratches caused by contact with various substances when handling products such as
66304j%, slipping agent described in Japanese Patent Publication No. 5B-34821, etc., Japanese Patent Publication No. 36-10466, No. 4
2-26187, 48-54964, etc., chelating agents, dyes, etc. can be optionally used.

In the present invention, when coating a photographic layer, an undercoat layer, and even a back layer on a support, for example, dip coating, air knife coating, curtain coating, or extrusion coating using a hopper as described in U.S. Pat. No. 2,681,294, etc. Various coating methods can be used.

The test method will be explained below.

(1) Adhesion test method for back layer support: Make 25 squares by making 6 cuts at 5 m/a intervals on the sample to be tested both vertically and horizontally.

Adhesive tape (Sumitomo 3M, Scotch, Mending Tape) was applied on top of this and quickly peeled off in the 180 rx direction, and the adhesive strength was evaluated on the following five scales based on the number of squares in the peeled back layer.

Equal length Number of peeled squares A O ~ 5 8 6 ~ 1° C 11 ~ 15 DI 6 ~ 20 E 21 ~ 25 As a photographic light-sensitive material, the adhesive strength that can withstand large moons is 8 or more in the above evaluation, preferably It is equivalent to A.

(2) Blocking property test sample was cut into 4 cm square pieces, the surface of the photographic layer and the surface of the back layer were overlapped, and a load of 800 Q was applied to the overlapped surfaces at 60°C and 70% R)+( 4 under conditions of relative humidity)
It was left for 8 hours.

After that, the surface of the photographic layer and the surface of the back layer are peeled off, and as the adhesive traces on the surface of the back layer, the adhesive surface is smooth and has a different glossiness than the non-adhesive surface.
Traces can be identified. The degree of adhesion was determined by this method for all tests of adhesion and blocking properties below.

〔Example] The present invention will now be explained in more detail with reference to Examples.

Example 1 A photographic layer having the composition shown in Table 1 was coated on one side of a cellulose triacetate film support having an undercoat layer on both sides and having a thickness of 120 .mu.m and dried.

Below is the first table in the margin! The iWI agent is 2-hydroxy-4,6-dichloro-s-
Triazine sodium salt was used, and sodium p-dodecylbenzenesulfonate was used as a surfactant.

The antihalation layer/yellow filter layer contains colloidal silver.

The composition of silver halide used in each photosensitive layer and the coating amount of silver are as follows.

Blue sensitive IA913.3 mol%+A99r 96.7%A
Q 2.2 Mm” Green sensitive IAaI 4.0 mol% + All 3r 96,0
%Ag3.1 o/iz red sensitive 11Aa13.5 mol%+AQ B r 96,
5% AQ 3. I Mm2 Samples were prepared by coating and drying the back layer having the layer structure shown in 2a on the other side of the above support in order from the first layer, and an adhesion test and a blocking test were conducted on these samples. .

In the following margin, as a hard rule, 0.5 Q of 2-hydroxy-4゜6-dichloro-s-triazine sodium salt is added to each layer.
/10G gelatin, and p-dodecylbenzenesulfonic acid sodium was used as a surfactant.

Also, here lipophilic substances are molecules in the method shown below! !
Liquid and terRait.

A liquid lipophilic substance di-n-octyl phthalate 2.0g Vinegar Fraudori Chill 1. OQB liquid gelatin aqueous solution 15% 2011 triisopropylnaphthalene sulfonate soda 2609C liquid Gelatin water MW 7% so mL Mix the above liquids A and B and use a valve-type homogenizer manufactured by Manton-Gorlin to make 250kl; l/C11l.
The mixture was emulsified under pressure to form an O/W type fractional dispersion. At this time, the particles of the dispersion in the gelatin aqueous solution were controlled to have the particle size viHo and aμ. Solution C was added to the obtained dispersion, and water was added to give a final composition of 8011 to obtain a dispersion of a lipophilic substance.

From the above results, it can be seen that the adhesion to the support requires a lipophilic substance, but on the other hand, in the conventional two-layer structure, the blocking resistance deteriorates. As the amount of the binder tII increases, the blocking resistance deteriorates significantly, and as the amount of binder tII in the layer above the layer containing the lipophilic substance increases, it improves slightly, but no major change is observed. In this case, despite increasing the binder layer by 12 layers in order to prevent the migration of lipophilic substances to the surface layer, no significant change was observed in the Belocking resistance compared to (2) and (3), which was used for WI2WJ. It is thought that the effect of the matting agent on blocking resistance decreased due to the change in the binder ratio. On the other hand, as in the present invention, 3! It can be seen that in the case of composition II and containing a lipophilic substance in the first WI, the adhesion to the support became stronger and the blocking property was also significantly improved.

In addition, in the configuration of the present invention, when the comparative sample and the total binder loss are constant, 131 is the E of the comparative samples (1) to (3).
I! It can have the same HItA configuration as 21111,
The results also show that waiting is excellent.

Furthermore, even when the amount of lipophilic substance is increased as in sample (9), all properties are superior to those of the comparative sample.

However, the film strength against scratches was somewhat inferior.

Example 2 The same photographic layer as in Example 1 was coated on one side of a cellulose triacetate film support with a thickness of 120μ and provided with a lower m layer on both sides, dried, and the other side of the support was 3rd on the side of
Pack layers having the configurations shown in the table were applied and dried in order from the 11th layer to prepare samples, and an adhesion test and a blocking test were conducted.

The following is a blank space in Table 3. Note that the same gelatin hardening agent and surfactant WJ activator as in TCY&Example-1 were used. Tricresyl phosphate was used as the lipophilic substance, dispersed in the same manner as in the fourth case of YCM Example-1, and added to the coating liquid.

From the above results, even if the back layer is made of 311SlIIt, the adhesion and blocking properties deteriorate in the comparative sample in which the layer closest to the support does not contain the lipophilic substance but the other layers contain it.

Therefore, as in the sample of the present invention, the 11th
most preferably contains a lipophilic substance.

Among these, in particular, those in which the second layer and the 311th layer do not contain lipophilic substances have shown good results in both adhesive strength and blocking properties. In addition, sample (17) and (
From the relationship 18), even if the amount of binder applied in the 12th layer is reduced, or even if the amount of binder applied in the 31st layer from sample (19) is reduced, the blocking resistance is superior to the comparative sample. Recognize.

Example 3 The same photographic layer as in Example 1 was coated on one side of a cellulose triacetate film support having a thickness of 120 μm and provided with an undercoat layer on both sides. On the other side, apply a back layer having the composition shown in Table 4 in order from the first layer,
A sample was prepared by drying.

The results of the adhesive sample and blocking test are as follows.

゛Left below margin 4 The lipophilic substance used is di-n-octyl phthalate.
It was dispersed in the same manner as in gm Example-1 and added to the coating solution.

The colloidal silica is Snowtex (manufactured by Kaguchi Kagaku Co., Ltd.) whose pH has been adjusted to 9.0 fCI with potassium hydroxide.

The same gelatin hardening agent and surfactant as in Example-1 were used.

Furthermore, the flatness of these samples was measured.

Flatness is expressed as 1/r: degree of curl, with the photographic layer facing up and the back layer facing down, and the curved radius being 1/r: the degree of curl. The results as shown in Table 5 below were obtained as the degree of curl under the climatic conditions.

From the results above the lower margin, for samples containing lipophilic substances in the back layer,
It can be seen that the flatness against changes in climatic conditions after development processing does not change much compared to samples that do not contain lipophilic substances.

Samples (22) to (21) of the present invention, which have remarkable effects on adhesive strength and blocking properties, have even better flatness.

In addition, even if the total amount of gelatin and the total amount of lipophilic substance in the back layer are the same, samples (24) and (25) containing a lipophilic substance only in the first layer closest to the support are It is also superior in terms of flatness compared to samples (21) and (22) in which the layer also contains some lipophilic substances. 2, sample (21
), (22), it is possible to reduce the total amount of gelatin without affecting the FIi adhesion and blocking properties, as in samples (26) and (27). can.

〔Effect of the invention〕

As explained in detail above, according to the present invention, in a light-sensitive material having a photographic layer on one side of a support and a back layer on the other side, the back layer has a structure of at least three layers, and By containing at least an essential oil-based substance in the layer closest to the support, the contact properties of the back layer to the support are increased, and the flatness of the photosensitive material is less likely to change due to changes in IJ [degrees], and blocking resistance is improved. It is also possible to IJ the characteristics immersed in it.

Patent applicant Konishiroku Photo Industry Co., Ltd. Procedural Amendment (
Method) % formula % 1. Indication of the case 1982 Patent Application No. 232576 2. Name of the invention Silver halide photographic light-sensitive material 3. Person making the amendment Relationship to the case Patent applicant address 1 Nishi-Shinjuku, Shinjuku-ku, Tokyo Chome 26-2 Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Co-educational student Shisei 4, agent 102 Address 2-2 Kudanminami, Chiyoda-ku, Tokyo @8J! Matsuoka Kudan Pill Telephone: 263-9524 February 6, 1985 Shipment date: February 26, 1985 6, subject to correction llll! Part 7 of the "Detailed Description of the Invention", Contents of Amendment (1) Clarity [lI, page 23, lines 9 to 10, r
The theory of the P
photoraphicProcessJ
Theory of the Photographic Process (The Th
theory of the photo.

-Graphic Process) J.

(2) rs surface and Co11oid on page 27 of the specification cylinder jf112th line to 13th line
ScienceJ says ``Surface and Colloid Science (5)
surface and Colloid Scien
ce) Correct it as J.

(3) Akira 111127j (II 7 [from line 118 r L udox A M , L udox
A S , L udox L S , L udox
TM, Ludox HS J and ``Ludox AM'', Ludox As
(Ludox AS), Ludox LS (Ludox
LS), Ludox TM,
/L/F Tux H8 (Ludox H8) J correction.

(4) rsyt on page 28, line 2 to line 3 of the specification
on C-30, 5yton 200J [Syton C-30, Syton 2
00 (Syton 200) Correct as J.

(5) rN a on page 28, line 4 to line 5 of the specification
lcoag 1030. N alcoag 10
60°N alcoaa ID -21-64J
0), Nalcoaa 1G6G (Nalcoaa 1
060), Nalcog 10-21-64 (N a
lcoaa ID-21-64) Corrected as J.

Claims (1)

[Claims] In a silver halide photographic material comprising at least one silver halide emulsion layer on one side of a support and a hydrophilic colloid layer on the other side of the support, the hydrophilic colloid layer is 1. A silver halide photographic material comprising at least three layers, wherein the layer closest to the support among the hydrophilic colloid layers contains at least a lipophilic substance.