JPH01307743A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make it possible to strongly stick between an anti-halation layer and a film supporting body by mounting a silver halide emulsion on the one side of a polyester supporting body, and a hydroxyalkyl alkylcellulose acetate phthalate layer on the another side of the polyester supporting body through an acetylcellulose layer, respectively. CONSTITUTION:At least one layer of the silver halide emulsion layers is mounted on the one side of the polyester supporting body, and a 2nd. layer composed of the hydroxyalkyl alkylcellulose acetate phthalate is mounted on the another side of the polyester supporting body via a 1st. layer composed of the acetylcellulose layer, respectively in the photosensitive material. And, the 2nd. layer of said material may be composed of hydroxyalkyl alkylcellulose acetate phthalate and a mixed ester of celluloseacetate having hexahydroxyphthalyl or tetrahydroxyphthalyl group. Thus, the anti-halation layer is strongly stuck to the polyester base on the photosensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an improvement in a backing layer when a polyester support is used as a support layer in a silver halide photographic light-sensitive material.

[Conventional technology]

In general, silver halide photographic materials (hereinafter referred to as "sensitized materials") have at least one photosensitive silver halide emulsion layer on one side of a plastic film support, and if necessary, an undercoat layer and an intermediate layer. layer, a filter layer, a surface protection layer, and a backing layer on the other side.

The purpose of providing a buffing layer on a photosensitive material is firstly to prevent haley silane, secondly to prevent charging, thirdly to impart scratch resistance, and fourthly to provide curl balance. In the present invention, a back layer provided for the purpose of preventing Halley's silane is referred to as a Halley's silane preventing layer. Halley's silane is usually reduced by providing a light absorption layer on one side of the support and absorbing light reflected to the photosensitive layer.

Many proposals have been made regarding the Halley silin prevention layer. Halley Silin Prevention 11: One example of a layer is a Halley Silin Prevention layer with carbon black or graphite dispersed therein. Colloidal carbon black dispersions useful as anti-Haley silane layers are described, for example, in U.S. Pat. No. 2,271,234. Another example of an antihalation layer is one that contains a colored material, such as a dye, that absorbs light in most of the visible spectrum.

On the other hand, as a binder for such an antihalation layer,
For example, cellulose acetate phthalate (hereinafter referred to as C
Various alkali-soluble substances such as AP) are preferably used.

Although CAP has many desirable properties for this purpose, it is difficult to use as an antihalation material when the surface of the silver halide emulsion layer and the surface of the antihalation layer come into contact with each other at high temperatures and high humidity. However, this tends to cause a problem of migration to the surface layer on the side of the silver halide emulsion layer. When using an antihalation layer made of CAP, such problems are likely to occur particularly in sensitive materials such as color films.

On the other hand, the typical processing method for color film for motion pictures, which is a sensitive material with an antihalation layer, is as follows:
Prior to the color development step, a pre-bath treatment and a water washing treatment are performed. This water washing process is a process for removing the antihalation layer, and the pre-bath bath process is a pretreatment process for removing the antihalation IlZ layer in this water washing process.

In such a pre-bath bath treatment-water washing process, the most preferable step in the step of removing the antihalation layer is that the antihalation layer is not completely removed in the pre-bath bath, but is easily and completely removed by washing with water. That is, although the antihalation layer adheres strongly to the support before the development process, it needs to be easily separated during the development process.

For this reason, as one of the means to solve the above-mentioned disadvantage that the antihalation layer and the emulsion layer surface tend to adhere to each other, as described in US Pat. No. 3,392,022, cellulose acetate is used. Xahydrophthalate (hereinafter referred to as CARIt P) or cellulose acetate tetrahydrophthalate (hereinafter referred to as CAT)
Techniques have been disclosed for using HP (referred to as HP) as a binder in antihalation layers. However, CAM
HP (or CAT) IP has the disadvantage that when processed with an alkaline photographic developer, the antihalation layer cannot be removed just by processing with Il'l, and cannot be removed without using methods such as forcibly wiping it off. have.

In order to improve this drawback, in Japanese Patent Publication No. 45-8835, CA)II(P) or CATHP is replaced with l of lower alkyl methacrylate and methacrylic acid:
A method is disclosed in which copolymers are used in a ratio of 3 to 3:1 (molar ratio). However, antihalation layers containing such copolymers have poor moisture resistance.
It has the disadvantage of causing adhesion if left in contact with the surface of the emulsion layer for a long time under high temperature and high humidity.

Therefore, the present inventors have previously proposed an antihalation layer consisting of ε-do[I-xyalkyl alkylcellulose acetate phthalate and (1) hexahydrophthalyl group, according to Japanese Patent Application Laid-open Nos. 61-94044 and 61-94095. Alternatively, an antihalation layer consisting of a cellulose ester having a tetrahydrophthalyl group and (ii) a hydroxyalkyl alkyl cellulose acetate phthalate is proposed, and firstly, it has excellent moisture resistance and is easily removable, and secondly, it has excellent moisture resistance and is easily removable. It was shown that in treatment p1, the silver halide material was not removed but was removed by washing with water, and thirdly, a silver halide photosensitive material having an antihalation layer in which the antihalation layer and the film support were firmly adhered was obtained.

[Invention tries to solve it! ! ! ! However, in this method, when a polyester support such as polyethylene tereclate is used as the film support, hydroxyalkyl alkyl cellulose acetate phthalate alone or (i) cellulose having hexahydrophthalyl group or tetrahydrophthalyl group is used. It was found that the adhesion between the Halley silin prevention layer consisting of a mixture of ester and (ii) hydroxyalkylalkylcellulose acetate phthalate and the polyester support was insufficient.

If this adhesive strength is weak, the anti-halation layer of the photosensitive material may peel off before processing, causing problems such as the anti-halation layer falling off during film processing or camera photography. Tend.

The present invention provides hydroxyalkyl alkyl cellulose acetate phthalate alone or (i) hexahyto 1:1
Cellulose esters having phthalyl or tetrahydrofucryl groups, and (ii) hydroxy? An object of the present invention is to provide a sensitive material having a Halley's silin preventing layer made of a mixture of rukylalkyl cellulose acetate phthalate, which can be strongly adhered to a polyester base, and which can be removed cleanly in a development process.

[Means to solve the problem]

As a result of various studies, the present inventor has discovered that hydroxyalkyl alkyl cellulose has at least one layer of silver halide emulsion on one side of a polyester support and a first layer consisting of an acenal cellulose layer on the other side. A cell LJ having a second layer consisting of acetate phthalate, or having the second layer containing (i) hydroxyalkylalkyl cellulose acetate phthalate, and (ii) a hexahydrofucryl group or a tetrahydrophthalyl group.
It has been found that the above-mentioned problems can be achieved by constructing the photosensitive material as a second layer made of a mixed ester.

The degree of acetylation of the acetyl cellulose used in the first layer is not particularly limited, but is usually 55 to 62%, preferably 58 to 6%.
The polymerization degree is generally 200 to 400, preferably 250 to 370, although there is no particular restriction on the degree of polymerization. The solid content of acetylcellulose is not particularly limited, but is usually 0.01 to 5 g, preferably 0.1 to 1 g per ml.

The solvent may be selected as appropriate and includes, for example, ketones, esters, aromatics, phenols, halogen solvents, and the like.

When using a mixture of hydroxyalkylalkylcellulose acetate phthalate and a cellulose ester containing a hexahydrophthalyl group or a tetrahydrophthalyl group as the second Halleysilin-preventing layer,
The ratio of hydroxyalkyl alkyl cellulose acetate phthalate to cellulose ester having a hexahydrophthalyl group or a tetrahydrophthalyl group is preferably t:3 to 381 in terms of weight ratio.

Examples of the cellulose mixed ester having a hexahydrophthalyl group or a tetrahydrophthalyl group used in the present invention include CA I (II P or CATIIP).
can be given. CAIIHP or CAT
There are no particular restrictions on each substituent in HP, but CA HH
In the case of P, 11 to 50% by weight of acetyl group and 10 to 70% by weight of hexahydrophthalyl group are preferable, particularly 15 to 35% by weight of acetyl group! %, hexahydrophthalyl 2 & 25 ~
Similarly in the case of CATHP, the range of 45% by weight is particularly preferred, acetyl JJ 1 to 50% by weight, especially 15 to 3% by weight.
5% by weight, 10-70% by weight of tetrahydrophthalyl group,
In particular, it is preferably 25 to 45% by weight. On the other hand, there are no particular restrictions on the various substituents of hydroxyalkylalkyl cellulose acetate phthalate, but hydro,
Xyalkoxy W2~? 031 (!it%, especially 3-1
(1.1 M%, 2 to 35% alkoxyl groups, especially 1
0 to 25% by weight, 1 to 50% acetyl group, especially 5 to 50% by weight
20% by weight, phthalyl MIO to 70% by weight, especially 20 to
The amount is preferably 40% by weight, the number of carbon atoms in the alkoxy group is preferably 1 to 4, and the number of carbon atoms in the hydroxyalkoxy group is preferably 1 to 4.

The total coating interval of the binder in the Halley anti-silence layer of the present invention is 0 per m'' for the sum of the two polymers.
．． The amount is preferably 0.05 to 5 g, particularly 0.2 to 1 g.

The viscosity ζ of the polymer used as a binder for the Halley silin prevention layer of the present invention is 50 g of polymer in each case.
acetone/methanol/methyl cellosolve (50:2
Dissolve in 250mj of a mixed solution (volume ratio: 5:25),
50 to 1000 cps, especially 10
It is preferable that it is 0-300 cps.

In the present invention, the solvent necessary for applying Haleysilane inhibitor I:N can be selected as appropriate. Examples include solvents.

Examples of the haleysilane inhibitor used include carbon dispersions (colloidal carbon).

In addition, when using a dye that absorbs light in the photographic wavelength range instead of colloidal carbon, this dye can be directly mixed with the binder used in the present invention, or the binder can be applied, and a dye layer is formed on the E side. It is also possible to coat the binder layer and allow the dye to penetrate into the binder layer.

Haleysilane-preventing dyes that can be used in the present invention include:
Well-known Spirit Blue CR (color index No.
, 689), Nigrosine Spirit Soluble (Color Index No. 8 (il), Alkaline Blue B (
Color index No. 704), Congo red (
Color index No. 370), etc.

The only requirement regarding the proportions of these antihalation substances is that there must be enough of the substance to absorb a substantial amount of the light that passes through the film base when the photographic film is exposed. That is the point. The carbon used as the haleysilane inhibitor is preferably milled by true milling, a homogenizer, or a mill of the type used for dye mixing.

In addition, the antihalation layer Rica heavy liquid in the present invention includes:
It is optional to use a coating film forming agent such as ethyl cellulose, shellac, or hydroxypropyl cellulose, or a paint dissolving aid such as acetin in a small amount, especially when using a carboxylic acid-based vinyl copolymer, A haleysilane prevention layer with excellent matte properties is formed.

Further, for the purpose of imparting slipperiness to the surface of the antihalation layer, for example, U.S. Pat.
Described in British Patent No. 1.143.118 Specification υ etc.
Silicone derivatives such as ζ, alkyl silicate sodium salts described in JP-A-Sho (i3-14141), etc. can be used together as the binder of the present invention, or can be applied as an overcoat.

Similarly, for the purpose of imparting surface mattness, particles of silicon dioxide, polymethyl methacrylate, polyacrylonitrile, carbon black, etc. with a particle size of 0.01 to 1
A matting agent having a thickness of Qμm, particularly 0.04 to 4μm, can be used in combination.

Next, the silver halide emulsion layer provided on the other side of the polyester support will be explained.

Various hydrophilic colloids are used in the photographic material of the present invention. For photographic emulsions and/or other photographs y1. Hydrophilic colloids used as binders for the constituent layers include, for example, gelatin, colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, sugar derivatives such as starch derivatives, and synthetic hydrophilic colloids. Examples of the colloid include polyvinyl alcohol, polyN-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylic fumid, derivatives thereof, and partially hydrolyzed sugars.

Compatible mixtures of two or more of these colloids are used if desired. The most commonly used of these is gelatin.

The photographic emulsion layer and other layers contain synthetic polymer compounds, such as latex-like water-dispersed vinyl compound polymers, especially compounds that increase the dimensional stability of photographic materials, either singly or in combination (different polymers). ), or in combination with hydrophilic, water-permeable colloids.
Specification No. 6.005, No. 2,739.137, No. 2,
No. 853.457, No. 3,062,674, No. 3゜4
No. 11.911, No. 3,488.708, No. 3,52
No. 5,620, No. 3,635.715, No. 3,607
, No. 290, No. 3,645,740, British Patent No. 1.
No. 186,699, No. 1.307.373, etc. Among these descriptions are alkyl acrylate, alkyl methacrylate, °? Acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkoxyalkyl acrylate, alkoxyalkyl methacrylate, styrene, butadiene, vinyl chloride, Copolymers and homopolymers selected from vinylidene chloride, maleic anhydride and itaconic anhydride are commonly used.

Hardening of the photographic emulsion and/or other photographic constituent layers may be carried out according to conventional methods. Examples of hardening agents include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, and bis(2-chloromethyl f5
R), 2-hydroxy-4,6-dichloro-1,3,
51 Reazine, et al. U.S. Patent No. 3.288,775, U.S. Patent No. 2.732.303°, British Patent No. 97
No. 4.723, No. 1.167.207, etc. Compounds containing reactive halogens such as divinyl sulfone, 5-a7tyl-1,3-diacryloylhexahydro-1,3,5-triazine, and others as described in U.S. Patent No. 3. [Specification of i35,718, 3', 232
．． 7G: No. 1, No. 3゜490.911, No. 3.6
No. 42,486, compounds having reactive olefins such as those shown in British Patent No. 994.8G9, N-hydroxymethylfucurimide, and other compounds having a reactive olefin, such as those shown in U.S. Patent No. 2.732.31G, etc. , same No. 2.586.
N-methylol compounds as shown in US Pat. No. 3,103,437, etc., isocyanate Zhao as shown in US Pat.
, 280, US Pat. No. 2,983,611, etc.; US Pat.
725. No. 294, US Pat. No. 2,725.295, etc., acid derivatives such as those shown in US Pat.
Carbodiimide compounds as shown in US Pat. No. 100.704, epoxy compounds as shown in US Pat. No. 3,091.537, US Pat. No. 3,321,313. Specification, No. 3,534.
Isoxazole compounds such as those shown in No. 292, halogenocarbo-1-dialdehydes such as mucochloric acid, diquaternary di-sane derivatives such as dihydroxydioxane and dichlorodioxane, N-carbamoylpyridinium salts, etc. , haloamidinium salts, or inorganic hardeners such as chromium brighten, zirconium sulfate, etc. Also, instead of the above compounds, compounds in the form of precursors, such as alkaline metal bisulfite aldehyde adducts, methylol V of hydantoin: conductors,
Primary aliphatic nitroalconyls and the like may also be used.

Silver halide photographic emulsions are usually prepared by mixing a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. This silver halide, °ζ is silver chloride,
In addition to silver bromide, mixed silver halides such as chlorinated, iodized, silver chloroiodobromide, etc. can be used.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material.

Those compounds are 4-hydro; tre-6-methyl-1,
3, 3,,? -Tetrazaindene, 3-methyl-benzothiazole, -phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts, and a large number of other compounds have been known for a long time.

Silver halide emulsions can also be chemically sensitized by conventional methods. Chemical sensitizers include, for example, gold compounds such as chlorauric acid salts and gold trichloride, salts of noble metals such as platinum, palladium, iridium, rhodium, and ruthenium, and sulfur compounds that react with silver salts to form silver sulfide. , stannous salts, amine M, and other reducing substances.

Photographic emulsions can be made by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or by using them in combination with styryl dyes, etc., to achieve spectral sensitization and strong coloring. Sensitization can be performed.

In addition, brighteners such as stilbene, triazine, oxazole, and coumarin compounds may be added to the non-light-sensitive photographic constituent layer, and ultraviolet absorbers such as benzotriazole, thiazolidine, and cinnamic acid ester compounds may be added.
Additionally, various known photographic filter dyes may be included as light absorbers.

In addition to the compound used in the present invention, if necessary, it may be used as a slip agent or an anti-adhesion agent, for example, US Pat.
32.305 specification, same number 4゜-042,399,
3,121.0 (io and British patent tube 1.4 (
Amides or esters of fatty acids and polyesters as described in GB 1 6,304 and GB 1 320 564, GB 1 320 564;
No. 0.565, U.S. Pat. and US Patent No. 3, 6.1? , 28 G Mei Tal
It may contain surface-active substances such as those described in the book I°C.

Further, as a matting agent, silica having a suitable particle size, an inorganic compound such as sodium chloride barium sulfate, an organic polymer such as polymethyl methacrylate, polystyrene, etc. can be contained.

(For example, U.S. Pat. No. 2,725,297 describes the use of antistatic agents in photographic constituent layers such as photographic emulsion layers, particularly in the outermost bands and anti-friction layers of photographic light-sensitive materials. , No. 2.972.535, No. 2,972.
No. 536, No. 2,972゜537, No. 2,972
, No. 538, No. 3゜033.679, No. 3,07
No. 2,484, No. 3,262.807, No. 3,5
No. 25.621, No. 3,615,531, No. 3.
No. 630.743, No. 3.653,906, No. 3
, 655,384, 3.655.386 and British Patent No. 1,222,154, 1,23
5,075;

Hydrophobic polymers such as those described in U.S. Pat.
．． Biguanide compounds such as those described in U.S. Pat. No. 591,590 and U.S. Pat.
Sulfonic acid type anionic compounds such as those described in U.S. Pat.
Phosphate ester as described in No. 291 and
class ammonium salts, also as described in U.S. Patent No. 2,88
Karaonic as described in Patent No. 2,157, No. 2.982.651, No. 3.399,995, No. 3.549.369, and No. 3.564,043. Compounds may also be used, for example in U.S. Patent No. 3.625.6
Nonionic compounds such as those described in U.S. Pat. Complex compounds such as those described in U.S. Pat.
17.834 Akira! It may contain organic molecules such as those described in Book II, No. 3655.387.

These compounds can be applied to any 411, whether black, white or colored.
Applicable to Class I photographic materials.

Silver halide emulsions include ortho emulsions, panchromatic emulsions, infrared emulsions, emulsions for recording invisible light such as X-rays, color photographic emulsions, such as emulsions containing color-forming couplers, emulsions containing dye developers, and bleaching emulsions. It includes various silver halide photographic emulsions such as emulsions containing dye r1 which can be dyed.

Color photographic emulsions may contain 2 to 4 equivalents of color-forming couplers, such as open-chain ketomethylene yellow-forming couplers such as the benzoylacetanilide or pivaloylacetanilide series, pyrazolone series, or indasilone series. Magenta color forming couplers, like
Cyanogen-forming chemicals such as phenolics or naphthols are preferably used. For example, Tokko Sho 4
8-18256, the magenta coupler described in Japanese Patent Publication No. 48-38416, the cyan coupler described in Japanese Patent Application Publication No. 48-42732, and U.S. Patent No. 2,428,054. Specification, 2nd and 4th
No. 49.966, No. 2゜455.170, No. 2.
600゜788, same No. 2.983.608, same No. 3
．． Colored couplers described in US Pat. No. 148.062 and the like, detachment-inhibiting couplers described in US Pat. No. 3,227,554, and the like can be used.

[Effect]

Although the Halley silin prevention layer has insufficient adhesion to the polyester support, it has strong adhesion to the acetyl cellulose layer and can be easily peeled off during the development process.
I do. Furthermore, for the polyester support? When a cetyl cellulose layer is applied and formed, it adheres strongly.

Therefore, in the present invention, the Halley silin prevention layer can be firmly adhered to the polyester support by laminating the Halley silin prevention layer on the polyester support via the acetyl cellulose layer, and furthermore, in the development process, the Halley silin prevention layer can be firmly adhered to the polyester support. The layer is easily made from the acetylcellulose layer! Aflit (Aflit), and is suitable as a sensitive material using polyester as a support.

The present invention will be further explained with reference to Examples below, but the present invention is not limited to these Examples. In addition, the addition amount "parts" in the Examples does not represent ffl■ parts.

(Example) 14 m of the first pJfp fabric solution A-F shown in Table 1 was applied to one side of a 120 μm thick polyester base.
G, which is the 2nd M coating solution shown in Table 2, was applied to -I: after drying at 90° C. for 3 minutes.

11 was spread on a 18m17m"l cloth and dried at 90°C for 3 minutes to form a base banking layer.
An undercoat layer is provided on the opposite side of the tongue layer, and on top of that is a Halley anti-silence layer, a red-sensitive emulsion layer, a gelatin intermediate layer, a green-sensitive emulsion layer, a yellow filter layer, and a blue-sensitive emulsion I [! i, Tamotsu 211! A motion picture color negative emulsion consisting of layers was applied sequentially. redness,
Silver iodobromide emulsions containing 6 mol % of iodine were used as the green-sensitive emulsions.

As the It-sensitive emulsion, a silver iodobromide emulsion containing 8 mol% of iodine was used.

eI: A transesterification catalyst was added to a mixture of 1 mol of terephthalic acid dimethyl ester, 1.7 mol of aethrene gellicol, and 0.8 mol of triethylene glycol.
Synthesized polyester.

Table 2 Second layer coating liquid composition Table 3 Sample The thus obtained sensitive material 1-14 was immersed for 5 seconds in an alkaline aqueous solution consisting of 5 parts of soda carbonate, 25 parts of Glauber's salt, and 1000 parts of water, and then further immersed in water. After cleaning, the degree of contamination with the alkaline aqueous solution, the detachment condition of the antihalation layer, and the detachment time were examined.

Further, a linear scratch of about 4 mm was made in the antihalation layer of Sensitive Materials 1 to 14 using a razor blade, and an adhesive tape was pasted thereon and then instantly peeled off. The anti-halation layer at that time! Table 4 shows the results of visual observation of the degree of All separation.

Table 4 Release of the antihalation layer 1111, peeling status, and self-A instead of CA l-111P as the second layer coating liquid.
A photosensitive material was prepared using T HP, and its detachment status, '
t, i #l When I investigated the situation, I found that the above CA HI (
Similar results were obtained for P.

〔Effect of the invention〕

The present invention provides hydroxyalkylalkylcellulose °1
A haleysilane prevention layer consisting of acetate phthalate alone or (i) hydro-tosialkylalkyl cellulose acetate fucrate and (ii) a cellulose ester having a hexahydrophthalyl group or a tetrahydrophthalyl group is applied via an acetyl cellulose layer. By laminating the haley silane prevention layer on the polyester support, the haley silane prevention layer can be firmly adhered to the polyester support, and the haley silane prevention layer can be easily peeled off from the acetyl cell layer during the development process. As a result, the antihalation layer has excellent moisture resistance, has strong adhesion between the antihalation layer and the polyester film support, and can be easily removed by washing with water without being removed by prebath treatment. This is a silver halide sensitive material that can be used.

Claims (2)

[Claims] (1) A polyester support has at least one layer of silver halide emulsion on one side, a first layer consisting of an acetyl cellulose layer on the other side, and a second layer consisting of hydroxyalkyl alkyl cellulose acetate phthalate.
A silver halide photographic material characterized by having a layer. (2) A claim characterized in that the second layer comprises (i) hydroxyalkylalkylcellulose acetate phthalate, and (ii) cellulose ester having a hexahydrophthalyl group or a tetrahydrophthalyl group. Item 1. Silver halide photographic material according to item 1.