JPH01296243A - Production of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the dimensional stability of the photosensitive material in case of a surrounding change and a development processing by winding the photosensitive material at a specified surface temp. of a supporting body applied an under coat layer thereon and then drying it. CONSTITUTION:A 1st. under coat layer which has a thickness of >=0.3mum and is composed of a copolymer contg. vinylidene chloride of 70-99.5wt%, and a 2nd. under coat layer of gelatin applied on the 1st. under coat layer are mounted on the both surfaces of a polyester supporting body, respectively. A hydrophilic colloid layer contg. a polymer latex is formed on at least one surface of the obtd. supporting body. And then, the supporting body which is applied with the under coat layer and dried it, is roll-wisely wound up controlling the surface temp. of the body to 35-60 deg.C. At that time, the supporting body being wound up, is preferably wrapped with a wrapping material having thermal insulating property and is allowed to settle for more than 8hr. The copolymer is exemplified by vinylidene chloride, methylmethacrylate or acrylonitrile copolymer, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a silver halide photographic material with improved film physical properties, and particularly to a method for producing a silver halide photographic material with excellent dimensional stability.

(Prior Art and its Problems) Silver halide photographic materials generally include a layer containing a hydrophilic colloid such as gelatin as a binder on at least one side of a support. Such a hydrophilic colloid layer has the disadvantage that it easily expands and contracts due to changes in humidity and temperature.

Dimensional changes in photographic materials due to expansion and contraction of the hydrophilic colloid layer are extremely important in printing photographic materials and optical materials that require reproduction of halftone images and precise line drawings for multicolor printing. This is a disadvantage.

Dimensional stability with little dimensional change (Dimens 1o
U.S. Pat. No. 320/λ50 discloses a technique for fully regulating the thickness ratio between a hydrophilic colloid layer and a support in order to obtain a photographic material with excellent nalstability. Special Public Show 3 Ter 4! , 27.2, 3ter 17702, 173-/34c1.2, 143-333/, U.S. Patent No. 2371.00, 7 Otsu 3 Otsu-3, 27
72/ll, No. 42J13g No. 2133≠5
No. 7, No. 3377911, No. 3 Hiroshi // No. 71, No. 3
≠//9/, described in Specification No. 2. In addition, the theoretical basis for the above technology is
, Umberger) in Photography Science and Engineering, page 6, page 73.
/9'47).

However, in the field of printing, where multicolor printing and reproduction of precise line drawings are required, improvements in dimensional stability have been strongly desired. Although it is particularly important that there be no difference in size before and after the processing steps that photographic film always goes through (developing, fixing, washing, drying), sufficient improvement cannot be achieved with technology that completely contains glass or polymer latex. .

This is because the support elongates due to water absorption during the treatment process, but even after the subsequent drying process, the elongation of the base does not return to its original state until a long period of time has elapsed, resulting in some elongation remaining in practical use.

Therefore, when comparing the dimensions of an untreated film and a treated film, the latter is often in an elongated state.

In the art, this phenomenon is expressed as poor dimensional stability due to processing, and this is a serious drawback in photographic materials for printing. In order to improve this drawback, Japanese Patent Application Laid-Open No. 60-3
6. ! No. 7 uses a technique in which both sides of a polyester film are coated with polyolefin and a support is used, and Patent Application Sho-Otsu J-Taku No. 733 uses a polyester support coated with a copolymer containing 70 to 99.5% by weight of vinylidene chloride. A technique using the body is disclosed. The technique disclosed in Japanese Patent Application No. 2-9'μ/33 is particularly excellent for Vi for improving the dimensional stability accompanying the processing of photographic materials for printing.

Generally, a long polyester support coated with an undercoat is transported to a winding chamber and wound around a core in the form of a roll. The temperature of the winding chamber is usually 20~. 2j'C1 relative humidity relative -6
It is air conditioned to a constant condition of 0% ℃H. However, the special request
The waterproof performance of the undercoat layer made of a vinylidene chloride copolymer on a polyester support obtained in the first process disclosed in No. 2-9≠/33 does not reach its inherent waterproof performance.

In order to make full use of its inherent waterproof performance, it is necessary to leave it for a long time after winding it up in a roll, or to place it in a temperature range where vinylidene chloride copolymer crystallization tends to proceed. If this operation were to be carried out, the undercoating process would have to be lengthened or the conveyance speed would have to be reduced, which would increase production costs. Therefore, the nine undercoat base, which had been rolled into an a-le shape in the winding room, was brought to another heating room and reboiled for 4 hours.
! ? 1 was carried out to improve crystallinity. The temperature of the heating chamber is 3
4'C to 60C.

However, in this method of improving crystallinity by reheating, the entire length of the long roll is reheated at a room temperature of 20 to JJ'C, so it takes a long time to reach the set temperature. There was a difference of 3 to 1 days between the outside of the roll and the core side of the roll to reach the set temperature, resulting in an unevenly coated support. Therefore, a method for producing a polyester support for photographic i+ materials having a polyvinylidene chloride-based undercoat layer that has uniform and high waterproof performance in a short period of time has been desired.

(Object of the Invention) The first object of the present invention is to provide a method for producing a silver halide photographic material having excellent dimensional stability due to environmental changes and dimensional stability due to processing.

A second object of the present invention is to provide a method for producing a silver halide photographic material that provides sufficient adhesion between a silver halide emulsion layer and a support.

A third object of the present invention is to provide a silver halide photographic material that has excellent dimensional stability due to environmental changes and processing, and has sufficient adhesive strength between a silver halide emulsion layer and a support. There is a particular thing.

The Vth object of the present invention is to coat a polyester support with an undercoat in a short period of time after drying, to have excellent dimensional stability due to environmental changes and processing, and to provide a coating between the silver halide emulsion layer and the support. The object of the present invention is to provide a silver halide photographic material capable of having sufficient adhesive strength.

(Structure of the Invention) The object of the present invention is to provide a first layer of undercoat, which is made of a copolymer containing vinylidene chloride of 70% to 100% polyurethane, and has a thickness of 0.3μ or more; Silver halide photographic film If &
In the manufacturing method of optical materials, is it necessary to roll up the undercoat so that the surface temperature after drying is 34'C to 60C? This was achieved using a unique photographic material.

(Specific Structure of the Invention) The vinylidene chloride copolymer in the present invention refers to a copolymer containing all vinylidene chloride units of 70 to 3% by weight, preferably 99% by weight. 3/-/3!3
Vinylidene chloride/acrylic ester/as described in No. 21z
A copolymer made of a vinyl monomer having an alcohol in the side chain, a copolymer made of vinylidene chloride/alkyl acrylate/acrylic acid described in US Pat. No. 2,132,371, US Pat. No. 691? , a copolymer of vinylidene chloride/acrylic nitrile/itaconic acid described in US Pat. Specific examples of compounds include the following. However, it is not limited to these.

()FF3 All numbers represent weight ratios.

Copolymer of vinylidene chloride: methyl acrylate: hydroxyethyl acrylate (13:/λ:j) Copolymer of vinylidene chloride: ethyl methacrylate: hydroxypropyl acrylate (12:10:) Vinylidene chloride: hydroxydiethyl methacrylate (
Copolymer of vinylidene chloride: methyl methacrylate Nyracronitrile (RiQ: Z2) Copolymer of vinylidene chloride: Butyl acrylate: Acrylic #jt (tag: p+2) Vinylidene chloride : Butyl acrylate : Itaconic acid (7
, T:
(Ri 3: μ: 3) Vinylidene chloride: Itaconic acid monoethyl ester (Ri 6
:q) copolymer vinylidene chloride: acrylonitrile: acrylic acid (LiA
:3.3:1.3) Copolymer of vinylidene chloride: methyl acrylate: acrylic acid (0:3:J) Copolymer of vinylidene chloride: ethyl acrylate: acrylic acid (2:j:J) Copolymer of vinylidene chloride: methyl acrylate = 3-chloro-2
- Copolymer of hydroxypropyl acrylate (7:7) Vinylidene chloride: Methyl acrylate: N-Copolymer of ethanol acrylamide (3:7:s) Vinylidene chloride: Methyl methacrylate: Acrylonitrile: Acrylic acid = As a method for coating a polyester support with the vinylidene chloride copolymer in the present invention, an aqueous dispersion of these polymers may be coated by a generally well-known coating method, for example,
dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar code method, gravure coating method, or U.S. Patent No. 61/29
Ho'7 Bar'fr described in Ko No.: Can be coated by the extrusion coating method used. There is also a so-called extrusion coating method in which a molten polymer is made into a film and is made to flow down onto a moving polyester, which is simultaneously cooled and laminated under pressure.

In order to further improve the adhesion between the polyester support and the polymer skin, the surface of the polyester support is subjected to chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, and activated plasma treatment. process,
High pressure steam treatment, desorption treatment, laser treatment, mixed acid treatment,
There is no problem with treatment such as ozone oxidation treatment.

In addition, in order to firmly adhere the polymer layer used in the present invention to the polyester base, K is based on U.S. Pat.
No. 37, No. 3, / 413, μ, No. 2/, No. j
, 30/, 30/ issue, same 3. ．． 27/, /7g issue, phenol, resorcinol, 0-cresol, m-cresol, trichloroacetic acid,
It is necessary to add a polyester swelling agent such as dichloroacetic acid, monochlor ff[, chloral hydrate, benzyl alcohol, etc. As these swelling agents, resorcinol is preferably used, but resorcinol has the drawback of often inducing spot failures during the manufacturing process.

A particularly preferred method for avoiding such drawbacks is to apply the entire polymer layer used in the present invention after subjecting the surface of the polyester support to glow discharge treatment.

The gummy discharge treatment in the present invention refers to any conventionally known method, for example, Japanese Patent Publication No. 3J-7371, No. 3
6-10331. No., same≠j−ko2θOda No., same daj−
-20oj No., same≠J-, 2μ0≠0, sameμl, -I
No. AEILLIO, U.S. Patent No. 3゜037.77-, No. 3. OK7, 7ri No. 3, same 3, /79. Hiroza No. 2, Hiroza No. 3
, 2gg, lz3g issue, 3,307, 2ri issue 9, 3rd issue
, 1μ, No. 733, direction 3. ILt1.2.33J, 3, IIL74, jO7, 3.76/, 2
No. 9, British Patent Tata No. 7.073, Japanese Unexamined Patent Publication No. 33-/2
262, etc. can be used.

The pressure during glow discharge is 0,00 j −u OTor
r, preferably no, o, x~, 1 Torr. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow and sparks will easily occur, which is dangerous and may even destroy the object to be treated. Discharge is generated by applying a high voltage between metal plates or metal rods spaced apart from each other by one pair or more in a vacuum tank. This voltage can take various values depending on the composition and pressure of the atmospheric gas, but normally within the above pressure range, a stable fixing glow discharge occurs between jOO and 3000V. A particularly suitable voltage range for improving adhesion is from 100 to 100V-ch.

Further, the discharge frequency is preferably JO)1z~2
0 MHz is the majority. Regarding discharge treatment strength,
0.0 because the desired adhesive performance can be obtained. Q/KV-A,
min/rr? ~jKV-h, min/rr? , preferably 0
．． 0JKV-A-min/d~/KV-A-min/rr? is the majority.゛The thickness of the vinylidene chloride copolymer layer in the present invention is preferably thick in order to suppress elongation of the base due to water absorption during the development process. However, if it is too thick, there will be problems in adhesion to the silver halide emulsion layer.

Therefore, the thickness is 0.3μ or more and jμ or less, preferably 0.3μ or more and 0μ or less.

When an emulsion layer is coated directly on the vinylidene chloride copolymer layer, there often arises the disadvantage that sufficient adhesion performance cannot be obtained. Therefore, the above polymer layer is used as the first undercoat layer,
A second undercoat layer made of gelatin and having adhesive properties to both is provided between the first undercoat layer and the emulsion layer. As the gelatin for the second undercoat layer, any gelatin commonly used in the industry can be used, such as so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, gelatin derivatives, modified gelatin, etc. Among them, lime-treated gelatin can be used. Gelatin and acid-treated gelatin are preferably used.

In the present invention, the second undercoat layer can be completely coated on the first undercoat layer by using gelatin dissolved in water or by any of the commonly known coating methods, such as dip coating, air knife coating, curtain coating, and roller coating. , wire barcode method, gravure coating method, or U.S. Patent No. 2
,1. g/,,! It can be coated by an extrusion coating method using Hotuno ξ- described in the tag number.

In order to further improve the adhesive strength between the first undercoat layer and the second undercoat layer, the surface of the first undercoat layer is subjected to conventional pretreatment such as corona discharge treatment, ultraviolet irradiation, and flame treatment. Good too.

Sufficient adhesion performance was obtained for the thickness of the gelatin layer,
In addition, it is preferable that the coating be as thin as possible within a coating range.

Therefore, the thickness is 0. Q is 7μ or more and 2μ or less, preferably in the range of O, OSμ or more/μ or less. The drying temperature after applying the first layer of undercoat is vinyl chloride/co! @It is preferable to set the temperature at a temperature that allows the body to exhibit waterproof performance.

In order to improve the waterproof performance, K must be formed on an undercoat film that is free from defects such as pinholes and cracks and has a high degree of crystallinity. Therefore, Fi as the drying temperature
The range is preferably from θ°C to 4tθ°C. If it is below gO 0 C, crystallization of the vinylidene chloride copolymer will progress slowly and peeling will easily occur between the support and the emulsion layer, which is not preferable. Pinholes occur when the temperature is 1170℃ or higher.
Defects such as cracks are likely to occur, and since the melting point is close to or exceeds the melting point of the vinylidene chloride copolymer, the degree of crystallinity is undesirable.

The drying temperature after applying the undercoat 1@λ layer is preferably set at a temperature that improves the adhesive performance between the polyester support and the emulsion layer and does not deteriorate the waterproof performance. Therefore, the drying temperature is preferably ljO°C or higher/lfO°C or lower. /30"C or less, sufficient adhesive strength between the polyester support and the emulsion layer cannot be obtained, and increasing the drying temperature improves the adhesive performance, but if the drying temperature is higher than 710"C, vinylidene chloride and This is not preferable because the degree of melting of the polymer crystals becomes severe and the decomposition of the polymer progresses.

The support after the undercoat drying process is sent to a winding chamber and wound into a roll. This winding chamber is generally at 1 temperature and 2 ON.
2J''C, relative humidity '10-, go % H, and the temperature of the undercoated support to be wound is also approximately room temperature.

The present invention is characterized in that when this undercoat support is wound up, the temperature of the undercoat support is high. In the conventional method, which is rolled up at room temperature and then reheated in a heating chamber to improve the waterproof performance of the vinylidene chloride undercoat layer, In this case, it takes 3 to 10 days to reach the set temperature, resulting in an undercoat support with uneven waterproof performance. Further, due to expansion of the support due to heating, blocking failure is likely to occur, especially on the core side. When winding the uninvented undercoat support, if it is rolled at a high temperature and kept warm, there will be no unevenness in waterproof performance due to differences in crystallinity between the outside of the roll and the core side, and the heating time required to improve the crystallinity is also very short. It can be shortened to The surface temperature of the undercoat support during winding is preferably 35 to 60°C. If the polyethylene terephthalate support is wound at a temperature of 60° C. or higher, it will be softened, and marks caused by the thickness of the end of the roll wound around the core will periodically form, causing failure of the undercoated support. Also 3
If the temperature is below 3°C, it will take a long time to improve crystallinity.

It is possible to adjust the surface temperature of the undercoat support during winding to t-33 to 60°C without making any major changes to the conventional undercoat drying process. Conventional / After drying the lower eI11@λ layer at a temperature of 30°C or higher and 0°C or lower, by blowing cold air or contacting it with a cooled roll before winding it up into a roll in the winding chamber. The surface temperature of the undercoat support was set at 20 to 23°C, which was approximately the same as the temperature of the winding chamber. Therefore, by completely reducing the amount of cold air or increasing the temperature of the cooling roll, the surface temperature of the undercoated support during winding can be easily lowered from 3j to 6.
It can be adjusted to 0°C. In addition, if the roll is completely wrapped in an insulating packaging material immediately after winding, the temperature will decrease significantly for more than the rFRI period required to impart waterproof performance to the polyvinylidene chloride undercoat layer, preferably for 70 hours. It can keep you warm enough. Furthermore, it is more effective to wrap the support in a heat-insulating packaging material and then leave it in a room heated to the same temperature as the support winding temperature.

The polyester used in the support of the present invention is a polyester whose main components are an aromatic dibasic acid and glycol. Typical dibasic acids include terephthalic acid, isophthalic acid, p-β-oxydiethoxybenzoic acid, Diphenylsulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, adipic acid, sebacic acid, azelain [, s-sodium sulfoisophthalic acid, diphenylene dicarboxylic acid, J,6-naphthalene dicarboxylic acid, etc., and glycols include H ethylene glycol, Propylene glycol, butanediol, neobenzene gelicol, /,
Examples include tLt-cyclohexanediol, /, Hiro-cyclohexane dimetatool, /, 4'-bisoxyethoxybenzene, bisphenol A5 diethylene glycol, polyethylene glycol, and the like.

Among the polyesters made of these components, polyethylene terephthalate is the most convenient in terms of availability.

There is no particular limit to the thickness of polyester, but it is approximately
~JOOμ, preferably ≠0μ to 200μ, is suitable for ease of handling and versatility. In particular, biaxially stretched crystallized materials are advantageous in terms of stability, strength, and the like.

Preferred examples of the polymer latex used in the present invention include alkyl esters, hydroxyalkyl esters, or glycidyl esters of acrylic acid, or alkyl esters, hydroxyalkyl esters, or glycidyl esters of methacrylic acid as monomer units, and have an average molecular weight of 100,000 or more, particularly preferably 3
It is a polymer of 00,000 to 500,000, and a specific example is shown by the following formula.

Polymer 1 (CHX-C1l.

COOC4H9 Polymer 2 (C1lt-C old) C00CxH* Polymer 3 * CHz CH) - Joy C00C! +15 Polymer 4 CH.

engineering (CI!! -C)-.

C00C,H.

Polymer 5 CI+3CHl −
C1l) -i-→CH, -C.

Polymer 6 C) hC0OC411
*C0OCII□C11-C11゜il Furthermore, regarding polymer latex,
5-5331, U.S. Pat. No. 2,852,386, 306
The descriptions in the specifications of No. 2614, No. 3411911, and No. 3411912 can be referred to.

The polymer latex used in the present invention is contained in at least one of the wood-philic colloid layers such as the silver halide emulsion layer, back layer, protective layer, and intermediate layer.

The present invention is particularly effective in ultra-high contrast sensitive materials containing hydrazine derivatives.

Regarding ultra-high contrast sensitive materials containing such hydrazine derivatives and image forming methods using the same, US Pat. No. 4,224,4
No. 01, No. 4.168,977, No. 4,166.7
No. 42, No. 4,241,164, No. 4.272,6
No. 06, JP 60-83028, JP 60-2186
No. 42, No. 60-258537, No. 42 (it-2237)
3 [Described in No. 1, etc.

As the hydrazine derivative L-form, those represented by the following general formula (1) are preferred.

One insect formula (+) Y In the formula, A represents an aliphatic group or an aromatic group, and B is a formyl store, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or an aryloxy group. It represents a carbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, a sulfaniyl group, or a heterocyclic group, and X and Y are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or fil-substituted alkylsulfonyl group. , or a substituted or WIQ-free arylsulfonyl group, or a substituted or WIQ-free acyl group.

-i Representative compounds among the compounds represented by formula (1) are shown below.

! -2) ■-4) Q CN! -5) ■-6) I-7) Furthermore, the present invention provides a method for obtaining high contrast by processing a photosensitive material containing a tetrazolium compound with a PQ type or MQ type developer containing a relatively high concentration of sulfite. This effect can also be achieved in Image forming methods using tetrazolium compounds are described in JP-A-52-18317, JP-A-53-17719, and JP-A-53-17720.

The silver halide emulsion of the photographic light-sensitive material used in the present invention is usually prepared by combining a water-soluble root 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. It is made by mixing.

As the silver halide, any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used, and there are no particular limitations on the grain form and size distribution.

The silver halide emulsion layer contains photosensitive silver halide, a chemical sensitizer, a spectral sensitizer, an antifoggant, a hydrophilic colloid (1″
F may contain gelatin), a gelatin hardening agent, a film physical property improver such as a surfactant, a thickener, and the like. Regarding these, see Research Disclosure, 17
6, page 17G, page 43 (December 1978), and JP-A-52-108130, JP-A-52-114328,
No. 52-121321, No. 53-3217, No. 53
The description in the specification of No.-44025 can be referred to.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 1,600 or more and described in Japanese Patent Publication No. 58-9412.

The surface protective layer contains a hydrophilic colloid such as gelatin as a binder and has a thickness of 0.3 to 3 μm, particularly 0.3 μm. 5-1. 5μ
The layer contains a matting agent such as fine particles of polymethyl methacrylate, colloidal silica, and optionally a thickening agent such as potassium polystyrene sulfonate, a gelatin hardening agent, a surfactant, a slip agent, and a UV absorber. It is made up of substances such as agents.

The back layer is a layer using a hydrophilic colloid such as gelatin as a binder, is non-photosensitive, and may have a single layer structure or a multilayer structure including an intermediate layer, a protective layer, etc.

The thickness of the back layer is 0.1μ to 10μ, and if necessary, it contains a gelatin hardener, a surfactant, a matting agent, a colloidal silica, a slip agent, and a UV ray as well as a silver halide emulsion layer and a surface protective layer. It may contain absorbents, dyes, thickeners, etc.

The method of the present invention can be applied to various photographic materials having a hydrophilic colloid layer, but typically photographic materials of the type that use halogen as a photosensitive component, such as photosensitive materials for printing, photosensitive materials for X-ray, etc. Material, -a negative photosensitive material, -mlJ
The effects of the present invention, which can be used in versatile photosensitive materials, general-use positive photosensitive materials, direct positive photosensitive materials, etc., are particularly remarkable in photosensitive materials for printing.

There are no particular limitations on the exposure method, development method, etc. of the photosensitive material of the present invention;
No. 52-114328, No. 52-121321, etc., and the descriptions in the above-mentioned Research Disclosure magazine can be referred to.

Also, JP-A-60-. As described in US Pat. You can also do that.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

Example-/ A rod electrode with a pseudo semicircular cross section of diameter 3 and length i and sm is 1O
aII& one piece was fixed on an insulating board. This electrode plate was fixed in a full vacuum tank, and a biaxially stretched polyethylene terephthalate film with a thickness of 700 μm and a width of λ1 μm was placed on a rod located /jam away from the electrode surface and directly facing the electrode surface.
It ran at a speed of 7 minutes.

Just before the film passes over the electrode, the film
0 cm heating roll with temperature controller 700℃
All power was distributed to the heating rolls so that they were in contact with each other seven times. Glow discharge brings the inside of the tank to 0. /Torr while applying a voltage of 2000 V to the above electrode. At this time, the electrode current was <z, yA. At this time P
The ET support received a total treatment of 0,/l, KVA min/rrl.

By applying pressure in this manner, an aqueous dispersion of a copolymer of vinylidene chloride: methyl methacrylate: 7 crylonitrile = 9Q: 1 wt. Dry at °C.

Furthermore, the lower l! made of this vinylidene chloride copolymer!
! ! A second undercoat layer of the following formulation (1) was applied to both sides of the seventh layer at g, k, 20 ml/f, and dried at 170°C.

After coating and drying the undercoat No. 1 *, samples were prepared by varying the winding temperature and heat retention time of the undercoat support as shown in Table 1. After cooling once and winding up into a roll, again,
Sample No. 13 was prepared which was placed in a heated room. Polyethylene terephthalate is rolled in sooom/roll. A silver halide emulsion layer of the following formulation (2) was then coated on one side of the support, and an emulsion protective layer of the following formulation (3) was further coated.9. On the opposite side, a back layer of the following formulation (4) and a back protective layer of the following formulation (5) were applied in order from the support side.

(1) Undercoat second layer prescription Gelatin 1.0 parts by weight Epichlorohydrin reaction product of polyamide consisting of diethylenetriamine and adipic acid 0.07 parts by weight Saponin
Add 0.07 parts by weight of water
100 parts by weight + 21/% O Silver Genide Emulsion Layer Formula: A mixed aqueous solution of silver nitrate, sodium chloride and potassium bromide in the presence of 2X/0 mole of rhodium chloride per #11 mole in an aqueous gelatin solution kept at 30"CK. was simultaneously added at a constant rate for 30 minutes to obtain a silver chlorobromide monodisperse emulsion with an average grain size of 002μ.

(α composition: 93 mol) This emulsion was desalted by the 70 curation method, and thiourea dioxide and 0.6 mol of thiourea dioxide and 0.6 mol of chloroauric acid were added,
The product was aged until the highest performance was achieved.

The following compounds were further added to the emulsion thus obtained.

λX / f” mol/Ag 1 mol /X /0-3-T:ni/k g/-[-A.

DA
．． 6-dichloro-6-hydroxy/, 3. J-1-Riazine sodium triwaum salt 30/-Total coated image amount of this coating solution: 3. ! P/lt? It was applied so that

(3) Emulsion protective layer formulation gelatin i, JPIn? 8i0
2 Fine particles (average particle size da μ) 30 kg/- Dotecylbenzenesulfonic acid sodium salt 30 kg/rr? j-
Nido O indazole /J Misaki/-/, 3-divinylsulfonyl- λ-P apanol jO Misaki/-N-, hair-
Fluo-a-octanesulfonyl-N-buta-pyrglycinebotaziwam salt 2297n? Ethyl acrylate latex (average particle size 0./μ) 300 towns/- (4) Back layer prescription gelatin λ, j Pldpi0
Wkp/rr? Za0g/lr? /, 3-divinylsulfonyl-coprobanol /30~/lr? Ethyl acrylate latex (average particle size o, iμ) 900■/-dihexyl-α-sulfosacnate sodium salt 3j■/R dotecylbenzenesulfonic acid sodium salt 3j/rr? (5
) Back protective layer prescription gelatin 7 0. ZaP/rr? Polymethyl methacrylate fine particles (average particle size 3μ) 20/-dihexyl-α-sulfosacnate sodium salt 10/-dotecylbenzenesulfonic acid sodium salt 1 of I97nz sodium acetate po■/rr? Sample! After being allowed to stand for two weeks in an atmosphere of RH, CjO, and RH, dimensional changes due to development were measured using the following method.

(6) Evaluation method for dimensional changes due to development processing
Drill one hole with a diameter of 1frxs at m intervals 1.2
After leaving it in a room at ℃30℃ for 2 hours, //100
The spacing between the two holes was accurately measured using a pin gauge with an accuracy of 0.01 mm. The length at this time is f X am. Next, after developing, washing, and drying using an automatic developing machine, the dimensions after 3 minutes were determined as Y? −. In the industry, the dimensional change rate (%) due to processing is ±0. It is said that there is no practical problem if the O content is 1% or less.

The development process was carried out using Fuji Photo Film Co., Ltd.'s FG-6 Oto0 automatic processor, and the developer and fixer were GRD-i and GRF manufactured by the same company.
-/gold was used under the treatment conditions of 3gC1O seconds.

The drying temperature at that time was 3°C.

Example 2 Polyethylene terephthalate treated with glow discharge as in Example 7 was coated with an aqueous dispersion of a copolymer of vinylidene chloride: methyl acrylate: itacon full=90:I:λ on both sides at 720°C. It was dried. Furthermore, a second undercoat layer similar to that in Example 7 was applied on both sides and dried at 130°C, and another was dried at 130°C without a second undercoat layer as shown in Cloth-λ. Undercoat supports were prepared by varying the winding temperature and heat retention time of the undercoat support. Next, apply the following formulation (1) to one side of the support.
A halogenated emulsion layer and (2) an emulsion retaining layer are coated, and on the opposite side, (3) a back layer and (4) a back protective layer of the following formulation are overlaid in order from the support side. And so.

fl) Silver halide emulsion layer formulation Emulsion A was prepared by the following method using the following solutions 1, n, and III.
was prepared.

Liquid I: Water 30θ, gelatin liquid ■Liquid: AgNO3t 00f, water 100ml ■Liquid:
NaαJ 7y, (NH4)3Rhα60.66”9s
4'00 ml of water Solutions (2) and (2) were simultaneously added at a constant rate to solution (2) kept at 0°C. After removing soluble salts from this emulsion by a conventional method well known in the art, gelatin is added to the emulsion, and then gelatin is added as a stabilizer.
+ 7-chitraazaindene and μm human axy-j
, A-trimethylene-/, 3゜ja, 7-thitraazaindyktm was added. The average grain size of this emulsion is 0.
The emulsion was a monodisperse emulsion of 1/3 μm, and the amount of gelatin contained per it/llr of the emulsion was 6 ops.

The following compounds were added to the emulsion thus obtained.

Polystyrene sulfonic acid sodium trilam salt 10 Misaki/rri/9
．． 2-bis(vinylsulfonylacetamido)ethane 100~/-ethyl acrylate latex (average particle size 0./μ) jootny/rr10.3”9
/ry? The coating solution obtained in this way is completely coated with silver! It was applied so that it became 39/lri.

(2) Emulsion protective layer formulated gelatin 1. sy/i polymethyl methacrylate fine particles (average particle size 3μ) jO■/rr? Dotesylbenzenesulfonic acid sodium salt, 2jff/rr?
Dihexyl α-sulfosacnate 'J'7mui/0Tn
9/lr? N-/-fluorooctanesulfonyl-N-probylglycine botadium salt 2 g/m'' polystyrene sulfonic acid sodium salt 3 g/-ethyl acrylate latex (average particle size 0.7μ), 1001n9/d colloidal silica 3jO■ /rr?゛ノ
'acid
-1...≦i/1 (3) Back layer prescription gelatin 211/rr? j
Oki/R dihexyl-α-sulfosacto sodium salt 20 cape/rrri sodium dodecylbenzenesulfonate 30 cape/rr? Polystyrene sulfonic acid sodium salt 30fJ! /rr?
/, 3-divinylsulfonyl-2-ya Panor A, 100m1/rr
? Ethyl acrylate latex (average particle size 0./μ), 200 pieces/rr? (
4) Back protective layer prescription gelatin/f/lr?
Polymethyl methacrylate fine particles (average particle size 3 μ) 110 K/rr/Dihexyl sulfosacnate sodium salt 10”l/rr?Dotecylbenzenesulfonic acid sodium salt 30 ■/-Polystyrene sulfonic acid sodium salt, 24 Cape/rr? Sodium acetate 30”9/rI? An adhesion test was conducted on samples 1 to 1. The adhesion here refers to the adhesion between the support and the emulsion layer and back layer, and the test method is as follows.

8. Adhesiveness test method for dry film On the emulsion surface to be tested, make 36 squares by making 7 vertical cuts at JW intervals, and apply adhesive tape (for example, Nitto Denki Kogyo@Saki, Knit) on top of the squares. Tape) Once all the tape is attached, quickly peel it off in the 7 and 06 directions. In this method, if the unpeeled portion is 90% or more, it is graded A, if it is 60% or more, it is graded B, and if it is less than 60%, it is graded 0. Strong adhesion that can be used in practical use as a photographic material is one that is classified as A grade in the above three-grade evaluation.

! , Wet film adhesion test method At each stage of development, fixing, and water washing, scratch marks were made on the emulsion side of the film in the processing solution using an iron VTT-2x mark.
The adhesion strength is evaluated by rubbing strongly with the tip of a finger j times and during the maximum peeling along the x line.

If the emulsion layer does not peel off on scratches, it is graded A, if the maximum peeling is within 3 m, it is graded f:B, and in other cases it is graded 0.

Adhesive strength sufficient for practical use as a photographic material is one classified as B or higher, preferably grade A, of the above three-level evaluation.

Example 3 Vinylidene chloride: Methyl methacrylate diacrylic nitrile: Acrylic acid
2: After coating and drying an aqueous dispersion of the copolymer of / on both sides,
．． It was coated so as to have a thickness of Jμ and dried at 720°C. Furthermore, a first layer of undercoat similar to Example 1 was applied on both sides and dried at 760°C. Undercoat supports were prepared by varying the winding temperature and heat retention time as shown in Table 3. Ta.

Next, on one side of the support, in order from the support side, the following silver halide emulsion layers/, -1 protection 1-/, and! Apply and
Dry. Next, the back layer and protective layer 3 were all coated on the opposite side and dried to prepare samples 7 to 7.

(11 Silver halide emulsion layer/Formulation I solution; water 300 at, gelatin 9 y Solution ■: AgNO3/00, water 't'00w11 [
Liquid A: Nacl! 37y, (N)i4) 3Rb
Q! 6i.

/Inl, 4'00 ml of water were added at a constant rate to the liquid (2) and the liquid (1A) kept at 45°C. After all soluble salts were removed from this emulsion by a conventional method well known in the art, gelatin was added to the emulsion, and gelatin was added as a stabilizer.
Chitraazaindene was removed. The average grain size of this emulsion is 0. ．． It is a monodispersed emulsion of 20μ, and the emulsion yield f/
The amount of gelatin contained in each sample was Oy.

The following compound gold was added to the emulsion thus obtained.

(Compound-A) j×70 mol/Ag1 mol (Compound-○) (Compound-C) 700~/rr? (Compound-2) 100~/W? Polystyrene sulfonic acid sodium salt 30kg/rr? N-
Oleoyl-N-methyltaurine sodium salt jOki/-/, 2-bis(vinylsulfonyl 7-1?)7mido)etay 7019/rr
? /-Phenyl-3-mercaptotetrazole 3/-Ethyl acrylate latex (average particle size 0./μ) tI0■/-The coating solution thus obtained was coated so that the total coated silver fi was 21/I.

(2) Silver halide emulsion layer formulation ■Liquid: 300d water, gelatin ■Liquid: AgNO3/0 (7y% water≠00d111
B solution; NaCl371- (NHK) RhC7!6
．． 2, 2"9, water≠00d Emulsion B=i was prepared in the same manner as Emulsion A, using Solution 2B instead of JIIA solution. This emulsion had an average grain size of 0.
It was a monodisperse emulsion of −θμ.

The following compounds were added to the emulsion B thus obtained.

Compound-a J
? -c 100fI9/w? 〃 −
2 ioo■/rr? I-ho
9 cape/ml polystyrene sulfonic acid sodium salt jO■/RN-oleoyl-N-methyltawarine sodium salt 4tOki/rr? 1,
．． 2-bis(vinylsulfonylacetamido)ethane IJ'9/rr? l-
Phenyl-3-mercaptotetrazole 3/rr? Ethyl acrylate latex (average particle size 0./lp) 1I01Rf/r
r? The coating solution thus obtained was coated so that the total coating was #i*2P/door.

(3) Protective layer l prescription gelatin /, 01/rr? Lipoic acid 3 towns/d Dotecylbenzenesulfonic acid sodium salt j Cape/lr? Compound-ha, 20 cape/rr? Poly(
3) Oxyethylene nonylphenol ether sulfate ester sodium salt 3W/rr? Polystyrene sulfonic acid sodium salt 10 capes/rr? KoO
■/rr? Ethyl acrylate latex (average particle size 0./it) 20019/rr?
(4) Protective layer λ prescription gelatin i, op/rr? Polymethyl methacrylate fine particles (average particle size 3μ) Aotty/rr
? Dotecylbenzenesulfonic acid sodium salt 20 Misaki/-N-perfluorooctanesulfonyl-N-propylglycine potadium salt 3'9/rr/Poly(degree of polymerization J) oxyethylene nonylphenol ether sulfate ester sodium salt IS Misaki 7rr? Polystyrene sulfonic acid sodium trilam salt, 2~/1ri (
5) Back layer prescription gelatin, 2. , SP/rr?
5o3K 803K ,,,,/.

! 50"19/rr? JOfn9/rr? Sodium dodecylbenzenesulfonate jO■/?7!"Dihexyl-α-sulfosacnate sodium salt KoO"f/rr?Polystyrene sulfonic acid 1-IJ Wham salt po■/rr ?／、
3-divinylsulfonyl-no-propanol /30k/rr? Ethyl acrylate latex (average particle size 0, /p) 300"9/
rr? (6) Protective layer 3 formulation (protective layer for back layer) Gelatin/P/rr? Polymethyl methacrylate fine particles (average particle size 3 μ) ≠01n9/rn' Dodecylbenzenesulfonic acid sodium salt /319/rrt Dihexyl α-sulfosacnate sodium salt 70 g/rr? Sodium salt of polystyrene sulfonate lO~/-Sodium acetate po■/-The samples thus prepared were tested for "cut-edge image". This "cut edge imprint" is caused by the fact that when the undercoat support is wound around the core, it is wound in such a way that it periodically runs over the edge of the roll, resulting in streaks in the width direction of the support at this position. , which refers to defects that remain as streaks even after emulsion and back coating.

Rank A: Does not occur after 73m from the winding core.

Rank B: Winding, does not occur after 6 to 30 m.

Rank C: winding, also occurs after 6 to 30 m.

In terms of production costs, up to rank B is allowed.

Procedural amendment

Claims (2)

[Claims] (1) First undercoat layer consisting of a copolymer containing 70 to 99.5% by weight of vinylidene chloride and having a thickness of 0.3μ or more, followed by a second undercoat layer consisting of a gelatin layer applied. In the method for producing a silver halide photographic material having a hydrophilic colloid layer containing a polymer latex on at least one side of a polyester support coated on both sides with 1. A method for producing a photographic material, which is characterized in that it is wound up into a shape. (2) The manufacturing method according to claim 1, wherein the polyester support that has been rolled up and dried undercoating is left wrapped in a heat-insulating packaging material for 8 hours or more.