JPS63304249A - Production of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the dimensional stability of a specified silver halide photographic sensitive material independently of environmental changes and processing by coiling the sensitive material so as to regulate the temp. of the film surface to 40-50 deg.C. CONSTITUTION:Both sides of a polyester support are coated with polymer layers each having >=0.3mum thickness and made of a copolymer contg. 70-99.5wt.% vinylidene chloride and a hydrophilic colloidal layer contg. polymer latex is formed on at least one side of the coated support. The resulting photographic sensitive material is coiled so as to regulate the temp. of the film surface to 40-50 deg.C. Thus, a long-sized photographic sensitive material having uniform and satisfactory dimensional stability over the entire material can be obtd. with high reproducibility.

Description

Detailed Description of the Invention (Technical Field) The present invention relates to a silver halide photographic material with improved film physical properties, particularly a silver halide photographic material with excellent dimensional stability. Regarding the manufacturing method.

(Prior art and its problems) Silver halide photographic materials generally have a layer of a hydrophilic colloid such as gelatin as a binder on one side of the support. It has the disadvantage of easily expanding and contracting 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 materials that require the reproduction of halftone images and precise line drawings for multicolor printing. This is a disadvantage.

Dimensional stability with little dimensional change
U.S. Pat. The technology of incorporating polymer latex in the hydrophilic colloid layer is disclosed in Japanese Patent Publication No. 3F-Hiro 272, Mukai 3 Ter 1770λ, 3-13.
μt2, same 4tt-gist.

U.S. Patent No. 237400, U.S. Patent No. 27434! No., same λ
772/6 issue, 2112314 issue, same number rj3'l
! No. 7, No. 3397911, No. 7! It is described in the specification of No. u/tytt and No. 3≠//P/Co. In addition, the theoretical support for the above technology is provided by J.
Photographic Science and Engineering (Photo, Sci.
, ang Eng, ) (/PI3 year) t Turf page 3.

However, in the printing field where multicolor printing and precise reproduction of line drawings are required, further improvement in dimensional stability is strongly desired. In particular, although dimensional stability is important before and after the processing steps that photographic films always undergo (developing, fixing, washing, and drying), techniques that incorporate polymer latex do not provide sufficient improvement.

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 particularly serious drawback in photographic materials for printing. In order to improve this drawback, Japanese Patent Application Laid-Open No. 40-3
No. 427 describes a technology using a support in which both sides of a polyester film are coated with polyolefin, which was published in the patent application Sho t Coater≠
/No.33 contains 70~Tata, 11111% vinyl chloride IJ
Techniques have been disclosed with polyester supports coated with dene-containing copolymers. The technique disclosed in Japanese Patent Application No. 62-2≠733 is particularly good for K in order to improve the dimensional stability accompanying the processing of photographic light-sensitive materials for printing. After being coated with the vinylidene chloride-containing copolymer, a sufficient effect could not be obtained unless it was left to stand for a long time. In order to shorten the standing time, the support was heat-treated, which had the disadvantage of insufficient adhesion between the spores, the emulsion layer, and the support. However, polyester coated on both sides with a vinylidene chloride-containing copolymer After coating the emulsion layer on the support and drying it, leave it for more than 2 hours in a heated state to avoid damaging the adhesive strength between the emulsifier and the support. (It has been found that sufficient dimensional stability can be obtained.However, when several thousand lengths of long photographic material are rolled and heated, it takes a certain amount of time to reach a specified temperature on the outside and inside of the roll.) As a result, photographic materials having different dimensional stability can be produced in one roll, which is a serious drawback.

(Object of the Invention) The object of the present invention is to solve the above-mentioned drawbacks of a polyester support coated on both sides with a copolymer containing vinyl chloride, and to provide a uniform and sufficient An object of the present invention is to provide a method for producing a photographic material that can produce a photographic material having excellent dimensional stability with good reproducibility.

A second object of the present invention is to provide a silver halide photographic material that has excellent dimensional stability due to environmental changes and dimensional stability due to processing. The object of the present invention is to provide a polyester support coated on both sides with a polymer layer made of a copolymer containing 70 to 99.5% vinylidene chloride and having a thickness of 0.3μ or more. In a method for producing a silver halide photographic material having a hydrophilic colloid layer containing a polymer latex on one side of the photosensitive material, the film surface temperature of the photosensitive material is ≠o-t.
This was achieved by a method for producing a photographic material, which is characterized in that it is wound up in an o'c manner.

(Member structure of the invention) The vinyl chloride IJ-dene copolymer in the present invention is 70 to
Tata, jIJ, amount chi, preferably! Copolymer containing vinylidene chloride of 1% by weight, JP-A-Shoyo/-/3r
J-2 is a copolymer consisting of vinylidene chloride/acrylic acid ester/vinyl monomer having alcohol in the side chain described in No. 1, US Patent λ,! ! 2. Copolymer consisting of vinylidene chloride/alkyl acrylate/acrylic acid of No. 371, US Pat. Vinyl chloride I described in No.
Examples include a copolymer of J-densyl chloride/acrylonitrile/itaconic acid, and a copolymer of vinylitine chloride/alkyl acrylate/itaconic acid described in US Pat. Specific examples of compounds include the following.

All numbers in parentheses represent weight ratios.

Copolymer of vinylidene chloride: methyl acrylate: hydroxyethyl acrylate (rj:/J:j) 11Z Copolymer of vinylidene: ethyl methacrylate: hydroxypropyl acrylate (12:10:l) Vinylidene chloride: hydroquine diethyl methacrylate (
Copolymer of vinylidene chloride: methyl methacrylate: acrylonitrile (RI0:I:λ) Copolymer of vinylidene chloride: butyl acrylate: acrylic acid (P≠:Hiro:Co) Vinylidene chloride: Gtylacrylate: Itaconic acid (7
j:ko O:! ) Copolymer of vinylidene chloride: methyl acrylate: itaconic acid (Rio:r:co) Copolymer of vinylidene chloride: methyl acrylate: methacrylic acid (2J:≠:3) Hinylidene chloride: itaconic acid monoethyl ester ( ri6
:≠) copolymer of vinylidene chloride:acrylonitrile:acrylic acid
:3.1:/, Copolymer of vinylidene chloride: methyl acrylate: acrylic acid (Rio:r:z) Vinylidene chloride: Ethyl acrylate: Acrylic #! 1
Copolymer of (R2:!:3) Vinylidene chloride: Methyl acrylate = Copolymer of 3-chlorocohydroxybrobyl acrylate (t≠:R:7) Vinylidene chloride: Methyl acrylate 2N-ethanol acrylamide ( Copolymer of 1!:10:j) In the method of coating a polyester support with the vinylidene chloride copolymer in the present invention, these polymers can be coated with a suitable 1!:10:j) copolymer. A solution dissolved in a mechanical bath agent or an aqueous dispersion may be applied by generally well-known coating methods such as dip coating, air knife coating, curtain coating, roller coating, wire bar r-toa, and gravure. Coat method or US patent! It can be coated by an extrusion coating method using the hot-resistance described in J Co., No. 61/, No. 2≠. There is also a so-called extrusion coating method in which a molten polymer is made into a film and flowed down onto a moving polyester, and the film is simultaneously cooled and applied to the edge under pressure.

In order to further improve the adhesive strength between the polyester support and the above polymer layer, 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. process,
High pressure steam treatment, desorption treatment, laser treatment, mixed acid treatment,
There is no problem with treatment such as ozone oxidation treatment.

Further, in order to firmly adhere the polymer layer used in the present invention to the polyester base, US Patent No. 3. λ≠! ,
No. 237, same! , /≠3. Sanko No. 1, same 1. ! 0/, 3
0/No. 3. core/.

Swelling agents for polyesters such as phenol, resorcin'r:u, o-cresol, m-cresol, trichloroacetic acid, dichloroacetic acid, monochloroacetic acid w, chloral hydrate, and benzyl alcohol, as described in No. 171. It is necessary to add □. 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 polymer layer used in the present invention to the surface of a polyester support which has been subjected to glow discharge treatment.

The glow discharge treatment in the present invention may be any conventionally known method, such as the Tokko Sho 3! -757 No. 3
No. 4-10334, No. 11tj-JJooda, No. ≠5
-22 oar, same France! -2≠otto issue, same p+-a
i4! to issue, US Patent 3IO! 7.7 Octopus, same! ,
0!7.7 Wjr, 3.17, Hirot2, 3.
Corr, tie issue, same! , 30F, 2 Tata, 3. ≠
Koda, 73! No. 3. ≠62,33! No. 3. ≠7
! , No. 307, J, 74/, , 2 Tata No., British Patent 2
No. 27.093, Tokukai Sho! J-/Kotakotλ etc. can be used.

The appropriate pressure during glow discharge is 0.001 to 20 Torr, preferably 00 to 20 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, causing sparks, which can be dangerous and even destroy the object being treated. The problem is to apply a high voltage between metal plates or metal rods that are spaced apart from each other by more than one pair.This voltage can take various values depending on the composition and pressure of the atmospheric gas. However, normally within the above pressure range, !OO~
A stable fixing glow discharge occurs between zooov. Particularly suitable voltage range h, xooo- for improving adhesion
There is aoooVc.

In addition, as seen in the prior art, the discharge frequency ranges from direct current to several tens of degrees, preferably 100 degrees! 014 z-co OM Hz is suitable. Regarding the discharge treatment strength, since the desired adhesive performance can be obtained, o,otKV-A-min/m-IKV-A-min/,2, preferably 0.0j
A suitable temperature is KV-A-min/rn2~/KV-A-min/rlL2.

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 the particles float too much, there will be problems in adhesion to the silver halide emulsion layer.

Therefore, the thickness is 0.3μ or more! μ or less, preferably 0. ! The range of μ to 0 Oμ is used. In the present invention, polyester mainly consists of aromatic dibasic acid and glycol. i. Typical dibasic acids in the polyester component include terephthalic acid, isophthalic acid, p-β-oxyethoxybenzoic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, adipic acid, sepa-7acic acid, and azelain. Acids, j-:i) Lium sulfoisophthalic acid, diphenylene dicarboxylic acid, j-f7 thalene dicarboxylic acid, etc., and glycol acids include ethylene glycol, phlopylene gellicol,
Butanediol, neoventrengelicol, l.

≠-cyclohexanediol, /, 4C-cyclohexane dimetatool, /, 4C-bisoxyethoxybenzene, bisphenol A1 diethylene glycol, polyethylene glycol, etc. b"=al.

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 the polyester, but it is about 1 μ~! A material having a diameter of about OQμ, preferably about ViμOμ to 200μ, is advantageous in terms of handling, precision, and versatility.

In particular, biaxially stretched crystallized materials are advantageous in terms of stability, strength, and the like.

In order to improve the adhesive strength between the polymer layer and the emulsion layer, a layer having adhesive properties to both of them can be provided as an undercoat. Further, in order to further improve the adhesion, the surface of the polymer layer may be subjected to conventional pretreatment such as roller discharge, ultraviolet irradiation, flame treatment, etc.

The manufacturing winding conditions used in the present invention will be explained.

Generally, photographic materials are coated using various coating methods, such as dip method, air knife method, extrusion method,
It is manufactured by coating a moving support such as an EL or two or more photographic coating liquids using a curtain method or the like, drying it, and then winding it around a core. Drying takes advantage of the sol/gelation phenomenon of gelatin, and immediately after it is applied to the support, it is solidified in a cooling zone, and then the temperature is gradually raised to reduce the amount of solvent evaporated per unit time, that is, the amount of solvent evaporated. During the constant rate drying period when the speed is constant, the evaporation rate of the solvent gradually decreases and almost no evaporation occurs. It will be completed after a while.

Typically, the drying zone is set to have a maximum drying temperature of about 4 co0C to about t0C.

After leaving the drying zone, the photographic material is subjected to humidity control, if necessary, and sent to a winding chamber where it is wound around a core in the form of a roll. Normally, the winding chamber is kept at normal temperature (11~0C) and normal humidity (j
O~6! The room is air-conditioned to maintain a constant temperature (relative humidity), and the temperature of the photographic material sent there is lowered and wound up at a temperature close to that of the winding room.

The present invention is characterized by keeping the temperature of the photographic light-sensitive material high during winding.By winding the photographic light-sensitive material in a heated state into a roll over several thousand meters, Because photographic light-sensitive materials are kept warm for a considerable period of time, the waterproofness of the copolymer layer containing polyvinyl chloride and lidene increases. There are also disadvantages such as insufficient waterproofness due to the fact that it takes a considerable time to reach the desired level of waterproofness, and uneven waterproofness that varies depending on the location of the roll. A photographic material with good quality can be obtained.

The outermost part of the roll is prone to heat dissipation, but there is also heat diffusion from the inside, so it can be kept warm for a relatively long time. ,
The outermost layer can also be kept warm.

A method of keeping the photographic material in a heated state when winding it around a core is to raise the temperature from the drying zone to the winding chamber to a high temperature, for example, 30'C-10'C, so that the temperature of the photographic material after drying is lowered. Alternatively, heating means may be provided in front of the winder. As a heating means, hot air is blown. The internal temperature of the wound roll-shaped photographic material is preferably controlled to be approximately 4AO00 to approximately z
o0cK It's fine if you can. It is not necessary that the coating film temperature of the photographic light-sensitive material be heated to approximately 1000m above the temperature when it is rolled up. After winding up, the coating film temperature can be maintained at about 0-1000 °C.

One or more heating means may be installed, and heating may be performed from the emulsion layer side of the photographic light-sensitive material, heating from the opposite side, or heating from both sides.

The amount of heat applied to the photographic light-sensitive material varies depending on the coating speed of the photographic light-sensitive material and the conditions of its texture.

Hydrophilic colloid layers of the photographic light-sensitive material of the present invention include a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer, etc., and hydrophilic colloids are used in these layers. Gelatin is most preferred as the hydrophilic colloid, and examples of the gelatin include so-called lime-treated gelatin, acid-treated gelatin, mortar-treated gelatin, gelatin conductor, modified gelatin, etc.
Any gelatin commonly used in the art can be used, but lime-treated gelatin and acid-treated gelatin are preferably used.

In addition to gelatin, proteins such as colloidal algumine and casein, cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; shield fermentation conductors such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol, d(IJ) -N-
Vinylpyrrolidone polyacrylic acid copolymer, polyacrylamide, or derivatives and partial hydrolysates thereof, etc. can be used. Mixtures of two or more of these colloids can be used if desired.

The polymer latex used in the present invention is a water-insoluble polymer with an average particle size of Qy+μ to oontμ, and the preferred amount used is 0.0 in dry weight ratio to gelatin used as a binder. /-7,0
and particularly preferably 0. /~o, r.

Preferred examples of the polymer latex used in the present invention include monomers such as alkyl esters of acrylic acid, hydroxyalkyl esters, acrylic acid esters, alkyl esters of acrylic acid, hydroxyalkyl esters, and methacrylic acid esters. as a unit, and has an average molecular weight of 100,000 or more, particularly preferably 3
00,000 to j00,000, and a beautiful example is shown by the following formula.

Polymer reference CH3 Polymer j CH3 Polymer A CH3 ■ H Furthermore, regarding polymer latex,
46-1337. US Patent 'Hsrzazrt No. 3
06267 No. 3≠/15'// No. 3 Hiroshi/15
The description in the '/λ specification can be referred to.

The polymer latex of the present invention is contained in one or more hydrophilic colloid layers such as a silver halide emulsion layer, a back layer, a protective layer, and an intermediate layer.

The invention can be particularly effective in ultra-high contrast sensitive materials containing hydrazine derivatives.

Regarding such ultra-high contrast sensitive materials containing hydrazine derivatives and image forming methods using the same, US Patent No. ≠1.2λ≠,
Da0/No., Hiromu, /At, No.77, Same≠, It4.
7'lλ issue, Mu≠, Ko≠/, /lμ issue, same issue, λ72
, No. 606, JP-A-60-r J OJ r No., same to
-2irttta, same tO-2! It is described in rlr No. 137, rlr No. 4/-223731, etc.

The hydrazine derivative used in the present invention is preferably one represented by the following general formula (I).

General formula (■) Y In the formula, A represents an aliphatic group or an aromatic group, and B represents a formyl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or aryloxycarbonyl group. a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, a sulfaniyl group, or a tetracyclic group, where X and Y are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or Represents a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

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

l-1) tc5H11 ■-3) ■-5) I-6) ■-7) Furthermore, the present invention provides a photosensitive material containing a tetrazolium compound in a PQ type or MQ type containing a relatively high concentration of sulfite. This effect can also be achieved in a method of obtaining high contrast by processing with a developer. Regarding the image forming method using a tetrazolium compound, see JP-A No. 113/7, Ibid. It is described in No. 3-/77/P and No. j3-777/O, etc.

The silver halide emulsion of the photographic light-sensitive material used in the present invention is usually prepared by combining a water-bathable complex salt (for example, silver nitrate) solution and a water-bathable halide (for example, potassium bromide) solution in a water-soluble polymer solution such as gelatin. mixed in the presence of

As the silver halide, any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used, and the grain form and size distribution K thereof are not particularly limited.

The silver halide emulsion layer contains photosensitive silver halide, chemical sensitizers, spectral sensitizers, anti-capri agents, hydrophilic colloids (% gelatin), gelatin hardeners, film physical property improvers such as surfactants, It can contain a thickener, etc. Regarding these, please refer to Research Disclosure Magazine, Vol. 76, Section 7j≠3 (Registered in 2017, 2013, and Japanese Patent Application Publication No. 10-117-117121).
same! Cole Co. 13 Co. No. 1, same! 3-3/No. 7, same j3
-Hiroshi4tOko! You can refer to the description in the specification of the No.

In particular, a surfactant preferably used in the present invention is a surfactant with a molecular weight of 600 described in Japanese Patent Publication No. 72
These are the above polyalkylene oxides.

The surface protective layer is made of hydrophilic colloid such as gelatin as a binder and has a thickness of 0.3 to 3μ, especially o! ~1. ! A matting agent such as microparticles of polymethyl methacrylate, colloidal silica, and optionally a thickening agent such as potassium eripolystyrene sulfonate, a gelatin hardening agent, a surfactant, and a stabilizing agent. , a UV absorber, etc.

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 having an intermediate layer, a protective layer, etc.

The thickness of the back layer is 0.7μ to 70μ, and if necessary, gelatin hardening agent, surfactant, matting agent, colloidal silica, dusting agent, etc., as well as the silver halide emulsion layer and the surface protection layer, It may contain UV absorbers, 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 using silver halide as a photosensitive component, such as photosensitive materials for printing and photosensitive materials for X-ray. It can be used in -acid negative photosensitive materials, -acid reversal photosensitive materials, general positive photosensitive materials, direct positive photosensitive materials, etc. The effects of the present invention 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 (for example, Japanese Patent Application Laid-Open No. 101130
No. 12-//44321, same! 13 calls 1
You can refer to the specifications of the issue, etc., and the descriptions in the above-mentioned Research Disclosure magazine.

Furthermore, as described in US Pat.

(Member Effects of the Invention) According to the present invention, a polyester support coated on both sides with a copolymer containing vinylidene chloride in a thickness of 0.3 μm or more is used. Silver halide photographic Takagi material with a hydrophilic colloid layer containing polymer latex on one side has a film surface temperature of 170-10.
A silver halide photographic light-sensitive material with excellent dimensional stability due to environmental changes and processing can be obtained by the manufacturing method of winding the film in such a manner as to form a 'C' shape.

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example-1 A semicircular bar electrode with a length of 170 cm and a diameter of 3 cm in cross section was fixed on a μ-thick insulating plate at intervals of 0 cm.

This electrode plate is fixed in a vacuum tank, and from this electrode surface /
jcm apart, the rod facing directly to the electrode surface has a thickness lOOμ width J
A biaxially oriented polyethylene terephthalate film of 0 cm was run at a speed of 0 cm. Immediately before the film passed over the electrode, a heating roll with a diameter of jOcm and a temperature controller was set at 0C and the heating roll was arranged so that the film was in contact with the electrode for one round. Glow release t is
While maintaining the inside of the tank at Torr, apply pressure to the above electrode.
This was done by applying a voltage of v. At this time, the electrode current was Q, jA. At this time, the PET support is o,
This means that it has been processed for i times KVA minutes/m2. In this way, an aqueous dispersion of a copolymer of vinylidene chloride/methyl acrylate/acrylic acid = yo:z:r weight % was applied to the glow discharge treated polyethylene terephthalate at varying coating thicknesses. -l as (sample αυ
~0e was created.

Furthermore, apply the undercoating liquid of the following prescription (1) at a rate of 10 m/? j
It was coated on both sides so that the temperature was t2. Next, a silver halide emulsion layer of the following formulation (2) was coated on the 10,000 side of the support, with an amount of silver ≠! ! Further, a protective layer of the following formulation (3) was applied thereon so that the ratio was 1/m 2 . On the other side, apply a back layer of the following formulation (4) with a thickness of 3. ! It was applied so that it became μ. The coated material leaving the drying zone was sent to a winding room and wound around a core, where it was coated with a length of λroom. The surface temperature of the coating film at the time of winding was 00. This roll was immediately heated in a Hiro Q0C heating room for 1 hour as A, and as B was a roll that was coated and dried in the same manner but was not put into the heating room.

Prescription (1) Undercoat layer prescription Gelatin / Reaction product of polyamide and epichlorohydrin consisting of ONN Koribe diethylenetriamine adipic acid 0.07 Saponin 0.01 Add water
100 prescription (2) Silver halide emulsion layer prescription Gelatin: 4 cg/2 chloride iodobromide @: ((lj:lQmomol Br:tri,!mol,T:l:).

! Molarity) Chloroauric acid: 0. l■/m2 Polymer latex: E-/i, zg7rn2 Sensitizing dye = 3-allyl-j-(co(l-ethyl)-termethyl-cochtracylyy-t-yv-yn-ethyrythene) rhodanine t19/nL 2 Stabilizer: μm hydroxy-5-methyl-1,3゜3a,7-titrazaindene 1 ott17rIL2 Polyoxyethylene compound l/m2 Surfactant: Thorium p-dodecylbenzenesulfonate g0/rn2 1O!da/ rn2 Prescription (3) Protective layer prescription gelatin /II/m2 Matting agent: Silica particles with an average particle size of 100 μm! Prescription (4) Back layer prescription Gelatin 4 tll/m2 Matting agent: Polymethyl methacrylate polymer latex with average particle size of 3.0-hiro and Qμ: E-/297 m2 Surfactant: p
- Potassium dodecylbenzenesulfonate ≠O■/
2 tio da/, 2 dye: dye (IJ, (IIJ and ([IJ's/:/:/
A mixture of 0.3 fi/rn2 dye (N SO3 rr
After drilling one nmo hole and leaving it in the room of Koj'cJt7SRH, the distance between each hole was accurately measured using a pin gauge with an accuracy of / / / 000 mm.

The length at this time is )(mm).Next, after developing, fixing, washing, and drying using an automatic processor, the dimension after 1 minute is '(rnm).The dimensional change rate due to processing ( %)
In this industry, if the dimensional change rate is 0.0/% or less, in practice,
It is said that there is no problem. For the development process, we used the FG-6to automatic processor manufactured by Fuji 4 Shin Film Co., Ltd., and the developer and fixer were the same company's IIi! ) i 3-j, using LF-301, 7
．． The treatment was carried out at 20C for 60 seconds. The drying temperature at that time was Hiro! It was 0C. The results are shown in Table-7.

Table 1 As is clear from the results in Table 1, a silver halide photographic photosensitive layer was coated on a polyester support coated with vinyl chloride=IJ-dene copolymer to a thickness of 0.3μ or more, and after drying. ,a
The samples placed in the ooc heating chamber show significantly better dimensional stability.

Example-2 The sample of Example-1 (on the same support as 14, the same...
Silver halide emulsion layer, protective layer, back layer length 2100%
It was painted over. At this time, the following measures were taken before winding up the fallen cloth.

(a) Immediately before winding up, the coated material was passed between a pair of heating rollers (roller outer surface temperature: 70 - 00c) and wound up so that the coating film surface temperature became uo 0c - Sample (21) (b) The temperature of the final drying zone was set to ≠z'C, and the film was rolled up so that the surface temperature of the film was 00C.
Sample (22) Sample +237 (24) was also obtained by winding it up in the same manner as samples (21) and (22) and then wrapping it in a heat insulating packaging material. Samples (Machi (22) +233 (24) were left at room temperature for 74 hours. Sample α4 placed in the heating chamber and samples (4~(24)
Table 2 shows the dimensional changes associated with the treatment of 24).

Sample +217 according to the present invention from Table-C. (22)
It can be seen that, after being rolled up, the sample α exhibits the same dimensional stability as the sample α which was heated in a greenhouse.

Actual 11f1 Example-3 Similar to sample (22) of Example-2, the length λ! 00m
I made a coating sample of g. After setting the surface temperature of the coating film to aooc and winding it up, it was wrapped in a heat insulating packaging material and kept for 2 hours, 2 hours, 27 hours, and 4 trips. i! At this time, a sample (bright, (32J), (34) was obtained.

Samples (21), (31), (32), (33) (3
The dimensional stability accompanying the treatment of No. 47 was measured.

As is clear from Table 3, storage at 7IO temperature condition By
More than an hour is sufficient.

Example-4 Thickness 10 treated with glow discharge in the same manner as Example-1
A support was prepared by coating uniaxially stretched polyethylene terephthalate with a thickness of 0μ on both sides with an aqueous dispersion of the polymer shown in Table 1 to a thickness of 1μ. On top of that, apply the base coating liquid of formulation (1) of Example-1.Od/m
2, and then coated with a silver halide emulsion layer of formulation (2) and a protective layer of formulation (3) in the same manner as in Example-1, and on the opposite side a backing layer of treatment (4). was coated on a length, dried, and then wound up using the method shown in Example M-2 (a). Thereafter, the samples (4
11-(48) were obtained.

Using this sample, the dimensional change rate due to treatment was measured in the same manner as in Example-1. The results are shown in Table-≠. The adhesion in the table is the adhesion between the support, emulsion layer and backing layer, and the test method is as follows.

1. Dry film adhesion test method Test: Make 36 cuts by making 7 vertical cuts at 011 intervals on the emulsion surface, and apply adhesive tape (for example, Nitto Electric Industry Co., Ltd., Knit- tape) quickly in the direction of B and tro'c. In this method, if the unpeeled portion is Ochi or more, it is grade A, if it is 10% or more, it is grade B, and if it is less than 10%, it is grade C. Adhesive strength that is sufficient for practical use as a photographic material is A of the above three-level evaluation.
It is classified into a class.

2. Wet film adhesion test method At each stage of development, fixation, and water washing, scratch the emulsion side of the film in the processing solution at the X mark using a metal straw, and then rub it firmly with the tip of your finger. Adhesion strength is evaluated during maximum peeling along the edge of the x.

A case where the emulsion layer does not peel off more than a scratch is graded A, a case where the maximum peeling is within 3 mm is graded B, and other cases are grade C. 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.

As is clear from the table, Samples 45 to 48 of the present invention have good adhesion between the support, emulsion layer, and backing layer, and have significantly improved dimensional stability.

Example-5 In the same manner as the sample (22) of Example-2, the length coj00
A t-roll was made of a sample coated with m. After setting the coating film surface temperature to 4Ao 0c and winding it up, it was wrapped in a heat insulating packaging material and kept at room temperature for 16 hours, and then 100m, 100m, 1100o, troom, xzo from the outer winding side.
As a result of examining the dimensional stability of the sample at the om location due to processing, it was all o and oor%, and no non-uniformity depending on location was observed, indicating good dimensional stability performance.

Example 6 The same silver halide emulsion layer, protective layer, and back layer were coated over a length jθOm for 30 coats on the same support as the sample α of Example 1. Before winding up this coated material, the following treatment was performed. Immediately before winding up, the coated film surface temperature is reduced to 30°C by passing the coated material between a pair of heating rollers (roller outer surface temperature 7Q to 0"c) and changing the conveyance speed.
'C,! It was wound up in such a way that 00<:, ao 0c. Thereafter, the samples were packaged with a heat-insulating packaging material and left at room temperature for 4 hours to obtain samples (61), (62), and (63).

The floating properties of the obtained samples (61) to (0) and (Yaku) and the dimensional stability accompanying treatment were evaluated.

The development process was carried out using the FG-JTO automatic processor manufactured by Fuji Photo Film Co., Ltd., and the developer and fixer were MS-z and LF manufactured by the same company.
-301 under the processing conditions of 3 cto seconds.

Table-! As is clear from Table 5, when the winding temperature is low, the dimensional stability performance is slightly insufficient, and on the other hand, when the winding temperature is high, the photographic properties deteriorate, so that the winding temperature is optimal between ao0c and zooc.

Patent applicant Fuji Photo Film Co., Ltd. Procedural amendment filed in July 1950 by the Commissioner of the Japan Patent Office * +, -
'.

1. Display of the incident Showa t2 year patent application No. 114043
No. 17 No. 2, Title of the invention Method for producing silver halide photographic light-sensitive materials 3, Relationship with the case of the person making the amendment Patent applicant contact information 10
6 2-26-30, Nishi-Azabu, Minato-ku, Tokyo Target of amendment The description in the "Detailed Description of the Invention" column 5 of the specification and the "Detailed Description of the Invention" section of the description of the contents of the amendment are as follows. Correct as expected.

l) First page l? row "Excellent" "Excellent" and correct it.

2) taJ page/-th line "Hidereku" "Suzuji" and correct it.

3) Page j/line j "Excellent" "Suzuji" and correct it.

4) Itj [th row] “I will punish you.” “Hard.” and correct it.

S) Line 17 on page 17 "Most preferably gelatin" "Most preferred, gelatin" and correct it.

6) Jth 7j[/th line “Excellent hole” "Excellent Nine" and correct it.

7) Page 27! row [4c0crILJ1k “Ko, j1rLJ and correct it.

8) Line 27 of page 27 “3QcILJ "0μm" and correct it.

9) Page λ7, line 10 "Kotm 7 minutes" "1007 FlZ minute" and correct it.

10) Page 27/line j [Torr J “0./TorrJ and correct it.

11) Line 17 of the core page “o, zhJ “≠, rAJ and correct it.

12) Page 27/Rth line “0.71jKVA min/m”Jt "0.z4KVA min/m"J and correct it.

13) Coat page // line ``Apply it to the length of 200?F1 to be wound around the core.''
is corrected to "Wound around the winding core with a length of 2!00rrL."

14) Page 31, line j “E-/J “Specific example polymer 3” and correct it.

15) 1st line directly below No. 36 “(ko/)J Delete.

16) 1st line directly below No. 36 [Processing (4) l- "Prescription (4)" and correct it.

Claims (2)

[Claims] (1) Contains polymer latex on at least one side of a polyester support coated on both sides with a polymer layer with a thickness of 0.3μ or more made of a copolymer containing 70 to 99.5% by weight of vinylidene chloride. In a method for producing a silver halide photographic material having a hydrophilic colloid layer,
A method for producing a photographic material, characterized in that the photographic material is wound up so that the film surface temperature is 40 to 50°C. (2) The manufacturing method according to claim 1, wherein the wound photographic material is left wrapped in a heat-insulating packaging material for 8 hours or more.