JPH02272535A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a good antistatic effect without changing with time by forming a polyester film of a specific acrylic polymer and sulfonated polystyrene and/or the salt thereof and confining the thickness of a coating layer to 0.001 to 5mum. CONSTITUTION:This silver halide photographic sensitive material is formed by using the biaxially stretched polyester film which is formed by applying the resin consisting of the acrylic polymer A and the sulfonated polystyrene and/or the salt thereof B and having 95/5 to 5/95 weight ratio on at least one surface of the polyester film, then stretching the film in at least one direction and confining the thickness of the coating layer to 0.001 to 5mum. The thickness of the coating layer is 0.001 to 3mum, more preferably 0.04 to 1mum after the biaxial stretching. The antistatic layer is provided on the photographic base in such a manner, by which the photosensitive material having the excellent antistatic property is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as "sensitive material") that has improved antistatic properties and dust retention, and in particular has improved film strength. This relates to a sensitive material with strong transparency and adhesive properties.

(Prior Art) Photographic materials generally consist of an electrically insulating support and a photographic layer. In many cases, electrostatic charges are accumulated when the electrostatic charges are removed or peeled off.This accumulated electrostatic charge causes many problems, but the most serious problem is that the accumulated electrostatic charges are discharged before the development process. As a result, the photosensitive emulsion layer is exposed to light, and when the photographic film is developed, dot-like spots or dendritic or feather-like cotton clumps are produced.This is what is called a static mark, and the photographic film For example, when it appears in medical or industrial X-ray films, it will be easily recognized that it will lead to a very dangerous decision. Or photosensitive material for plate making (
In the case of GRAPHISOQARTS sensitive materials, static marks can stain the print, and in the case of industrial lithographic materials, electronic wiring diagrams may be missing, causing serious trouble. This phenomenon becomes apparent only after development, and is one of the most troublesome problems.

Furthermore, these accumulated electrostatic charges may cause secondary failures such as dust adhering to the film surface or inability to apply uniformly.

As mentioned above, such electrostatic charges are often accumulated during the production and use of photographic materials. This occurs due to separation of the support surface and emulsion surface, etc. In addition, in the finished product, the separation of the haze side and the emulsion side when the photographic film is wound and changed, or the mechanical parts or fluorescent intensifying screen in an automatic 1-photography machine for X-ray film. This occurs due to contact separation between the parts.

Furthermore, in the case of plate-making photosensitive materials, printer burn-in may be caused by time or corrections. It can also occur due to contact with other packaging materials. Static marks in photographic light-sensitive materials induced by such accumulation of electrostatic charges become more noticeable as the upper limit of sensitivity of photographic light-sensitive materials and processing speed increase. Particularly in recent years, as photographic materials have become more sensitive and are subjected to harsh handling such as high-speed coating, high-speed photographing, and high-speed automatic processing, the occurrence of staphylococcus has become even more likely.

Furthermore, the presence of dust after development has become a serious problem in recent years, and improvement thereof is also important.

The best way to eliminate these electrostatic disturbances is to increase the electrical conductivity of the material so that the electrostatic charge can be quickly dissipated before the accumulated charge is discharged.

Therefore, methods have been considered to improve the conductivity of supports and various coated surface layers of photographic materials, and attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. It's here.

For example, US Pat. No. 2.882.157, US Pat.
No. 535, No. 3,062,785, No. 3.262,8
No. 07, No. 3.514,291, No. 3,615,53
No. 1, No. 3,753.716, No. 3,938,999
For example, polymers such as those described in U.S. Pat. No. 2,982.651, U.S. Pat.
Surfactants and active agents such as those described in US Pat. No. 3,457.076, US Pat. No. 3,454.625, US Pat.
Colloidal silica as described in No. 525.621 is known.

However, many of these materials exhibit specificities depending on the type of film support and photographic composition, giving good results for certain film supports and photographic emulsions and other photographic components, but not for other different films. Not only are supports and photographic components completely useless for antistatic purposes, but photographic properties may also be adversely affected.

In addition, Japanese Patent Publication No. 35-6646 describes a technique for using stannic oxide as an antistatic treatment agent, but this technique uses amorphous stannic oxide colloid, and its conductivity It is a material that has humidity dependence and loses its function as a conductive layer under low humidity, and is essentially no different from the various substances described above.

On the other hand, for example, in U.S. Patent No. 3,062,700 and Japanese Patent Application Laid-Open No. 143431/1989, the conductivity of the conductive material is almost dependent on temperature as a conductive material used as a conductive support for photographic light-sensitive materials or electrostatic recording materials. Not crystalline zinc oxide,
It is known to use metal oxides such as stannic oxide and indium oxide. However, in order to obtain good antistatic properties using these crystalline metal oxide particles in photographic light-sensitive materials, it is necessary to use a large amount of metal oxide in the binder of the constituent layers. As a result, the transparency of the photographic light-sensitive material is extremely reduced, making it unusable as a photographic material, and the metal oxide is separated into powder.

Therefore, the present invention provides a photosensitive material having excellent antistatic properties by providing an antistatic layer on a conventional photographic support (polyester film).

The polyester film support having an antistatic layer used in the present invention is described in detail in JP-A-64-9242, and the present invention uses this support to form a photographic material. .

(Object of the Invention) The first object of the present invention is to provide a photographic light-sensitive material that is well prevented from charging without changing over time. A second object of the present invention is to provide a photographic material that is antistatic without impairing its transparency. A third object of the present invention is to provide an antistatic photographic material with excellent film strength.

(Disclosure of the present invention) These objects of the present invention provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on at least one side of a polyester film support. One side is made of an acrylic polymer (A) and a sulfonated polystyrene and/or its salt (B), and the weight ratio of (A)/(B) is 9.
This is achieved by a silver halide photographic light-sensitive material characterized in that it is a two-wheel stretched polyester film, which is stretched in at least one direction after coating a resin having a ratio of 515 to 5/95, and the thickness of the coated layer is 0.001 to 5 μm. Ta.

The method for manufacturing the two-wheel stretched polyester film used in the present invention is described in JP-A-64-9242, and can be used as is in the present invention.

The polyester film of the present invention is polyethylene terephthalate (hereinafter abbreviated as PET) or PET component.
A film consisting of a copolymer containing 0 mol% or more. There is no particular limit to the thickness of the film after stretching, but it is approximately 12
The thickness is preferably from μm to 500 μm, preferably from 40 μm to 200 μm.

The thickness of the coating layer composed of component (A) and component (B) of the present invention is 0.001 to 3μ after biaxial stretching.
m1 preferably 0.01 to 1 μm1, more preferably 0.
04 to 1 μm. If the thickness of the coating layer is less than 0.001 μm, the antistatic effect will not be sufficient, and the thickness of the coating layer will be less than 3 μm.
If it is coated in excess of this amount, the transparency will decrease.

In particular, the weight ratio of (A/B) is 9515 to 70/30,
Preferably 90/10 to 75/25, or 10/9
0 to 5/95 and the coating film thickness to 0.001 to 5 μm, it is preferable because the transparency of the coating film is further improved;
/B), and the coating film thickness is 0.04 to 2.
When expressed as μm, antistatic properties, transparency, easy adhesion,
It is particularly preferred because it has good coating toughness and good adhesion to the substrate.

Furthermore, heat-resistant agents, weather-resistant agents, inorganic particles, other water-soluble resins, emulsions, and the like may be added to the coating material within a range that does not impede the effects of the present invention.

For example, by adding inorganic fine particles to the coating composition of the present invention,
Biaxially stretched materials are more preferred because they can provide improved antistatic properties, easy adhesion, and easy sliding properties without impairing transparency.

Typical examples of inorganic fine particles to be added include silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, and calcium carbonate. The average particle size of the inorganic fine particles is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm, and still more preferably 0.08 to 2 μm, and the blending ratio with respect to the solid content in the coating material is 0 by weight. The amount is preferably from 0.05 to 10 parts, more preferably from 0.91 to 5 parts.

Furthermore, various organic or inorganic polymeric or low molecular weight hardeners (singly or in combination) may be added to the coating composition of the present invention.

The polymer hardener used in the present invention preferably has at least two or more hardening groups in the same molecule for reacting with hydrophilic colloids such as gelatin, and has a molecular weight (number average molecule 1) of 3,000 or more. means a compound.

Examples of the hardening group for reacting with hydrophilic colloids such as gelatin include aldehyde groups, epoxy groups, active halide groups (such as dichlorotriazine), active vinyl groups, and active ester groups. Further, it is sufficient that there are at least two of these groups in the same molecule of the polymeric hardening agent, but the number is preferably 10 to 5,000. Also,
The molecular weight of the polymer hardener may be 3,000 or more, but a molecular weight of about 3,000 to 500,000 is preferably used.

Generally, hydrophilic polymers having hardening groups for reacting with hydrophilic colloids such as gelatin are preferably used, but even if they are not hydrophilic, they can be emulsified and dispersed in the coating (if necessary). It can also be used by dissolving and dispersing it in a solvent.

Examples of the polymeric hardening agent used in the present invention include dialdehyde starch, polyacrolein, and U.S. Pat.
Polymers having aldehyde groups, such as the acrolein copolymers described in US Pat. No. 6,029, US Pat. No. 3,623,87
Polymer having epoxy groups as described in No. 8, U.S. Patent No. 3
．． ．． 362.827, Research Disclosure Magazine 17333 (1978), etc. Polymers containing dichlorotriazine groups, JP-A-56-668
Polymers having active ester groups described in No. 41, JP-A-56-142524, U.S. Pat. No. 4.16
1.407, JP-A No. 54-65033, Research
Examples include polymers having an active vinyl group or a group serving as a precursor thereof, as described in Disclosure Magazine 16725 (197B), etc. Among these, polymers having an active vinyl group or a group serving as a precursor thereof are preferred. Particularly preferred are polymers in which an active vinyl group, or a group serving as a precursor thereof, is bonded to the polymer main chain by a long spacer, as described in JP-A-56-142524.

Specific examples of the polymer hardener used in the present invention are shown below.

P +CUZ CM±b, +CHZ CH+, sco
c.

NHC(CII+)zclIzsOzNA 0C11
z(JlzOCOC)lzCIIzSOzCll=CI
IzP P +Cll2-CHmo.

+C)1. −℃±,.

P-5 -(-C112CI+-)-92+CL-Ctl+ec
oc.

Nll, NIICII□NHCO
CII□CI(250□Cll=CH2P +011□Cll)-b s + C1l□-CIl+
*sco c.

NIIC(Ctlx)zcIIzsOJa NIIC
IIzNtlCOCllzCIIzSOzCII=CI
Iz P +011□-CIt + q. +C11, -C1ll
.

7' HP-7 CH3 P (-NIICHCO-)- (C1lz-h2GO□CIl□CH-CH.

\1 P One←C1+□ CII+60 +C11□ CHsu1゜ (The numbers represent molar ratios.

Furthermore, the polymeric hardener that can be used in the present invention, like the polymer described above, has at least two hardening groups in the same molecule from the beginning to react with hydrophilic colloids such as gelatin. In addition to polymers, hydrophilic colloids coated using a hydrophilic colloid hardening agent such as gelatin and a polymer that reacts with the hardening agent to give a polymer having at least two hardening groups in the same molecule. This term includes those that create a polymeric hardener in the layer.

As a low-molecular hardening agent, for example, [The Theory] by T.H.
To the Photographic Process (The T
theory to the Photographic
Process) J, 4th edition, pages 77 to 84 are used, and among them, low molecular weight hardeners containing a vinyl sulfone group, an aziridine group, or a triazine ring are preferred, and particularly Kaisho 53-412
21 and 60-225143 are preferred.

Specific examples of low-molecular hardeners that provide high-molecular hardeners used in the present invention are shown below, but the invention is not limited thereto.

(Clh = Cf1SO□CHzCONHCH) z
(C11□=CH3OzCHzCQNI(C1h) t
cNzC1l□= cuso□CH2ClICH2SO
7cu=cnzO■ +1-4 CIl□-CIISOzC)IzSOzCH=CHIC
1h = CH-3O□CtlzOCHz-3o! -C
I = CLC1lz ” CH30zCIIzCllz
ClhSOzCII = CHzOHC of the present invention (CHl>, CH0 Formalin [(CIl□=Cl1SO□CUtI01+1zNc
IIZcH□SO, to salt C'\ /CHO CI+2011 Na CH, O11 H-14 H Chromium brightened polymer with sulfinic acid groups, phenolic hydroxyl groups as described in U.S. Pat. No. 4.207.109 No. 4,215.19
Examples include polymers having active methylene groups described in No. 5.

Specific examples of polymers used to provide the polymeric hardener used in the present invention are shown below.

In addition, the polymer used to make the polymer hardener used in the coating agent must contain at least two nucleophilic groups in the same molecule that react with the low-molecular hardener of hydrophilic colloids such as gelatin. Such polymers include, for example, a polymer having a primary amino group described in British Patent No. 2.011,912, a polymer having a primary amino group described in JP-A No. 56-4141, and a polymer having (-CHt- CH ÷ Hz NH.

1,000 Hz CH+ re + C14z C
H+q.

COCHz NH (CHz) + N Hz N Hz-(
-CIl□-CIf + +.

+011□-C1l±,.

+CHt　C”)’-+.

+011□ C　H　-)-　Q.

(The numbers represent molar ratios.

The amount of the polymer used to provide the hardener and polymer hardener that can be used in these coatings is 0.05 to 30% by weight based on the total solid content in the coating.
parts, preferably 05 to 15 parts.

The above coating material is stretched after application, but if the coating composition is within the range of the present invention, the coating film will not crack due to stretching, and will have good adhesion, antistatic properties, and easy adhesion to the polyester film of the base material. , a biaxially stretched polyester film with excellent transparency can be obtained.

In particular, in order to more clearly exhibit the effects of the present invention, in the process of stretching after coating, it is preferable to stretch the coating film in the presence of water, although this may be done before or after drying the coating film. To achieve this, it is recommended to use methods such as lowering the concentration of the coating material, lowering the stretching temperature within a range that does not cause the coating film to dry out after film curling, nesogging stretching, and stretching heat treatment, and increasing the stretching speed. It is valid. Specifically, the coating concentration is 0.5 to 10 wt%, preferably 1 to 5 wt%, and the stretching temperature is 85 to 250°C, preferably 5 to 2% from ↓.
It is preferable that the temperature is 00°C. The stretching speed needs to be selected appropriately depending on the stretching temperature. For example, when the stretching temperature is 85°C, it is 5 to 15 m/min, and when the stretching temperature is 135°C, it is 20 to 70 m/min.
/min, a suitable coating film can be obtained.

Next, a typical method for producing a two-wheel stretched polyester film of the present invention will be described, but the method is not limited thereto.

Polyester resin is melted at a predetermined temperature, extruded into a sheet onto a cooling drum, and stretched at a predetermined temperature in the transverse direction at a predetermined magnification. It may be applied directly onto the uniaxially stretched longitudinal polyester film after stretching, but in order to improve the coating properties and adhesion to the substrate, corona discharge treatment, ultraviolet irradiation treatment, etc. in air or other various atmospheres may be applied. plasma treatment,
It is more preferable to carry out a surface activation method such as flame treatment or electron beam treatment, or a surface etching method using a chemical such as acid, alkali, amine aqueous solution, or trichloroacetic acid.

Coating can be performed using known methods such as gravure coating, reverse coating, barcode coating, and spray coating. After the coating, the uniaxially stretched polyester film is continuously dried appropriately, or stretched in a direction perpendicular to the previous stretching direction while drying, and then heat treated or stretched in the perpendicular direction. The biaxially oriented polyester film produced by the above manufacturing method, which is re-stretched in the longitudinal direction and heat-treated, is compared with the case where the coating of the present invention is applied on a two-wheel oriented heat-set polyester film that has undergone normal crystal orientation. , the adhesion to the base polyester film is extremely high, and the transparency is also excellent.

By mixing an acrylic polymer and a sulfonated polyethylene and/or its salt in a specific ratio and providing a coating layer with a specific thickness on a biaxially stretched polyester film after two-wheel stretching, even after biaxial stretching, Since there are no cracks in the coating film, it is possible to obtain a two-wheel stretched polyester film that has excellent antistatic properties, transparency, and easy adhesion, and has good adhesion to the substrate.

Furthermore, in the present invention, it is possible to further coat other layers on the conductive polyester film obtained above to improve transparency and easy adhesion. For example, gelatin may be used as a binder for forming these layers. , polyvinyl alcohol, poly(meth)acrylic esters, polyvinyl acetate, polystyrenes, cellulose, #Ns, vinylidene chloride, etc., and each may be used alone or in a mixture.

Among these, polystyrenes, vinylidene chloride, and gelatin are particularly preferable for adhesion between the layers for providing the hydrophilic colloid layer of the sensitive material on the conductive film of the present invention, and for example, styrene/butadiene (SBR) is particularly preferable. Mention may be made of polymers vinylidene chloride/ethyl acrylate/itaconic acid. Furthermore, these may be a single layer or may have a structure of two or more layers, for example, a two-layer structure of a styrene/butadiene layer and a gelatin layer (in this case, dichloro-hydroxytriazine may be contained in both layers as a hardening agent). ), a 2N structure of vinylidene chloride-aqueous polyester layer/gelatin layer, or a three-layer structure of ethyl acrylate layer/vinylidene chloride layer/gelatin layer, etc. are preferably used. It is even more preferred to pre-treat and activate the film (eg, corona, heat, electron beam, ultraviolet, acid, alkali, etc. treatment) before applying each layer.

These layers may each be made of a single binder or a mixture, and may also contain other materials (
For example, a matting agent, a hardening agent, a surfactant, etc.) may be included.

The photosensitive material of the present invention is characterized by having at least one photosensitive silver halide emulsion layer on the above-mentioned two-wheel stretched polyester film. In this case, the antistatic layer may be provided on both sides or one side of the support. , even one side can have sufficient antistatic properties. In addition, when the photosensitive silver halide emulsion is provided on only one of the supports,
Preferably, the antistatic layer is provided on the opposite side (hack side).

When coating the photosensitive material layer on the antistatic layer, a coating liquid (generally a hydrophilic colloid liquid) that forms the photosensitive material layer may be applied as it is, but corona treatment, heat treatment, or
Ultraviolet irradiation, flame treatment, electron beam irradiation, acid or alkali treatment, etc. may also be performed.

The sensitive material of the present invention will be described in detail below.

The sensitive material of the present invention is composed of a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer, an antihalation layer, etc., and these are mainly used as a hydrophilic colloid layer.

In this case, binders for the hydrophilic colloid layer include, for example, proteins such as gelatin, colloidal albumin, and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids. Examples include polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof and partially hydrolyzed dispersions, dextran, polyvinyl acetate, polyacrylic ester, rosin, etc., as required. Mixtures of two or more of these colloids may also be used.

Among these, gelatin is the most used, and gelatin here refers to so-called lime-processed gelatin, acid-processed gelatin, and enzyme-processed gelatin.

In addition to being able to replace part or all of gelatin with synthetic polymeric substances, so-called gelatin derivatives, i.e. amino groups, imino groups, as functional groups contained in the molecule,
A hydroxy group or a carboxyl group treated or modified with a reagent having one group capable of reacting with them, or a graft polymer in which molecular chains of a polymeric substance are bonded may be used in place of the hydroxy group or carboxyl group.

In the present invention, a fluorine-containing surfactant can also be used in combination. The layer containing the fluorine-containing surfactant used in this case may be present in any of the constituent layers of the photographic light-sensitive material, but the protective layer is preferred, and the outermost layer is particularly preferred.

Preferable fluorine-containing surfactants to be used in combination with the present invention have a fluoro-alkyl group, alkenyl group, or aryl group having 4 or more carbon atoms, and have an anionic group (sulfonic acid (salt), sulfuric acid (salt), salt), carboxylic acid salt),
Phosphoric acid (salt)), cationic group (amine salt, ammonium salt, aromatic amine salt, sulfonium salt, phosphonium salt), betaine group (carboxyamine salt, carboxyammonium salt, sulfoamine salt, sulfoammonium salt,
Examples include activators having a phosphoammonium salt) or a nonionic group (substituted or unsubstituted polyoxyalkylene group, polyglyceryl group, or sorbitan residue).

These fluorine-containing surfactants are disclosed in JP-A-49-1゜722, British Patent No. 1,330,356, and JP-A-53-84.
No. 712, No. 54-14224, No. 50-11322
No. 1, U.S. Patent No. 4,335°201, U.S. Patent No. 4,347
, 308, British Patent No. 1.417,915, Japanese Patent Publication No. 52-26687, No. 57-26719, British Patent No. 59-
No. 38573, JP-A-55-149938, JP-A No. 54-
No. 48520, No. 54-14224, No. 58-200
No. 235, No. 57-146248, No. 5819654
No. 4, British Patent No. 1.439.402, etc.

Preferred specific examples of these are described below.

1-　I　　C,F,? to SO3 Summer-20? F+5COONa 1-3　　　　　　CjH.

CaF+tSO□N-CHIC0OK 5Ht CeF + tso tN + CH2C1IC)+2
O-)-1-(-CIIz+-SOJaH C,H.

CaF + qsOtN + CHzCllzO-h-(
-Ctl, zsl5O3NaC@F+ySOJCHzC
H2OP-ONaNa ■ Cs F + , CHzCHzOOCCHICsHl?
OOCCH 80, INa CH.

C, F+, 5OzNCHzCHz@N CHzCOO
8C,,+(!S CH.

I] Ce F + q S O□N CHz CHt” N
CHz CHt S Oz.

H3 ■ CH3 CeF, ff5o! NCH2CH2”N-CH3Hi ■0 C.I.

C+ o F t 1coo+ cHZcl(, o +
-T-r7r-fCHzcIlcHzo + 4 t1
■ -14 C3゜HI Cs F I? S Oz N + CHz CHt
O÷12.5HtH5 C, F,, SO□N+C11-CI! □−〇＋−T−(
-CII2CH20+Tff7+C11□CIt C1
1□0±, HCl1ff
01+ In the present invention, nonionic surfactants may be used, and these compounds are described, for example, in U.S. Pat. No. 454,625,
3,552,972, 3,655,337, JP 51-9610, JP 53-29715, JP 54-89626, JP 57-85764,
It is described in Japanese Patent Application No. 5'l-90909, "New Surfactant" by Hiroshi Horiguchi (Sankyo Publishing, 1975), etc.

Specific examples of nonionic surfactants preferably used in the present invention are shown below.

Compound Example 1 1 CIIHz s COO+ CH* CHz
O÷. HICI? Hff3cOO+cHzCHto + s +
C1h-CH-CH2+ 3 + C1l zcIl
! O+ 5llO■ 1 4 C+zHzsO+CH2CHzO++o
H15C+bHz10+CHzCHtO+ I□H■ C+ s H3S O+ CHz CHCHz OchiT
1,000 CHz CHzO+H ■ ■ H H Ctllq-t C4119-t The layer to which the nonionic surfactant used in the present invention is added is not particularly limited as long as it is at least one layer of the photographic light-sensitive material, such as a surface protective layer, an emulsion layer, Examples include an intermediate layer, an undercoat layer, and a bank layer. Among these, the preferable additive layer is a surface protective layer, which may be either on the emulsion layer side or the bank layer side, but it is more preferable to add it to both surface protective layers. When the surface protective layer is composed of two or more layers, any of these layers may be used, or the surface protective layer may be further overcoated.

The amount of the nonionic surfactant used in the present invention may be 0.0001 to 1 g per square meter of the photographic material, more preferably 0.0002 to 0.5 g.
A particularly preferred range is 0°0003 to 0.2 g. Moreover, two or more types of nonionic surfactants of the present invention may be mixed.

In the present invention, another antistatic agent can also be used in combination, and by doing so, a more preferable antistatic effect can be obtained. Such antistatic agents include, for example, U.S. Pat.
No. 3.062785, No. 3,262,807,
No. 3,514.291, No. 3,615,531, No. 3753.716, No. 3,938.999, No. 4.
No. 070.189, 4. , 147,550, German Patent No. 2,800.466, Japanese Patent Application Publication No. 4891.165, Japanese Patent Application Publication No. 48-94,433, German Patent No. 49-46.733,
Polymers such as those described in U.S. Pat. No. 50-54.672, U.S. Pat. No. 50-94,053, U.S. Pat.
Metal oxides, colloidal adhesives, barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, colloidal silica, etc. as described in No. 45゜833, No. 3,525,621, etc. Alternatively, a so-called mantle agent made of powdered silica or the like can be mentioned.

Also, ethylene glycol, propylene glycol, 11
．． 1-Trimethylolpropane etc.'yp 1980-89
Polyol compounds such as those shown in No. 626 can be added to the protective layer or other layers of the present invention.

The present invention is 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 Pat. No. 4224.40
No. 1, No. 4,168.977, No. 4,166.74
No. 2, No. 4.241.164, No. 4,272.60
No. 6, JP-A-60-83028, JP-A No. 60-21864
No. 2, No. 60258537, No. 6 L-223738
It is stated in the number etc. As the hydrazine derivative, those represented by the following general formula (Q) are preferred.

General formula (Q) A-11-N-B 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, or a carbamoyl group. group, alkoxy or aryloxycarbonyl group, sulfinamoyl group, alkoxysulfonyl group, thioacyl group, thiocarbamoyl group, sulfaniyl group, or heterocyclic group, and X and Y are both hydrogen atoms, or one is a hydrogen atom and the other is substituted or It represents an unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

-a Representative compounds among the compounds represented by formula (Q) are shown below.

C, 11°Q-2) Q-7) SH Q-8) Q-10) N = N Q-11) N = N Furthermore, the present invention provides photosensitive materials containing tetrazolium compounds at relatively high concentrations This effect can also be achieved in a method of obtaining high contrast by processing with a PQ type or MQ type developer containing sulfite. Image forming methods using tetrazolium compounds are described in JP-A-52-18317, JP-A-53-17719, and JP-A-53-17720.

The photosensitive material according to the present invention includes ordinary black-and-white silver halide photosensitive materials (for example, black-and-white photosensitive materials for projection, black-and-white photosensitive materials for X-ray, black-and-white photosensitive materials for printing, infrared photosensitive materials, etc.), and conventional multilayer photosensitive materials. Color photosensitive materials (e.g. color reversal film,
(color negative film, color positive film, etc.) and various photosensitive materials. It is particularly effective for silver halide light-sensitive materials for high-temperature rapid processing and high-sensitivity silver halide light-sensitive materials.

The silver halide photosensitive material according to the present invention will be briefly described below.

A hydrophilic colloid similar to the binder for the photographic layer and the binder for the surface protective layer is used.

Other known surfactants may be added alone or in combination to the photographic constituent layer of the present invention. Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsion dispersion, enhancement, and other improvements in photographic properties.

These surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide type, glycerin type, and glycidol type, higher alkylamines, and quaternary surfactants.
Cationic surfactants such as ammonium salts, pyridine and other heterocycles, phosphoniums or sulfoniums; Anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, phosphoric esters, and amino acids. , aminosulfonic acids, and amphoteric surfactants such as sulfuric acid or phosphoric acid esters of amino alcohols.

Also, in the present invention, lubricating compositions, such as U.S. Patent No. 3,079,837, U.S. Pat. Modified silicones such as those shown in No. 537 and Japanese Patent Publication No. 52-129520 can be included in the photographic constituent layer.

The photographic light-sensitive material of the present invention includes U.S. Patent No. 3,
No. 411,911, 3. 411. 912, Japanese Patent Publication No. 45-5331, etc., may be included.

Further, the photographic light-sensitive material of the present invention includes U.S. Pat.
The alkyl acrylate latex described in Japanese Patent Publication No. 45-5331 and the like can be included.

The silver halide grains in the emulsion may have a regular crystal shape such as a cube or an octahedron, or may have an irregular crystal shape such as a spherical shape, a plate shape, a potato shape, etc.
It may consist of a mixture of particles of various crystalline forms, which may have irregular crystalline forms or may have composite forms of these crystalline forms. Further, tabular grains having a grain size of 5 times or more the grain thickness are preferably used in the present invention (for details, refer to RESEARCH II DIS
CLOSUI? E Volume 225 Item 22534
P, 20-P, 58. January issue, 1983, and JP-A-58-127921 and JP-A-58113926).

In the present invention, the photosensitive silver halide emulsion may be a mixture of two or more types of silver halide emulsions. The emulsions to be mixed may differ in grain size, halogen composition, sensitivity, etc. A substantially non-photosensitive emulsion (which may or may not be covered on the surface or inside) may be mixed with the photosensitive emulsion, or may be separated into separate layers. For example, in the same layer as a spherical or potato-shaped photosensitive emulsion and a photosensitive silver halide emulsion consisting of tabular grains with a grain size of 5 times or more the grain thickness, or in JP-A-58127921.
It may be used in different layers as described in the publication. When used in different layers, the light-sensitive silver halide emulsion consisting of tabular grains may be on the side closer to the support or, conversely, on the side farther away.

The silver halide emulsion layer and other hydrophilic colloid layers in the photographic light-sensitive material of the present invention can be hardened with various organic or inorganic hardening agents (singly or in combination). Typical examples include mucochloric acid, formaldehyde, trimethylolmelamine, glyoxal, 2,3-dihydroxy-14-dioxane, 2,3-dihydroxy-
5-methyl-14-dioxane, succinaldehyde,
Aldehyde compounds such as glutaraldehyde; divinyl sulfone, methylene bismaleimide, 13.5-triacryloyl-hexahydro-S triazine, 1.3.
5-Trivinylsulfonylhexahydro-5-) riazine bis(vinylsulfonylmethyl)ether, 1.3-
Active vinyl compounds such as bis(vinylsulfonylmethyl)propanol-2, bis(α-vinylsulfonylacetamido)ethane; 2,4-dichloro-6-hydroxy-S-triazine sodium salt, 2,4-dichloro- Active halogen compounds such as 6-medoxys-) riazine, ethyleneimine compounds such as 2.4.6-1-ly/ethyleneimino-s-triazine, and also the aforementioned polymer hardeners and low molecular hardeners Film agent (
HP1-14P9, H1-1417, etc.);

Types of silver halide used in the silver halide emulsion layer, surface protective layer, etc. of the photographic light-sensitive material of the present invention, manufacturing method, chemical sensitization method, antifoggants, stabilizers, hardeners, plasticizers, lubricants, Coating aids, matting agents, brighteners, spectral sensitizing dyes, dyes,
There are no particular restrictions on color couplers etc. For example, Research Disclosure magazine
Disclosure) Volume 176, pages 22-31 (19
(December 1978) can be referred to.

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

Example 1 ■-1) Preparation of base Polyethylene terephthalate with an intrinsic viscosity of 0.68 was
It was melted at 80°C and extruded onto a cooling drum at about 50°C.

Further, the film was stretched 3.5 times in the longitudinal direction at about 100° C. by roll stretching and subjected to corona discharge treatment in air, and then the following water-soluble coating material was applied to one side.

Acrylic polymer (A): An acrylic polymer (average molecular weight: 500,000) in which 2.5 parts by weight each of a carboxyl group and a methylol group were introduced as functional groups into methyl methacrylate/ethyl acrylate (50,150 mol %) was used.

Sulfonated polystyrene and/or its salt (B); SO
□0-x° group with X' ion and H', molecular weight approximately 7
10,000 sulfonated polystyrene was used.

Make the weight ratio of (A)/(B) 93/7 and add 4w of water.
diluted to t% and further made into inorganic fine particles with an average particle size of 1.3μ
A coating material was prepared by adding 0.3 parts by weight of silica of m to the solid content in the coating material.

The coating thickness after biaxial stretching of the coating material using a gravure coater is 0.
After coating to a thickness of 1 μm, it was stretched 3.5 times in a direction perpendicular to the previous stretching direction at 110° C. and 10 m/min.
Heat treated at 220℃, film thickness 180/Jm
A biaxially stretched polyester film having a coating of IIUW and a diameter of 0.1 μm was obtained. As shown in Table 1, this film has good transparency and antistatic properties with no cracks in the coating.
It also had excellent adhesion and easy adhesion to polyethylene terephthalate.

The antistatic two-wheel stretched polyester film thus obtained was designated as Base A.

Base B was prepared in exactly the same manner as Base A except that the weight ratio of (A)/(B) was 20/80.

Furthermore, base C was prepared by adding hardener compounds H-7 and HP-1 to base A. At this time, [1]]-7 and HP-1 were added in such a manner that their solid content was 5% by weight of the total.

Next, in base A, instead of the acrylic polymer, a water-soluble polyester with a molecular weight of about 30,000 consisting of [Na salt of terephthalic acid 15-sulfoisophthalic acid/ethylene glycol (85/15/100 mol%)] was used. A biaxially stretched polyester film was obtained as Base D in the same manner as Heis A except that a polymer was used. This base had significant cracks in the coating film and was poor in antistatic effect and transparency.

A composition similar to Base A was applied to one side of a two-wheel stretched polyester film without a coating layer, which had undergone crystal orientation. The coating was carried out so that the thickness after drying was 0.1 μm after corona discharge treatment, and the coating was dried at about 160° C. for 2 minutes. This film was designated as Base E.

In addition, in base E1, the composition is changed from base A to base C.
Base F was created in exactly the same way except that it was changed to 1.

In addition, in base A, a base containing no CB) was prepared and designated as base G.

Furthermore, after corona discharge treatment on both surfaces of bases A to G obtained in this way, a layer (0.2 μm) consisting of SDR latex and dichloro-hydroxytriazine, gelatin and 1,2-bis(vinylsulfonylacetamide) was formed. ) A layer (0.2 μm) consisting of ethane was applied sequentially to both sides.
Dry at 0°C and prepare final bases A-1-G-1.
And so.

1-2) Composition of the dyed layer? + Ron Kujino's L method The following dyes were ball milled by the following method. Water (21.7 m and 6.7% Triton
"Surfactant aqueous solution (2,65g) (Rohm & l
1aas) in a 60-screw cap bottle. A 1.00 g sample of dye was added to this solution. Zirconium oxide (ZrO) beads (40ml) (21m diameter)
was added, the container with a tight lid was placed in the mill, and the contents were ground for 4 days. Take out the container and pour out the contents 12.
It was added to a 5% aqueous gelatin solution (8.0 g). The new mixture was placed on a roll mill for 10 minutes to reduce foam, and the resulting mixture was then filtered to remove the ZrO beads.

Dye Coo)l Application Method The surfactant sodium p-octylphenylethoxyethoxyethanesulfonate and the hardener (his(vinyl-sulfonylmethyl)ether) were added to the dye-gelatin melt described above. The melt produced from the latter mixture was then applied to the aforementioned bases A-F at a dye coverage of 0.08 g/f.
fl, gelatin coating amount 0.4 g/m, surfactant 0.0
Both sides were coated at a concentration of 26 g/M and hardener 0.0168/mf.

1-3) Constituent water of emulsion layer: 30 g of gelatin, 5 g of potassium bromide, 0 potassium iodide in water 11
．． Add 0.5 g of silver nitrate aqueous solution (5 g as silver nitrate) and 0.73 g of potassium iodide into a container kept at 75°C while stirring.
An aqueous solution of potassium bromide containing was added over 1 minute using a double jet method. Furthermore, silver nitrate aqueous solution (145 as silver nitrate)
g) and an aqueous potassium bromide solution were added by a double jet method.

The addition flow rate at this time was accelerated so that the flow rate at the end of addition was eight times that at the beginning of addition. After this, 0.37 g of an aqueous potassium iodide solution was added.

After the addition, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, 60g of gelatin was continuously added, and p
H was adjusted to 6.5. The temperature was raised again to 56°C, and the sensitizing dye anhydro-5,5'di-chloro-9-ethyl-3
, 3'-di(3-sulfopropyl)oxacarbonanine hydroxide sodium salt 650 μm was added, and then chemical sensitization using gold and sulfur enhancement was performed.

The obtained emulsion had a hexagonal plate shape with a projected area diameter of 0°85μ.
The average thickness of m1 was 0.158 μm.

4-hydroxy-6methyl-1 was added to this emulsion as a stabilizer.
．． 3.3a,7-chitrazaindene and 2.6-bis(hydroxyamino)-4-diethylamino-1,3,5-
1-Ryazine and trimethylolpropane were added.

Furthermore, the following compounds were added (350■/resistant) CH3C6
H13N In addition, p-octylphenoxyjethoxyethanesulfonic acid sodium 0.01 g/d as a coating aid, dodecylbenzenesulfonate 0.005 g/d, and as a thickener,
Polybotacium p-vinylbenzenesulfone) 0.
03g/n (, Polymer latex (poly [ethyl acrylate/nuccrylic acid = 97/3) particles]
Degree of polymerization 10) Oquine ethylene bori [degree of polymerization 3] Adsorbed with oxyglyceryl dodecyl ether [3% by weight of particles], average particle size = 0.1 μm) 0.4 g/M,
Sodium polyacrylate (molecule ff 1.2 million) 0.1
g/n(,1,2-bis(vinylsulfonylacetamido)ethane 0.04 g/m', trimethylol.

■-4) Composition of protective layer Mugelatin 1.2g/mm Polyacrylamide (molecular weight 45,000) 0.2g/n (Mudextran (molecular weight 38,000) 0.2g/mm Sodium polyacrylate 0 0.02 g/m Sodium styrene sulfonate 0.01 g/n (Mucolloidal silica (particle size 0.02 μm) 0.04 g/rd Mu poly (degree of polymerization 10) Oxyethylene cetyl ether 0.02 g/m Poly (degree of polymerization 10) Oxyethylene poly(degree of polymerization 3) Glyceryl-p-octylphenyl ether 0.02gZrdC, Hff Cs1l+, SOJ+ CH2Cl120 +T+C
11z + n5OzNa0.001g/r# 0.0005 g/m C1(3 A C,li, IC0NH-(-C11,-)-, N
-C112COO"l11 0.001g/m J7 Mu CaH1tSO□1l-(-C11□c11.to
+T+CIIzCl+CHzQ→-, ++0!1 0.01g/m Potassium nitrate 0.05g/ip -
, t-octylphenoxyethoxyethoxyethoxyethanesulfonic acid sodium salt 02g/m 4-hydroxy-6-methyl-1,3,3a, 7 Tetrazaindene 0.04g/m cetyl palmitate (dobucilbenzenesulfonic acid sodium salt) Particle size: 0.11 μm) 0.005 g/m methylsiloxane (dispersed with dioctyl-α-sulfocomucate sodium citrate).

Particle size: 0.12 μm) Liquid paraffin (dispersed with dioctyl-α-sodium sulfosuccinate. Particle size: 0.11 μm) 0.05, g/n (0.005 g/m) Polymethyl methacrylate fine particles (average particle size: 3.0 μm) 8 μm, 4.8 to 2.8 μm (abundance of 80% or more) 0.04 g/m For the above emulsion layer and protective layer, a solution was prepared so that the gelatin content was 4 wt%, and the basic content of each layer was It was prescribed.

Then, the amount of silver coated on each side of the bases A to F created in 1) is 1
．． 9 g/n (and coated on both sides. Also, the coating was done in such a way that each layer was arranged in such a way that the dyeing layer, emulsion layer, and protective layer were arranged from the side closest to the support. Regarding the samples prepared as shown in Table 1. We conducted an evaluation.

developer, fixer, I went to the street.

Developer concentrate> Potassium hydroxide Sodium sulfite Diethylene triamine Pentaacetic acid Carbonate Potassium borate Hydroxynon diethylene glycol 4-Hydroxymethyl-4 Methyl-1-phenyl-3 Pyrazolidone 5-Methylhensitriazole Make 14 with water (p) (10゜〈Fixer concentrate) Ammonium thiosulfate Sodium sulfite Ethylenediaminetetraacetic acid diacetate and development process are adjusted to the following 56.6g 00g 6, 7g 16.7g 10g 83.3g 0g 11.0g 2g 60) 60g 0g Sodium trihydrate 0.10g Sodium hydroxide Add In with 24ff water (adjust to pH 5.10 with acetic acid).

Automatic developing machine Second processing developing tank 6
．． 57! 35°C x 10.5 seconds fixing tank 6.5
ρ 35℃×9 seconds washing tank 6.5J 20°
cx7, dry for 5 seconds
50℃Dry to Dry processing time
When starting the 45-second development process, each tank was filled with the following processing solution.

Developing tank 2: 333 ml of the above developer concentrate, 667 ml of water
ml and a starter 10 containing 2 g of potassium bromide and 1.8 g of acetic acid was added to bring the pH to 10.15.

Fixing tank 2 250 ml of the above fixer concentrate and 75 ml of water
〇- (1) Static mark test After conditioning an unexposed sample at 25°C and 10% RH for 2 hours, test the static mark on the sample against various materials in a dark room under the same air conditioning conditions. After rubbing with a rubber roller and a urethane roller to see if the
The film was developed with the developer described above, fixed, and washed with water, and the degree of static mark generation was examined.

In Table 1, the degree of static mark occurrence was evaluated in the following four stages.

A: No static marks were observed at all B:
Slightly recognized C:
Fairly observed D: Observed on the entire surface (2) Test with dust The sample (20 cm x 2
0 cm) was thoroughly rubbed with gauze to examine the adhesion of cigarette ash. Evaluation was performed in the following four stages.

A: No dust was observed at all.

B: A little dust was observed.

C;/F was considerably observed.

D: was strongly recognized.

(3) Transmittance test Using an unexposed sample that was developed and fixed as described in (1), the total light transmittance was measured.

Sample 1-1 (control) is set as 100,
The relative values for this are shown in Table 1 as relative transmittances. In addition, Zenko 1i! Transmittance was measured according to ASTM D-L OO3.

(4) Adhesion test The completed sample was placed in an atmosphere of 25°C and 50% RH for 2 hours.
After standing for a period of a period of a period of 10 minutes, an adhesion test was conducted using the method described below. The surfaces tested here were the surfaces provided with the antistatic layers of bases A to G.

(a) Adhesion test method for dry film On the surface to be tested, make 36 squares by making 7 cuts at 5ρ intervals vertically and horizontally, and apply adhesive tape (for example, Nitto Electric Industries ■) Attach the knit tape)
In this method, which involves rapid peeling in the 180' direction, 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. Adhesive strength sufficient for practical use as a photographic material is one that is classified as grade A of the above three-level evaluation.

(b) Wet film adhesion test method At each stage of development, fixation, and water washing, scratch the film at the X mark using an iron pen in the processing solution, and then scratch it firmly with the tip of your finger.
Adhesive strength was evaluated during maximum peeling along the x line.

A case where the constituent layer does not peel off after the scratch is removed is graded A, a case where the maximum peeling is within 5 cranes is graded B, and other cases are grade 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.

As can be seen from Table 1, the control sample using Base G-1, which does not contain the conductive material (B), is significantly inferior in terms of static mark occurrence and dust adhesion.

-Sample 1-2.1-4.1 using the base of the strength tree invention
-5 was excellent in all evaluations, but Samples 1-3 and -6, in which the antistatic layer was applied after two-wheel stretching, were accompanied by deterioration in permeability and adhesion. It can be seen that when a water-based polyester (instead of (A)) was used in No. 1, there was a worsening of dust adhesion after treatment and a worsening of adhesiveness.

From the above, it is clear that the present invention is significantly superior to conventional techniques.

In addition, although excellent images were obtained for both the control sample and the sample of the present invention, the comparative sample was accompanied by a decrease in photographic sensitivity and unevenness of the image, and from this point as well, the present invention is superior. is clear.

Example 2 2-1) Preparation of bases After corona discharge was applied to both sides of bases A-G prepared in Example 1-1), the following three layers of undercoat were applied to both sides, and bases A-2 to G- It was set as 2. The base thickness was set to 100 μm after biaxial stretching.

Synthesis of poly(methyl methacrylate-co-ethyl acrylate-co-acrylic acid) Weigh out 1.5 g of sodium dodecyl nitrate into a 11-three flask equipped with a stirring device and a reflux tube, and add 300 g of water.
Dissolve in cc. Next, the reaction vessel was placed under a nitrogen stream for 7
The temperature is raised to 5° C. and stirred at 20 rpm. Here, 3
% potassium persulfate aqueous solution was added, and then a mixed solution of 150 g of methyl methacrylate, 87.5 g of ethyl acrylate, and 12.5 g of acrylic acid was added dropwise over 3 hours.

3% potassium persulfate 10 times a total of 6 times every 30 minutes after the start of dripping
g was added. After the completion of dropping the monomer mixture, the reaction vessel was kept at 75° C. for another 2 hours to obtain an aqueous dispersion of a copolymer with an average molecular weight of 250,000. This aqueous dispersion was neutralized with a 10% aqueous potassium hydroxide solution and adjusted to pH 7.0 three times.

To the aqueous dispersion of this copolymer, 2.4 dichloro, 6 hydroxy 1,3.5) riazine sodium was added in an amount of 4% by weight based on the solid content of the copolymer, and the average particle size was 2μ for each level.
A liquid to which polystyrene fine particles were added in such a manner that the polystyrene fine particles were spread at a density of 1.0 ■/'' was used as a coating liquid for the first layer of undercoat.

The conductive biaxially stretched polyethylene terephthalate film of the present invention was subjected to corona discharge treatment under the following conditions. The film transport speed was 30 m/min, the distance between the corona discharge electrode and the polyethylene terephthalate film was 3 mm, and the electric power was 200 watts. An aqueous dispersion of the copolymer synthesized by the above method was coated on both sides of corona discharge-treated polyethylene terephthalate to a dry film thickness of 0.2 μm, and dried at 185°C. This layer is called the first undercoat layer. In addition, the film transport speed is 30 m/min,
A corona discharge electrode was subjected to corona discharge treatment with a distance of 1.8 m from a polyethylene terephthalate film and a power of 120 watts, and then vinylidene chloride, methyl methacrylate, methyl acrylate, and acrylonitrile-90 were applied.
:5:4:1, by weight, an aqueous dispersion of the copolymer was applied on both sides to a dry film thickness of 0.3 μm, and I 20
It was dried at 'C. Further, on the second undercoat layer made of this vinylidene chloride copolymer, treatment was performed at a film transport speed of 30 m/min, a distance between the corona discharge electrode and the polyethylene terephthalate film of 1.8 mm, and a power of 250 watts.
On top of that, as the third layer of undercoat, apply 2 of the undercoating liquid of the following formulation (A).
It was coated on both sides to give a coating thickness of 0-/m and dried at 170°C.

Next, a silver halide emulsion of the following formulation 22) was coated on the side of the support without the conductive layer, and an emulsion protective layer of the following formulation 2-3) was further coated. On the opposite side (conductive layer side), in order from the support side, a back layer of the following formulation 24), and a back layer of the following formulation 2-
The bank protective layer of 5) was applied and used as a sample.

(a) Undercoat 3rd layer formulation Gelatin 1.0% by weight Methyl cellulose 0.05% by weight 2-2) Silver halide emulsion layer formulation 2X per mole of silver in an aqueous gelatin solution kept at 50°C
An aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes in the presence of 10-' moles of rhodium chloride to obtain an average particle size of 0.2.
A silver chlorobromide monodisperse emulsion of μ was prepared. (C18 composition 95
(mol%) This emulsion was desalted by the flocculation method, 1 mol of thiourea dioxide and 0.6 ml of chloroauric acid were added, and the emulsion was aged at 65°C until the highest performance was obtained. It made me frown.

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

n-C+ZH2% 2X10-" mol/A g 1 mol 4X10-' mol/A g 1 mol KBr 20
+ng/m polystyrene sulfonic acid sodium salt 40nw/m2.6
-Dichloro-6-hydrowaxy 1.3.5-1-Ryazine sodium salt 30ml/rd This coating solution was coated to give a coated silver amount of 3.5g/+yr.

2-2) Emulsion protective layer formulation The following compounds were further added to the protective layer of Example 1. Note that the gelatin content was 1.5 g/m.

Dodecylbenzenesulfonic acid sodium salt 0.05 g/n (Sodium acetate 0.03 g/m Bank layer formulation gelatin 2°5 g/m 5-Nitroindazole 0.015 g/m 1.3-
Divinylsulfonyl 2-propatol o, 05g/n (N-perfluorophthanesulfonyl-N-probylglycine botadium salt 2.7m ethyl acrylate latex (average particle size 0.1μ) 0.2g/mOJ OJ o3Na 503K SO, 40μ/M Dodecylbenzenesulfonic acid sodium salt 2-4) Bank protective layer formulation Prepared in the same manner as in Example ①.

It was set to 1.0 g/m.

35μ/I gelatin is 80mg/resistant to SO, K SO3 1.3-divinylsulfonyl 2-propateurethyl acrylate latix (average particle size 0.1 μ) Dihexyl α-sulfosacnate sodium salt 50μ/resistant 900 nv/m 35 ■/1 The prepared sample was evaluated in exactly the same manner as in Example 1. Sample 22.2-4.2- created using the base of the present invention
As can be seen from the table, Sample No. 5 is excellent in all aspects of static mark generation, dust sticking, permeability, and adhesion.

On the other hand, control sample 2-1 and sample 2-3.2-6.2-7 using the comparative base cannot satisfy all of the requirements of static marks, dust, transparency, and adhesiveness.

Example 3 Bases A-2 to G-2 created in Example 2 (however, PET
The first undercoat layer was removed (the film thickness was 100 μm after biaxial stretching), and the second undercoat layer was made by copolymerizing sodium 2,4-dichloro-6-hydroxy-13,5-triazine with vinylidene chloride. Bases A-3 to G-3 were prepared in the same manner as in Example 2, except that 4% by weight of the combined product was added.

Using this base, a sample was prepared which was a multilayer color photosensitive material consisting of each layer having the composition shown below.

However, the base thickness of PET was adjusted to 100 μm after two-wheel stretching.

At this time, the photosensitive layer was formed in the order of the 1st layer to the 16th layer on the side without the base conductive layer, and the back layer was applied on the conductive layer side of the base in the order of the 1st layer and the 2nd layer. .

(Composition of the photosensitive layer) The coating amount is expressed in g/m of silver for silver halide and colloidal silver, and the amount expressed in g/m for coupler additives and gelatin. The number of moles of the dye is expressed per mole of silver halide in the same layer. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

U■; Ultraviolet absorber, 5olvH high boiling point organic solvent, Ex
F: Dye, ExS Child sensitizing dye, ExC: Cyan coupler, EXM: Magenta coupler ExY: Yellow coupler, cpai additive 1st layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.9 V-1 V-2 V-3 olv ExF-1 ExF-2 2nd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag+ 4 mol%, uniform-Agl type, f
, y equivalent diameter 0.4 μm, change in sphere equivalent diameter faJ error 37%
, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0.03 0.06 0.07 0.08 0.0I Olol 0.4 0.8 2.3X10-'1.4X10-' 2. 3X10-'8.0X10-' 0.17 0.03 0.13 Gelatin ExS-2 ExS-5 ExS-7 ExC-1 ExC-2 ExC-3 3rd layer (mid-sensitivity red-sensitive emulsion layer) Iodobromide Silver emulsion (Ag! 6 mol%, core shell ratio 2:
1 internal high Agl type, equivalent sphere diameter 0.65 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.65 Silver iodobromide emulsion (Ag1 4 mol) %, average-Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0.1 Gelatin 1.0ExS-
12XIO”' Ex S -21,2X10-'EχS-52X10-' ExS-77 Layer) Silver iodobromide emulsion (Ag1 6 mol%, core shell ratio 2:1
Internal high Agl type, equivalent sphere diameter 0.7μm, coefficient of variation of equivalent sphere diameter 25%, diameter/thickness ratio 2゜5) Coating amount gelatin ExS-1 ExS-2 ExS-5 ExS-7 xC-1 xC-4 olv-1 olv-2 pd-7 5th layer (intermediate layer) Gelatin V-4 V-5 pd-1 Polyethyl acrylate latex olv-1 Platy particles, 0.9 0.8 1.6X10- '1.6X10-'1.6X10-' 6 Xl0-' 0.07 0.05 0.07 0.20 4.6X10-' 0.6 0.03 0.04 0.1 0.08 0.05 6th layer (low-angle green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, uniform-Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, diameter/ Thickness ratio 2.0) Coated silver 1i 0.18 Gelatin 0.4ExS-
32X10-'ExS-47XIO-'ExS-51XIO-' x M -50,11 ExM-70,03 Ex Y -80,01 Solv-10,09 Solv-40,01 7th layer (medium Sensitivity green emulsion layer) Silver iodobromide emulsion (Ag! 4 mol%, core shell ratio 1:
1 surface height Agl type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter/thickness ratio 4.0) Application 1 l O, 27 Gelatin 0.6ExS-3
2×10-' ExS-47 ) Silver iodobromide emulsion (Ag1 8.7 mol%, ratio 3:4
: 2 multilayer structure particles, 24 mol from Ag+-containing old interior,
0 mol, 3 mol%, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 1.6) Coated silver amount 0.7 Gelatin 0.8E x
S -45,2X10-'ExS-51xio-' Ex S -80,3xlO-' ExM-50,I ExM-60,03 Ex Y -80,02 Ex C-10,02 ExC-40,01 Solv-10,25 Solv-20,06 Solv-40,01 Cpd-71XIO-' 9th layer (middle layer) Gelatin 0.6Cp d
-10,04 Polyethyl acrylate Latinx 0.12Sol
v-10,02 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag1 6 mol%, internal high Agl type with core-shell ratio 2:1, equivalent sphere diameter 0.7 μm, equivalent to sphere) Coefficient of variation in diameter 25%, plate-like grains, diameter/W ratio 2.0) Coated S reversal amount 0.68 Silver iodobromide emulsion (Ail 4 mol%, uniform Agl type, equivalent sphere diameter 0.4 μm) , coefficient of variation of equivalent sphere diameter 37%, plate-shaped particles, diameter/IW ratio 3.0) Coated silver amount 0.19 Gelatin 1. .

EχS-36X10-' ExM-100,19 Solv-10,20 11th layer (yellow filter layer) Yellow colloidal silver 0.06 Gelatin 0.8Cp d -2
0.13 Solv-], 0.13C
p d -10,07 Cp d -60,002 H-10,13 No. 121 (Low frequency blue emulsion layer) Silver iodobromide emulsion (Ag 14.5 mol %, uniform-Agl type,
Equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount 0.3 Silver iodobromide emulsion (Ag1 3 mol%, uniform-Agl type, Equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 30%, plate-shaped particles, diameter/yL ratio 7.o) Application 11i! it 0.
15 Gelatin 1,8ExS-6
9X10-' Ex C-1o, 06 Ex C-40,03 ExY-90,14 ExY-110,89 Solv-10,42 13th layer (middle layer) Gelatin 0.7ExY-
120,20 Solv-10,34 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10 mol%, internal high Agl type, f7R equivalent diameter 1.0 μm, coefficient of variation of sphere equivalent diameter 25%
, multiple twinned plate-like grains, diameter/yJ-view ratio 2. o) Coated silver amount 0.5 Gelatin 0.5ExS-
61XIO-' EχY -90,01 ExY-110,20 Ex C-10,02 Solv-L O, 10th
5 layers (first protective layer) Fine grain silver iodobromide emulsion (Agl 2 mol%, homogeneous -Agl
Mold, equivalent sphere diameter 0.07 p m) coated silver l O,
12 Gelatin 0.9UV-4
0,11 UV-50,16 Solv-50,02 ) i-10,13 Cpd-50,10 Polyethyl acrylate latex 0.09 No. 16
Layer (second protective layer) Fine grain silver iodobromide emulsion (Agl 2 mol%, uniform Agl
Mold, equivalent sphere diameter 0.07 μm) Coated silver M O.

Gelatin polymethyl methacrylate particles (diameter 1.5 μm) Poly(methyl methacrylate/methacrylic acid) (molar ratio 60:40, diameter 2.1 μm) ■】-1 C, I+? C6F, 7SO□NCII□C00K 0,55 0.1 0.1 0,17 0.005 0.002 In addition to the above components, each layer contains emulsion stabilizer Cpd-3.
(0,07g/m), surfactant Cpd-4 (0,0
3 g/n() was added as a coating aid.

(Composition of back layer) 6-back 1st layer - Gelatin - α-sulfosuccinic acid dioctyl ester sodium salt - Sodium polystyrene sulfonate O-back 2nd layer - Gelatin polymethyl methacrylate (average molecular weight 3.5 μm) - Poly (methyl methacrylate) - methacrylic acid; molar ratio 60/40) average molecular weight 2.1 μm ・Sodium p-octylphenoxydiethoxyethanesulfonate ・2.6-dichloro-4-h(g/r+f) 4.6 droxy-1, 3,5 monotriazine sodium salt 0.01 V-4 U■ 4 Tricresyl dibutyl phthalate (t) CaL Solv-5 Trihexyl phosphate xF-1 O N(Czlls)z xF N(Calls)z xS-5 xS xS-8 xC ■ xC ExC-3 ExC (i) C411qOCONI1 01;1lzl;lhs and lhL;υ2+1 and l xM-10 xM-5 xM xY-9 xY-11 cP d-5 cp d-7 ■ C11゜cP d-3 pct C,11,2 cp d-4 pd-2 pd-6 υ C1h=CIl-5o!-C11,-L;UNII-L
llzN=03N The obtained sample was developed using an automatic developing machine according to the method described below.

Processing method step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38℃ 15mj 2
ON bleaching 6 minutes 30 seconds 38℃ 10d
401 water washing 2 minutes 10 seconds 35℃ LO
++t! 21! Fixed 4 minutes 20 seconds 38
℃ 20m1 304! Water washing (1) 1 minute 05 seconds 35℃ (2) 101 Countercurrent piping system from fil.

Washing with water (2) 1 minute OO seconds 35℃ 20 layers 1
101 stable 1 minute 05 seconds 38℃ 10
rntIOA drying 4 minutes 20 seconds 55°C Replenishment amount is 350 cJ Next, write down the composition of the treatment solution.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.11-Hydroxyethyrythene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4- (N-Ethyl-N β-hydroxyethylamino)-2 = H by adding methylaniline sulfate solution (Bleach solution) Sodium ferric ethylenediaminetetraacetate 3.0 4.0 30.0 1.4 1.5Q1 2 .4 4.5 1.01 10.05 Mother liquor (g) 30.0 1.01 10,10 Replenisher (g) Trihydrate 100.0 140.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Aqueous ammonia (27%) 6.5. d Add water 1.01 pH6.0 (Fixer) Mother liquor (g) 11.0 1B0.0 40.0 2.5mA! 1.0! 5.5 Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 1.0 Sodium sulfite 7.0 12.0 Sodium bisulfite 5.0 9.5 Ammonium thioFi'M acid aqueous solution (70%) 170. 0mf 240
．． Add 0ml water 1. OA 1.
0ρpH6,76,6 (washing solution) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-120B manufactured by Rohm and Haas). Water was passed through a mixed bed column packed with 400) to reduce the concentration of calcium and magnesium ions to 3/p or less, and then 20/1 sodium isocyanurate dichloride and 1.5 g/l of sodium sulfate were added. Added.

The pH of this solution was in the range of 6.5-7.5.

(stabilizer) Formalin (37%) polyoxyethylene p-7nononylphe nyl ether (average Degree of polymerization 10) Ethylenediaminetetravinegar acid disodium salt add water pH Mother liquor (g) Replenisher (g) 2, 0 ml 3, 0 ml 0.3 0.45 0.05 0.0B 1.012 1.01! 5.0-8.0 5.0-8.0 The obtained sample was evaluated in the same manner as in Example 1.

The results are shown in Table 3.

Sample 3 using the base of the present invention as shown in Table 3
-2.3-4.3-5 shows excellent performance (static mark occurrence, dust adhesion, transparency, adhesion), but on the other hand, sample 3-3.3- using a comparative base 6.3-7
It can be seen that this is accompanied by significant dust adhesion and deterioration of permeability and adhesion.

From the above, it can be seen that the present invention is significantly superior in all respects to conventional antistatic supports.

Claims (1)

[Scope of Claims] 1) A silver halide photographic material having at least one photosensitive silver halide emulsion layer on at least one side of a polyester film support, wherein the polyester film is on at least one side of the support. , consisting of an acrylic polymer (A) and a sulfonated polystyrene and/or a salt thereof (B),
A biaxially stretched polyester film in which a resin having a weight ratio of (A)/(B) of 95/5 to 5/95 is applied and then stretched in at least one direction, and the thickness of the applied layer is 0.001 to 5 μm. A silver halide photographic material characterized by: 2) Acrylic polymer and sulfonated polystyrene and/or
2. The silver halide photographic material according to claim 1, wherein the layer coated with a resin made of a silver halide or a salt thereof contains a curing agent.