CA2040156A1 - Packaged silver halide photographic materials and process for their production - Google Patents

Abstract

ABSTRACT
The improved process for producing a packaged silver halide photographic material that has hydrophilic colloidal layers, at least one of which is a light-sensitive silver halide emulsion layer, on a support having an antistatic layer comprising a hydrophobic polymer latex having either an ethylene oxide chain or an amide chain or both, a water-soluble conductive polymer and an epoxy compound, is characterized in that during the coating and drying of a hydrophilic colloidal layer on at least one side of said silver halide photographic material, said layer is brought into contact with air having a temperature of 35 - 80°C
and/or a relative humidity of 5 - 25% for at least 5 seconds within 5 minutes from the time when the average surface temperature of the coated layer has rose to a point that is 1°C lower than the drying temperature and, furthermore, said silver halide photographic material, after the end of the drying of both sides thereof, is maintained in an atmosphere having a dew point of no higher than 16°C until the end of the packaging step. The improved packaged photographic material produced by this method is also disclosed.

Description

2 ~

PAC~AGED SILVER HALIDE PHOTOGRAPF~IC
M~TERIALS AND PROCESS FOR T~IEIR PRODUCTION
BACKGROUND OF THE INVENTION
This invention relates to packaged s:ilver halide photographic materlals (which are hereinafter sometimes re-ferred to simply as "light-sensitive materials'') and a process for producing them. More particularly, the presen-t invention relates to packaged light-sensitive materials that have high transparency, that insure strong adhesion between a hydrophilic colloidal layer and an antistatic layer, that exhibit very e-ffective anti-static properties and that hence are particularly suited -for use in photomechanical processes. The present invention also relates to a process -~or producing such improved packaged light-sensitive materials.
Plastic films that are customarily used as transparent supports have a great tendency to collect static charges, which o-ften limits the use of those -~ilms in practical applications. For example, transparent supports such as polyethylene terephthalate films which are used in silver halide photographic materials are highly prone to collect static charges under low-humidity conditions such as in winter. I-~ light-sensltive materials are charged electrically, discharging electricity will cause an electric shock to operators who handle them or "static 2 ~ 5 ~

marks" will develop in the light-sensitive materials.
Further, electrostatically deposited -foreign matter such as dust particles can produce pinholes and other sur-face defects that will substantially deteriorate the quality o-f the light-sensitive materials.
Prevention of static buildup has become particularly important these days in the photographic industry where it is common practice to coat highly sensitive photographic emulsions at high speed or to expose highly sensitive photographic materials in large volumes with automatic printers.
Under these circumstances, antistatic agents are customarily used in light-sensitive materials and those which are used commonly today include fluorine containing surfactants, cationic sur-factants, amphoteric sur-factants, surfactants or high-molecular weight compounds that contain a polyethylene oxide group, as well as polymers that contain a sul-fonic acid or phosphoric acid group in the molecule. Particularly many proposals have been made with a view to adjusting -the triboelectric series with the aid of fluorine containing surfactants or to provide improved conductivity using conductive polymers. See, for example, JP-A-49-91165 (the term "JP-A" as used hereinafter means an 5 ~

"unexamined publshed Japanese patent application") and JP-49-121523, which disclose examp:les of using ionic polymers having a dissociative group :in the backbone chai~l.
These prior art technlques, however, have had the problem that their antistatic action is signif`icantly reduced by pho-tographic development. This would be because alkalies used in the development step, acids used in the -fixing step, and water used in the washing step deprive the antistatic agents o-f their effectiveness during processing.
I~ processed -~:ilms are to be subsequently used in printing as in the case of light-sensitive materials for platemaking, dust particles will collect to produce pinholes and other sur-face defects on the light sensitive materials. To avoid this problem, JP-A-55-84658, JP-61-174542, etc. have proposed the use o-f an antistatic layer comprising a water-soluble conductive polymer having a carboxyl group, a hydrophobic polymer havlng a carboxyl group, and a polyfunctional a~iridine. The methods described in those patents have the advantage that the desired action o-f the antistatic layer is retained even after photographic processing. On the other hand, i-f the applied antistatic coat is dried at an increased speed in order to improve the e-f-ficiency o-f production, the transparency o-f the antistatic layer will decrease to an unacceptably low level.

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To deal with this problem, it has been proposed that a hydrophobic latex having either an ethylene oxlde chain or an amide chain or both be used in an antis-tatic layer. As it turned out, however, the adhesion between the antistatic layer and the overlying hydrophilic colloidal layer deteriorated at elevated humidities.
SUMMARY OF THE INVENTION
The present invention has been achieved under these circumstances and has as an obJect providing a process -for producing a packaged light-sensitive material that retains an antistatic property even after processing, that exhibits high transparency under rapid drying conditions, and insures good adhesion between a hydrophilic colloidal layer and the antistatic layer.
Another obJect o-f the present invention is to provide an improved packaged light-sensitive material produced by said process.
As a result of the intensive studies conducted in order to attain these ob~ects, the present inventors found that the first obJect of the present invention could be achieved by a process for producing a packaged light-sensitive material that has hydrophilic colloidal layers, at least one o-f which is a light-sensitive silver halide emulsi.on layer, on a support having an antistatic layer comprising a hydrophobic polymer latex having either an 20~15~

ethylene ox-~de chain or an amide chain or both, a water-soluble conductive polymer and an epoxy compound, which process is characterized ln that during the coating and drying of a hydrophilic colloidal layer on at least one side Oe said light-sensi-tive material, said layer is brought into contact to air havlng a temperature O-e 35 -80C and/or a relative humidity O-r 5 - 25% for at least 5 seconds within 5 minutes from the time when the average surface temperature of the coatèd layer has rose to a point that is 1C lower than the drying temperature and, furthermore, the light-sensitive material, after the completion of the drying of both sides thereof, is maintained in an atmosphere having a dew point (which is hereinafter sometimes abbreviated to "DP" as required) O-e no higher than 16~C until the end of the packaging step.
The second object of the present invention can be attained by the improved packaged light-sensitive material that is produced by said process.
The present inventors also found that the above-stated objects could be attained more effectively by containing either a tetrazolium compound or a hydrazine compound or both in the silver halide emulsion layer.
DETAILED DESCRIPTION OF THE INVENTION
Photographic layers are usually coated on a light-sensitive material and dried by the following procedure: a ~O~S6 coating solution that comprises a gelatin composition is applied onto a support; the applied solution is cooled to solidify in cold air having a dry-bulb temperature O-r -lo to 15C; then, the temperature is elevated to dry the coated layer. However, drying under the elevated ' temperature is primarily for -the purpose of enhancing the drying speed and the coated layer is usually brought into contact with air having ambient temperature at the point o-f time when the drying ends.
In the step of the process of the present invention where at least one of hydrophilic colloidal layers is applied and cooled to become dry by gelling gelatin, the layer is brought into contact with air at 35 - 80C for at least 5 seconds within 5 minutes from the time when the average surface temperature of the coated layer has rose to a point that is 1C lower than the average temperature of the drying ambient air.
The "timé when the average surface temperature of the coated layer has rose to a point that is 1C lower than the air which it contac-ts" usually corresponds to the water content of the hydrophilic colloidal composition, for example, a gelatin composition, that is typically within the range of 60 - 20% and, in practice, the drying process can be considered to have ended at that point. The coated layer is brought into contact with air at 35C - 80C for at least 5 seconds within 5 minutes from that point. It was quite surprising that this contact was very ef-fective in improving the adhesion between the hydrophilic colloidal layer and the antistatic layer that deteriorated on account of the hydrophobic latex in the antistatic layer which contained either an ethylene oxide chain or an amide chain or both.
Bringing the light-sensitive ma-terial into contact with air at 35 - 80C corresponds substantially -to contact with air having a relative humidity o-f 5 - 25%. Equally good results are achieved in the present invention by bringing the light-sensitive material into contact with air having a relative humidity O-r 5 - 25%.
The "time when the coating and drying operations end "as used herein means the time at which the light-sensitive material has been brought lnto contact with air (e.g. dry air~ having a temperature O-r 35 - 80C and/or a relative humidity o-f 5 - 25%.
Bringing the light-sensitive material into contact with air at the time when the drying operation ends is e-ffective for the purposes o-f the present invention. When a layer is coated and dried on one side of the support and then another layer on the other side, the above-described treatment need not be performed in the coating and drying process for both sides of the support and applying said ~ .

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treatmen-t to only one side of the support will su-f-fice.
However, in a particularly pre-ferred embodiment, said treatment is per-formed in the coating and drying process for both sides o-f the support.
In order to ship the thus treated silver halide photographic material as the -f:inal product, it must be packaged a-fter the coating and drying operations ended for both sides o-f the support. The obJects o-f the present invention can be attained only when all the steps following the end of the coating and drying of both sides o-f the light-sensitive material until it is packaged are performed in an environment having a DP (dew point) o-f no higher than 16C ~with the moisture in the package being also taken into account).
In the practice o-f the present invention, desired e-ffects are attained by per-forming the drying operation under the conditions described above and the drying media that can be used are not limited to dry air alone and other suitable media can be employed such as far in-frared rays and microwaves. For the sake o-f convenience, the -following description of the present invention centers on the case where dry air is used as a drying medium.
The term "dry air" as used herein means air that is to be brought into substantial contact with the light-sensitive material, that is supplied for the purpose of drying or controll:ing humidity, and that is blown directly against the light-sensitive material. This term does not mean air that is present between adJacent turns o-f the roll o-~ light-sensitive material tha-t has been wound up a-fter coating and drying operations, nor does it mean air that is present between sheets of the light-sensitive material that have been stacked one on another a-eter being cut to a desired size.
The "steps -f`ollowing the end of the coating and drying process until the light-sensitive material is packaged"
typically include steps such as winding up, cutting and packaging and sometimes include other steps such as the storage and transport o-f the light-sensitive material.
The term "air that is to make substantial contact with the light-sensitive material" as used herein means air that is in contact wi-th the light-sensitive material whlle the latter does not make contact with anything but air. Light-sensitive materials are o-ften transported either in a "bulk" form as they have been wound up onto a roll, or in a stack as individual sheets cut to a desired size are superposed one on another. To take the "bulk" -form as an example, one may safely conclude that neither side of the support makes substantial contact with the ambient air in which the bulk is placed as long as -the portion of the bulk where adjacent turns of the light-sensitive material g 2 ~

contact each other is concerned. Therefore, the -following case is included as an embodiment o-f the invention recited iIl claim 1: a-~ter the coating and drying process has been completed under the conditions specified by the present invention, the light-sensitive material is wound up onto a roll while making contact with air h~ving a DP not higher than 16C; the bulk is then transported through air having a DP not higher than 17C; and therea-fter the bulk is unwound, cut to a desired size and packaged while making contact with air having a DP not higher than 16C.
The term "packaging" as used herein means protecting the light-sensitive material o~ interest by sealing it with a material (e.g. in a bag) that is light-fast, moistureproo-~and pre-~erably heat-resistant.
The water-soluble conductive polymer to be contained in the antistatic layer is described below. This water-soluble conductive polymer is a polymer having at least one conductive group selected -from among a sul-fonic acid group, a sulfate ester group, a quaternary ammonium salt, a tertiary ammonium salt and a carboxyl group. Such conductive groups are pre-ferably present in an amount o-f at least 5 wt% per polymer molecule. The water-soluble conductive polymer may also contain a hydroxyl group, an amino group, an epoxy group, an aziridine group, an active ~ 0 ~

methylene group, a sul-~inic acid group, an aldehyde group or a vinylsul-rone group.
The water-soluble conductive polymer pre-ferably has a molecular weight o~ 3,000 - 100,000, more pre-ferably 3,500 - 50,000.
Speci-~ic, but non-limiting, examples Or the compounds that can be used as the water-soluble conductive polymer in the present invention are listed below.

(The remaining space is left blank.) --~CII 2 - Cll) 9 0 (Cll 2 -d~n COO~I

SO3Na Mn= 10000 --~CII 2 - C~l) 6 0 ~CII 2--ICI~ O
~1 COOil ~ ' _ SO3Na Mn= 7000 --~CIl2--Cl~ o ~CIl--ICII~Io COOII COOII
~ -.
SOgNa Mn= 5000 .
A--~
tCII 2 - C11-3 3 o (Cll - ICl13 4 0 COOII COOII

SOgNa Mn= SOoo .

..
` :
.

2 ~

Cl~3 2--Cll) a o~ ~CII 2--C3 f~ COO N a ,. , ~ _ .
Mn= 20000 SO3 Na C~13 --~ CIl 2 - Cll~ ~ o ~CII 2 - C3 4 0 d~ cooll Mn= 8000 --~CII 2- Cll~ 95 ~CII 2- IC~
~ COOI{
~JI !
Cl{2OSO3Na hln . 8000 ::

--~CII 2 - Cll~ o o ~CII 2 - ICll~ I o ~ CON11 2 ~JI _ Mn--6000 :; SO 3 L i 2~15~

tcll 2 - C11-3 IJ O - ~CII 2--CH-3, O ~CII 2 - Cl H3 COOII

S03 Na Mn . l sn oo A-- l O
Dextran su-lfate Degree of substitution 3 O Mn= 500000 tC112 - Cl~l)so ~C~12 - Clll~
COOC 2 IT.~ 011 . . SO3Na Mn 10000 CII 2- C113 60 ~ CII 2-C~ O
COOC 2 H ~ 011 "~ hln= 7000 SO3 Na -~C1~2- Cll-}~- tCI12- ICII),O
CONII ~ Nll 2 Mn= 15000 SO3Na ~CII 2 C113 6 (~ ~CII 2 Cll~o COOC}12~7 I Mn= 5000 SO3Na A - 1 5 Cl13 --~CH2-CI13~o -- ~CI12-C)~o , COOC211~0ll Mn= 20000 SO3 Na ~ .
: A - I 6 Cl13 --~CII 2 - Cll) ~ o ~CII 2 - C~
'~D COOC 211~ N~ -I Mn= 8000 -~~lS~

--~CI12-CI1~95 ~CI12-CII-~ O O
11 il COOCI12CC~I2CCI13 Mn . 25000 Cll 2OSO3 Na --~C112 - C~l) ,3 0 .(CII 2 - Cll~, O
CONH~SO2CII= CH2 Mn . 6000 SO3Li --~CII 2 - C113 3 O- ~C~I 2 - Cl 11-3, O ~C~I 2 - Cl ~13, ~
COOC2~1~01l COOC112 b7 Mn-. 15000 SO3 Na ~01~

Dextran sulfate (degree of substitution, 2.0; Mn =
1.00, 000 ) --~CII 2--C11-3 6 0 ~ CII 2--C~ 3 4 o S03 Na Mn . 1 0 0 0 0 (The remaining space is left blank.) 2 ~

In the compounds ~-1 to A-21, Mn represents the average molecular weight (more specielcally, number average molecular weight) as measured by GPC and expressed in terms o~ polyethylene glycol.
The hydrophobic polymer latex to be contained in the antistatic layer has either an ethylene oxide chain or an amide chain or both and is composed Or so-called "latex particles" that are substantially insoluble in water. This hydrophobic polymer is obtained by polymerizing any combinations of monomers as selected -from among styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, ole-~in derivatives, halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile, etc. Pre-ferably, styrene derivatives, alkyl acryla-tes and alkyl methacrylates are contained in an amount o~ at least 30 mol%, more pre-~erably at least 50 mol%.

he remaining space is le~t blank.

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Pre-ferred examples of the monomer having an amido group that can be used to form a latex having an amide chain are represented by the following general -~ormula (I):
R
CH2= C

(L)a R 1 (I) CON <

where R is a hydrogen atom or a lower alkyl group having l - 4 carbon atoms; L is a divalent group; a is O or l; and Rl and R2 are each a hydrogen atom or a lower alkyl group having l - 6 carbon atoms.

Specific examples of the monomer represented by the general ~ormula (I) are listed below.

(1) CH2= CH

(2) CH3 CH2= C

(3) CH2=CH

(4) C~12= CH

C ON H ~ C ON H 2 CH2= CH CH3 CON <

2 ~

A latex can be made -from the hydrophobic polymer by either one of the following two methods: emulsion polymerization; and dissolving a solid polymer in a low~
boiling solvent to -form a dispersion in which it is -finely dispersed and thereafter the solvent is distilled O-f-r.
Emulsion polymerization is pre-ferred since it yields a latex comprised o-f -fine and uni-eormly sized particles.
The hydrophobic polymer will achieve its intended function if it has a molecular weight of at least 3,000 and the transparency of the antistatic layer is substantially independent of the molecular weight o-f that polymer.
A polyalkylene oxide chain is pre-ferably introduced into the hydrophobic polymer latex by copolymerizing it with monomers havin~ a polyalkylene oxide chain.
Preferred examples o* the monomers used for this purpose are represented by the following general -formula (M):

R
CH2= C (M) L- X
where R is a hydrogen atom, a halogen atom, a lower alkyl group or -CH2 -L-X; L is -CO0-, -CO~- or an aryl group having 6 - 12 carbon atoms (where R1 is a hydrogen atom, an aryl group, a lower alkyl group or X); and X is t R2-O ~ R3 (wher-e R~ is at least one member selected -from among -CH2C~12-, -CF12C~, -CH2CH2CH2-, -CH2CHCH2-, -CF~2CH2CH2CH2-and -CH2CHCH2-;

OH
R3 is a hydrogen atom, a lower alkyl group, an alkylsul-fonic acid group or a salt thereof, an alkylcarboxylic acid group or a salt thereo-~; and n is an integer o-~ 2 - 70).
Speci*ic, but non-limiting examples, o-f the monomer represented by the general -formula (M) are listed below.

(The remaining space is left blank.) ', .

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Cl12 = Cll Cl12 = Cll COO-~CI12CI120 t211 COO-~CI12C1120t~i:}1 M--3 M--'I
Cll 2 = Cll Cll 2 = C~l CQO~-CI12CI120 tloll COO~C112C1120 ~11 ICII~ ' .IC~
C~l 2 = C Cll 2 = C
COO-~C112C1120 t5 11 COO~CI12C1120 ~11 ICII ~ Cll 2 = C~l Cl12 = C CONII-~ Cl12C1120-~sll COO-(-CI12C1120 t20 11 Cl12 = Cll Cl12 = Cll CONII-~CI12C1120~11 ~(CI12CI120)sn Cll 2 = Cll COO-~CI12CI120 ~5 ( Cl12CI110-35 Cll~

Cll 2 = C
C00 ~ C11 2 C11 2 0 ) I o ( C1-1 2 Cll C11 2 ) ~ o lï

M-- 1 3 Cll Cl1 2 = C
C00-~CI12CI120 )2 ~CH2CI10 )lo Cl13 Cll 3 M-- I ~l ICII
Cll 2 = C
C00 ~~ Cll 2 CllO ) s 11 Cll 3 M - I 5 Cl12 = Cll 0-~ Cl~ 2 Cll 2 0 -)~11 M - 1 6 Cl12 = Cll ~ , ~
Cl120-~ Cl12C1120-)loll M-- I 7 Cl12 = Cll I

COO-(--Cl12CI120 ~SO3Na : ~ ~ M- I 8 Cl12=Cll C00-~CI12CI120 ~1 ~S03Na - 23 ~

. , . . ' `
.

~0~01~

M-- I 9 Cl12 = Cll COO-~CI12CI120 ),~ SO3Na M--2 0 ICl13 Cl1 2 = C
eOOt~CI12CI120 ~3 SO3Na M--2 I Cll Cll 2 = C
COO-~CI12CI120 ) I 5 S03 Na Cll 3 Cll 2 = C
COO -~CI12Cl120 -)~tCI12-)~SO3Na M--2 3 Cl12=CII
,(- Cl12CI120 ~.~ SO3Na CON
~ Cl12CI120t~SO3Na M- 2 '1 Cll~
Cll 2 = C
CONlltC112C1120-33 S03Na M--2 5 Cil3 Cll 2 = C-CONII--~Cil2CI120~ CI12~SO3Na .
,.

' .

2~4~

M- 2 6 Cll Cl12=C
,4 Cil2CI120 )~ ~CI12~$03Na CON
~ Cl12CI120--)6 ~C112-~S03Na M- 2 7 Cl12=CII

Cll 2 0 -~ Cll 2 Cll 2 0 -), O S03 Na M--2 8 Cl12=CII
d~
~ ' Cl120-~CI12CI120 )~ (Cl12-)~SO3Na Cll~
Cll 2 = C
COO ~ CI12 CI12 0 ~ CII 2-)~COON a Cll 2 = C
; I ,(,Cl12CI120 )6 ~CI12~COONa CON
~ Cl12CI120-)~CI12~COONa Cll 3 I
Cl12=C
~ ~ CONII-~CI12CI120--3~CI12~COONa :

.

.. . . . . .

1 5 ~

Specieic examples o-t` the hydrophob:Lc polymer latex that can be used in the present invention are listed below.

B - I
-~CIl 2 Cll) 5 o~CII 2 Cll3.~o ~ Ctl2CI
~ COOC.Ill9-n CON~12 --~CII2CII3 3 o ~CIl 2 C113 6 0 - - - ~CIl 2 COOC~119-n CONI12 B - 3 Cl~3 t Cll2C113~ 6 (-Cll2C-~o ~CII2CII~-~ COOCI13CONI12 B -: -~CII2CII~ ~CII 2 Cll~2~CII 2 C1131 ~CII 2 C~
: ~ COOC.I]19-n COOII CONI12 B--5 Cl13 Cl13 ~C~I 2 C113~ ~Ctl 2 C113 .~ 5(Cll 2 C~ s ~ C~I 2 C), O
COOC.~119- nCOOII CONI12 .~"

B--6 Cl13 --~C~I 2 C113~ ~ CII 2 Cl 113 .~ 2 ~Cll 2 C3 8 ~CII 2 C~l~
~ COOC~119- n COOC4119 CONI12 tCI12C~1320 (C}12Cil~-70 ~CI12C~1~5 (C~12C~13 ~D COOC2~15 CONI12 COOi'l . . .

B--8 Cl13 Cl13 --~CII 2 Cll) ~ CII 2 C~ s O ~CII 2 C3 2 o ~D COOC~119-n CONIICI13 -C~13 C113 t Cil 2 ~ O ~CII 2 C 3 5 ~CII 2 C~13, O (Cll 2 C113 5 ~CII 2 C~
~DCOOII COOC41~9- n bONI12 COOC~119-n Cl13 --~CII 2 C3 7 0--~CII 2 C11-3 5 ~Cll 2 C~13 5 ~ Cll 2 C113 2 0 COOCI13 COOC.I119- n COOII CONII~CONI12 Cl1 3 Cl1 3 C~ 3 ~CH 2 C) 7 5 (Cll 2 C113 1 5 ~CII 2 C) S (Cil 2 C-)~
COOCI13 COOC211.~011 CONI12 COO(C21140-)~ll . . .

~CII 2 C113 9 9 (Cll 2 C113 COO(C21~03 - 28 ~

2~ 15~

--~CII 2 Cil3 q o ~CII 2 Cl13 2 5 tCil 2 Cj il3~
COOC .I 1{ 9--n COO (C 211~ 0)~CH 2 CliCI12 03~H

B~
Cl13 ~CII 2 C113 s o ~ ~CII 2 C113 3 5 ~CII 2 C3 1 o--~CII 2 C113~
~D COOC.~il9--n COOC4119-n COO--~C21140~11 --~CI12Cl{).~o (Cl~2Cll)s3 (Cil2C11)2 ~CIt2Clt3 COOC411s COO~C211~03~H COOlt ,~, B-- 1 6 Cl13 --~CII 2 C113 a o (Cll 2 Cll) I o ~Cil 2 C) ~ o ~D COOII CONll(C21i40~ 1 5 .

2~015~
. . .

Cll 3 --~CI12CI13~9 ~CI12CI1327 ~CI12CI133 ~C~12C-)~
COOC.~119--n 100C3115SO3K COO--~C211~0)~ 11 COO(C211~0)sso3Na --~CII 2 ~ 5 o ~Cll 2 1 113-~ 5 ~CIl 2 C3 s COOC.~lla--n COO(C211~0)sso3Na Cl13 Cl13 ~CII 2 C113~C11 2 Cll~ ~ 2 ~CII 2 C3 u ~CII 2 C) 5 ~1 COOC~19--n COOCI12~7 COO(C21!~0)5C311~SO3Na ; Cl13 I

--~CII 2 C~13 2 o ~CII 2 Cll) 2 o ~CII 2 Cil3 s O ~CII 2 C3 ' O
~,D CN CONIICCII 2SO3 Na Cl120(C211~0-)~ll .

% ~ 6 Cll 3 CQ
--~CIl 2 Cl{3 3 o ~CIi 2 03 2 o--~CII 2 C~ C]I 2 C~l~
COOC4119 - n CQ ~D

Cil 2 -O~C2 il~O~-SO3 Na tCII 2 C113~C112 Cl{3 5 ~CII 2 Cil3 ~ O ~CII 2 C113 s ~CH 2 Cli3 5 CONIIOC.,119 COOC.,}i9-n COO(C2}1~0)lo}1 ~D

SO3 Na Cil3 C}13 --~C}I z C) a 5(Cil z Cll) a (CH 2 C}13 5 ~Cil 2 C3~
COOCil3 I COOII I C}13 COC(C2il.~0)5(Cil2lCI103~oil CONllCCli2SO3Na Cl13 C1{3 Cil 3 Cll 3 ~CH z C3 a o (Cli z C113, 0 ~CII z C3 5 ~CIi 2 C3 5 COOCH3 COOC2il5011 COO(C2H~O) I oll CllO

.

Cll~ Cl13 tCII 2 C3 7 5 ~Cll Z l Il) 1-0 ~Cll 2 1 113 5 ~CII 2 C~
COOC411D--n COOII ~I COO(C~IIDO)2011 COOC2114 N~

Cll 3 Cll 3 C~l 3 --~C~I 2 Cll)., 5 (Cll 2 C3 4 o ~CII 2 C3 5 ~CII 2 C) 5 CN . COOC~ n COOII COO(C21140) 1 oll The epoxy compound to be used in the antistatic layer pre-ferably contains a hydroxyl group or an ether bond.
The following are specific, but non-limiting, examples o-f the epoxy compound that can be used in the present invention.

:

2~4~15~

ICll 2 - O - C~l 2 - C~ CII 2 Cll- O- C112 - C~ C112 Cll z - O - Cll 2 - CII~-~C~I 2 IC~l 2 - O- Cll 2 - Cll~-~C112 Clll- 011 Cll 2--O--Cll 2--Cll~-~CII 2 E~- 3 011 011 Cll 2 -Cll -Cll 2 -O-CII 2 -C~ CII-CII -Cll -Cll 2 -O-cll 2 -CII-~CII 2 O Cll 2 -CII-CII 2 0 01l O

Cll 2 -CII-CII 2 -O-CII 2 -CII-CII-CII-CII-CII 2 -O-CII 2 -CII-CII 2 Cllj CII-CII~C C-CII~-CII-CII~ ~l .

.. . .

C~l 2 -O- (Cll 2 - C~l -Cll 2 -O - Cll 2 - ICll - Cll 2 -O) 3 -Cll\ 011 0 Cll\
- Cll/ ~o/ Cll/

Cll 2 -CII-CII 2 -O-CII 2 -Cl ~I-CII 2 -O-CII 2-CII-CII 2 -O-c~l 2 -Cll-cll 2 o 011 ~o/

Cll 2 - Cll - Cll 2 - O--Cll - Cll--O - Cll 2 - Cll--CH, 112C~ ~CII- C~ll- C112 - O- C112 - Cll~-~C~12 Oil Cll 2 -Cll -Cll 2 -O- Cll 2 - Cll 2 -O - Cll 2 - Cll - Cll 2 Y \o/

Cll 2--Cll--Cll 2--O--(Cll 2--Cll 2--O) D--Cll 2 Cll Cll 2 \o \O

-- 3a~ --2~15~

The hydrophobic polymer latex i9 contained in the antistatic layer in an amount that pre-ferably ranges -from 10 to 1,000 mg/m2, more pre:rerably from 100 to 500 mg/m~.
The water-soluble conductive polymer is contained irl the antistatic layer in an amount that pre-ferably ranges from 50 to 2,000 mg/m2, more pre-ferably from 100 to 1,000 mg/m2.
The epoxy compound is contained in the antistatic layer in an amount that preferably ranges -from 10 to 500 mg/m2, more preferably -from 50 to 300 mg/m .
A dispersant can be used in the antistatic layer. A
suitable dispersant is selected from among nonionic sur-factants, with polyalkylene oxide compounds being pre-ferred. Polyalkylene oxide compounds are those compounds which contain at least 3 but no more than 500 polyalkylene oxide chains in the molecule. Such polyalkylene oxide compounds can be synthesized by the condensation reaction between polyalkylene oxides and compounds having an active hydrogen atom such as aliphatic alcohols, phenols, aliphatic acids, aliphatic mercaptans or organic amines, or by condensing polyols such as polypropylene glycol or polyoxytetramethylene polymers with aliphatic mercaptans, organic amines, ethylene oxide or propylene oxide. The polyalkylene oxide compounds need not contain only one polyalkylene oxide chain in the molecule but they may contain two or more segments o-f a block copolymer as the polyalkylene oxide chain. In this case, the total degree of polymerization o-f polyalkylene oxide segments is preferably in the range o-f 3 - 100. The amount of addi-tion o-f the polyalkylene oxide compound pre-ferably ranges -from 1 to 500 mg/m2, more preferably from 10 to 200 mg/m2.
Specific but non-limiting examples o-f the polyalkylene oxide compounds that can be used in the present invention are listed below.
Exemplary compounds Ao - 1 ) HO(CII2CH20)nH ~n=4~

Ao-- 2 ~ HO(CH2CH2O)nH . ~n=35) Ao-- 3 ~ IIO~CH2CHzO)nH ~n = 135 Ao - 4 ~ HO(CI12CH2O)nH ~n= 225~

Ao - 5 ~ HO(CH2CH20)nH ~n=450) Ao - 6 ~ n-C~H~O(CII2CH20)QH ~Q=20) Ao - 7 ~ n-C8HI70(CH2CH20)Qll ~Q=30) Ao - 8 ~ n-C~2ll2so(cH2cH2o)QH ~Q=30) Ao - 9 j n ~ CgHI~ ~ O(CH2CH2O)QH
~Q=30~
Ao-- 10~ n--Cl2H2sS(CH2CH2O)Q H ~Q2 3~) Ao - 11~ C~H3S(CH2CH2O)nCOCH2CH2COOH ~n = 50 - 3~ -2~4~5~

.. . ...... . . . . .

Ao-- 12) HO(CH2CH20)Q(CH2)m(CI12CI120)nCOCH2CH2COOH
~Q~n=70, m=5) Ao-- 13~ IlO(CI12CH20)Q(CHCH20)m(CI12CH20)nH
CH~ ~O.+n= 15, m= 17 Ao-- 14~ HO(CI12CH20)Q(CHCH20)m(CH2CH20)nH .
CH~ ~Q + n = 30, m = 35 Ao-- 15) HO~CH2CH20)Q(CHCH20)m(CH2CH20)nH
C2Hs ~Q-~ n = 15, m= 15 ~ .
~ Ao-- 16~ HO(CH2CH20)Q(CHCH20)m(CH2CH20)nH
C2Hs ~Q+n=30, m=15) Ao-- 17) HO(CI12CH20)Q(CH2CH2CH2CI120)m(CH2CH20)nH
~Q~n=23, m=21) ' Ao-- 1~ HO(CH2C~120),~(CH2CH2C112CI120)m(CH2CH20)n}1 ~Q+ n = 38, m= 15) ~: ~ Ao-- 19~ HO(CH2CH20)Q(CHCH20)m(CH2CI120)nH
CH2ocH3 ~Q~ n= 15, m= 15) .
' 2~15~

.

Ao - 20) HO(CH2CZI20)Q(CHCI120)m(CH2CH20)nH
cll,OCH~ ~Q-~n= 30. m= 15) .
Ao - 21~ n- C~2H2so(cHcH2o)Q(cll2cH2o~nH
. CHzOCH3 ~Q = 7, m= 30 Ao - 22~ n- Cl2Hzss(cHcHzo)Q(cllzcHzo)mH
CH3 ~Q= 7, m= 30 Ao - 23~

HOOCCH2CHzCO(CHzCH20)Q(CH2CH2--e CHzCHzO)m,(CH2CHzO)nCCHzCHzCOOH
~Q-~n = 15, m= 15) Ao - 24~ 0 Il HOOCCHzCHzCO(CHzCH20)Q(C}lCHzO)m--o CH3 (CH2CH20)nCCH2CH2COOH
~Q ~ n= 15, m= 20) Ao - 25) / (CHzCH20)~H
C~2Hz5N ~
(CH 2 Cll 2 O)nH
(Q+ n = 30) :

- : .

5~

Ao-- 26) C~ 7113 3CO-~C~12C~1203~oll Ao~ 27~
~C~12COOCsl~ g OCI12CI{2~QO/~o~CHzCH203 OtC112C~120~
-~ m ~ n = 20 Ao~ 28) ~CZI2CH20 C~ 7113 sCON Q
2 cH 2 o~m~l + m = 1 2 The ren~1~ ing space is left blank.) . . .

' .

2~4~6 The hydrophobic polymer latex, water-soluble conductive polymer, epoxy compound and polyalkylene oxide compound which are contained in the antistatic layer may be used either on ~heir own or as admixtures.
The surface of the antistatic layer preferably has a pH not higher than 8.0 but too low values of pH are not desirable from the viewpoint of film stability. A
particularly preferred pH range is from 3.0 to 7.5.
The antistatic layer may be located closer to a transparent support than light-sensitive silver halide emulsion layers (which are hereina-fter sometimes referred to as "light-sensitive layers"); alternatively, the antistatic layer may be located on the back side o-f the support, or on the side opposite the light-sensitive layers.
The antistatic layer described above is formed on a transparent support by coating procedures. All kinds of photographic transparent substrates can be used but polyethylene terephthalate or cellulose triacetate -films that transmit at least 90% of visible light are preferred.
Such transparent supports are prepared by methods that are well known to one skilled in the art; i-f desired, they may be blued by adding dyes in small amounts that do sub-stantially no harm to light transmlssion. After corona discharge treatment, the supports may be coated with a -- ~0 --2~a0l~6 subbing layer that contains a latex polymer. Corona discharge is preferab:Ly applied with an energy of 1 mW - L

kw/m2 per min. In a particularly pre-ferred embodiment, the support subbed with a la-tex layer is subJected to a second corona discharge treatment be-fore the antistatic layer is applied.
The side of the support which does not have any llgh-t-sensitlve silver halide emulsion layer (the layer on this side :Ls hereinafter sometimes referred to as the "bac~ing layer") pre-ferably has a specific sur-face resistance of no more than 1.0 x 1012~, more pre-ferably 8 x 1011~ and below.
The antistatic layer on the support is overlaid with at least one light-sensitive silver halide emulsion layer.
It is pre-ferred for the purposes of the present invention that a hydrazine compound is contained in one or more light-sensitive silver halide emulsion layers.
The hydrazine compounds to be preferably used in the present invention are represented by the following general -formula (H):
Q~ Q2 X, R,- N - N - C- R 2 (H) .
where R1 is a monovalent organic residue; R2 is a hydrogen atom or a monovalent organic residue; Q1 and Q2 are each a -- ~1 --2 ~ 5 ~

hydrogen atom, an optionally substituted alkylsul-fonyl group, or an optionally substituted arylsul-fonyl group; X

is an oxygen atom or a sulfur atom.
Among the compounds represented by the general formula (~1), one in which X1 is an oxygen atom and R2 is a hydrogen atom is particularly pre-ferred.
Monovalent organic groups represented by R1 and R2 include aromatic residues, heterocyclic residues and aliphatic residues.
Il]ustrative aromatic residues include a phenyl group and a naphthyl group, which may have such substituents as alkyl, alkoxyl acylhydrazino, dialkylamino, alkoxycarbonyl, cyano, carboxyl nitro, alkylthio, hydroxyl, sul-fonyl, carbamoyl, halogen, acylamino, sulfonamido, urea and thiourea. Substituted phenyl groups include 4-methylphenyl, 4-ethylphenyl, 4-oxyethylphenyl, 4-dodecylphenyl, 4-carboxyphenyl, 4-diethylaminophenyl, 4-octylaminophenyl, 4-benzylaminophenyl, 4-acetamido-2-methylphenyl, 4-(3-ethylthioureido)phenyl, 4-[2-(2,4-di-tert-butylphenoxy)butylamido]phenyl and 1,1-dibenxylsemicarbazide.
Illustrative heterocyclic residues are 5- or 6-membered single or fused rings having at least one o-f oxygen, nitrogen, sulfur and selenium atoms. These rings - ~2 -2~4~

may have substituents. Specleic examp:Les of heterocyclic residues incl-ude: pyrroline, pyridine, quinoline, indole, oxazole, benzoxazole, naphthoxazole, imidazole, benzimida~ole, thiazol:ine, thiazole, benzothiazole, naphthothiazole, selena~ole, benzoselenazole and naphthoselenazole rings.
These hetero rings may be substituted by alkyl groups having 1 - 4 carbon atoms such as methyl and ethyl, alkoxyl groups having 1 - 4 carbon atoms such as methoxy and ethoxy, aryl groups having 6 - 18 carbon atoms such as phenyl, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups, cyano group, amido group, etc.
Illustrative aliphatic residues include straightehained or branched alkyl groups, cycloalkyl groups, substituted alkyl or cycloalkyl groups, alkenyl groups and alkynyl groups. Exemplary straight-chained or branched alkyl groups are alkyl groups having 1 - 18, preferably 1 - 8, carbon atoms, such as methyl, ethyl, isobutyl and 1-octyl. Exemplary cycloalkyl groups include those having 3 - 10 carbon atoms, such as cyclopropyl, cyclohexyl, adamantyl, etc. Substituents on alkyl and eycloalkyl groups include an alkoxyl group (e.g. methoxy, ethoxy, propoxy or butoxy), an alkoxyearbonyl group, a carbamoyl group, a hydroxyl group, an alkylthio group, an amido group, an aeyloxy group, a cyano group, a sulfonyl - ~3 -2 ~

group, a halogen atom (e.g. Cl, Br, F or I), an aryl group (e.g. phenyl, halogen-substituted phenyl or alkyl-substituted phenyl), etc. Speci-fic examples o-f substituted cycloalkyl group include 3-methoxypropyl, ethoxycarbonylmethyl, ~-chlorocyclohexyl, benzyl, p-methylbenzyl and p-chlorobenzyl. An exemplary alkenyl group is an allyl group, and an exemplary alkynyl group is a propargyl group.
Pre:~erred examples o-f the hydrazine compound that can be used in the present invention are listed below and it should be unders-tood that they are by no means intended to limit the scope o-f -the present invention.

(The remaining space is left blank.) 2 ~ 6 Exemplary compounds ~ NHNIICIIO

CH3- ~ N~INlICHO

nc s 1l I I CONH ~ NHNHCHO

. . .

ncsH I g - c - CONII ~ NHNHC~10 :~ ~ H - 5 . ~ CONII ~ NHNHCHO

2~1~015~

tCsH
tCsH I I~OCHCNH g~NHNHCHO
" C2Hs ~Cs~ll l O - O --tCsHI 1~ ~OC}ICNH ~NHNHC-CH~
,", , C2Hs H -- 8 tCsHIl ~CsHI ~O(CH~NHCNH~;~NNNHCHO

H -- 9 tCsHI I
O O
tCsHI ~O(CH2)~NHCNH~NHNIICCH20CH3 tCsl~ l, O O
tCsHI ~OCHCNH~NHNHC~
C2Hs HOH2 20~15~

. . ..

/C5H " (t) (~)CsHIl ~ O(CH2)3NHCONH ~ NHNHCOCON~

6Hll(t) ~C5 H, ~ O(CH 2 ) 3NHCONH ~ NHNHCOCON/
CH= CH2 C5Hl,(t) (t)C5H, ~ O(CH2)~NHCONH ~ NHNHCOCO
` . CH20H
~,;
.
~ ~ : H - 1 4 : ~C5H " (t) ~t)C5H~ ~ O(CH2)~NHCON~ ~ NHNHCOCO- CH2 C~120~1 :~: ::: :

CsH
(t)C5H " ~ O~CH2)2NHCONH ~ NHNHCOCON
: . ~ CH20H

: ~ .

~ - 47 -2 ~

C 8 H l 7 N~ICNH ~ N}IN}ICOCON
.

/ C s }~
(t)CsHIl ~O(CH2)~NHNHCONH~NHNHCOCH~OCH3 .
..

n - CI oH2 10~;~ CH = N~ N}INIICOCH20CH 3 .
. : . .~, . . .
,'h~, ' ,,"`1. ' H - 19 , " .~ ~ ~ . n--Cl oH2 10~ CH2NH~ NHNHCOCH20GH3 , . i ~ . ~ . . .
.~ . . . . .
.

n - C 8 H l 7 ~ CON}I ~ NHN}ICOCH 2 OCH 3 ~ :.
.
:
' . . .
' ' . .

.

.

2 0 ~

CN NIICONH ~ N HNHCOCH 2 OCII 3 NNIICONH~3 NHNHCOC}J20Ca3 LC5H, 10 tCsHI l-~OCHCNH~NNIICON~NHNHCOCH20CH3 C2Hs CH3 ;

!

: , ' ' ~C6HI I . CHJ
LcsHl I~O(CHz)~NllCONH~N{~CH3 C}l 3 .

~C s tC~HII ~ O(CH2),NIICONH ~ NIINHCON~

.

2~15~

~ NHNIICHO

~ NHNllCOOC2Hs Br N ~ NHNHCOCH 3 NHCOCH 20~ CsH
CsH

~ NHCNII ~ NHNHCHO

. .

2 ~

r ~ NHCNII ~ NHNHSO 2 N<
OCI~H2 9 H - 3l (t)CsHIl ~ OCHCONH ~ N}INHCHO
~t)Cs~lll . ~

~ N.
CH 3~ ~ NHNHSO 2 CH3 ; . ~ NHCO ~ N- N

H - 33 CH3 ~ N
~ ~ NIINHCHO
CH3 ~ NHCOICHO ~ CsHI1(~) C2Hs - C6H,I(t) : ~ H - 34 ~ ~ .
12 H 2 so~So2 Nll ~ NHNHCHO

.

N~NIINIICO~CH2)30~--Cs}l~
CsH I ~ ( t) Cll 3 N~9--NHNHCH0 Cll~ CON~I(CH2)~0$~CsHI ~(L) C s H I l ( t ) Cl lH2 sO~NllC0 ~NHN}IIClCH3 S

0~--N~ NHNHCO ICHO ~ C s H
C2Ns CsH 1 l ( t.) , 3 ~ NIINHCH0 :

~401~

~ ~I \ NHNHCOCH20 ~ CsHIl(t) CsH

.
NHNHCHO
. ~' ..

H - ~2 CONH(CH2)~0 ~ CsHIl(t) ~1 \ NHNHCHO

NHNHCHO
CH~

' 2 ~ 6 [~ NIIN}ICOC~10 -~ C 11 ( ~) /C}13 ~/N}INIICON \C~I

~ NHNHSO 2--~3 OC I 2 IJ 2 5 6 ~NIlNll6cll 20cll 3 ~CI12 0 .
~' .
~The remaining: space is le:Et blank . ) ,.-, -~

2 al ~

The hydrazLIle compounds o-f the general formula (H) are incorporated in a silver halide emulsion layer and/or in a non-light-sensitive layer that is on the same side Or a support as where a silver halide emulsion layer is present.
Pre~erably, the hydrazine compounds are incorporated in a silver halide emulsion :Layer and/or an underlying layer.
The hydrazine compounds are pre-ferably added in amounts o-f 10 5 - 10 1 mole per mole o-f silver, more preferably 10 4 -10- mole per mole of silver.
It is also pre-ferred -~or the purposes o-f the present invention that a tetrazolium compound is contained in one or more light-sensitive silver halide emulsion layers.
The hydra~ine compounds that can be used in the present invention are represented by the following general -~ormula (T):
R,-N IN-R~
N~ ~N - (X9)n-where substituents R1, R2 and R3 on the phenyl group are each a hydrogen atom, or pre-ferably, a group having a negative or positive Hammett's sigma value (tSP) which is a measure o-f electron withdrawing property, with groups having a negative o-f being particularly pre-ferred.

2 ~

Discussions of the Hammett's sigma value in phenyl substitution are found in the report of C. Hansch et al., Journal of Medical Chemistry, Vol. 20, p. 304, 1977 and in many other papers. Examples o-f particularly pre-rerred groups having a negative sigma value include: methyl ~P =
-0.17; all parenthesized values that -follow refer to ~P);
ethyl (-0.15); cyclopropyl (-0.21); n-propyl (-0.13); iso-propyl (--0.15); cyclobutyl (-0.15); n-butyl (-0.16); iso-butyl (-0.20); n-petyl (-0.15); cyclohexyl (-0.22); amino (-0.66); acetylamino (-0.15); hydroxyl (-0.37); methoxy (-0.27); ethoxy (-0.24); propoxy (-0.25); butoxy (-0.32); and pentoxy (-0.34). These groups are all useful as substituents in the compounds of.the general formula (T).
Specific but non limiting examples of the compounds of the general formula (T) that can be used in the present invention are listed below.

- - (The remaining space is left blank.) 2~4~156 Exemplary compound . . .

T--1 /yN--IN/~c~13 CQ~

N = N

T--2 //N--Ng~C~13 CQ~

~ N=N~CH3 T--3 //N I /~FH3 CQ3 N = N(D~CI13 C8,~ //N Ni~/ CH~ CQ~

//N--N/~CTIJ
CH3~ C~ I CQ~
N N ~--OC~I

.

~01 ~

//N--N /~ C~
N = N'~QCH3 //N--N ~ OCII
C\ I CQ~
OCII, T--8 /CzHs //N--IN CQ~
N--N (E) ~

Cz~ls T--9 //N--N/~C2Hs C2H6 ~ C\ I CQ~
N = N ~C2 ~1 s .
T -10 //N--I ~C,}i~ CQ~

N= N ~C~H7 ~01~6 .

T--11 //N--I /~ isoC311~ CQ~

N = N ~ isoCJH7 T - 12 .
OC211s //N--IN ~ : CQ~
N = N ~OC211s ' .

T--13 ~ isoC3117 CQ~

N = N~OCH

' ~ . ~ ! nC I 2 H 2 s N = N~

~;~ C nC, 2112 5 CQ

N = N'~ nC , 2 1l 2 5 2al~0~5~

~ 1 .
. T -16 ~ CQ~

. ~; N=N~

C CQ
N = N~Nil 2 T -18 . ~ CH3 ~/N--N
~C I . CQO,~
N=N ~ CH3 (The remaining space is left blank.) .

.

2~0~L~6 The tetrazolium compounds to be used in the present invent:Lon can be easily synthesized by known methods, ~or example, the one described in Chemical Reviews, 55, 335-483.
The tetrazolium compounds represented by the general -~ormula (T) are pre-ferably used in amounts ranging from about 1 mg to 10 g, more preferably from about 10 mg to about 2 g, per mole o-f the silver halide contained in the silver halide photographic material.
A matting agent is preferably incorporated in the outermost layer o-~ the side of a support that has light-sensitive silver halide emulsion layers.
The matting agent to be used in the present invention may be of any known types including: the particles of inorganic materials such as silica (Swiss Patent No.
330,158), a glass powder (French Patent No. 1,296,995), and alkaline earth metals or carbonates o-f cadmium, zinc, etc.
(British Patent No. 1,173,181); and the particles o-f organic materials such as starch (U.S. Patent No.
2,322,037), starch derivatives (Belgian Patent No. 625,451 and British Patent No. 981,198), polyvinyl alcohol ( Examined Japanese Patent Publication (JP-B) No. 44-3643), polystyrene or polymethyl methacrylate (Swiss Patent No.
330,15~), polyacrylonitrile (U.S. Patent No. 3,079,257), and polycarbonates (U.S. Patent No. 3,022,169).

2~15~

These matting agents may be used either on their own or as adm:ixtures. The shape o-f the particles O-e which the matting agents are formed may be regular or irregu]ar.
Regular particles are preferably spherical but may assume other -forms such as a plate and a cube. The matting agents pre-ferably have an average particle size o-f 0.1 - 20 llm, with the range of 1 - 10 llm being more preferred. The size of non-spherical matting agents is expressed by the diameter of a sphere having the same volume as that of a particle in the matting agent of interest.
By the expression "a matting agent is contained in the outermost layer" is meant that at least part of the matting agent need be contained in the outermost layer. If necessary, part o-f the matting agent may extend beyond the outermost layer to reach the underlying layer.
In order for the matting agent to per-form its basic function, part of the matting agent is desirably exposed on the surface. Part or all of the matting agent added may be exposed on the surface.
The matting agent may be added either by applying a coating solution that has the matting agent dispersed therein or by spraying the matting agent after a coating solution has been applied but before it is dried. If two or more kinds o-f matting agents are to be added, the two methods may be employed in combination.

- ~2 -2 (~

The silver halide emulsion to be used in the light-sensitive material of the present invention may incorporate any types o-f silver halides such as s:ilver bromide, silver chloride, silver iodobromide, silver chlorobromide and silver chloroiodobromide that are commonly employed in silver halide emulsions. Silver halide grains may be prepared by any o-f the acid, neutral and ammoniacal methods.
Silver halide grains may have a uniform distribution of silver halide composition in their interior or they may be core/shell grains having different silver halide compositions in the interior and the surface layer. The grains may be of such a type that a latent image is predominantly formed on the surface or they may be of a type that forms a latent image predominantly in the interior.
The silver halide emulsions to be used in the present invention may be stabilized with vario-us compounds such as those described in U.S. Patent Nos. 2,444,607, 2,716,062, 3,512,982, West German Paten-t Publication Nos. 1,189,380, 2,058,626, 2,118,411, JP-B-47-4417, West German Patent Publication No. 2,149,789, as well as JP-B-39-2825 and 49-13566. Preferred examples of such compounds include:
pyrimidine compounds such as 5,6-trimethylene-7-hydroxy-S-~al4~

triazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy-S-tr:Lazolo(1,5-a)pyrimidine, 7-hydroxy-S-triazolo(1,5-a)pyrimidille, and 5-methyl-6-bromo-7-hYdroxy-S-triazolo(:L,5-a)pyrimidine; gallic acid esters or salts such as isoamyl gallate, dodecyl gallate, propyl gallate and sodium gallate; mercaptans such as 1-phenyl-5-mercaptotetrazole and 2-mercaptobenzothiazole;
benzotriazoles such as 5-bromobenzotriazole and 5-methylbenzotriazole; and benzimidazoles such as 5-nitrobenzimidazole.
An amino compound may be incorporated in the l:ight-sensitive material of the present invention and/or in a developing solution used -for its development.
For enhanced developability, developing agents such as Phenidone and hydroquinone, or restrainers such as benzotriazole may be incorporated in emulsion layers.
Alternatively, such developing agents or restrainers maybe incorporated in the backing layer in order to improve the ability o-f processing solutions.
Gelatin is a hydrophilic colloid that can be used with particular advantage in the present invention. Gelatin tha-t can be used in the present invention may be alkali or acid processed. I-f ossein gelatin is to be used, it is pre-ferably freed of calcium or iron. The pre-ferred calcium content is 1 - 999 ppm, with the range o-f 1 - 500 ppm being ~4~

particularly pre-~erred. The pre-~erred iron conten-t is 0.01 - 50 ppm, with the range of 0.1 - 10 ppm being particularly preferred. The calcium or iron content can be adjusted by passing an aqueous gelatin solution of interest through an ion-exchanger.
The following developing agents may be used to develop the light-sensitive material o-f the present invention:
catechol, derivatives thereo-f (e.g. 4-chlorocatechol, 4-phenylcatechol and 3-methoxycatechol), pyrogallol, derivatives thereo~ (e.g. 4-acetylpyrogallol), ascorbic acid, derivatives thereo-f (e.g. sodium ascorbate), chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2,3-dibromohydroquinone and 2,5-diethylhydroquinone;
HO-(CH=CII)a-NH2 type developing agents, representative examples of which are ortho- and para-amlnophenols such as 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol and N-methyl-p-aminophenol;
H2N-(CH=CH)a-NH2 type developing agents, such as 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, N-(4-amino-3-methylphenyl)-morpholine, and p-phenylenediamine; and heterocyclic developing agents such as 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone, 1-phenyl-2 ~

4,4-dimethyl-3-pyrazolidone and l-phenyl-4-methyl~4-hydroxymethyl-3-pyrazolidone), 1-phenyl-4-amino~pyrazolone and 5-aminouracil.
Other developing agents that can be used e-~:rec-tively in the present invention are described in T.H. James, "The Theory o-f the Photographic Process", Fourth Edit:Lon, pp.
291~334, Macmillan Publishing Co., Inc., 1977, and Journal O-r the American Chemical Society, Vol. 73, p. 3,100,1951.
The developing agents described above may be used either on their own or as admixtures. Pre-ferably, they are used as admixtures.
The developing solutions to be used in developing the light-sensitive material o-f the present invention maY
contain sul-fites as preservatives wi-thout compromising -the advantages of the present invention. Hydroxylamine or hydra~ide compounds may also be used as preservatives.
Preservatives are pre-ferably used in amounts o~ 5 ~ 500 g, more pre~erably 20 ~ 200 g, per liter o-f the developing solution.
The developing solutions may also contain glycols as organic solvents and suitable glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4~butanediol and 1,5~pentanediol, with diethylene glycol being pre-~erably used. These glYcols are preferably used in amounts o-f 5 ~ 500 g, more pre-~erably 20 - 200 g, per liter of the developing solution. These glycols may be used either on their own or as admixtures.
The light sensitive material of the present invention can be provided with very high storage stability by processing it with developing solutions that contain the development restrainers described above. The developing solutions -formulated as described above pre-Ferably have pH
values of 9 - 13, with the range of 10 - 12 being more pre-ferred from the viewpoints o-f preserving ef-fect and other photographic characteristics. As for cations in the developing solution, potassium ions are more ef-fective in enhancing the activity o-f developing solutions than sodium ions and hence the content of potassium ions is preferably as high as possible.
The light-sensitive material of the present invention can be processed under various conditions. As for the temperature for processing, say development, it is preferably 50C or below, with the range o-F ca. 25 - 40C
being particularly preferred. The development will in most cases end within 2 minutes but satisfactory results can often be obtained by rapid processing that lasts -for 10 -50 seconds. Other processing steps than development, such as washing with water, stopping, stabilization and -Fixing may be performed under appropriate conditions. If necessary, prehardening, neutralization and other additional steps May be employed. Some o-f these steps other than development may be omitted as required. Development may be manual (as in tray development or rack development) or mechanical (as in roller development or hanger development).
The concept of the present invention is applicable to all kinds o-f light-sensitive materials that have at least one light-sensitive silver halide emulsion layer provided on a support, as exempli-~ied by color photographic materials , X-ray photographic materials, and photographic materials -for use in photomechanical processes to make printing plates.
The rollowing examples are provided for the purpose o-f further illustrating the present invention but are in no way to be taken as limiting.
Example 1 Samples o-f negative-acting silver halide photographic material -for use as light-sensitive materials to be subJected to contact exposure in a daylight room were prepared by the following procedure.
Preparation o~ emulsion A silver chlorobromide emulsion containing 2 mol% AgBr was prepared as fol]ows.
An aqueous solution conta:ining 23.9 mg of potassium pentabromorhodate per 60g of silver nitrate, sodium - ~8 -2~01~6 chloride and potassium bromide and an aqueous solution of silver nitrate were mixed in an aqueous gelatin solution under agitation by a double-Jet method at 40C -for 25 minutes to prepare a $ilver chlorobromide emulsion comprising grains with an average size o-f' 0.20 l~m.
To the emulsion, 200 mg o-f 6-methyl-4-hydroxy-1,3,3a,7-tetraazaindene (stabilizer) was added and the mixture was washed with water and desalted. To the desalted mixture, 20 mg o-f 6-methyl-4-hydroxy-1,3,3a-7-tetraazaindene was added and the mixture was subjected to sul-fur sensitization. Therea-fter, the necessary amount o-f gelatin was added and 6-methyl-4-hydroxy-1,3,3a,7-tetraazaindene was -further added as a stabilizer.
Subsequently, the mixture was worked up with water to a total volume Or 260 ml, whereby a complete emulsion was obtained.
Preparation o-f latex (L) for addition to the emulsion A sodium salt oY dextran sulfate (O.25 kg; KMDS of Meito Sangyo Co., Ltd.) and 0.05 kg o-f ammonium persulfate were added to 40 L of water. To the stirred solution (81C), a mixture of 4.51 kg of n-butyl acrylate, 5.49 kg o-f styrene and 0.1 kg of acrylic acid was added under a nitrogen stream over a period o-f 1 h. Therea-fter, 0.005 kg of ammonium persulfate was added and the mixture was , 2 ~

stirred -for 1.5 h, cooled and adjusted to a pH o-f 6 with aqueous ammonia.
The resulting latex solution was filtered through Whatman GF/D -filter and worked up with wa-ter to a total volume o-f 50.5 kg, whereby a monodispersed latex (L) comprising particles with an average size of 0.25 llm was prepared.
The additives listed below were added to the previously prepared emulsion and a coating solution -for silver halide emulsion layer was prepared as described below.
Preparation of emulsion coating solution Nine milligrams Oe compound (A) was added as a biocide to the previously prepared emulsion. The pH o-f the mixture was adjusted to 6.5 with 0.5 N sodium hydroxide.
Subsequently, 360 mg o-f compound (T-2) was added. Further, 5 ml o-f a 20% solution o-f saponin, 180 mg o-f sodium dodecylbenzenesul-fonate, 80 mg o-f 5-methylbenzotriazole and 43 ml Oe latex solution (L) were added, with all amounts being based on one mole of silver halide. Thereafter, 60 mg o~ compound (M) and 280 mg o-~ a water-soluble styrene-maleic acid copolymer (thickener) were successively added and the mixture was worked up with water to a total volume of 475 ml to prepare coating solution A -for emulsion layer.

2 ~

Then, a coating solution -for emulsion protective layer was prepared in the following manner.
Preparation o-f emulsion protective coating solution Pure wa-ter (280 ml~ was added to gelatin (50 g~ to swell it and the swollen gelatin was dissolved at 40C.
Therea-fter, a 1% aqueous solution o-f compound lZ) (coating aid), compound (N) (-filter dye) and compound (D) were successively added, and the pH of the resulting solution was adJusted to 6.0 with aqueous citric acid. Further, 1 g of a mat-ting agent comprising irregular shaped silica particles with an average size o-f 6 l~m was added and the mixture was worked up with water to a volume o-f 1,000 ml, whereby a coating solution -for emulsion protective layer was obtained.
Compound (T-2) Compound (Z) ~3 113 C~\C~N ~ Cll 3 Cll 2 - Cll2(Cll2)~Cll~
N aO I S--C11~0 - Cl12 C112 CII (C113 ) 2 Compound (M) Compound (N) ~ ~ Cll ,/ ~CII----1~--Cll C~13 Cll~ ¢l SO~ Na 2 ~ 6 Compound (A) Compound (D) c~J~s--N~`~CII 110~,011 C02C~115 A coaking solution for backing layer was subsequently prepared in the ~ollowing ~lanner.
Preparation o-f backing coating solution B-l Gelatin (36 g) was swollen in water and heated to dissolve in water. Thereafter, three dye compounds (C-l), (C-Z) and (C-3) were added to water in respective amounts o~ 1.6 g, 310 Mg and 1.9 g, and 2.9 g o~ compound (N) was also added as an agueous solution. The resulting aqueous solution was added to the gelatin solution. Subsequently, 11 ml o~ a 20% aqueous solution o-~ saponin and 5 g o-~compound (C-4) as a physical property modi-~ier were added.
To the resulting solution, 800 g o-~ a water-soluble styrene-maleic acid copolymer was added as a thickener to adjust the viscosity o-~ the solution. Further, the pH o-~the solution was ad~usted to 5.4 with an aqueous solution of citric acid. Finally, 144 mg o-~ glyoxal was added and the solution was worked up with water to a total volume Or 960 ml to prepare a backing (BC) coating solution B-l.

2~01~6 Compound (C~
(Cl13)2N~ C~sN(CI13)2 d~
~J~CII 2 SO 3 Compound ( C - 2 ): C11 2 SO 3 11 /N~ CII= Cll- C7~ ~CO211 Compound (C-3): SO 3 Na Clla 11 ~ Cll ~ Cl13 ~N/~O lloJ~N' ~ ~ .
SO3K Sû3K
Compound (C-4):

Copolymer latex of ,e (Cll 2--f 113 m and --(Cll 2--f3 C02 Ca 11~ ce (m:n - 1:1) Subsequently, a coating solution B-2 for backing protective layer was prepared in the following manner.
: Preparatio f coating solution B-2 - 2 ~ 6 Gelatin (50 g) was swollen in water and heated to dissolvé in water. Thereafter, a sodium salt o-f bis(2-ethylhexyl)-2-sulfosuccinate, sodium chloride and glyoxal were added in respective amounts o-f 340 mg, 3.4 g and 1.1 g. To the resulting mixture, a polymethyl methacrylate powder comprising spherical particles with an average size o-f 4 ~Im was added as a matting agent to provide a coat weight o-f 40 mg/m2. The mixture was worked up with water to a total volume of 1,000 ml to prepare coating solution B-2 for backing protective layer.
Preparation o-f support having an antistatic layer Subbed polyethylene terephthalate -films were subjected to corona discharge with an energy of 50 W/m per minute.
Thereafter, antistatic solutions having the composition shown below were coated onto the base -films at a rate o-f 30 m/min using a roll -fitted coating pan and an air knife to give the coat weights also shown below. The selected combinations o-f three components o-f the antistatic solution are shown in Table 1.

Water-soluble conductive polymer (A) 0.6 g/m2 Hydrophobic polymer particles (B) 0-3 g/m2 ~poxy curing agent (E) 0.15 g/m2 Nonionic sur-factant [HO(CH2CH20)35H] 0.06 g/m 2 ~

The applied coatings were dried and heated at 140C
for 90 seconds to prepare supports (NE-1 to NE-3 as shown in Table 1) having antistatic layers.
Table 1 Base Water-soluble conductive Hydrophobic Curing polymer (A) polymer (B) agent (E) NE-3 A-4 Comparative compound B E-5 Comparative compound B
- ~CII 2 - Cll~-~ 7 ~CII 2 - C~ (Cllz~C1113~o ~1 ' CO 2 C ~ 1I D ~001l Pre~aration o-f test samples Backing layer coating solution B-1 and backing protective layer coating solution B-2 were applied simultaneously onto one side o-f each of the supports NE-1 to NE-3 which had the antistatic layers described above.
I The emulsion coating solution and the emulstion protective layer coating solution were applied simultaneously in superposition on the other side o-f each support. The individual coated emulsion layers were dried until their average sur~ace temperature rose to a point 1C lower than 2~4~ ~6 the temperature of drying air and within 5 minutes after that temperature was reached, further drying was performed under the conditions shown in Table 2.
Table 2 Run Dry-bulb Relative Drying DP, C Remarks temperat- humidity, time, ure, C % sec D-1 30 50 40 15Comparison D-2 35 22 2 15 do.
D-3 35 22 10 16Invention D-4 35 22 40 16 do.
D-5 80 22 40 16 do.
D-6 35 22 10 18Comparison D-7 80 22 40 18 do.
D-8 30 30 10 16 do.
Dew point After the drying o-f both sides of each support was completed, the samples were maintained at given dew points (DP) (see Table 2) until the end of the packaging step.
Method_of evaluation The test samples thus prepared were developed and sub~ected to other steps of photographic processing.
Thereafter, the light transmittance, speci-~ic sur-face resistance and the adhesion of antistatic layers o-f each sample were measured. Transmittance measurements were 2~4~1~6 conducted with a haze meter Model T-2~00DA o-f Tokyo Denshoku Co., Ltd, and specific sur-face resistance measurements were conducted with a teraohmmeter Model VE-30 of l~awaguchi Electric Works Co., Ltd. at 23C and 55~ r.h.
Adhesion o-f antistatic layers was evaluated by the following procedure: after rehumidi-fication àt 23~C and 75%
r.h. for one day, a grid pattern of s~uare notches were cut into the coatings under the same conditions. An adhesive tape was applied onto the cross-hatched and thereafter pulled o-f-f quickly. The adhesion strength of the coatings was evaluated in terms of the area that separated from the support, using the following criteria:
5, no separation;
4, up to 30% of the tape-covered area separated;
3, more than 30% up to 70% o-f the tape-covered area separated;
2, more than 30% up to 100% o-~ the tape-covered area separated;
1, not only the tape-covered area but also other areas separated.
Photographic processing Formula of developing solution Recipe A
Pure water (ion-exchanged water)150 ml Ethylenediaminetetraacetic acid disodium sal-t 2 g Diethylene glycol 50 g Potassium sul-fite (55% w/v aq. sol.) 100 ml Potassium carhonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide q.s. to adJust the pH o-~ developing solution to 10.9 Potassium bromide 4.5 g Recipe B
Pure water (:lon-exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% aq. sol.) 0.3 ml 5-Nitroindazole 110 ml 1-Phenyl-3-pyrazolidone 500 mg Just be-fore use, recipes A and B were successively dissolved in 500 ml of water and the mixture was worked up to a total volume o-~` 1,000 ml.
Formula of ~ixing solution Recipe A
Ammonium thiosul~ate (72.5% w/v aq. sol.) 230 ml Sodium sul~ite 9.5 g Sodium acetate (3H20) 15.9 g Boric acid 6.7 g Sodium citrate (2H20) 2 g Acetic acid (90% w/w aq. sol.) 8.1 ml Recipe B
Pure water (ion-exchanged water)17 ml Sul-furic acid (50% w/w aq. sol.) 5.8 g Aluminum sul-fate (aq. sol. with 8.1% w/w o-f Al203) 26.5 g Just prior to use, recipes A and B were successively dissolved in 500 ml of water and the mixture was worked up to a total volume o-f 1,000 ml. The worked up fixing solution had a pH o-f ca. 4.3.
Pro_essing scheme Step Temperature, C_ Time, secTank capacity, L
Development 34 15 20 Fixing 34 15 20 WashingR.T. 10 15 Drying 40 10 The time of each step included the "solution crossover time" to the subsequent step.
The results o-f measurements and evaluation on the respective test samples are shown in Table 3 below.

2~o~

Table 3 Sam- Support Drying Light Speci-~ic Adhe- Remarks ple with an- condi- trans- surface sion tistatic tion mittance, resist-layer % ance, ~
1 NE-1 D-1 93 5.0xlO11 2Comparison 2 NE-1 D-2 93 5.0xlO11 2 do.
3 NE-1 D-3 96 5.0X1011 5Invention 4 NE-1 D-4 95 5.0xlO11 5 do.
5 NE-1 D-5 97 5.0xlO11 5 do.
6 NE-2 D-1 93 5.0xlO11 2Comparison 7 NE-2 D-2 94 5.0xlO11 2 do.

8 NE-2 D-3 96 5.0xlO11 5Invention 9 NE-2 D-4 95 5.0xlO11 5 do.
lONE.-2 D-5 97 5.0xlO11 5 do.
11 NE-3 D-1 78 5.0xlO11 2Comparison : 12 NE-3 D-4 79 5.0xlO11 4 do.
13 NE-1 D-6 94 5.0xlO11 3 do.
14 NE-1 D-7 93 5.0xlO11 3 do.
15 NE-1 D-8 94 5.0xlO11 2 do.

2 ~

Example 2 Additional samples were prepared as in Example 1 except that hydrazine compound (H-8) was used as a contrast-increasing agent in place of tetrazolium compound (T-2). The results were similar to those obtained in Example 1. The development step was conducted at 38~C -~or 20 seconds using developing solution B having the recipe shown below.
Compound (H-8):
Csll " (t) O
(t)Csll ~ 1 ~O(Cll 2) ~ NlICNll~;~NllNllCI10 Developing solution B
Hydroquinone 45.0 g N-Methyl-p-aminophenol hemisul-~ate 0.8 g Sodium hydroxide 15.0 g Potassium hydroxide 55.0 g 5-Sul~osalicylic acid 45.0 g Boric acid 35.0 g Potassium sul-fite 110.0 g Ethylenediaminetetraacetic acid disodium salt 1.0 g Potassium bromide 6.0 g 5-Methylbenzotriazole 0.6 g n-Butyl diethanolamine 15.0 g Water to make 1,000 ml (pH = 11.6) 2~1P~6 xamp~e 3 Samples O-r negative-acting film for darkroom photography were prepared as in E~ample 1 except in the following points: the amount of potassium pentabromorhodate used in the making o-f an emulsion was 25 ug per 60 g of silver nitrate; silver chlorobromide con~aining 25 mol%
AgBr was used; spectral sens:Ltizer (C) was added during chemical sensitization. The results of experiments conducted on the samples were entirely the same as in Example 1.
Spectral sensitizer (C): Cll2CIi2CN S

Example 4 C2114S03K
Samples o-f high-sensitivity negative-acting -film -for use in daylight room were prepared by the -followlng procedure.
Preparation o-f samples Solution B (see below) was added to solution A (also see below) in an atmosphere rendered acidic with nitric acid (pH 3.0) while the silver potential (EAg) was held at 170 mV. Mixing was per-formed by a double-jet method with EAg being controlled using 1 N NaCl. Solution C (see below) was also added at the same reaction temperature and flow 2~4015~

rate -for the -first 2 minutes O-r additlon; -therea-fter, solution C was added at a rate 0.99 times as -fast as the initlal rate, wi-th the EAg o-f solution B being controlled with 1 N NaCl. The silver halide emulsions thus prepared comprised silver halide grains having an average size o-f 0.08 um.
Solution A
Gelatin 5.6 g Polyisopropylene/polyethyleneoxy-disuccinic acid ester (Na salt) in 10% ethanol solution 0.56 ml Sodium chloride 0.12 g Conc. nitric acid 0.43 ml Distilled water 445 ml Solution B
Silver nitrate 60 g Conc, nitric acid 0.208 ml Distilled water 85.2 ml Solution C
GeIatin 3 g Polyisopropylene/polyethyleneoxy-disuccinic acid ester (Na salt) in 10% ethanol solution 0.3 ml Potassium bromide 4.2 g Sodium ch.lori.de 18.6 g 2~4~15~

Na3RhCl6 (1% aq. sol.) 0.02 ml Distilled water 87.3 ml Solution D
Celatin 1.4 g Polyisopropylene/polyethyleneoxy-disuccinic acid ester (Na salt) in 10% ethanol solution 0.14 ml Distilled water 48.8 ml The silver halide grains thus formed contained 90 mol%

AgCl and ~ x 10 6 moles of rhodium per mole of silver halide. Their monodispersity was 8 - 15%.
For EAg measurements, a metallic silver electrode and a double-~unction type saturated Ag/AgCl reference electrode were used (the electrode con-~iguration was the double-junction type described iIl JP-A-57-197543).
Solutions B and C were added using a varlable--flow, roller tube type metering pump.
During the addition of solutions B and C, portions of each emulsion were sampled and examined under an electron microscope. Since no new grains had formed, it was veri-fied that the addition of those solutions did not exceed the critical growth rate o-f grains in the system.
To each o-f the thus prepared emulsions, a - c, 6-methyl-4-hydroxy-1,3,3a,7-tetraazaindene was added in an amount of 2 0 ~ 6 200 mg per mole of silver halide. After pH adJustment to 5.7 with sodium carbonate, solution D was added. Then, each silver halide emulsiorl was washed with water and desalted in the usual manner. Subsequently, 6-methyl-4-hydroxy-1,3,3a,7-tetraazaindene and potassium bromide were added in respective amounts o-f 58 mg and 150 mg per mole of silver halide, and suL-fur sensitization was then per-formed.
Therea-fter, 6-methyl-4-hydroxy-1,3,3a,7-tetraazaindene (stabilizer) and gelatin were added in respective amounts of 570 mg and 25 g per mole o-f silver halide. Further, the additives identi-fied below were added to prepare coating solutions -for emulsion layer. In addition, respective coating solutions for an emulsion protective layer, a backing layer and a backing protective layer were prepared in entirely the same manner as in Example 1. Supports which were also the salne as those used in Example 1 were coated with these -four solutions to prepare samples as In Example l. When the samples were processed as in Example 1. the results were entirely the same as obtained ln Example 1.
Additives to emulsion coating solution Saponin 100 mg/m2 Potassium bromide 3 mg/m2 Desensitizing dye (DS-1~ 1 mg/m2 Sodium hydroxide 10 mg/m2 - ~5 -2~0~56 Tetrazolium compound (T-2) 45 mg/m2 Sodium dodecylbenzenesul~onate21 mg/m2 Butyl acrylate/styrene~acrylic acid copolymer latex 1 g/m2 5-Methylbenzo-triazole 10 mg/m2 5-Phenyl-1-mercaptotetrazole 11.5 mg/m2 2-Mercaptobenzimidazole-5-sul-fonic acid1 mg/m2 Benzyl-triphenylphosphonium chloride5 mg/m2 Compound (M) 5.8 mg/m2 DS-1: C}l~ Cll3 ~NJ~

Cllo ~ N0~CII2).~S03 Example 5 Additional samples were prepared as in Example 4 except in the -following points: the desensitizing dye (DS-1) and the tetrazolium compound (T-2) in the emulsion coating solutions were replaced by 10 mg/m2 O-r hydrazine compound (H-8); and compound (0) identified below was added in an amount of 20 mg/m2 to the emulsion protective layer coating solution.

- 8~ -Compourld (o) 20401~
Cll~ Cl12-- C112~ ~ \C~lls CII~S02-N~ N C~
02N ~ ~

Evaluation SOaNa The samples were evaluated by the same method as in Example 4 except that development was performed at 38UC for 20 seconds using developing solut:Lon B (as used in Example 2). The results were the same as in Example 4.
As :Ls clear -from -the foregoing description, the present invention provides a packaged antistatic light-sensitive material that is highly transparent and that insures strong adhesion between hydrophilic colloidal layers and antistatic layers. The invention also prov:ides a process -for producing such an improved packaged light-sensitive ma-terial.

(The remaining space is left blank.) - ~7 -

Claims (6)

1. The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-l.A process for manufacturing a packaged silver halide photographic material comprising a step of producing a silver halide photographic material having a support a hydrophilic colloidal layer at least one of which is a light sensitive emulsion layer and an antistatic layer containing a hydrophobic polymer latex having either an ethylene oxide chain or an amide chain or both a water-soluble conductive polymer and an epoxy compound thereon and a step of packaging said silver halide photographic material, wherein said producing step comprises:
   a) providing said hydrophilic colloidal layer on said support; and b) drying said hydrophilic colloidal layer by contacting said hydrophilic colloidal layer with air heated at 35 -80°C and has a relative humidity of 5 - 25% for not less than 5 seconds within 5 minutes after the average surface temperature of said hydrophilic colloidal layer becomes lower than a temperature for said drying by l°C; and said packaging step comprises maintaining said silver halide photographic material in an atmosphere having a dew point of not higher than 16°C until the end of packaging said silver halide photographic material.
2. 2. A process according to claim 1 wherein said light-sensitive silver halide emulsion contains either a tetrazolium compound or a hydrazine compound or both.
3. 3. A packaged silver halide photographic material comprising a silver halide photographic material having a support, a hydrophilic colloidal layer and an antistatic layer containing a hydrophobic polymer latex having either an ethylene oxide chain or an amide chain or both, a water-soluble conductive polymer and an epoxy compound thereon, wherein said silver halide photographic material is produced by steps comprising:
   a) providing said hydrophilic colloidal layer on said support; and b) drying said hydrophilic colloidal layer by contacting said hydrophilic colloidal layer with air heated at 35 -80°C and has a relative humidity of 5 - 25% for not less than 5 seconds within 5 minutes after the average surface temperature of said hydrophilic colloidal layer becomes lower than a temperature for said drying by 1°C; and packaged by a step comprising maintaining said silver halide photographic material in an atmosphere having a dew point of not higher than 16°C until the end of packaging said silver halide photographic material.
4. 4. A packaged silver halide photographic material according to claim 3 wherein said light-sensitive silver halide emulsion layer contains either a tetrazolium compound or a hydrazine compound or both.
5. 5. A process according to claim 2 wherein said tetrazolium compound is represented by the following general formula (T):
   
   (T) where substituents R1, R2 and R3 on the phenyl group are each a hydrogen atom, or preferably, a group having a negative or positive Hammett's sigma value (.delta.p) which is a measure of electron withdrawing property.
6. 6. A process according to claim 2 wherein said hydrazine compound is represented by the following general formula (H):
   
   (H) where R1 is a monovalent organic residue; R2 is a hydrogen atom or a monovalent organic residue; Q1 and Q2 are each a hydrogen atom, an optionally substituted arylsulfonyl group, or an optionally substituted arylsulfonyl group; X1 is an oxygen atom or a sulfur atom.