CN1639636A - Silver halide photosensitive material and method of forming image - Google Patents
Silver halide photosensitive material and method of forming image Download PDFInfo
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- CN1639636A CN1639636A CNA028293193A CN02829319A CN1639636A CN 1639636 A CN1639636 A CN 1639636A CN A028293193 A CNA028293193 A CN A028293193A CN 02829319 A CN02829319 A CN 02829319A CN 1639636 A CN1639636 A CN 1639636A
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- silver halide
- expression
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- alkyl
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
- G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
- G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
- G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
- G03C7/30535—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site not in rings of cyclic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C2200/00—Details
- G03C2200/27—Gelatine content
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
A silver halide photosensitive material which can give an image giving an excellent stereoscopic feeling and having improved evenness even when the paper pulp amount is small. The silver halide photosensitive material is characterized in that it comprises: a photographic printing paper substrate comprising a paper base and a water-resistant resin coating layer formed on each side of the base; and at least one silver halide emulsion layer formed on the substraste, and that the amount of the paper based is 110 to 154 g/m<2>.
Description
Technical field
The present invention relates to silver halide photographic sensitive material and image forming method, relate to inferior quality in detail, cheap and picture characteristics becomes bad less silver halide photographic sensitive material and image forming method.
Background technology
Because silver halide photographic sensitive material (below be also referred to as photosensitive material) contrast is excellent and have high sensitivity, therefore be widely used.By to silver halide photographic sensitive material exposure, when development treatment forms image, as exposure method, look like to carry out analogue exposure by negative map mostly, but in recent years, as adopt as situation that the digital scanning of laser scanning exposure exposes in continuous increase.
On the other hand, as the support of printer, generally adopt the photograph photographic pape support that the water-resistant resin coating forms is set on the two sides of paper substrate body with the photographic pape of silver halide photographic sensitive material.But this support uses paper pulp fiber at pars intermedia, because this paper pulp fiber price rising is bigger, causes the consumption of the forest reserves in addition, therefore wishes to reduce its consumption.But under the situation that reduces paper quality simply, when the image of observing as reflected image, visually image color is thin out, and its result exists what is called to lose the defective of image stereoscopic sensation, distinct sense.In addition, known should tendency under the situation of beam flying exposure back formation image, the generation especially easily.In addition, with the face of the silver halide emulsion layer coated side opposite side of paper support on have under the situation of character image, when observing its image, also exist the situation of easy generation image speckle.
Therefore, first purpose of the present invention is to provide paper quality few, and the high silver halide photographic sensitive material of image stereoscopic sensation visually.
Second purpose of the present invention is to provide and can be observed visually excellent image, and the less silver halide photographic sensitive material of image speckle.
The 3rd purpose of the present invention is to provide paper quality few, even and also can form the image forming method of the silver halide photographic sensitive material of excellent image when beam flying exposes.
Summary of the invention
Above-mentioned purpose of the present invention realizes by following various formations.
(1) silver halide photographic sensitive material, it has at least 1 layer the silver halide emulsion layer that contains on support at the photograph photographic pape that has the water-resistant resin coating on the paper substrate body two sides, and the quality that it is characterized by this paper substrate body is 110-154g/m
2, and this silver halide emulsion layer that contains of at least 1 layer contains the compound shown in the following general formula (1):
General formula (1)
(in the formula, R
AThe expression alkyl, R
BExpression halogen atom or alkoxy, R
CExpression-COOR
D1,-COOR
D2COOR
D1,-NHCOR
D2SO
2R
D1,-N (R
D3) SO
2R
D1Or-SO
2N (R
D3) R
D1R
D1The organic group of representing 1 valency, R
D2The expression alkylidene, R
D3Expression alkyl, aralkyl or hydrogen atom; Y
AThe organic group of representing 1 valency, n represent 0 or 1, R
EAnd R
FRepresent hydrogen atom or alkyl respectively).
(2) silver halide photographic sensitive material, it has at least 1 layer the silver halide emulsion layer that contains on support at the photograph photographic pape that has the water-resistant resin coating on the paper substrate body two sides, and the quality that it is characterized by this paper substrate body is 110-154g/m
2, and this at least 1 layer contain silver halide emulsion layer and contain the compound shown in the following general formula (2):
General formula (2)
(in the formula, R
1The expression alkyl, naphthenic base or aryl, R
2Expression alkyl, naphthenic base, acyl group or aryl, R
3Expression can be at the nuclear substituted group of benzene; N represents 0 or 1; X
1Be illustrated in reaction when developing the oxysome coupling of host and can take off the group of leaving away, Y
1The expression organic group).
(3) as (1) or (2) described silver halide photographic sensitive material, the gross mass that it is characterized by gelatin is at 6.2g/m
2Below.
(4) as (1) to (3) each described silver halide photographic sensitive material, it is characterized by with the face of described photograph photographic pape with the face opposite side that contains silver halide emulsion layer of support on, have character image.
(5) image forming method is characterized by and (1) to (4) each described silver halide photographic sensitive material carried out beam flying exposure back formation image.
Embodiment
The inventor etc. study specially at above-mentioned problem, found that as among using support at the photograph photographic pape that has the water-resistant resin coating on the paper substrate body two sides, quality by making the paper substrate body is at particular range, and by using specific yellow coupler, can realize image stereoscopic sensation height visually, and the silver halide photographic sensitive material that image speckle phenomenon is little is realized the present invention thus.
Below the present invention is described in detail.
Be generally used for the support of the photographic pape of silver halide photographic sensitive material, the water-resistant resin coating is set on the two sides of its paper substrate body, use from can be 240-340 ℃ of resin that melt extrudes suitably selecting at the water-resistant resin that is covered on the body paper surface.As such resin, can be used alone or as a mixture for example polyolefin resin of polypropylene (PP), ldpe resin (LDPE), high density polyethylene (HDPE), wire low density polyethylene (LLDPE) etc., or stacked use.In the present invention, the quality that it is characterized by paper pulp fiber contained in the paper substrate body is 110-154g/m
2, be preferably 120-154g/m
2, 130-148g/m more preferably
2
On at least 1 layer of water-resistant resin coating of the face side of coating silver emulsion,, preferably make its inorganic pigment that contains titania etc., blueing agent, fluorescer etc. from forming the viewpoint of better quality.The form of titania can be Detitanium-ore-type, also can be rutile-type, but because rutile-type can further be brought into play effect of the present invention, the therefore preferred rutile-type that uses.
In the present invention, with the opposite side that contains the silver halide photographic emulsion layer of support on preferably have character image.This is the photographic pape fabricator's of printing sign etc., is printed between paper substrate body and the inner-surface coated resin etc.
Below, yellow color development coupling agent shown in the general formula of the present invention (1) is described.
In above-mentioned general formula (1), as R
AThe alkyl of expression can be enumerated the alkyl of straight chain, side chain or ring-type, for example methyl, ethyl, isopropyl, the tert-butyl group, dodecyl, 1-hexyl nonyl, cyclopropyl, cyclohexyl, adamantyl etc.
These alkyl can further be substituted; as its substituting group; for example can enumerate halogen atom (chlorine atom, bromine atoms etc.), aryl (for example phenyl, to uncle's octyl phenyl etc.), alkoxy (for example methoxyl etc.), aryloxy (for example 2,4-two tertiary pentyl phenoxy groups etc.), sulfonyl (for example methane sulfonyl etc.), acyl group (for example acetyl group, benzoyl etc.), sulfoamido (for example dodecyl sulfoamido etc.), hydroxyl etc.
R
ABe preferably branched alkyl, be preferably the tert-butyl group especially.As R
BThe alkoxy of expression can be enumerated the alkoxy of straight chain, side chain, for example methoxyl, ethoxy, 1-Methylethyl oxygen base, tert-butoxy, dodecyl oxygen base, 1-hexyl oxygen in ninth of the ten Heavenly Stems base etc., wherein preferred methoxyl.
As R
BThe halogen atom of expression can exemplify out chlorine atom, bromine atoms, fluorine atom, is preferably the chlorine atom.
At R
CExpression-COOR
D1,-COOR
D2COOR
D1,-NHCOR
D2SO
2R
D1,-N (R
D3) SO
2R
D1Or-SO
2N (R
D3) R
D1In, as R
D1The organic group of representing 1 valency, be preferably the function that has as anti-diffusion base, for example be preferably alkyl (for example be dodecyl, octadecyl etc.) or the aryl (2 of carbon number at the straight or branched more than 10,4-diamyl phenyl etc.), more preferably carbon number is at the alkyl of the straight or branched more than 14.As R
D2The expression alkylidene, preference is as being propylidene, trimethylene etc.As R
D3Representing alkyl, be preferably the alkyl of straight chain, side chain, is methyl, ethyl, isopropyl etc. for example, as aralkyl, can enumerate benzyl etc.As R
CBe preferably-COOR
D1Group.
As R
EAnd R
FThe alkyl of expression, can enumerate carbon number is the straight chain of 1-10, the alkyl of side chain, is methyl, ethyl, propyl group, isopropyl, butyl, hexyl etc. for example, is preferably methyl especially.
As Y
A1 valency organic group of expression, can exemplify out alkyl (for example is ethyl; isopropyl; the tert-butyl group etc.); alkoxy (for example methoxyl etc.); aryloxy group (for example being phenoxy group etc.); acyloxy (for example is a methyl ketonic oxygen base; benzoyloxy etc.); amide group (acetamido for example; phenylcarbonyl group amido etc.); carbamyl (for example is a N-methylamino formoxyl; N-phenyl amino formoxyl etc.); alkylsulfonamido (for example being ethyl sulfonamide base etc.); aryl-sulfonyl amino (for example being phenyl-sulfamide base etc.); sulfonamide (for example is a N-propyl group sulfamoyl; N-phenyl sulfamoyl base etc.); imide (for example is the succinic acid imide; glutaric acid imide etc.).
Yellow color development coupling agent shown in the general formula (1) can be synthetic by existing known method.In addition, the compound shown in the general formula (1) more than 2 kinds be can use, perhaps in the scope of not damaging effect of the present invention, the coupling agent shown in the general formula (1) and other coupling agents are used in combination.
In the present invention, the coating weight of yellow color development coupling agent is preferably 0.50 * 10 in the silver halide photographic sensitive material
-3To 1.10 * 10
-3Mole/m
2, be preferably 0.60 * 10 especially
-3To 1.00 * 10
-3Mole/m
2Represent the total amount of any yellow color development coupling agent in the coating weight of this so-called coupling agent, and be not only the content of compound shown in the general formula (1).
In the compound shown in the above-mentioned general formula (1), preferred compound is R
CHave ester and connect basic compound.
As the instantiation of the compound shown in the general formula (1), the Compound I-1 that can enumerate the 0047-0048 section record that the spy opens flat 10-142756 communique is to the compound shown in the I-23.
Below compound shown in the above-mentioned general formula of the present invention (2) is described.In above-mentioned general formula (2), as R
1Represent alkyl, can enumerate the various groups of methyl, ethyl, isopropyl, the tert-butyl group, dodecyl etc.These R
1The alkyl of expression also comprises and further has substituent alkyl, as substituting group, can exemplify out halogen atom, aryl, alkoxy, aryloxy, alkyl sulphonyl, amide group, hydroxyl etc.
As R
1The naphthenic base of expression except cyclopropyl, cyclohexyl etc., also can be enumerated organic hydrocarbon residue of being formed by 2 above naphthenic base condensations (for example adamantyl etc.).R
1The naphthenic base of expression comprises and has substituent naphthenic base, as this substituent example, can enumerate with as R
1Shown in the same group of above-mentioned exemplary group of alkyl substituent.As R
1The aryl of expression can be enumerated phenyl etc., and this aryl comprises and has substituent aryl.As this substituent example, can enumerate with as R
1Shown in the same group and the alkyl of substituent above-mentioned exemplary group of alkyl.As R
1, be preferably branched alkyl.
As R
2Alkyl, naphthenic base or the aryl of expression can be enumerated and R
1The same group, and comprise respectively and have substituent group.As substituting group, can enumerate and R
1In the same group of above-mentioned exemplary group.In addition, as acyl group, can exemplify out the various groups of acetyl group, propiono, bytyry, benzoyl etc.This acyl group comprises and has substituent acyl group.As R
2, being preferably alkyl, aryl, alkyl more preferably most preferably is carbon number and is the low alkyl group below 5.In addition, as R
3Commutable group on the phenyl ring of expression can be enumerated halogen atom (for example chlorine); alkyl (ethyl for example; isopropyl; the tert-butyl group etc.); alkoxy (for example methoxyl); aryloxy group (for example phenoxy group); acyloxy (acetoxyl group for example; benzoyloxy etc.); amide group (acetamide for example; benzamide etc.); carbamyl (for example is a N-methylamino formoxyl; N-phenyl amino formoxyl etc.); alkylsulfonamido (for example being the ethyl sulfonamide base); aryl-sulfonyl amino (for example being the phenyl-sulfamide base); sulfonamide (for example is a N-propyl group sulfamoyl; N-phenyl sulfamoyl base etc.) and imide (for example be the succinic acid imide; glutaric acid imide etc.).
Use Y
1The organic group of expression is preferably the group that following general formula (Y-2) is represented.
General formula (Y-2)
-(J)
P-R
4
In the formula, R
4Expression contains an organic group with conjugated group of carbonyl or sulphonyl unit.P represents 0 or 1.
At R
4In, as group, can enumerate ester group, amide group, carbamyl, uride base, carbamate groups etc. with carbonyl unit.As group, can enumerate sulfonyl, sulfoamido, sulfamoyl, aminosulfonyl amido etc. with sulphonyl unit.
J represents-N (R
5) CO-or-CON (R
5)-, R
5Expression hydrogen atom, alkyl, aryl or heterocyclic radical.
As R
5The alkyl of expression can be enumerated methyl, ethyl, isopropyl, the tert-butyl group, dodecyl etc.In addition, as R
5The aryl of expression can be enumerated phenyl or naphthyl etc.As R
5The heterocyclic radical of expression can be enumerated pyridine radicals etc.
These R
5The various groups of expression comprise and have substituent group.As substituting group; it is not particularly limited; as representational substituting group, can enumerate halogen atom (for example chlorine etc.); alkyl (ethyl for example; isopropyl; the tert-butyl group etc.); aryl (phenyl for example; p-methoxyphenyl; naphthyl etc.); alkoxy (ethoxy for example; benzyloxy etc.); aryloxy group (for example phenoxy group); alkyl sulfenyl (for example ethyl sulfenyl etc.); artyl sulfo (for example phenyl sulfenyl etc.); alkyl sulphonyl (for example beta-hydroxy ethylsulfonyl etc.); aryl sulfonyl (for example benzenesulfonyl); acetylamino (the alkyl-carbonyl-amino of acetamide etc. for example; the aryl-amino-carbonyl of benzamide etc.); carbamyl (for example is the alkyl-carbamoyl of N-methylamino formoxyl etc.; the aryl-amino-carbonyl of N-phenyl amino formoxyl etc.); acyl group (the alkyl-carbonyl of acetyl group etc. for example; the aryl carbonyl of benzoyl etc.); sulfoamido (for example is the alkylsulfonamido of sulfonyloxy methyl amine etc.; the aryl-sulfonyl amino of phenyl-sulfamide base etc.); sulfonamide (for example is the alkylsulfamoyl group of N-methyl sulfamoyl etc.; the ammonia aryl sulfonyl of N-phenyl sulfamoyl base etc.); hydroxyl; cyano group etc.
As X
1Group expression and that break away from during the oxysome generation coupling reaction of development main agents can exemplify out the group shown in following general formula (Y-3) or the general formula (Y-4), is preferably the group shown in the general formula (Y-4) especially.
General formula (Y-3)
-OR
6
In general formula (Y-3), R
6Expression contains substituent aryl or heterocyclic group.
General formula (Y-4)
In above-mentioned general formula (Y-4), Z
1Expression forms the required non-metallic atom group of 5-6 unit ring jointly with nitrogen-atoms.As this non-metallic atom group, for example can enumerate replace or unsubstituted methylene, methine ,=C=O ,-NR
A(R
AWith above-mentioned R
5Definition identical) ,-N=,-O-,-S-,-SO
2-etc.
The yellow coupler of above-mentioned general formula (2) expression, R
1, R
3Or Y
1Part also can be in conjunction with forming disome.
The instantiation of the yellow coupler shown in the above-mentioned general formula of the present invention (2) can be enumerated Y-1 that the spy opens the record of flat 6-102637 communique instructions 0045-0049 section to the compound shown in the Y-20.
Below the scan exposure by light beam that the present invention relates to is described.
The scan exposure by light beam that the present invention relates to generally is to be carried out wire exposure (grating exposure: main sweep) and to photosensitive material (subscan) combination that relatively moves of the vertical direction with respect to this wire exposure directions implement by light beam.For example, more employing be at the periphery of cylindric drum or fixing photosensitive material on interior week, when making the drum rotation carry out main sweep on one side by one side illumination beam, make sense of rotation vertical moving the mode (drum mode) to implement subscan of light source with respect to drum, perhaps by multifaceted prism illumination beam to rotation, with sense of rotation horizontal scanning (main sweep) folded light beam of multifaceted prism, simultaneously with the sense of rotation vertical transport of the relative multifaceted prism of photosensitive material in the mode (multifaceted prism mode) of implementing subscan etc.In addition, adopting exposure device, and under the situation of the light source more than the photosensitive material width that wherein is exposed side by side with array-like, when substituting the part suitable, can catch, can consider to be included in the scan exposure of the present invention with main sweep with the array-like light source.
As the kind that can be used for light source of the present invention, the solid state laser that can use light emitting diode (LED), gas laser, semiconductor laser (LD), LD or LD is used as excitation source and the combination of the 2nd high harmonic dimensions of variability spare (being so-called SHG element) etc. also can be used any known light source.
In the present invention, the contained gelatin total amount of silver halide photographic sensitive material is preferably at 6.2g/m
2Below, 5.7g/m more preferably
2Below.
The material that can in silver halide photographic sensitive material of the present invention, use, except above-mentioned inscape, can also use for example silver halide photographic emulsions, the emulsion adjuvant, process for increasing sensitivity, speckle prevents agent, stabilizing agent, irradiation prevents dyestuff, fluorescer, yellow coupler, the magenta coupling agent, the cyan coupling agent, the beam split sensitizing coloring matter, the emulsification dispersion method, surfactant, prevent look turbid reagent, bonding agent, hardener, lubricant or matting agent, support, blueing agent or last red dose, coating process, exposure method, color development development host, disposal route, development processing apparatus, spies such as treating agent open all cpds and the method for the 0106th section record of a flat 11-347615 communique Instructions Page 9 left side the 0044th section to the 14th a page left side the 17th row of the 22nd row.
Below adopt embodiment that the present invention is specified, but embodiments of the present invention are not limited by this.
Embodiment 1
(making of sample 101)
At basic weight is 180g/m
2The two sides of paper pulp on the lamination high density polyethylene, make the paper delivery support, wherein have the printing type face of " TEST " literal within it on the face.But be coated with on the side that contains silver halide emulsion layer, by the lamination molten polyethylene and wherein disperse to contain to have implemented the surface-treated anatase-type titanium oxide, producing the reflection support with the content of 15 quality %.After this reflection support carried out Corona discharge Treatment, the gelatin undercoat is set, further applies the various layers of formation shown below, produce sample 101 as silver halide photographic sensitive material.As hardener, use H-1, H-2, as antiseptic, use F-1.
[formation of sample 101]
The 7th layer of (protective seam) [g/m
2]
Gelatin 1.00
DBP????????????????????????????????????0.002
DIDP???????????????????????????????????0.002
Silicon dioxide 0.003
The 6th layer (UV-absorbing layer)
Gelatin 0.40
AI-1???????????????????????????????????0.01
Ultraviolet light absorber (UV-1) 0.084
Ultraviolet light absorber (UV-2) 0.027
Ultraviolet light absorber (UV-3) 0.114
Anti-pollution reagent (HQ-5) 0.04
PVP????????????????????????????????????0.03
The 5th layer (sense red beds)
Gelatin 1.30
Feel red property chlorine silver bromide emulsion (Em-R) 0.21
Cyan coupling agent (C-1) 0.25
Cyan coupling agent (C-2) 0.08
Pigment image stabilization agent (ST-1) 0.10
Anti-pollution reagent (HQ-1) 0.004
DBP??????????????????????????????????0.10
DOP??????????????????????????????????0.20
The 4th layer (UV-absorbing layer)
Gelatin 0.94
Ultraviolet light absorber (UV-1) 0.196
Ultraviolet light absorber (UV-2) 0.063
Ultraviolet light absorber (UV-3) 0.266
AI-1?????????????????????????????????0.02
Anti-pollution reagent (HQ-5) 0.10
The 3rd layer (green layer)
Gelatin 1.30
AI-2?????????????????????????????????0.01
Feel green property chlorine silver bromide emulsion (Em-G) 0.14
Magenta coupling agent (M-1) 0.20
Pigment image stabilization agent (ST-3) 0.20
Pigment image stabilization agent (ST-4) 0.17
DIDP?????????????????????????????????0.13
DBP??????????????????????????????????0.13
The 2nd layer (middle layer)
Gelatin 1.20
AI-3?????????????????????????????????0.01
Anti-pollution reagent (HQ-2) 0.03
Anti-pollution reagent (HQ-3) 0.03
Anti-pollution reagent (HQ-4) 0.05
Anti-pollution reagent (HQ-5) 0.23
DIDP?????????????????????????????????0.04
DBP??????????????????????????????????0.02
Fluorescer (W-1) 0.10
The 1st layer (the blue or green layer of sense)
Gelatin 1.20
Sense green grass or young crops property chlorine silver bromide emulsion (Em-B) 0.26
Yellow coupler (Y-1) 0.70
Pigment image stabilization agent (ST-1) 0.10
Pigment image stabilization agent (ST-2) 0.10
Anti-pollution reagent (HQ-1) 0.01
Pigment image stabilization agent (ST-5) 0.10
Image stabilizing agent A 0.15
DNP????????????????????????????0.05
DBP????????????????????????????0.15
Support: polyethylene layer platen (containing micro-colorant)
Wherein, the addition of above-mentioned each silver emulsion is by expression that silver is converted.
Below show in detail the various adjuvants that adopt in said sample 101 making.
DBP: dibutyl phthalate
DNP: phthalic acid dinonyl ester
DOP: phthalic acid dioctyl ester
DIDP: phthalic acid two Permethyl 99A base esters
PVP: polyvinylpyrrolidone
H-1: four (ethene sulfonymethyl) methane
H-2:2,4-dichloro--6-hydroxyl-s-triazine sodium
HQ-1:2,5-two uncle's octyl group quinhydrones
HQ-2:2,5-two-secondary dodecyl quinhydrones
HQ-3:2,5-two-secondary myristyl quinhydrones
The HQ-4:2-second month in a season-dodecyl-5-second month in a season-myristyl quinhydrones
HQ-5:2,5-two [(1,1-dimethyl-4-hexyloxy carbonyl) butyl] quinhydrones
Image stabilizing agent A: to tert-octyl phenol
(50%) (46%) (4%) mol ratio
[preparation of sense green grass or young crops property silver emulsion]
Spend 30 fens clockwise be incubated in 2% aqueous gelatin solution of 40 ℃ 1 liter, add simultaneously below (A liquid) and (B liquid), control pAg=7.3, pH=3.0 simultaneously, further cost was added following (C liquid) and (D liquid) in 180 minutes simultaneously, controlled pAg=8.0, pH=5.5 simultaneously.At this moment, the control of pAg is implemented according to the method that the spy opens clear 59-45437 number record, adopted sodium hydrate aqueous solution to implement the control of pH.
(A liquid)
Sodium chloride 3.42g
Sodium bromide 0.03g
Add water 200ml
(B liquid)
Silver nitrate 10g
Add water 200ml
(C liquid)
Sodium chloride 102.7g
K
4IrCl
6??????????????4×10
-8mol/molAg
K
4Fe(CN)
6????????????2×10
-5mol/molAg
Potassium bromide 1.0g
Add water 600ml
(D liquid)
Silver nitrate 300g
Add water 600ml
After interpolation is finished, after 5% デ モ-Le N aqueous solution that adopts that flower king ア ト ラ ス company makes and 20% magnesium sulfate solution carry out desalination, mixed with aqueous gelatin solution, obtain mean grain size and be 0.71 micron, size distribution coefficient of alteration and be 0.07, the silver chloride containing ratio is the monodispersion cubic emulsion EMP-1 of 99.5 moles of %.After this, except the interpolation time of change interpolation time of (A liquid) and (B liquid) and (C liquid) and (D liquid), adopt the mode the same, obtain mean grain size and be 0.64 micron, size distribution coefficient of alteration and be 0.07, the silver chloride containing ratio is the monodispersion cubic emulsion EMP-1B of 99.5 moles of % with EMP-1.
With respect to above-mentioned EMP-1, adopt following compound under 60 ℃, to carry out optimum chemical sensitizing, in addition, equally also carry out optimum chemical sensitizing with respect to EMP-1B after, according to the mixed sensitizing of the ratio of counting 1: 1 with the silver amount EMP-1 and EMP-1B, obtain sense green grass or young crops property silver emulsion (Em-B).
Sodium thiosulfate 0.8 moles/mole AgX
Chlorination auric acid 0.5 moles/mole AgX
Stabilizing agent: STAB-1 3 * 10
-4Moles/mole AgX
Stabilizing agent: STAB-2 3 * 10
-4Moles/mole AgX
Stabilizing agent: STAB-3 3 * 10
-4Moles/mole AgX
Sensitizing coloring matter: BS-1 4 * 10
-4Moles/mole AgX
Sensitizing coloring matter: BS-2 1 * 10
-4Moles/mole AgX
[feeling the preparation of green property silver emulsion]
Except the interpolation time of change interpolation time of (A liquid) and (B liquid) and (C liquid) and (D liquid), adopt the mode the same, obtain mean grain size and be 0.40 micron, size distribution coefficient of alteration and be 0.08, the silver chloride containing ratio is the monodispersion cubic emulsion EMP-2 of 99.5 moles of % with EMP-1.Except the interpolation time of change interpolation time of (A liquid) and (B liquid) and (C liquid) and (D liquid), adopt the mode the same, obtain mean grain size and be 0.50 micron, size distribution coefficient of alteration and be 0.08, the silver chloride containing ratio is the monodispersion cubic emulsion EMP-2B of 99.5 moles of % with EMP-1.
With respect to above-mentioned EMP-2, adopt following compound under 55 ℃, to carry out optimum chemical sensitizing, in addition, equally also carry out optimum chemical sensitizing with respect to EMP-2B after, according to the mixed sensitizing of the ratio of counting 1: 1 with the silver amount EMP-2 and EMP-2B, obtain sense green property silver emulsion (Em-G).
Sodium thiosulfate 1.5 moles/mole AgX
Chlorination auric acid 1.0 moles/mole AgX
Stabilizing agent: STAB-1 3 * 10
-4Moles/mole AgX
Stabilizing agent: STAB-2 3 * 10
-4Moles/mole AgX
Stabilizing agent: STAB-3 3 * 10
-4Moles/mole AgX
Sensitizing coloring matter: GS-1 4 * 10
-4Moles/mole AgX
[feeling the preparation of red property silver emulsion]
Except the interpolation time of change interpolation time of (A liquid) and (B liquid) and (C liquid) and (D liquid), adopt the mode the same, obtain mean grain size and be 0.40 micron, size distribution coefficient of alteration and be 0.08, the silver chloride containing ratio is the monodispersion cubic emulsion EMP-3 of 99.5 moles of % with EMP-1.In addition, obtaining mean grain size is that 0.38 micron, coefficient of alteration are 0.08, the silver chloride containing ratio is the monodispersion cubic emulsion EMP-3B of 99.5 moles of %.
Above-mentioned relatively EMP-3, adopt following compound under 60 ℃, to carry out optimum chemical sensitizing, in addition, after EMP-3B equally also carries out optimum chemical sensitizing relatively, according to the mixed sensitizing of the ratio of counting 1: 1 with the silver amount EMP-3 and EMP-3B, obtain sense red property silver emulsion (Em-R).
Sodium thiosulfate 1.8 moles/mole AgX
Chlorination auric acid 2.0 moles/mole AgX
Stabilizing agent: STAB-1 3 * 10
-4Moles/mole AgX
Stabilizing agent: STAB-2 3 * 10
-4Moles/mole AgX
Stabilizing agent: STAB-3 3 * 10
-4Moles/mole AgX
Sensitizing coloring matter: RS-1 1 * 10
-4Moles/mole AgX
Sensitizing coloring matter: RS-2 1 * 10
-4Moles/mole AgX
STAB-1:1-(3-acetamido phenyl)-5-mercapto-tetrazole
STAB-2:1-phenyl-5-mercapto-tetrazole
STAB-3:1-(4-ethoxyl phenenyl)-5-mercapto-tetrazole
In addition, in the red property emulsion of sense, in every 1mol silver halide, add 2.0 * 10
-3The SS-1 of mole.
Below show in detail used various adjuvants in the above-mentioned various colour sensitivity emulsion preparation.
Thus, with the sample made as sample 101.
(making of sample 102-113)
Except in the manufacturing process of said sample 101, beyond the kind of the yellow coupler of adding with the paper pulp basic weight of used support and in the 1st layer changes according to the array mode shown in the following table, according to the manufacturing process making sample 102-113 the same with said sample 101.
(making of sample 114)
Except in the manufacturing process of said sample 112, employed gelatin amount in the whole layer is reduced with same ratio, make that the total gelatin amount is 6.0g/m
2In addition, make sample 114 according to the manufacturing process the same with said sample 112.
Show in detail in the following table according to the various samples of producing with upper type.
The 1st layer of remarks of the paper pulp of specimen coding support
The basic weight yellow coupler
(g/m
2)
101 180 Y-1 comparative examples
102 160 Y-1 comparative examples
103 153 Y-1 comparative examples
104 160 Y-2 comparative examples
105 153 Y-2 the present invention
106 147 Y-2 the present invention
107 135 Y-2 the present invention
108 100 Y-2 comparative examples
109 160 Y-3 comparative examples
110 153 Y-3 the present invention
111 147 Y-3 the present invention
112 135 Y-3 the present invention
113 100 Y-3 comparative examples
114 135 Y-3 the present invention
Below show in detail the yellow coupler Y-2 and the Y-3 that in said sample is made, use.
(evaluations of various samples)
The relative various samples of producing in the manner described above are according to the printing and the development treatment of carrying out portrait images as following scan exposure.Scan exposure adopts semiconductor laser (excitation wavelength is 650nm), He-Ne gas laser (excitation wavelength is 544nm), argon gas laser instrument (excitation wavelength is 458nm) as light source, based on view data various laser beams are modified tone to light quantity by AOM, it is reflected by multifaceted prism, implement main sweep at each sample, simultaneously with main scanning direction opposing vertical direction on carry photosensitive material, carry out the subscan exposure, the output portrait images.At this moment, beam diameter adopts control device of light beam to determine, makes BGR be 100 microns.
After this, the various samples that exposed are according to the method described above carried out development treatment, produce the colored printing of portrait images by following development treatment operation.
Treatment process treatment temperature time magnitude of recruitment
38.0 ± 0.3 ℃ of 45 seconds 80ml/m of color development development
2
35.0 ± 0.5 ℃ of 45 seconds 120ml/m of blix
2
Stabilization 30-34 ℃ of 60 seconds 150ml/m
2
Dry 60-80 ℃ 30 seconds
Below show the composition of development treatment liquid.
[color development development flow container liquid and additional liquid] jar liquid replenishes liquid
Pure water 800ml 800ml
Triethylenediamine 2g 3g
Diethylene glycol 10g 10g
Potassium bromide 0.01g-
Potassium chloride 3.5g-
Potassium sulfite 0.25g 0.5g
N-ethyl-N-(β-amsacrine second
Base)-3-methyl-4-amino aniline sulfuric acid 6.0g 10.0g
Salt
N, N-diethyl hydramine 6.8g 6.0g
Triethanolamine 10.0g 10.0g
Diethylene triamine five acetic acid five sodium-salt 2.0g 2.0g
Fluorescer (4,4 '-diaminobenzene second
2.0g?????????????2.5g
Alkene benzyl sulfonic acid redundant organism)
Sal tartari 30g 30g
By adding water, make that total amount is 1 liter, jar liquid is adjusted into pH=10.10, will replenish liquid and be adjusted into pH=10.60.
[blix flow container liquid and additional liquid]
2 water salt 65g of diethylene triamine five ferrous acetate ammoniums
Diethylene triamine five acetic acid 3g
ATS (Ammonium thiosulphate) (70% aqueous solution) 100ml
2-amino-5-sulfydryl-1,3,4-thiazole 2.0g
Ammonium sulfite (40% aqueous solution) 27.5ml
By adding water, make that total amount is 1 liter, adopt sal tartari or glacial acetic acid to be adjusted into pH=5.0.
[stabilization flow container liquid and additional liquid]
O-phenyl phenol 1.0g
5-chloro-2-methyl-4-isothiazoline-3-ketone 0.02g
2-methyl-4-isothiazoline-3-ketone 0.02g
Diethylene glycol 1.0g
Fluorescer (チ ノ パ-Le SFP) 2.0g
1-hydroxy ethylene-1,1-disulfonic acid 1.8g
Bismuth chloride (45% aqueous solution) 0.65g
7 water salt 0.2g of magnesium sulphate
PVP???????????????????????????????1.0g
Ammoniacal liquor (ammonium hydroxide 25% aqueous solution) 2.5g
Nitrile three acetic acid trisodium salt 1.5g
By adding water, make that total amount is 1 liter, adopt sulfuric acid or ammoniacal liquor to be adjusted into pH=7.5.
Portrait images according to each sample of producing with upper type is carried out visualization by 10 observers,, estimate rank according to 10 grades image stereoscopic sensation and image speckle patience are estimated, obtain its mean value according to following benchmark.
[relief evaluation]
1: the deep or light difference of figure and ground is low, shows as plane picture
5: find the deep or light of figure and ground, stereoscopic sensation and distinct sense are arranged slightly
10: the deep or light difference of figure and ground is clear and definite, and stereoscopic sensation and distinct sense are strong
[evaluation of image speckle patience]
1: when image surface was observed, the literal of inner face printing showed in image brightly
5: when image surface was observed, when seeing through printing and seeing, the literal of inner face printing showed
10: when image surface was observed, the literal of inner face printing did not show fully
In above-mentioned various evaluation ranks, to the rank beyond above-mentioned, 2-4,6-9 are respectively with 1,5,10 is benchmark, cut apart by five equilibrium and set.
In addition, carry out serializing, obtain paper consumption rank by paper pulp basic weight to sample support in above-mentioned each sample production.This amount is for judging the index of each sample economy (cost), the not enough 160g/m of paper pulp basic weight
2The time be zero, greater than 160 to not enough 180g/m
2The time be *, 180g/m
2More than be * *.
Each evaluation result by above acquisition has been shown in the following table.
| Specimen coding | The paper consumption | The image stereoscopic sensation | Image speckle patience | Remarks |
| ??101 | ??×× | ??6.5 | ??5.9 | Comparative example |
| ??102 | ??× | ??6.4 | ??5.8 | Comparative example |
| ??103 | ??○ | ??6.1 | ??5.8 | Comparative example |
| ??104 | ??× | ??7.6 | ??5.9 | Comparative example |
| ??105 | ??○ | ??7.6 | ??5.9 | The present invention |
| ??106 | ??○ | ??7.5 | ??5.8 | The present invention |
| ??107 | ??○ | ??7.4 | ??5.1 | The present invention |
| ??108 | ??○ | ??4.1 | ??3.1 | Comparative example |
| ??109 | ??× | ??7.2 | ??5.7 | Comparative example |
| ??110 | ??○ | ??7.2 | ??5.7 | The present invention |
| ??111 | ??○ | ??7.0 | ??5.4 | The present invention |
| ??112 | ??○ | ??7.0 | ??5.0 | The present invention |
| ??113 | ??○ | ??4.0 | ??2.9 | Comparative example |
| ??114 | ??○ | ??7.2 | ??5.1 | The present invention |
Embodiment 2
In embodiment 1, use NPS-868J that Konica Corp makes as automatic processing machine, use ECOJET-P as handling chemical reagent, according to handle title CPK-2-J1 turn round handle after, according to the method the same with embodiment 1 each characteristic is estimated, the result can recognize and confirm that sample of the present invention has more excellent image stereoscopic sensation and image speckle patience with respect to the comparative example sample.
Utilizability on the industry
As previously discussed, by silver halide photographic sensitive material of the present invention, even paper pulp amount is less, also can realize the image that image excellent stereoscopic feeling and image speckle patience improve.
Claims (5)
1. silver halide photographic sensitive material, it has at least 1 layer the silver halide emulsion layer that contains on support at the photograph photographic pape that has the water-resistant resin coating on the paper substrate body two sides, and the quality that it is characterized by this paper substrate body is 110-154g/m
2, and this silver halide emulsion layer that contains of at least 1 layer contains the compound shown in the following general formula (1):
General formula (1)
(in the formula, R
AThe expression alkyl, R
BExpression halogen atom or alkoxy, R
CExpression-COOR
D1,-COOR
D2COOR
D1,-NHCOR
D2SO
2R
D1,-N (R
D3) SO
2R
D1Or-SO
2N (R
D3) R
D1R
D1Represent 1 valency organic group, R
D2Expression alkylidene, R
D3Expression alkyl, aralkyl or hydrogen atom; Y
ARepresent 1 valency organic group, n represents 0 or 1, R
EAnd R
FRepresent hydrogen atom or alkyl respectively).
2. silver halide photographic sensitive material wherein has at least 1 layer the silver halide emulsion layer that contains on support at the photograph photographic pape that has the water-resistant resin coating on the paper substrate body two sides, the quality that it is characterized by this paper substrate body is 110-154g/m
2, and this silver halide emulsion layer that contains of at least 1 layer contains the compound shown in the following general formula (2):
General formula (2)
(in the formula, R
1The expression alkyl, naphthenic base or aryl, R
2Expression alkyl, naphthenic base, acyl group or aryl, R
3Expression can be at the nuclear substituted group of benzene, and n represents 0 or 1; X
1Be illustrated in reaction when developing the oxysome coupling of host and can take off the group of leaving away, Y
1The expression organic group).
3. silver halide photographic sensitive material as claimed in claim 1 or 2, the gross mass that it is characterized by gelatin is at 6.2g/m
2Below.
4. as each described silver halide photographic sensitive material of claim 1 to 3, it is characterized by with the face of described photograph photographic pape with the face opposite side that contains silver halide emulsion layer of support on, have character image.
5. image forming method is characterized by and each described silver halide photographic sensitive material of claim 1 to 4 carried out beam flying exposure back formation image.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2002/007312 WO2004010218A1 (en) | 2002-07-18 | 2002-07-18 | Silver halide photosensitive material and method of forming image |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1639636A true CN1639636A (en) | 2005-07-13 |
Family
ID=30490758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA028293193A Pending CN1639636A (en) | 2002-07-18 | 2002-07-18 | Silver halide photosensitive material and method of forming image |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1639636A (en) |
| WO (1) | WO2004010218A1 (en) |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05173288A (en) * | 1991-12-24 | 1993-07-13 | Oji Paper Co Ltd | Support for photograph printing paper |
| DE4302678A1 (en) * | 1993-02-01 | 1994-08-04 | Schoeller Felix Jun Papier | Recyclable substrate |
| JPH06332107A (en) * | 1993-05-19 | 1994-12-02 | Fuji Photo Film Co Ltd | Base for photographic paper |
| JPH07175170A (en) * | 1993-12-20 | 1995-07-14 | Fuji Photo Film Co Ltd | Photographic sensitive material |
| JPH07239530A (en) * | 1994-03-01 | 1995-09-12 | Fuji Photo Film Co Ltd | Supporting body for photogrpahic print paper |
| JPH07270969A (en) * | 1994-03-28 | 1995-10-20 | Fuji Photo Film Co Ltd | Support for photographic printing paper |
| JPH0882891A (en) * | 1994-09-09 | 1996-03-26 | Fuji Photo Film Co Ltd | Substrate for photographic printing paper |
| US6107014A (en) * | 1998-06-09 | 2000-08-22 | Eastman Kodak Company | Raw stock for photographic paper |
| US6030742A (en) * | 1998-11-23 | 2000-02-29 | Eastman Kodak Company | Superior photographic elements including biaxially oriented polyolefin sheets |
| JP2000352792A (en) * | 1999-06-14 | 2000-12-19 | Konica Corp | Silver halide photographic sensitive material |
| JP2001115396A (en) * | 1999-10-14 | 2001-04-24 | Mitsubishi Paper Mills Ltd | Support for imaging material |
| JP2002072430A (en) * | 2000-09-04 | 2002-03-12 | Konica Corp | Silver halide photographic sensitive material |
-
2002
- 2002-07-18 WO PCT/JP2002/007312 patent/WO2004010218A1/en not_active Application Discontinuation
- 2002-07-18 CN CNA028293193A patent/CN1639636A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004010218A1 (en) | 2004-01-29 |
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