CN1427301A - Siver halide colour photograph sensitive material - Google Patents
Siver halide colour photograph sensitive material Download PDFInfo
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- CN1427301A CN1427301A CN 02155876 CN02155876A CN1427301A CN 1427301 A CN1427301 A CN 1427301A CN 02155876 CN02155876 CN 02155876 CN 02155876 A CN02155876 A CN 02155876A CN 1427301 A CN1427301 A CN 1427301A
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Abstract
To provide a silver halide color photographic sensitive material that is excellent in suitability to rapid processing, suppresses deterioration of performance in long-term storage and gives good graininess. The silver halide color photographic sensitive material having at least one red-sensitive layer, at least one green-sensitive layer and at least one blue-sensitive layer in order from the support side on one side of a transparent support is characterized in that, when the RMS (root mean square) granularity of a magenta image after color development at a light exposure point (E) giving (the minimum density of the magenta image)+0.35 is represented by G, the RMS granularity of a cyan image at the light exposure point (E) by R and the total amount of coated silver by AG (g/m2), the above G, R and AG have relation represented by AG*(G+R)/2<=45.
Description
Technical field
The present invention relates to that a kind of rapid processing adaptability is good, the silver-halide color photo photosensitive material that mis-behave is improved and graininess is good in the long preservation.
Technical background
Silver halide picture photosensitive material (being designated hereinafter simply as " photosensitive material "), the product that is called as high mature on the one hand, on the other hand to desired performance, reach many-sides such as the performance change that causes with the preservation condition variation is very little in high sensitivity, high image quality, it requires level to raise just gradually in recent years.In addition, as market environment around the silver halide picture photosensitive material, for example, in being called as common photochromatic mode, photograph with colour negative, adopt the optical instrument developing and printing on color sensitive paper and obtain photochrome the image information on the negative film that is recorded in after the development, but this technology high development in recent years, bring the so-called miniature picture chamber of small-sized, the simple and easy developing and printing processor that is arranged on the street corner into by the film after will photographing, at one hour with the interior coloured image that just can obtain high image quality.
In addition, in recent years, in order to resist with electronic photo materials such as the digital camera of competing mutually, digital hardware copied material, in order to keep the superiority of silver halide picture photosensitive material, will continue further to improve its performance, for example high sensitivity, high image quality, further shorten the processing time and promptly handle just further rapidly and quicken.
In order to adapt to above-mentioned various desired characteristic, all technical schemes have been proposed, for example can enumerate, at United States Patent (USP) the 4th, 434, No. 226,4,439, No. 520,4,414, No. 310,4,433, No. 048,4,414, No. 306,4,459, disclose the technology of using the tabular silver halide particle in No. 353 grades, improved look enhanced sensitivity efficient, the sensitivity of raising is arranged, improved sensitivity with the shape of particle relation, owing to the special optical property of flat particle improves acutance and raising camera coverage etc. as what advantage can be enumerated by the enhanced sensitivity pigment.By adopting above-mentioned particle technology can improve quality to a certain extent, but be based on people's present situation more and more higher, expect that its performance further improves its quality requirements.
On the other hand, can improve sensitivity to a certain extent by the tabular silver halide particle that uses high-aspect-ratio, but have following shortcoming on the contrary again.
Promptly, the beam split enhanced sensitivity degree of the tabular silver halide particle of high-aspect-ratio is different because of the composition of silver halide particle, but the tabular silver halide particle that the amount of the enhanced sensitivity pigment that adds in order to give colour sensitivity and length breadth ratio are low is compared, generally the amount that needs wants many, therefore, cause the deterioration of residual look or graininess because of the difference of development treatment environment, especially problem becomes more obvious in the rapid developing system of popularizing recently.
As the corresponding means that address the above problem, design effectively reduces the use amount of silver halide as far as possible or reduces the adaptability of the thickness raising of photosensitive material to the development treatment variation, but in these methods, though can improve residual look, but then along with the minimizing of Tu Yinliang, sensitivity reduction, graininess worsen, in the long preservation photographic fog rise, the fatigue state for the treatment of fluid and cause that the deterioration that level changes, present situation are to have contradiction taking into account on Treatment Stability, storage stability and high sensitivity, the high image quality.
Summary of the invention
In view of the above problems, the object of the invention be to provide that a kind of rapid processing adaptability is good, the silver-halide color photo photosensitive material that mis-behave is improved and graininess is good in the long preservation.
Above-mentioned purpose of the present invention is finished by following aspect.
1. silver-halide color photo photosensitive material, it is characterized in that, its support side with the side from the transparent support respectively is the red photographic layer that contains 1 layer of cyan coupler at least, at least the green photographic layer that contains 1 layer of magenta colour coupler, and the blue photographic layer that contains 1 layer of yellow colour former at least, wherein, to be made as G in the RMS granularity of the magenta chromophore image in the exposure point (E) of Cmin+0.35 of the magenta chromophore image after giving the color development development treatment, the RMS granularity of the cyan chromophore image in this exposure station (E) is made as R, when the thickness except that support is made as Hd (μ m), this G, the relation of this R and this Hd is represented as shown in the formula (2).
Formula (2)
Hd×(G+R)/2≤210
2. silver-halide color photo photosensitive material, it is characterized in that, its support side with the side from the transparent support respectively is the red photographic layer that contains 1 layer of cyan coupler at least, at least the green photographic layer that contains 1 layer of magenta colour coupler, at least the blue photographic layer that contains 1 layer of yellow colour former, wherein, to be made as G in the RMS granularity of the magenta chromophore image in the exposure point (E) of Cmin+0.35 of the magenta chromophore image after giving the color development development treatment, the RMS granularity of cyan chromophore image in this exposure station (E) is made as R, when total silver coating amount is made as AG (g/m2), this G, the relation of this R and this AG is represented as shown in the formula (1).
Formula (1)
AG×(G+R)/2≤45
3. silver-halide color photo photosensitive material, it is characterized in that, its support side with the side from the transparent support respectively is the red photographic layer that contains 1 layer of cyan coupler at least, at least the green photographic layer that contains 1 layer of magenta colour coupler, at least the blue photographic layer that contains 1 layer of yellow colour former, wherein, to be made as G in the RMS granularity of the magenta chromophore image in the exposure point (E) of Cmin+0.35 of the magenta chromophore image after giving the color development development treatment, the RMS granularity of cyan chromophore image in this exposure station (E) is made as R, and total silver coating amount is made as AG (g/m
2), when removing the outer thickness of support and being made as Hd, the relation of this G, this R, this AG and this Hd is represented as shown in the formula (3).
Formula (3)
AG×Hd×(G+R)/2≤700
4. aforementioned 2 or 3 described silver-halide color photo photosensitive materials is characterized in that, aforementioned total silver coating amount AG is 2.0～6.0g/m
2
5. aforementioned 1 or 3 described silver-halide color photo photosensitive material is characterized in that aforementioned thickness Hd is 10～20 μ m.
6. each described silver-halide color photo photosensitive material in aforementioned 1～5, it is characterized in that, the length breadth ratio that contains more than 50% of its total projection area of one deck at least of each photographic layer is more than 2, and each particle has the tabular silver halide particle of 30 above dislocation lines.
7. each described silver-halide color photo photosensitive material in aforementioned 1～6, it is characterized in that, aforementioned green photographic layer is made up of ISO layer, middle light sensitivity layer and low speed layer at least, and coloured magenta colour coupler of light sensitivity layer is more than 1.1 times with respect to the ratio of colourless magenta colour coupler in this.
8. each described silver-halide color photo photosensitive material is characterized in that in aforementioned 1～7, and the total amount of the yellow colour former in the aforementioned blue photographic layer is 0.8～1.7mmol/m
2
9. each described silver-halide color photo photosensitive material is characterized in that in aforementioned 1～8, and the total amount of the magenta colour coupler in the aforementioned green photographic layer is 0.3～0.9mmol/m
2
10. each described silver-halide color photo photosensitive material is characterized in that in aforementioned 1～9, and the total amount of the cyan coupler in the aforementioned red photographic layer is 0.7～1.6mmol/m
2
In view of the above problems, the inventor furthers investigate, graininess in the specific exposure fields (low exposure fields) is worsened, or the keeping quality in handling rapidly, the deterioration reason of image quality is analyzed, found that, by under given conditions with the granularity of magenta and cyan image and the long-pending setting that is coated with the silver amount, or the long-pending setting of the thickness that the granularity of magenta and cyan image is outer with removing support under given conditions, or by both combinations can obtain good rapid processing adaptability with this, storage stability and good graininess in the long preservation, thus the present invention finished.
Promptly, particularly the region of underexposure (also we can say " foot areas ") to uneven obviousization of graininess carry out the result of image analysis, to influential silver-colored the measuring of the picture characteristics of under-exposure part, promptly, by with long-pending the be designed to optimum balance of silver point number, can reach stability in the rapid processing and good graininess with the graininess that forms image.Equally, by with long-pending the be designed to optimum balance of thickness, can take into account advantages of excellent stability and these two opposite characteristic of raising graininess for rapid processing variation with the graininess that forms image.
Specifically, be by total silver coating amount AG is made as 2.0～6.0g/m
2Scope, thickness Hd is made as 10～20 mu m ranges, the total projection area use more than 50% length breadth ratio more than 2 and per 1 particle contain the tabular silver halide particle of the dislocation line that has more than 30, green photographic layer is made of ISO layer, middle light sensitivity layer and low speed layer at least, ratio with respect to coloured magenta colour coupler of the colourless magenta colour coupler of light sensitivity layer in this is located at more than 1.1 times, and the total amount of the yellow colour former in the blue photographic layer is located at 0.8～1.7mmol/m
2Scope, the total amount of the magenta colour coupler in the green photographic layer is located at 0.3～0.9mmol/m
2Scope, the total amount of the cyan coupler in the red photographic layer is located at 0.7～1.6mmol/m
2Scope, or the combination of selecting to suit from them is finished.
Below the present invention will be described in detail.
In the invention relevant with aforementioned 1, contain at least 1 layer red photographic layer successively respectively on the support side of the side from transparent support, in the silver-halide color photo photosensitive material of green photographic layer and blue photographic layer, the RMS granularity of giving the magenta chromophore image in the exposure point (E) of Cmin+0.35 of the magenta color image after the color development development treatment is made as G, the RMS granularity of the bluish-green chromophore image in this exposure point (E) is made as R, when will the thickness except that support being made as Hd (μ m), this G, this R, and this Hd is characterised in that there is the relation of above-mentioned formula (2) expression Hd * (G+R)/2≤210 in they, preferred Hd * (G+R)/2 be 150～210, more preferably 150～200.
In the present invention, so-called Cmin is meant the optical concentration (being designated hereinafter simply as " concentration ") after the color development of unexposed portion in the silver-halide color photo photosensitive material develops, what is called is given the Cmin+0.35 exposure point of magenta color development concentration, just be meant the sample after the silver halide picture photosensitive material color development development that changes exposure according to intensity is carried out concentration determination, making is represented exposure by transverse axis, the family curve that longitudinal axis indicated concentration constitutes, as the concentration in the family curve of magenta concentration, be meant the needed exposure point of the concentration that will obtain Cmin+0.35, with common used wedge in this field, light source ladder wedge exposure by colour temperature 5400K, with British Jouranal of Photography Annual1988, P.196-198 after the C-41 of Ji Zai Eastman Kodak's system handles, according to the colour sensitivity of silver halide emulsion layer, measure with X-rite corporate system densimeter respectively and calculate.In addition, in said determination, from exposing to the color development development treatment, the temperature of experiment photosensitive material remains on 20 ± 5 ℃, relative humidity and remains under 60 ± 10% the atmosphere, and development treatment is to finish with interior in 6 hours more than 30 minutes in that exposure is back.
In addition, give the RMS granularity G of the middle magenta color image of exposure point (E) of magenta color development concentration Cmin+0.35, calculate by following formula (A).
Formula (A)
G＝log
10(RMS×0.55)
By opening scan area 750 μ m
2(the wide 5 μ m of slit, the long 150 μ m of slit) miniature development density meter scans, value behind 1000 times of the standard deviations of the change of the concentration value of concentration determination sample number more than 100 is as each brightness, is RMS to value defined of this impartial average gained, according to the following formula calculating concentration.In addition, when measuring the RMS granularity of magenta color image, separate light filter as green glow and use the Wratten filter W-99 of Eastman Kodak's system to measure.
In addition, the RMS granularity R of cyan concentration, the Wratten filter W-26 that is used as Eastman Kodak's system of red light separation light filter replaces green glow to separate light filter, in addition, measure equally with above-mentioned, calculate the value of gained according to above-mentioned formula (A) and calculate RMS granularity R.
So-called thickness except that support among the present invention is meant surface from photography side support to the most surperficial dry film thickness of photography side photosensitive material, and unit represents with μ m.As assay method, can use scanning electron microscope to the section of photosensitive material the indirect method for measuring of photographing calculate.In the present invention, thickness is for satisfying the scope of aforementioned 2 or aforementioned 3 described formulas (2) or formula (3), as long as and have needed operability just not have particular restriction as the photochrome photosensitive material, but in the invention relevant with aforementioned 5, it is characterized in that thickness is 10～20 μ m, more preferably 13～17 μ m.
Aforementioned by satisfying in the present invention (2) defined terms can provide a kind of rapid processing adaptability good, the silver-halide color photo photosensitive material that mis-behave and graininess are good when improving long preservation.
In the present invention, the realization means that are used to satisfy aforementioned formula (2) defined terms there is not particular restriction, but as used colour coupler, just need carry out suitable selection according to reactivity or color emissivity, or according to their combination, by the colour coupler use amount that the color development efficient that improves colour coupler is cut down per unit area, the design that the thickness of formation layer will approach.
In the 2nd invention, it is characterized in that, contain respectively successively the silver-halide color photo photosensitive material of at least 1 layer red photographic layer, green photographic layer and blue photographic layer on support side from a side of transparent support, the RMS granularity of giving magenta chromophore image in the exposure point (E) of Cmin+0.35 of the magenta color image after the color development development treatment is made as G, the RMS granularity of the cyan chromophore image in this exposure point (E) is made as R, and total silver coating amount is made as AG, and (unit is g/m
2) time, this G, this R, and this AG represent that with the relation of aforementioned (1) formula AG * (G+R)/2≤45 preferably AG * (G+R)/2 is in 30～45 scope.
The total silver-colored value of the per unit area when so-called total silver coating amount AG is meant silver halide etc. is scaled argent among the present invention, what is called is scaled argent and is meant that the silver emulsion that will contain in the photosensitive material is scaled equimolar argent and calculates, in addition, also comprise and calculate whole non-photosensitive silver emulsion or collargol, the g/m of unit
2Expression.In the present invention, total Tu Yinliang satisfies the 2nd or 3 the formula (1) or the condition and range of (3), and, just there is not particular restriction as long as have required level as color sensitive material, but in the 4th described invention, it is characterized in that total silver coating amount is 2.0～6.0g/m
2, be preferably 2.5～4.0g/m
2
By satisfying the relation of aforementioned formula (1) among the present invention, can provide a kind of rapid processing adaptability good, mis-behave in the improvement long preservation, and the good silver-halide color photo photosensitive material of graininess.
In silver-halide color photo photosensitive material of the present invention, as the means that are used to satisfy aforementioned regulation formula (1), no particular restriction, but preferably use the method for following record.
In the 6th invention, it is characterized in that, the one deck at least in each photographic layer contain the total projection area more than 50% for length breadth ratio more than 2 and each particle have the tabular silver halide ion of 30 dislocation lines.This means are to be one of preferred means of the relation that reaches formula (1).
So-called tabular silver halide ion among the present invention (following also abbreviate as " flat particle ") is meant from the viewpoint of crystallography and is categorized as metacrystal.So-called metacrystal is meant the crystal that has more than one twin plane a particle the inside, the article of the classification criterion Network ラ イ Application of twin crystal form and モ イ サ one report is 99 pages of " Photographishe Korrespondenz " 99 volumes in the silver halide particle, is described in detail with in 57 pages of 100 volumes.
About the tabular silver halide particle among the present invention, the silver halide particle of the twin plane more than 2 that is parallel to each other that preferred particle inside has.These twin planes are with respect to the substantially parallel existence of face (being called " principal plane ") that has maximum area in the plane that forms flat particle surface.Particularly preferred in the present invention form is to have two parallel twin planes, in silver emulsion of the present invention, it is more than 3 below 50 that the particle more than 50% of the total projection area of preferred flat particle contains silver iodide and length breadth ratio, and more preferably length breadth ratio is more than 4 below 30.
The length breadth ratio of the so-called tabular silver halide particle among the present invention is meant and can be adjusted in the above-mentioned required scope by suitably selecting known manufacture method in this technical field.
In addition, the length breadth ratio of silver halide particle can be calculated the particle diameter of each silver halide particle and the thickness of particle by following method, calculates by following formula then.
The thickness of length breadth ratio=particle diameter/particle
Tabular silver halide particle among the present invention preferably has the tabular silver halide particle of the principal plane of two twin planes (111) parallel with principal plane, preferred 0.2～15 μ m of mean grain size, more preferably 0.3～10 μ m, most preferably 0.4～5 μ m.
So-called mean grain size among the present invention is meant the arithmetic mean of particle diameter ri.Should illustrate, three of significant figure, the minimum bit numeral rounds up, the number of measuring particle be at random more than 1000.Be the circle that is scaled homalographic with respect to the principal plane of the tabular silver halide particle projection image when vertical direction is observed at this said particle diameter ri as the time diameter.In addition, the ri of particle diameter machine amplifies 1～70,000 times with electron microscope with silver halide particle to take pictures, and the area during by particle diameter on this photograph of practical measurement or projection obtains.
In the present invention, be used to calculate the projected area and the thickness of each particle of the particle diameter of silver halide particle or length breadth ratio, can calculate by following method.Be produced on and be coated with as the known latex balloon of interior target particle diameter on the support and make the sample of the parallel-oriented silver halide particle of principal plane and substrate, give shade by the carbon evaporation to particle from certain angle after, make the duplicating sample by common duplicating method.This sample is carried out electron micrograph, calculate the projected area and the thickness of each particle with image processing apparatus.In this case, the projected area of particle can be calculated by interior target projected area, and the length of the shade that the thickness of particle can be by internal standard and particle is calculated.
In the present invention, except that flat particle of the present invention, single particle arbitrarily such as emulsion that disperses that can also share the wide polydispersion emulsion of size distribution, narrow diameter distribution is during preferably according to following formula definition size distribution, size distribution is lower than 30%, more preferably less than 25%.
Size distribution (%)=(standard deviation/mean grain size of particle diameter) * 100
Mean grain size and standard deviation are calculated by the particle diameter ri of following formula definition.
The tabular silver halide particle preferably contains silver iodide in the present invention, preferred 0.5～30 mole of % of the average silver halide content of tabular silver halide particle, more preferably 1.0～15 moles of %.
The agi content of silver halide particle can pass through EPMA (Electron Probe MicroAnalyzer method, electron probe micro-analysis meter method) and calculate.Specifically, silver halide particle is not contacted mutually, disperse to make sample fully, irradiating electron beam when arriving below-100 ℃ with cooled with liquid nitrogen, by obtaining, determine the agi content of this each silver halide particle from the silver of each silver halide particle radiation and the characteristic X-ray intensity of iodine.
By said method, the silver halide particle more than 100 is calculated the agi content of each silver halide particle, its mean value is as average silver iodide content.
About the tabular silver halide particle among the present invention, preferably each particle has the dislocation line more than 30.The form of dislocation line can suitably be selected, and for example can select the dislocation line that linearly exists with respect to the specific direction in particle crystallization orientation, or crooked dislocation line.Further, also can select to exist, or exist only in the privileged site of particle, for example be limited to the form that has dislocation line at particle edge (peripheral part) along whole particle; Be limited to the form that there is dislocation line in principal plane; Or there is form of dislocation line etc. near concentrating on the summit.In the tabular silver halide emulsion relevant, preferably there is dislocation line in the edge of particle at least, also preferably has dislocation line in edge and principal plane with the present invention.
As the dislocation line in the tabular silver halide particle of the present invention, no particular restriction, but more than 50% of total projection area of preferred silver halide particle, preferred particle more than 80% have dislocation line more than 30 at each particle of edge.When in above-mentioned tabular silver halide particle, introducing dislocation line, preferably use the compound of silver iodide particulate or release halogen ion.
In making tabular silver halide particle of the present invention, can use oxygenant, silver halide grains or the ultrafiltration etc. of reduction enhanced sensitivity, silver.Utilize these creating conditions of tabular silver halide particle to open the method that waits record for flat 2001-242583 number with reference to the spy.
Preferably contain at least a in polyvalent metal atom, polyvalent metal atom ion, polyvalent metal atom complex or the polyvalent metal atom complex ion at tabular silver halide particle of the present invention.
About these using method, can open disclosed methods such as flat 2001-75243 with reference to the spy.
In the manufacturing of tabular silver halide emulsion of the present invention, except that above condition, can open clear 61-6643 number with reference to the spy, 61-14630 number, 61-112142 number, 62-157024 number, 62-18556 number, 63-92942 number, 63-151618 number, 63-1634512 number, 63-2202238 number, 63-311244 number, the XV part of the I item of RD38957 and III item, RD40145 etc. is selected suitable condition.
In the present invention; except that above-mentioned tabular silver halide particle, also can share with the silver emulsion of record among the ResearchDisclosure ( being labeled as RD ) 308119.Below the source is put down in writing in expression.[] RD308119 993I-A 993I-A994E 994E 994E 994E 993I-B 993I-B 994I-C 994I-C 995I-D 995I-F 995I-F 995I-G 995I-G 9951-H ( ) 995I-H 995I-I 995II-A
In the present invention, the emulsion behind silver emulsion use physics slaking, chemical slaking and the beam split enhanced sensitivity.The dose that uses in this technology is disclosed among the RD17643, same 18716 and together 308119.Below represent disclosed position.Are exposed to light accidentally and prevent agent 998VI item 24～25 649 stabilizing agent 998VI items 24～25 649 in [project] RD3081109 page or leaf RD17643 RD18716 chemical sensitizer 996III-A item 23 648 minutes photosensitizing agent 996IV-A～J item 23～24 648～9 rich shade sensitizer 996IV-A-E, J item 23～24 648～9
In the present invention, silver emulsion preferably with selenium compound, be to carry out chemical sensitization under the condition of 30～70mV, pH6.0～7.0 at silver-colored current potential, and contain the compound of general formula (1) expression.
General formula (1)
R
1-(S)
m-R
2
In general formula (1), R
1And R
2Represent fatty group, aromatic series base, heterocyclic radical respectively separately or be bonded to each other to form the atom group of ring.In addition, R
1And R
2Can be identical also can be inequality, R
1And R
2When being respectively aliphatic group, also can mutually combine forms ring.M preferably represents 2～6 integer.
To selenium compound, the chemical sensitization method that can preferably use among the present invention, can open that 2000-235240,2001-117189,2001-194740 etc. are put down in writing with reference to the spy.
Below, further enumerate preferred means of the present invention.
One of its method, the 7th invention, formation as green photographic layer, at least constitute by ISO layer, middle light sensitivity layer and low speed layer, coloured magenta colour coupler of light sensitivity layer is more than 1.1 times with respect to the ratio of colourless magenta colour coupler in being somebody's turn to do, preferred 1.5～10.0 times, more preferably 2.0～10.0 times.So-called colourless magenta colour coupler among the present invention, be meant before color development develops, do not present painted, the colour coupler that is magenta after color development develops, so-called coloured magenta colour coupler, be meant present before color development develops yellow or yellow beyond painted, after color development developed, yellow colour killing presented the colour coupler of magenta.
In the present invention, be used for the colour coupler use amount of the per unit area of above-mentioned medium green color sensation photosphere, preferred 0.1～0.3mmol/m
2, more preferably 0.1～0.2mmol/m
2
In addition, in the present invention,, can improve the consumption of each colour coupler in each photographic layer as the means of control thickness, particularly for take into account with silver-halide color photoelement in required dark light degree, preferred following condition.
In the 8th invention, it is characterized in that the total amount of yellow colour former is 0.8～1.7mmol/m in the blue photographic layer
2, more preferably 0.9～1.5mmol/m
2
In addition, in the 9th invention, it is characterized in that the total amount of magenta colour coupler is 0.3～0.9mmol/m in the green photographic layer
2, more preferably 0.4～0.7mmol/m
2
In addition, in the 10th invention, it is characterized in that the total amount of cyan coupler is 0.7～1.6mmol/m in the red photographic layer
2, more preferably 0.8～1.3mmol/m
2
The colour coupler total amount of per unit area among so-called the present invention, consumption sum after the mole that is meant expression yellow colour former, magenta colour coupler, cyan coupler and coloured quality agent converts does not contain DIR colour coupler, BAR colour coupler in the consumption and other discharges the colour coupler of useful residue.
Below, can be used in the example of various colour couplers of the present invention, be recorded among the following RD, below the relevant record position of expression.[project] RD308119 page or leaf RD17643 yellow colour former 1001VII-D item VIIC-G item magenta colour coupler 1001VII-D item VIIC-G item cyan coupler 1001VII-D item VIIC-G item coloured quality agent 1001VII-G item VIIG item DIR colour coupler 1001VII-F item VIIG item BAR colour coupler 1001VII-F item other discharge the colour coupler 1001VII-F item alkali solubility colour coupler 1001VII-E item of useful residue
As can be used in yellow colour former of the present invention, can use the various colour couplers of putting down in writing among the above-mentioned RD, but the yellow colour former of preferred 2 equivalent acyl amino types, more preferably the spy opens the colour coupler of disclosed general formula (I)～(III) expression among the 2001-75245.
As can be used in magenta colour coupler of the present invention, can use the various colour couplers of putting down in writing among the above-mentioned RD, but preferred 2 equivalent pyrazolone colour couplers, more preferably special colour coupler of being willing to disclosed general formula (I) expression among the 2001-15797.
As can be used in cyan coupler of the present invention, can use the various colour couplers of putting down in writing among the above-mentioned RD, but preferred 2 equivalent urea nitrile (ureidocyan) colour couplers, more preferably open the colour coupler that disclosed general formula (VI) is represented among the 2001-75245 and share, and more preferably open the compound as the high boiling solvent use of disclosed general formula (A)～(E) expression among the 2000-284430 the spy with the spy.
Be used for coloured magenta colour coupler of the present invention, can use the various colour couplers of putting down in writing among the above-mentioned RD.
In the 3rd invention, contain respectively successively the silver-halide color photo photosensitive material of at least 1 layer red photographic layer, green photographic layer and blue photographic layer on the support side of the side from transparent support, the RMS granularity of giving magenta chromophore image in the exposure point (E) of Cmin+0.35 of the magenta color image after the color development development treatment is made as G, the RMS granularity of the chromophore image in this exposure point (E) is made as R, total silver coating amount is made as AG (g/m
2), when will the thickness except that support being made as Hd, it is characterized in that this G, the relation of this R, this AG and this Hd such as above-mentioned formula (3) AG * Hd * (G+R)/2≤700, preferred AG * Hd * (G+R)/2 is in 500～700 scope.
The 3rd defined terms can preferably realize means by each that suitably select above-mentioned formula (1) and formula (2), or realizes by their combination.
As the adjuvant that in silver-halide color photo photosensitive material of the present invention, adds, can add by the dispersion method of putting down in writing among the RD308189XIV.
When using common compact camera or high power zoom, in the low speed photosensitive material, because causing hand vibrations, inconvenience easily arbitrarily uses, so the preferred specific photographic sensitivity of the silver-halide color photo photosensitive material among the present invention is the photosensitive material more than 160, and is preferred especially more than 200.Photographic sensitivity specific among the present invention can pass through JIS K 7614-1981 method, opens test method in paragraph numbering [0035]～[0036] of flat 6-67350 communique according to the spy specifically and calculates and try to achieve.
Can be used in known photograph adjuvant of the present invention, be also recorded among the ResearchDisclosure.Below represent relevant record position.The antifouling toner 1002 VII-I items of [project] [RD308119 page or leaf] [RD17643] [RD18716] 25 650 pigment image stabilizing agents 1001 VII-J items 25 whitening agent 998V 24 ultraviolet light absorbers 1003 VIII-I items
XIII-C item 25～26 light absorbers 1003 VIII 25～26 light scattering agents 1003 VIII filter dyes 1003 VIII 25～26 adhesives 1003 IX 26 651 antistatic agents 1006 XIII 27 650 solid film 1004 X 26 651 plasticizer 1006 XII 27 650 lubricants 1006 XII 27 650 activating agents, coating assistant 1005 XI 26～27 650 delustering agents, 1007 XVI developers (being contained in the photosensitive material), 1001 XXB items
Each of silver-halide color photo photosensitive material of the present invention taken a picture and constituted layer, and preferred calcium content is below 50ppm, below the preferred especially 40ppm, more preferably below the 30ppm.If calcium content is when big, the film in the development treatment causes atrophy or devitrification and can not be in practical application rapidly.
Form the calcium in the gelatin that constitutes tunic of taking a picture, by producing in the raw material, still for obtaining calcic gelatin of the present invention, also can be to the selection of raw material, processing such as selection of creating conditions and ion-exchange are made up.
As ion-exchange treatment, can be used as extract gelatin in the ox bone, pigskin etc. of raw material after spent ion exchange resin (for example IRA type of Rohm and Hass company) carry out ion-exchange.
Calcium ion content after the ion-exchange treatment quantitatively, can carry out quantitatively with the method for putting down in writing in gelatin test method(s) (abbreviating バ ギ イ method as), the sixth version according to the photograph that gelatin test method(s) contract review conference formulates.
In the present invention, can use the support of putting down in writing among the XIX of 647～648 pages of 28 pages of aforementioned RD17643, RD18716 and RD308119.
Silver-halide color photo photosensitive material of the present invention can be various layers such as to be constituted, constitute along layer, contrary layer, unit by what put down in writing in the aforementioned RD308119VII-K item.
Silver-halide color photo photosensitive material of the present invention can carry out development treatment by the common method of record in the XIX item of aforementioned RD17643,28～29 pages of RD18716,647 pages and RD308119.
[embodiment]
Below enumerate embodiment and be elaborated, but the invention is not restricted to these embodiment.
Embodiment 1
[preparation of sample 101]
On the tri acetyl cellulose film support of the thickness 120 μ m that are provided with prime coat, form layer from supporting the side to form each shown in following table 1～table 4 successively, the sample 101 of preparation multi layer colour photosensitive material.In addition, be every square metre of represented gram number if the addition of each raw material of putting down in writing in the table does not have special record.In addition, silver halide and collargol be scaled silver scale show that enhanced sensitivity pigment (representing with SD) is represented with the suitable molal quantity of 1 moles of silver.[table 1]
[table 2]
[table 3]
[table 4]
| Layer title | The adjuvant name | Addition |
| [the 1st layer] antihalation layer | Black collargol UV-1 CM-1 OIL-1 OIL-3 gelatin | ?????0.14 ?????0.30 ?????0.080 ?????0.160 ?????0.500 ?????1.50 |
| [the 2nd layer] middle layer | CC-1 OIL-3 gelatin | ?????0.035 ?????0.115 ?????0.70 |
| The red photographic layer of [the 3rd layer] low speed | Iodine silver bromide emulsion a iodine silver bromide emulsion c SD-1 SD-2 SD-3 C-1 CC-1 D-1 AS-2 OIL-2 gelatin | ?????0.23 ?????0.06 ?????0.68×10 -5?????1.15×10 -5?????5.40×10 -5?????0.30 ?????0.054 ?????0.02 ?????0.001 ?????0.300 ?????0.96 |
| The red photographic layer of light sensitivity in [the 4th layer] | Iodine silver bromide emulsion b SD-1 SD-2 SD-4 C-1 CC-1 D-1 D-3 AS-2 OIL-2 gelatin | ?????0.28 ?????1.65×10 -4?????2.90×10 -5?????0.92×10 -5?????0.23 ?????0.038 ?????0.01 ?????0.001 ?????0.001 ?????0.270 ?????0.96 |
| Layer title | The adjuvant name | Addition |
| The red photographic layer of [the 5th layer] ISO | Iodine silver bromide emulsion a iodine silver bromide emulsion b iodine silver bromide emulsion c SD-1 SD-2 SD-3 C-1 C-2 CC-1 D-3 AS-2 OIL-2 gelatin | ????0.03 ????0.14 ????0.38 ????9.40×10 -5????8.80×10 -6????5.35×10 -5????0.12 ????0.03 ????0.03 ????0.004 ????0.002 ????0.190 ????0.84 |
| [the 6th layer] middle layer | AS-1 OIL-1 gelatin | ????0.20 ????0.25 ????0.91 |
| The green photographic layer of [the 7th layer] low speed | Iodine silver bromide emulsion a iodine silver bromide emulsion d SD-4 SD-5 SD-6 M-1 CM-1 D-2 D-3 AS-2 X-2 AS-3 OIL-1 gelatin | ????0.17 ????0.07 ????1.01×10 -4????1.07×10 -5????1.15×10 -5????0.35 ????0.12 ????0.017 ????0.001 ????0.001 ????0.098 ????0.045 ????0.490 ????1.440 |
| Layer title | The adjuvant name | Addition |
| The green photographic layer of light sensitivity in [the 8th layer] | Iodine silver bromide emulsion d SD-4 SD-5 SD-6 M-1 CM-1 D-2 D-3 AS-2 X-2 AS-3 OIL-1 gelatin | ????0.35 ????2.65×10 -4????3.20×10 -5????4.10×10 -5????0.10 ????0.05 ????0.001 ????0.005 ????0.001 ????0.015 ????0.007 ????0.150 ????1.08 |
| The green photographic layer of [the 9th layer] ISO | Iodine silver bromide emulsion a iodine silver bromide emulsion e SD-4 SD-5 SD-6 M-1 CM-1 AS-2 X-2 AS-3 OIL-1 gelatin | ????0.02 ????0.36 ????6.82×10 -4????3.25×10 -5????5.56×10 -6????0.056 ????0.023 ????0.002 ????0.012 ????0.006 ????0.090 ????1.20 |
| [the 10th layer] yellow colour filter | Yellow colloidal silver AS-1 OIL-1 gelatin | ????0.06 ????0.07 ????0.06 ????1.08 |
| Layer title | The adjuvant name | Addition |
| [11th layer] low speed cyan photographic layer | Iodine silver bromide emulsion a iodine silver bromide emulsion f iodine silver bromide emulsion g SD-7 SD-8 Y-1 AS-2 OIL-1 gelatin | ????0.14 ????0.11 ????0.06 ????2.21×10 -4????5.45×10 -5????1.00 ????0.002 ????0.400 ????2.04 |
| [the 12nd layer] ISO cyan photographic layer | Iodine silver bromide emulsion e iodine silver bromide emulsion h SD-7 SD-8 Y-1 AS-2 D-4 OIL-1 gelatin | ????0.23 ????0.23 ????7.92×10 -5????1.65×10 -5????0.100 ????0.002 ????0.025 ????0.040 ????0.76 |
| [the 13rd layer] the 1st protective seam | Iodine silver bromide emulsion i UV-1 UV-2 X-1 gelatin | ????0.22 ????0.10 ????0.06 ????0.04 ????0.70 |
| [the 14th layer] the 2nd protective seam | PM-1 PM-2 WAX-1 gelatin | ????0.10 ????0.018 ????0.02 ????0.55 |
In addition, removing the combinations thereof beyond the region of objective existence, can also add coating assistant SU-1, SU-2, SU-3, disperse additive SU-4, viscosity modifier V-1, stabilizing agent ST-1, weight-average molecular weight: 10,000 and weight-average molecular weight: 100, two kinds of polyvinylpyrrolidones of 000 (AF-1, AF-2), lime chloride, inhibitor AF-3, AF-4, AF-5, AF-6, AF-7, solid film H-1, H-2 and antiseptic Ase-1.
The feature of each iodine silver bromide emulsion that is used to prepare above-mentioned sample 101 is as shown in table 5.For iodine silver bromide emulsion c, d, e, f, g, h, mean grain size is represented with the diameter (mean value) of the round a great deal of that projected area equates, for iodine silver bromide a, b, mean grain size is represented with a cubical length of side (mean value), in addition, for iodine silver bromide i, mean grain size uses the bulb diameter (mean value) of being calculated by planimeter to represent.
[table 5]
| Silver emulsion | Mean grain size (μ m) | Average iodine degree content (mole %) | Average depth-width ratio |
| Iodine silver bromide emulsion a | ????0.27 | ????2.0 | ????- |
| Iodine silver bromide emulsion b | ????0.81 | ????2.6 | ????3.7 |
| Iodine silver bromide emulsion c | ????1.38 | ????7.6 | ????6.5 |
| Iodine silver bromide emulsion d | ????0.75 | ????2.7 | ????3.7 |
| Iodine silver bromide emulsion e | ????1.45 | ????2.6 | ????7.0 |
| Iodine silver bromide emulsion f | ????0.38 | ????8.0 | ????- |
| Iodine silver bromide emulsion g | ????0.81 | ????8.0 | ????1.5 |
| Iodine silver bromide emulsion h | ????1.09 | ????8.0 | ????2.0 |
| Iodine silver bromide emulsion i | ????0.043 | ????1.9 | ????- |
Each emulsion in the table 5 beyond the iodine silver bromide emulsion i of record behind each sensitizing coloring matter of record, adds sodium thiosulfate, chlorination auric acid, potassium rhodanide etc. and carries out chemical sensitization in adding table 1～4, makes the relation of photographic fog-light sensitivity optimum.
(preparation of sample 102)
In the preparation of above-mentioned sample 101, except that the gelatin amount with each red photographic layer, each green photographic layer, each blue photographic layer reduces 20% other identical preparation samples 102 with 101 without exception.
(preparation of sample 103)
In the preparation of above-mentioned sample 102, except that the gelatin amount with each red photographic layer, each green photographic layer, each blue photographic layer reduces 10% other identical preparation samples 103 with 102 without exception.
(preparation of sample 104)
In the preparation of above-mentioned sample 102, except that the gelatin amount with each red photographic layer, each green photographic layer, each blue photographic layer reduces 20% other identical preparation samples 104 with 102 without exception.
(preparation of sample 105)
On the tri acetyl cellulose film support of implementing prime coat thickness 120 μ m, form layer from supporting the side to form each shown in following table 6～table 9 successively, the sample 105 of preparation multi layer colour photosensitive material.In addition, the addition of each raw material of putting down in writing in the table is not represented with per 1 square metre of suitable gram number as there being special record.In addition, silver halide and collargol be scaled silver scale show that enhanced sensitivity pigment (representing with SD) is represented with the suitable molal quantity of 1 moles of silver.[table 6]
[table 7]
[table 8]
[table 9]
| Layer title | The adjuvant name | Addition |
| [the 1st layer] antihalation layer | Black collargol UV-1 CM-1 OIL-1 gelatin | ????0.13 ????0.30 ????0.11 ????0.23 ????1.20 |
| [the 2nd layer] middle layer | The OIL-3 gelatin | ????0.267 ????0.89 |
| The red photographic layer of [the 3rd layer] low speed | Iodine silver bromide emulsion a iodine silver bromide emulsion k SD-1 SD-2 SD-3 C-1 CC-1 D-1 AS-2 OIL-4 gelatin | ????0.31 ????0.22 ????1.28×10 -4????1.78×10 -5????8.40×10 -5????0.324 ????0.056 ????0.014 ????0.002 ????0.320 ????1.06 |
| The red photographic layer of light sensitivity in [the 4th layer] | Iodine silver bromide emulsion j iodine silver bromide emulsion l SD-1 SD-2 SD-4 C-1 CC-1 D-1 D-3 AS-2 OIL-4 gelatin | ????0.08 ????0.40 ????2.56×10 -4????3.50×10 -5????1.72×10 -4????0.219 ????0.044 ????0.024 ????0.002 ????0.002 ????0.001 ????0.84 |
| Layer title | The adjuvant name | Addition |
| The red photographic layer of [the 5th layer] ISO | Iodine silver bromide emulsion l iodine silver bromide emulsion o SD-1 SD-2 SD-3 C-1 C-3 CC-1 D-3 AS-2 OIL-4 gelatin | ????0.10 ????0.38 ????7.11×10 -5????9.78×10 -6????4.72×10 -5????0.046 ????0.041 ????0.019 ????0.003 ????0.001 ????0.088 ????0.84 |
| [the 6th layer] middle layer | AS-1 OIL-1 gelatin | ????0.20 ????0.25 ????0.91 |
| The green photographic layer of [the 7th layer] low speed | Iodine silver bromide emulsion j iodine silver bromide emulsion k SD-4 SD-5 SD-6 M-1 CM-1 D-2 D-3 AS-2 X-2 AS-3 0IL-1 gelatin | ????0.23 ????0.10 ????1.17×10 -4????1.28×10 -5????1.61×10 -5????0.275 ????0.085 ????0.003 ????0.001 ????0.001 ????0.069 ????0.033 ????0.410 ????1.14 |
| Layer title | The adjuvant name | Addition |
| The green photographic layer of light sensitivity in [the 8th layer] | Iodine silver bromide emulsion k iodine silver bromide emulsion l SD-4 SD-5 SD-6 M-1 CM-1 D-2 D-3 AS-2 X-2 AS-3 OIL-1 gelatin | ????0.09 ????0.33 ????3.83×10 -4????4.00×10 -5????5.00×10 -5????0.101 ????0.039 ????0.001 ????0.012 ????0.001 ????0.014 ????0.007 ????0.280 ????1.06 |
| The green photographic layer of [the 9th layer] ISO | Iodine silver bromide emulsion j iodine silver bromide emulsion n SD-4 SD-5 SD-6 M-1 CM-1 AS-2 X-2 AS-3 OIL-1 gelatin | ????0.02 ????0.48 ????1.01×10 -4????3.78×10 -5????6.33×10 -6????0.058 ????0.029 ????0.001 ????0.015 ????0.007 ????0.141 ????1.11 |
| [the 10th layer] yellow colour filter | Yellow colloidal silver AS-1 OIL-1 gelatin | ????0.06 ????0.07 ????0.09 ????0.90 |
| Layer title | The adjuvant name | Addition |
| [11th layer] low speed cyan photographic layer | Iodine silver bromide emulsion j iodine silver bromide emulsion l iodine silver bromide emulsion m SD-7 SD-8 Y-2 AS-2 OIL-1 gelatin | ????0.11 ????0.17 ????0.17 ????2.78×10 -4????7.17×10 -5????0.925 ????0.003 ????0.371 ????1.91 |
| [the 12nd layer] ISO cyan photographic layer | Iodine silver bromide emulsion m iodine silver bromide emulsion p SD-7 SD-8 Y-2 AS-2 D-4 OIL-1 gelatin | ????0.03 ????0.25 ????2.78×10 -5????1.83×10 -5????0.078 ????0.001 ????0.038 ????0.047 ????0.61 |
| [the 13rd layer] the 1st protective seam | Iodine silver bromide emulsion i UV-1 UV-2 X-1 AF-6 gelatin | ????0.22 ????0.10 ????0.06 ????0.04 ????0.003 ????0.70 |
| [the 14th layer] the 2nd protective seam | PM-1 PM-2 WAX-1 gelatin | ????0.10 ????0.018 ????0.02 ????0.55 |
In addition, remove the combinations thereof beyond the region of objective existence, can also suitably add coating assistant SU-1, SU-2, SU-3, disperse additive SU-4, viscosity modifier V-1, stabilizing agent ST-1, weight-average molecular weight: 10,000 and weight-average molecular weight: 100, two kinds of polyvinylpyrrolidones of 000 (AF-1, AF-2), lime chloride, Gu inhibitor AF-3, AF-4, AF-5, AF-6, AF-7 are film H-1, H-2 and antiseptic Ase-1.
The feature of each iodine silver bromide emulsion in addition of used table 5 record is as shown in table 10 in the preparation of above-mentioned sample 105.For iodine silver bromide emulsion k, l, m, n, o, p, mean grain size is represented with the suitable diameter (mean value) of circle that projected area equates, for iodine silver bromide j, mean grain size is represented with a cubical length of side (mean value), in addition, for iodine silver bromide emulsion k, l, m, n, o, p, the result that mean grain size is observed the dislocation line in the silver halide particle with preceding method, the particle of total projection area more than 50% of confirming each emulsion is the tabular silver halide particle with 30 above dislocation lines.
[table 10]
| Silver emulsion | Mean grain size (μ m) | Average iodine degree content (mole %) | Average depth-width ratio |
| Iodine silver bromide emulsion j | ????0.28 | ????2.0 | ????- |
| Iodine silver bromide emulsion k | ????0.61 | ????3.1 | ????5.43 |
| Iodine silver bromide emulsion l | ????0.89 | ????3.7 | ????6.10 |
| Iodine silver bromide emulsion m | ????0.95 | ????8.0 | ????3.07 |
| Iodine silver bromide emulsion n | ????1.43 | ????3.9 | ????6.76 |
| Iodine silver bromide emulsion o | ????1.50 | ????3.1 | ????6.60 |
| Iodine silver bromide emulsion p | ????1.23 | ????7.9 | ????2.85 |
Each emulsion of table 10 record behind each enhanced sensitivity pigment of record, adds triphenylphosphine selenide, sodium thiosulfate, chlorination auric acid, potassium rhodanide etc. and carries out chemical sensitization in adding table 6～9, makes the relation of photographic fog-light sensitivity optimum.
(preparation of sample 106)
In the preparation of above-mentioned sample 105, the addition that removes M-1 in the 8th layer becomes 0.048g, and the addition of CM-1 becomes outside the 0.079g, other identical preparation samples 106 with 105.
(preparation of sample 107)
In the preparation of above-mentioned sample 105, except that the gelatin amount with each red photographic layer, each green photographic layer, each blue photographic layer reduces 10% without exception, remaining and preparation 105 identical preparation samples 107.
(preparation of sample 109)
In the preparation of above-mentioned sample 108, the addition that removes the OIL-4 in each red photographic layer reduces outside 37%, the 7 layer of same minimizing 25% of the addition with 8 layers OIL-1 other identical preparation samples 109 with 108 without exception.
(preparation of sample 110)
In the preparation of above-mentioned sample 109, except that the gelatin amount with each red photographic layer, each green photographic layer, each blue photographic layer reduces 10% other identical preparation samples 110 with 109 without exception.
(preparation of sample 111)
In the preparation of above-mentioned sample 110, except that the gelatin amount with each red photographic layer, each green photographic layer, each blue photographic layer reduces 10% other identical preparation samples 111 with 110 without exception.
The detailed content of each used compound as shown below in the preparation of above sample 101～sample 111.
OIL-4????????????????????????????OIL-3
Whiteruss
H
9C
4OOC (CH
2)
8COOC
4H
9 
Ase-1 (following 3 kinds of mixture of ingredients)
(composition A) (composition B) (composition C)
Composition A: composition B: composition C=50: 46: 4 (mol ratio) H-1
CH
2＝CHSO
2-CH
2CONHC
2H
4NHCOCH
2-SO
2CH＝CH
2 
Total silver coating amount AG (g/m of Zhi Bei sample 101～111 like this
2) with the measurement result of thickness Hd (μ m) except that support as described later shown in the table 11.
" exposure and colour development are handled "
About the sample 101～111 of above preparation, carried out the wedge type exposure with the light source of colour temperature 5400K with 1/200 second after, handle in the reference color development treatment (handling A) of following expression and colour development rapidly under 2 conditions of (treatments B) and handle.
(treatment conditions) treatment process processing time treatment temperature magnitude of recruitment * color development develop 1 minute 30 seconds 38 ± 2.0 ℃ of 830ml of 38 ± 0.3 ℃ of 780ml bleachings in 3 minutes 15 seconds, 38 ± 2.0 ℃ of 150ml photographic fixing in 45 seconds stablize 55 ± 5.0 ℃ of dry 1 minute of 60 seconds 38 ± 5.0 ℃ of 830ml-
* magnitude of recruitment is every 1m
2The value of photosensitive material.
(composition of each treating fluid)
Color development developer solution, bleaching liquid, stop bath, stabilizing solution and other additional liquid use following material.
＜color development developer solution〉water 800ml potash 30g sodium acid carbonate 2.5g sodium sulfite 3.0g sodium bromide 1.3g KI 1.2mg hydroxylamine sulfate 2.5g sodium chloride 0.6g4-amino-3-methyl-N-ethyl-N (beta-hydroxyethyl) aniline sulfate 4.5g diethylene-triamine pentaacetic acid 3.0g NaOH 1.2g
Add water move to 1L, adjust pH to 10.06 with the sulfuric acid of potassium hydroxide or 20%.
＜color development developer replenisher solution〉water 800ml potash 35g sodium acid carbonate 3g sodium sulfite 5g sodium bromide 0.4g hydroxylamine sulfate 3.1g4-amino-3-methyl-N-ethyl-N (beta-hydroxyethyl) aniline sulfate 6.3g potassium hydroxide 2g diethylene-triamine pentaacetic acid 3.0g
Add water move to 1L, adjust pH to 10.18 with the sulfuric acid of potassium hydroxide or 20%.
＜bleaching liquid〉water 700ml1,3-diaminopropanetetraacetic acid iron (III) ammonium salt 125g ethylenediamine tetraacetic acid 2g sodium nitrate 40g ammonium bromide 150g glacial acetic acid 40g
Add water move to 1L, adjust pH to 4.4 with ammoniacal liquor or glacial acetic acid.
＜bleaching replenishes liquid〉water 700ml1,3-diaminopropanetetraacetic acid iron (III) ammonium salt 175g ethylenediamine tetraacetic acid 2g sodium nitrate 50g ammonium bromide 200g glacial acetic acid 56g
Behind ammoniacal liquor or glacial acetic acid adjustment pH to 4.4, add water move to 1L.
＜stop bath〉water 800ml ammonium thiocyanate 120g ATS (Ammonium thiosulphate) 150g sodium sulphite 15g ethylenediamine tetraacetic acid 2g
Behind ammoniacal liquor or glacial acetic acid adjustment pH to 6.2, add water move to 1L.
＜photographic fixing replenishes liquid〉water 800ml ammonium thiocyanate 150g ATS (Ammonium thiosulphate) 180g sodium sulphite 20g ethylenediamine tetraacetic acid 2g
Behind ammoniacal liquor or glacial acetic acid adjustment PH to 6.5, add water move to 1L.
＜stabilizing solution and the stable liquid that replenishes〉water 900ml is to octyl phenyl polyoxyethylene ether (n=10) 2.0g dimethylolurea 0.5g hexamethylene tetramine 0.2g1,2-benzisothiazole-3-ketone 0.1g siloxane (UUC makes L-77) 0.1g ammoniacal liquor 0.5ml
After adding water move to 1L, adjust pH to 8.5 with the sulfuric acid of ammoniacal liquor or 50%.
[treatments B: colour development is handled rapidly]
(treatment conditions) treatment process processing time treatment temperature color development development 42 ℃ of bleachings in 100 seconds 38 ℃ of photographic fixing-1 24 in 24 seconds second 38 ℃ of photographic fixing-2 24 second 38 ℃ of stable-1 16 second 38 ℃ of stable-2 16 seconds 38 ℃ of stable-3 15 seconds 38 ℃ of (composition of each treatment fluid)＜color development developer solutions〉sodium sulfite 6.0g potash 35.0gN, N-two (sulfoethyl) azanol disodium 8.0g DTPA .0g KBr 1.1 * 10-2Mol/L polyvinylpyrrolidone (molecular weight 40,000) 3.0g/L potassium iodide 1.2 * 10
-5Mol/L4-amino-3-methyl-N-ethyl-N-(beta-hydroxyethyl) aniline sulfate 0.035mol/L
Add water move to 1L, adjust pH to 10.3 with the sulfuric acid of potassium hydroxide or 50%.
＜bleaching treating fluid〉1,3-trimethylen-edinitrilo-tetraacetic acid iron (III) ammonium salt 160g1,3-trimethylen-edinitrilo-tetraacetic acid 7g ammonium bromide 60g maleic acid 90g
Add water move to 1L, adjust pH to 3.0 with the sulfuric acid of ammoniacal liquor or 50%.
＜photographic fixing treating fluid〉ATS (Ammonium thiosulphate) 180g sodium thiosulfate 20g sodium sulphite 10g sodium carbonate 2g ethylene dinitrilotetra-acetic acid 2g
Add water move to 1L, adjust pH to 6.5 with ammoniacal liquor or 50% sulfuric acid.
＜stabilized treatment liquid〉between-hydroxy benzaldehyde 1.5g ethylenediamine tetraacetic acid 0.2g sal tartari 0.2g beta-schardinger dextrin-0.2g NaOH 0.03g
Add water move to 1L.
" each evaluating characteristics "
(characteristic making)
To carrying out each sample of above-mentioned exposure and each development treatment, carry out concentration determination with X-rite corporate system densimeter, make and represent the family curve that exposure, longitudinal axis indicated concentration constitute by transverse axis.
(mensuration of granularity G and granularity R)
Handle with standard in the family curve of the sample that A handles, as the image of magenta color development, the RMS granularity G to the magenta color image of giving Cmin+0.35 exposure point measures according to preceding method.In addition, the RMS granularity ground with the cyan image in the exposure point is calculated with identical method, the result of gained is as shown in table 11.
(worsen the evaluation of amplitude according to the different dark light degree rectilinearity of treatment conditions: the mensuration of relative standard deviation ratio)
According to the family curve of handling the sample after A handles with standard, from the exposure point (E of the red-color concentration of giving Cmin+0.3
0) with the interval of Δ logE=0.30 exposure (E to 6
1, E
2, E
3... .E
6) carry out each red-color concentration mensuration, calculate each characteristic slope γ (tan θ) of each exposure station.
Specifically, exposure point E
0With E
1Between characteristic slope γ (E
0/ E
1) calculate by following formula.
γ (E
0/ E
1)=(E
0R concentration-E
0Red-color concentration)/Δ logE (=0.30)
Below, calculate the slope γ in remaining 5 zones according to same method.
Then, to using the sample after treatments B (handling rapidly) is handled, use the same method the slope γ that calculates between the following exposure point.
Respectively handle every characteristic slope (γ) 6 points for what measure, calculate each relative standard deviation, calculate the relative standard deviation ratio by following formula by above method.
The relative standard deviation ratio=standard deviation of the slope γ of processing (treatments B)/standard is handled the standard deviation of the slope γ of (handling A) rapidly
To liken the index of the dark light degree change that causes for the treatment conditions difference by the relative standard deviation of aforementioned calculation to.In addition, relative standard deviation is than being that value with sample 101 is 100 relative value.Be worth more for a short time, the dark light degree change that causes because of treatment conditions are different is just little, the expression preferred value.
(comprehensive evaluation of storage stability)
To prepare above-mentioned manufactured samples 101～111 each two groups, a part carry out freezing preservation with it as standard model.Another part was preserved 10 under the atmosphere of 40 ℃ of temperature, humidity 70%, and it is handled sample as worsening.Both with the light source of 5400K with after 1/200 second exposure-processed, standard model aforementioned processing A (standard processing), force to worsen sample and carry out the colour development processing with treatments B (handling rapidly), sample that each of gained developed is measured the concentration of green photographic layer, acquired character curve with X-rite corporate system densimeter then.From this family curve, calculate Cmin (photographic fog),, force to worsen the difference of handling the Cmin that obtains with the combination of treatments B and represent with 100 relative value with respect to the standard model of sample 101 and the Cmin of the combination gained of handling A.It is good more to be worth more little expression storage stability.
In addition, sample about each combination, calculate each RMS granularity G and RMS granularity R by preceding method, calculate standard model respectively and worsen the combination of handling with treatments B (G+R)/2 with (G+R)/2 of the combination of handling A with pressure, each of sample 101 makes up difference and represents with 100 relative value.The more for a short time graininess that changed by condition of value changes just more little.
Result by above gained is as shown in table 11.[table 11]
| The sample sequence number | Total silver coating amount AG (g/m 2) | Thickness Hd (μ m) | Granularity | ??※1 | ??※2 | ??※3 | ??※4 | ????※5 | Storage stability | Remarks | ||
| ??G | ??R | ????Dmin | Graininess | |||||||||
| ????101 | ????3.28 | ????19.2 | ??16.1 | ??13.5 | ??14.8 | ??49 | ??284 | ??932 | ????100 | ????100 | ????100 | Comparative example |
| ????102 | ????3.28 | ????17.7 | ??16.4 | ??13.9 | ??15.2 | ??50 | ??269 | ??882 | ????98 | ????98 | ????108 | Comparative example |
| ????103 | ????2.99 | ????17.7 | ??18.1 | ??15.5 | ??16.8 | ??50 | ??297 | ??889 | ????96 | ????95 | ????103 | Comparative example |
| ????104 | ????3.85 | ????17.9 | ??14.4 | ??12.0 | ??13.2 | ??51 | ??236 | ??910 | ????107 | ????125 | ????134 | Comparative example |
| ????105 | ????3.89 | ????17.6 | ??13.7 | ??9.9 | ??11.8 | ??46 | ??208 | ??808 | ????88 | ????90 | ????94 | The present invention |
| ????106 | ????3.89 | ????17.5 | ??12.5 | ??9.9 | ??11.2 | ??44 | ??196 | ??762 | ????86 | ????85 | ????88 | The present invention |
| ????107 | ????3.54 | ????17.5 | ??15.1 | ??11.1 | ??13.1 | ??46 | ??229 | ??812 | ????95 | ????94 | ????105 | Comparative example |
| ????109 | ????3.54 | ????17.0 | ??13.4 | ??10.6 | ??12.0 | ??42 | ??204 | ??722 | ????85 | ????82 | ????86 | The present invention |
| ????110 | ????3.54 | ????16.2 | ??13.5 | ??10.7 | ??12.1 | ??43 | ??196 | ??694 | ????81 | ????75 | ????80 | The present invention |
| ????111 | ????3.23 | ????16.1 | ??14.1 | ??11.5 | ??12.8 | ??41 | ??206 | ??666 | ????79 | ????72 | ????76 | The present invention |
※1：(G+R)/2?????????????????????????※2：AG×(G+R)/2
※3：Hd×(G+R)/2?????????????????????※4：AG×Hd×(G+R)/2
※ 5: handle adaptability r relative standard deviation ratio rapidly
According to table 11 as can be known, satisfy the sample of condition of Hd of the present invention * (G+R)/2≤210, graininess is good, it is good to handle adaptability rapidly, storage stability is good, dark light degree stability (γ relative standard deviation value) in rapid processing the and pressure deterioration are handled sample and are worsened by the graininess that rapid treatment combination causes especially, are significantly improved with respect to sample 107,105.
In addition, in the sample that further satisfies the condition of AG of the present invention * (G+R)/2≤45, also can confirm and above-mentioned the same good result.
Further also draw, satisfy the sample of condition of AG * Hd of the present invention * (G+R)/2≤700, graininess is good, and it is good to handle adaptability rapidly, and storage stability significantly improves.
Clearly demarcated according to this, can provide rapid processing adaptability good, the mis-behave in the improvement long preservation, and the good silver-halide color photo photosensitive material of graininess.
Claims (10)
1. silver-halide color photo photosensitive material, it is characterized in that, its support side with the side from the transparent support respectively is the red photographic layer that contains 1 layer of cyan coupler at least, at least the green photographic layer that contains 1 layer of magenta colour coupler, and the blue photographic layer that contains 1 layer of yellow colour former at least, wherein, to be made as G in the RMS granularity of the magenta chromophore image in the exposure point (E) of Cmin+0.35 of the magenta chromophore image after giving the color development development treatment, the RMS granularity of the cyan chromophore image in this exposure station (E) is made as R, when the thickness except that support is made as Hd (μ m), this G, the relation of this R and this Hd is represented as shown in the formula (2).
Formula (2)
Hd×(G+R)/2≤210
2. silver-halide color photo photosensitive material according to claim 1, it is characterized in that, its support side with the side from the transparent support respectively is the red photographic layer that contains 1 layer of cyan coupler at least, at least the green photographic layer that contains 1 layer of magenta colour coupler, at least the blue photographic layer that contains 1 layer of yellow colour former, wherein, to be made as G in the RMS granularity of the magenta chromophore image in the exposure point (E) of Cmin+0.35 of the magenta chromophore image after giving the color development development treatment, the RMS granularity of cyan chromophore image in this exposure station (E) is made as R, and total silver coating amount is made as AG (g/m
2) time, this G, the relation of this R and this AG is represented as shown in the formula (1).
Formula (1)
AG×(G+R)/2≤45
3. silver-halide color photo photosensitive material according to claim 1, it is characterized in that, its support side with the side from the transparent support respectively is the red photographic layer that contains 1 layer of cyan coupler at least, at least the green photographic layer that contains 1 layer of magenta colour coupler, at least the blue photographic layer that contains 1 layer of yellow colour former, wherein, to be made as G in the RMS granularity of the magenta chromophore image in the exposure point (E) of Cmin+0.35 of the magenta chromophore image after giving the color development development treatment, the RMS granularity of cyan chromophore image in this exposure station (E) is made as R, and total silver coating amount is made as AG (g/m
2), when removing the outer thickness of support and being made as Hd, the relation of this G, this R, this AG and this Hd is represented as shown in the formula (3).
Formula (3)
AG×Hd×(G+R)/2≤700
4. according to claim 2 or 3 described silver-halide color photo photosensitive materials, it is characterized in that aforementioned total silver coating amount AG is 2.0～6.0g/m
2
5. according to claim 1 or 3 described silver-halide color photo photosensitive materials, it is characterized in that aforementioned thickness Hd is 10～20 μ m.
6. according to the described arbitrary silver-halide color photo photosensitive material of claim 1～5, it is characterized in that, the length breadth ratio that contains more than 50% of its total projection area of one deck at least of each photographic layer is more than 2, and each particle has the tabular silver halide particle of 30 above dislocation lines.
7. according to the described arbitrary silver-halide color photo photosensitive material of claim 1～6, it is characterized in that, aforementioned green photographic layer is made up of ISO layer, middle light sensitivity layer and low speed layer at least, and coloured magenta colour coupler of light sensitivity layer is more than 1.1 times with respect to the ratio of colourless magenta colour coupler in this.
8. according to the described arbitrary silver-halide color photo photosensitive material of claim 1～7, it is characterized in that the total amount of the yellow colour former in the aforementioned blue photographic layer is 0.8～1.7mmol/m
2
9. according to the described arbitrary silver-halide color photo photosensitive material of claim 1～8, it is characterized in that the total amount of the magenta colour coupler in the aforementioned green photographic layer is 0.3～0.9mmol/m
2
10. according to the described arbitrary silver-halide color photo photosensitive material of claim 1～9, it is characterized in that the total amount of the cyan coupler in the aforementioned red photographic layer is 0.7～1.6mmol/m
2
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP386009/2001 | 2001-12-19 | ||
| JP2001386009A JP2003186157A (en) | 2001-12-19 | 2001-12-19 | Silver halide color photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1427301A true CN1427301A (en) | 2003-07-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02155876 Pending CN1427301A (en) | 2001-12-19 | 2002-12-13 | Siver halide colour photograph sensitive material |
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| Country | Link |
|---|---|
| JP (1) | JP2003186157A (en) |
| CN (1) | CN1427301A (en) |
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2001
- 2001-12-19 JP JP2001386009A patent/JP2003186157A/en active Pending
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2002
- 2002-12-13 CN CN 02155876 patent/CN1427301A/en active Pending
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