CN101178536A - Silver halides colourful photographic paper - Google Patents
Silver halides colourful photographic paper Download PDFInfo
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- CN101178536A CN101178536A CNA2007101853571A CN200710185357A CN101178536A CN 101178536 A CN101178536 A CN 101178536A CN A2007101853571 A CNA2007101853571 A CN A2007101853571A CN 200710185357 A CN200710185357 A CN 200710185357A CN 101178536 A CN101178536 A CN 101178536A
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Abstract
The relates to a silver halide color photo paper, comprising a supporting element, an imaging layer, at least one yellow silver halide blue sensing layer, at least one product color silver halide green sensing layer, at least one cyan silver halide red sensing layer and at least one no color hydrophilic colloid layer. Besides, the three color sensing layers all comprise a polymer which has a common formula A; wherein, the contents of the blue sensing layer and the green sensing layer are respectively 0.03 to 0.07g/m<2>, while the content of the red sensing layer is 0.06 to 0.12g/m<2>. In the common formula A, R1 is C1 to C4 alkyl; and R2 is H or C1 to C4 alkyl. The invention is characterized in that the generation of the cyan hidden coloring matter is decreased in the pH value bleach-fix processing liquid, thereby having good developing stability; and the blue sensing emulsion has strong imaging capability and low photographic fog, thereby having excellent imaging and processing properties.
Description
Technical field
The present invention relates to a kind of photographic material, particularly a kind of silver halides colourful photographic paper.
Background technology
The development of color sensitive material always is along desirable colour reproduction trulyr, more bright-coloured, processes the direction more convenient, quick, that environmental pollution is littler, more energy-conservation simultaneously and develops.We have known that in silver halide colour photographic sensitive material the product of the silver halide oxidation arylamine color developer of exposure and colour coupler reaction generate dyestuff, thereby form chromatic image.In this photographic system, generally use subtractive color process to reproduce the chromatic image that forms by Huang, product and blue or green dyestuff.In the photographic manufacture field,, advocate and to get express developed and reduce additional dose according to the needs in market.In order to realize getting express developed processing, it should be highly active requiring silver emulsion and used colour coupler on the one hand, and factors such as the component of washing processing soup, processing temperature, pH value also are indispensable key factors on the other hand.
In silver-halide color printing paper manufacture process, in order to form the image of cyan dye, use phenol type colour coupler usually, mainly comprise two types as B formula and C formula
Among the formula B, R is for containing C
10～C
20Groups; Among the formula C, R1, R2 are the aralkyl group.
The coupling of formula B colour coupler is active high, and it forms dyestuff and has good color tone and bright, dark fadedness, but the reducing dyes current potential is higher, floats at low PH and decides in the working fluid, easily forms more leuco dye, causes blue or green dye density low, can not satisfy the rapid processing requirement; Formula C chromophoric dyestuffs has the characteristics of reduction potential, is difficult for forming leuco dye, but its anti-bright fadedness and tone are unsatisfactory, and manufacturing cost is higher.For suppressing the formation of cyan colour coupler leuco dye in the processing bleach-fixing liquid, someone is by optimizing the molecular structure of cyan colour coupler, employing has the colour coupler of the blue or green dyestuff of low reduction potential, and the blue or green dyestuff that forms as bisamide type phenol colour coupler has very low reduction potential, is difficult for forming latent blue or green; The somebody improves the washing processing soup, suppresses latent blue or green formation, such as add the compound that cupric chloride, vanadium pentoxide, potassium persulfate etc. have oxidisability in bleach-fixing liquid, improves the oxidizing potential of bleach-fixing liquid, thereby obtains high blue or green dye density; Also the somebody reduces the silver amount that is coated with of blue or green layer below (Huang layer, product layer), thereby yellow layer of minimizing and product layer help reducing blue or green leuco dye formation to the consumption of bleach-fixing liquid oxidability (ferric ion); Also the somebody adds the acrylate monomer polymkeric substance contain alkoxyalkyl and reduces leuco dye and generate, contain as adding therein-the ethylenically unsaturated monomers polymkeric substance of COOM (M is hydrogen or kation) improves leuco dye and generates.In the method that above-mentioned improvement leuco dye forms, also unsatisfactory for the effect of the formula of use B colour coupler.
For improving the rapid development characteristic of silver halide ticker tape, the general high silver chloride emulsion that has all adopted greater than 95%, and reduce the size of silver emulsion particle as far as possible, to obtain developing powder faster, but, after the silver halide particle size reduced, a greatest problem of existence was exactly that light sensitivity is on the low side.Particularly with the blue layer of the silver halide sense of the close yellowly of support, can be by changing particle shape, as make the T particle, improve the absorption and the efficiency of light absorption of dyestuff, thereby improve light sensitivity; Some precious metal ions that also can mix in emulsion reduce the compounding machine meeting in light induced electron and hole, thereby raising light sensitivity, as adding sensitizing dye respectively in the physical ripening, the chemical ripening stage that prepare emulsion, chemical sensitization and spectral sensitization intersection are carried out, and prepare the emulsion of the high sense of particulate thus; Other has at the inner complex compound of introducing the iron that contains the cyanogen part, ruthenium, osmium of silver halide particle, improves the high illumination reciprocity failure characteristic of ticker tape; In these technology, although disclose the method for improving high illumination reciprocity failure, at latent image stability, developing to add also exists unsolved problem aspect the photographic fog tolerance in man-hour.Especially the blue layer of silver halide sense need improve aspect adaptation rapid development processing.
Summary of the invention
The technical problem to be solved in the present invention is that a kind of silver halides colourful photographic paper that blue layer has good rapid development processing characteristics of feeling is provided.
For addressing the above problem, the technical solution used in the present invention is:
A kind of silver halides colourful photographic paper, this material comprises the imaging layer of support and autochromy silver halide, it comprises the blue layer of silver halide sense of one deck yellowly at least, at least the silver halide green layer of one deck finished product look, at least one deck becomes the silver halide sense red beds of cyan, at least one deck hydrophilic colloid layer of quality not also needs in addition:
(1) feel the polymkeric substance that chromatographs contain general formula A at three, wherein sense consumption blue, green layer is respectively 0.03～0.07 gram/m
2, sense red beds consumption is 0.06～0.12 gram/m
2,
Among the general formula A, R
1Be C
1～C
4Alkyl; R
2Be H or C
1～C
4Alkyl;
(2) content of silver chloride is 97mol% or more in the silver emulsion of the blue layer of sense, and the content of silver iodide is 0～0.3mol%, and has the noble metal complexes phase in silver in the position at 95%～100% place, distance chlorosulfonylation silver particle center.
Above-mentioned silver halides colourful photographic paper, described noble metal complexes are the noble metal complexes phase of cyano-containing ligand mutually.
Above-mentioned silver halides colourful photographic paper, the silver halide particle in the described sense chromatograph contains at least 97% silver chloride, and also contains two or more noble metal complexes phase.
Above-mentioned silver halides colourful photographic paper contains the iridium complex compound phase that has thiazole or substituted thiazole ligand in the silver halide particle in the described sense chromatograph, consumption is 1.0*10
-5～1.0*10
-9Mol/molAg.Above-mentioned silver halides colourful photographic paper, in the blue layer of the described sense silver halide particle, the content of silver iodide is 0.1～0.3%mol, and has the noble metal complexes phase in silver in the position at 95%～98% place, distance chlorosulfonylation silver particle center, its consumption is 1.0*10
-4～1.0*10
-8Mol/molAg.
Above-mentioned silver halides colourful photographic paper, contain formula B colour coupler or formula B and formula C colour coupler in the described sense red beds:
Among the formula B, R is for containing C
10～C
20Groups;
Among the formula C, R
1For having aralkyl group, the R of sulfuryl
2Be the aralkyl group.
Above-mentioned silver halides colourful photographic paper, the blue layer of described sense contains the colour coupler of formula D:
Among the formula D, R is the C20～C30 groups that contains hexatomic ring.
Above-mentioned silver halides colourful photographic paper, described green layer contain colour coupler E and anti-fading agent F:
Among the formula E, R
1Be hydrogen atom, methyl or butyl; R
2Be C
1～C
5Alkyl; R
3Be C
10～C
20Long chain alkyl group or include aryl or sulfur-bearing, nitrogen five yuan, the C of hexa-member heterocycle
10～C
20Long chain alkyl group;
Among the formula F, R
4For hydroxyl, phenoxy group or contain sulfonic group and the hexatomic ring of nitrogen-atoms; R
5Be hydrogen atom, C
10～C
20Alkyl, hydroxyl or aryl.
The present invention is a kind of silver halide colour photographic sensitive material, is meant the material that adopts Photoactive silver-halide to form image.Silver halides colourful photographic paper provided by the invention comprises the imaging layer of support and autochromy silver halide, it comprises the blue layer of silver halide sense of one deck yellowly at least, at least the silver halide green layer of one deck finished product look, at least one deck becomes the silver halide sense red beds of cyan, at least one deck hydrophilic colloid layer of quality not, wherein:
(1) added the polymkeric substance of following general formula A at three photographic layers:
Among the general formula A, R1 is C
1～C
4Alkyl, preferable methyl or normal-butyl, more preferably normal-butyl; R
2Be H or C
1～C
4Alkyl is preferably H or butyl, more preferably H; Among the general formula A, m: n: k=1: 1: 0.8.Be fit to of the present inventionly can be:
Polymkeric substance adds fashionable, and sense is blue, the consumption of green layer is respectively 0.03～0.07 gram/m
2, preferred 0.03～0.05 gram/m
2, sense red beds consumption is 0.06～0.12 gram/m
2, preferred 0.07～0.10 gram/m
2
(2) content of silver chloride is 97mol% or more in the silver emulsion of the blue layer of sense, and the content of silver iodide is 0～0.3mol%, and has the noble metal complexes phase in silver in the position at 95%～100% place, distance chlorosulfonylation silver particle center.
Among the present invention, contain Formula B colour coupler or Formula B and the combination of general formula C colour coupler in the sense red beds:
In the Formula B, R is the C that contains hexatomic ring
10～C
20Alkoxy grp; Among the general formula C, R
1, R2 is the aralkyl group.
The colour coupler that is fit to Formula B of the present invention can be:
The colour coupler that is fit to general formula C of the present invention can be:
Among the present invention, contain the colour coupler of general formula D in the blue layer of sense:
R among the formula D is the C that contains hexatomic ring
20～C
30Groups.
Being fit to general formula D colour coupler of the present invention can be:
Among the present invention, its green layer contains colour coupler E and anti-fading agent F:
Among the formula E, R
1Be hydrogen atom, methyl or butyl; R
2Be C
1～C
5Alkyl; R
3Be C
10～C
20Long chain alkyl group or include aryl or sulfur-bearing, nitrogen five yuan, the C of hexa-member heterocycle
10～C
20Long chain alkyl group;
Among the formula F, R
4For hydroxyl, phenoxy group or contain sulfonic group and the hexatomic ring of nitrogen-atoms; R
5Be hydrogen atom, C
10～C
20Alkyl, hydroxyl or aryl.
Being fit to general formula E colour coupler of the present invention can be:
Being fit to general formula F anti-fading agent of the present invention can be:
Among the present invention, the silver halide particle in its three photographic layers contains at least 97% silver chloride, and also contains two or more noble metal complexes.In the blue layer of the sense wherein silver halide particle, the content of silver iodide is 0～0.3%mol, preferred 0.10～0.3%mol, and more preferably 0.15mol% adds the implantation site and with silver is being the position of metering apart from particle center 90%, forms to contain the silver iodide phase; In applied noble metal complexes, a kind of for having the iridium complex compound of thiazole or substituted thiazole ligand, consumption 1.0*10
-5～1.0*10
-9Mol/molAg, preferred 5.0*10
-5～1.0*10
-8Mol/molAg, more preferably 5.0*10
-5～5.0*10
-7Mol/molAg; It adds the implantation site is silver halide particle top layer or inferior top layer, generally with silver is being the position of metering apart from particle center 70%～95%, forms to contain the iridium complex compound phase, preferred 85%～95% position, more preferably 90%～95% position; Its adding mode can regularly add in the silver halide particle forming process, also can fully mix the back in advance with halogen liquid and regularly add; Another kind is the noble metal complexes of cyano-containing part, only need to have a cyano group ligand in its part at least, preferably iron, ruthenium or osmium coordination, contain the complex compound that 4 above cyano group ligands get, more preferably K
4Ru (CN)
6Compound, it adds the implantation site and is generally silver halide particle inside or top layer; Generally with silver be the position of metering apart from particle center 70%～85%, among the present invention, in the blue layer of sense silver halide particle, in silver 95%～100% place in distance chlorosulfonylation silver particle, there is the noble metal complexes phase of cyano-containing part in preferred 96～98% position, and not containing this type of complex compound phase in zone than this more close particle surface in zone, its consumption is 1.0*10
-4～1.0*10
-8Mol/molAg, preferred 1.0*10
-5～1.0*10
-7Mol/molAg.
When obtaining silver emulsion of the present invention, can also make granule interior further contain the heavy metal ion adulterant, containing of can adding comprises mercury, iron, osmium, the isoionic salt of rhodium or complex compound, the salt or the complex compound of preferred mercury, rhodium, the complex compound that more preferably contains rhodium ion, use amount are 1.0*10
-5～1.0*10
-8Gmol/molAg.
Silver halide photographic emulsions of the present invention can prepare by precipitation silver halide crystal in the gelatin substrate.The preparation method of silver emulsion of the present invention comprises settling step, desalination step and chemistry and the spectral sensitization step that forms silver halide crystal by the reaction between water-soluble silver and the water-soluble halide.
The particle of silver halide of the present invention preferably has the cubic granules of the mean grain size of 0.3～1.0 μ m.Preferred monodisperse system emulsion.Single emulsion that disperses is meant that the coefficient of alteration (s/r) of silver halide particle particle diameter is 0.25 or lower emulsion.R is a mean grain size, and s is the standard deviation of particle diameter.Grain diameter is to represent with the mean value of the diameter of a circle of the projected area that equals particle, and used size distribution coefficient of alteration is the value that the size grade scale deviation is obtained divided by mean grain size.
Silver emulsion of the present invention is handled through chemical sensitization and spectral sensitization effect usually.Chemical sensitization comprises known sulphur sensitizing, golden sensitizing and reduction sensitization.Silver emulsion of the present invention preferably passes through sulphur gold sensitizing known in the art or colloidal state aurosulfo sensitizing.Sulphur gold sensitizing can use the compound as sodium thiosulfate, tetra chlorauric acid or its salt, thiocyanic acid gold to carry out.The amount of adding compound is 10
-3～10
-8Mol/molAg, preferred 10
-4～10
-6Mol/molAg; Spectral sensitization is selected the known optical sensibilization dyestuff in camera technique field for use, each photographic layer can be used alone, also can use two or more sensitizing dye combinations that emulsion is carried out spectral sensitization, sense of the present invention is blue, sense is green, preferred following respectively one or both combinations of sense red beds, makes it obtain light sensitivity with the exposure light source optimum matching.
In preparation, storage or the photographic process of emulsion or photosensitive material, silver emulsion of the present invention can comprise various for preventing the compound of photographic fog or stable photographic property.More specifically, can add known a large amount of compounds as antifoggant or stabilizing agent, it comprises thiazole salt such as benzothiazolium salt, benzotriazole salt such as nitrobenzene and triazolam, mercapto-tetrazole (particularly 1 one phenyl, one 5 mercapto-tetrazoles), benzene thiosulfonic acid, benzenesulfinic acid and salt, double sulfide etc.In these compounds, preferably mercapto-tetrazole and benzene thiosulfonic acid salt.As shown in the formula:
Silver halides colourful photographic paper among the present invention can be with various technology exposure images, as Research DISclosure, and vol.365,1994, described in the Item 36544.Both can use in negativity processing optical equipment, and also can process use in various digit explosure equipment, the present invention is preferred for adopting the monochromatic digital scanning exposure system of high density.
Silver halides colourful photographic paper of the present invention can use any known washing processing method to process, as Research Disclosure, vol.365,1994, ltem 36544 and Theory of photographicprocess (T.H.James, 4th edition, Macmillan, New York, 1977) described in.RA-4 rapid processing technology as known in the art, i.e. the washing processing of fixing time 45 seconds is floated in colour development 45 seconds, and the PH of bleach-fixing liquid is about 6.0 or lower; For quickening the desilverization, more preferably pH value is lower than 5.0 bleach-fixing liquid.Silver halides colourful photographic paper of the present invention has good rapid development, floats fixed flushing stability in the rapid processing system.
The preparation process of silver halides colourful photographic paper: each of silver halides colourful photographic paper layer arrangement architecture is at ResearchDisclosure, vol.365,1994, Item36544, have a detailed description among the section xl, concrete arrangement architecture is as follows: each layer below coating on the poly paper support of being coated with of gel subization:
Sealer
The uv absorption layer 2.
The sense red beds
The uv absorption layer 1.
Green layer
Interlayer
The blue layer of sense
Support (paper substrate)
In the manufacture process of silver halides colourful photographic paper, prepare at first that above-mentioned sense indigo plant, sense are green, the emulsion of sense red beds and utilize method well known in the art that used colour coupler, ultraviolet absorber, anti-pollutant are dissolved in to be dispersed in the high boiling solvent to become emulsion in the gelatin, then emulsion, emulsion being mixed and add additives such as surfactant, hardener, anti-irradiation dyestuff, polymkeric substance is coated on the poly paper support of being coated with of gel subization, condensation, drying obtain color photographic paper color photo paper.
Silver halides colourful photographic paper provided by the invention floats at low pH value and to decide in the working fluid, has reduced the generation of blue or green leuco dye, has good flushing stability; Implementing under the high illumination conditions of exposure, the blue-sensitive emulsion development capability is strong, photographic fog is low, has good rapid development processing characteristics.
Embodiment
Below by example the present invention is described in more detail, but the protection that the present invention requires is not limited in this.
Comparative example 1
Ground floor (the blue layer of sense) coating weight (g/m2)
Blue-sensitive emulsion (SB) silver 0.25
Gelatin 1.20
Yellow colour former D1 0.43
Image light stabilizer F1 0.10
Solvent R-1 0.30
Solvent R-2 0.20
The second layer (interlayer)
Gelatin 0.85
Anti-pollutant KB-1 0.09
Solvent R-1 0.06
Solvent R-3 0.03
A2 0.03
The 3rd layer (green layer)
Green-sensitive emulsion (SG) silver 0.10
Gelatin 1.00
Product look colour coupler E1 0.25
Image light stabilizer F1 0.20
Solvent R-1 0.10
Solvent R-4 0.05
The 4th layer (the ultraviolet absorber layer 1.)
Gelatin 0.80
Anti-pollutant KB-1 0.10
Ultraviolet absorber UV-1 0.20
Ultraviolet absorber UV-2 0.08
Solvent R-1 0.15
Solvent R-3 0.03
Solvent R-4 0.12
Layer 5 (sense red beds)
Magenta-sensitive emulsion (SR) silver 0.17
Gelatin 0.90
Cyan coupler B1 0.37
Ultraviolet absorber UV-1 0.10
Solvent R-1 0.25
Solvent R-3 0.10
Layer 6 (the ultraviolet absorber layer 2.)
Gelatin 0.55
Anti-pollutant KB-1 0.03
Ultraviolet absorber UV-1 0.16
Ultraviolet absorber UV-2 0.04
Solvent R-1 0.09
Solvent R-3 0.02
Solvent R-4 0.05
Layer 7 (sealer)
Gelatin 0.80
Surfactant J-1 0.22
Hardener H-1 0.12
Preparing the used compound of above-mentioned each layer is shown in hereinafter
CH2＝CH-SO2-CH2-SO2-CH＝CH2
H-1
Blue-sensitive emulsion SB preparation
In 1 liter of 4% aqueous gelatin solution, add 3g sodium chloride, then to wherein adding 130 milligrams of sulfide compounds.Keeping under 65 ℃ of conditions and the strong agitation, the sodium-chloride water solution of the 2.0M of the 2.0M silver nitrate aqueous solution of adding 1mol and 1mol is settled out high silver chloride emulsion in the aqueous solution of gained; During silver halide particle forms,, between distance particle center 0～70%, add radium chloride sodium complex 1.0*10 in silver
-8Mol/molAg between distance particle center 75～80%, adds 1.0*10
-7The six cyano group potassium ruthenate compounds of mol/molAg between distance particle center 90～95%, add (5-methylthiazol)-5 potassium hexachloroiridate compounds, consumption 5.0*10
-6Mol/molAg; Adopt sedimentation or ultrafiltration to carry out desalting processing then, add down 80 gram gelatin, the PH of this emulsion is adjusted to 5.2～5.4 at 45 ℃, the PCI value is adjusted to 1.3～1.4, observes from electron microscopic image, and this particle is a Cubic Emulsion, its particle diameter is 0.65 μ m, and coefficient of alteration is 0.09; Add stabilizing agent W4 and sensitizer sodium thiosulfate 1.0*10 down at 60 ℃
-6Mol/molAg, gold potassium chloride 1.0*10
-6Mol/molAg carries out best chemical sensitization, adds the blue sensitizing dye Y-2 of sense then and carries out spectral sensitization, further adds W2 compound and potassium bromide solution.
Green-sensitive emulsion SG preparation
In 1 liter of 4% aqueous gelatin solution, add 2g sodium chloride, then to wherein adding 20 milligrams of sulfide compounds.Keeping under 53 ℃ of conditions and the strong agitation, the sodium-chloride water solution of the 3.0M of the 3.0M silver nitrate aqueous solution of adding 1mol and 1mol is settled out high silver chloride emulsion in the aqueous solution of gained; During silver halide particle forms,, between distance particle center 0～70%, add radium chloride sodium complex 1.0*10 in silver
-6Mol/molAg between distance particle center 90～95%, adds (5-methylthiazol)-5 potassium hexachloroiridate compounds, consumption 1.0*10
-5Mol/molAg; Adopt sedimentation or ultrafiltration to carry out desalting processing then, add down 80 gram gelatin, the PH of this emulsion is adjusted to 5.2～5.4 at 45 ℃, the PCI value is adjusted to 1.3～1.4, observes from electron microscopic image, and this particle is a Cubic Emulsion, its particle diameter is 0.35 μ m, and coefficient of alteration is 0.10; Add stabilizing agent W4 and sensitizer sodium thiosulfate 5.0*10 down at 60 ℃
-6Mol/molAg, gold potassium chloride 5.0*10
-6Mol/molAg carries out best chemical sensitization, adds the green sensitizing dye M-2 of sense then and carries out spectral sensitization, further adds W2 compound and potassium bromide solution.
Magenta-sensitive emulsion SR preparation
In 1 liter of 4% aqueous gelatin solution, add 2g sodium chloride, then to wherein adding 25 milligrams of sulfide compounds.Keeping under 55 ℃ of conditions and the strong agitation, the sodium-chloride water solution of the 3.0M of the 3.0M silver nitrate aqueous solution of adding 1mol and 1mol is settled out high silver chloride emulsion in the aqueous solution of gained; During silver halide particle forms,, between distance particle center 0～70%, add radium chloride sodium complex 5.0*10 in silver
-6Mol/molAg between distance particle center 75～80%, adds 1.0*10
-6The six cyano group potassium ruthenate compounds of mol/molAg between distance particle center 90～95%, add (5-methylthiazol)-5 potassium hexachloroiridate compounds, consumption 3.0*10
-6Mol/molAg; Adopt sedimentation or ultrafiltration to carry out desalting processing then, add down 80 gram gelatin, the PH of this emulsion is adjusted to 5.2～5.4 at 45 ℃, the PCI value is adjusted to 1.3～1.4, observes from electron microscopic image, and this particle is a Cubic Emulsion, its particle diameter is 0.40 μ m, and coefficient of alteration is 0.10; Add stabilizing agent W4 and sensitizer sodium thiosulfate 5.0*10 down at 60 ℃
-6Mol/molAg, gold potassium chloride 1.0*10
-6Mol/molAg carries out best chemical sensitization, adds the red sensitizing dye C-1 of sense then and carries out spectral sensitization, further adds potassium bromide solution and W2 compound.
Embodiment 1
Ground floor (the blue layer of sense) coating weight (g/m2)
Blue-sensitive emulsion (SB1) silver 0.25
Gelatin 1.20
Yellow colour former D1 0.43
Image light stabilizer F1 0.10
Solvent R-1 0.30
Solvent R-2 0.20
Polymer A 2 0.03
The second layer (interlayer)
Gelatin 0.85
Anti-pollutant KB-1 0.09
Solvent R-1 0.06
Solvent R-3 0.03
The 3rd layer (green layer)
Green-sensitive emulsion (SG) silver 0.10
Gelatin 1.00
Product look colour coupler E1 0.25
Image light stabilizer F1 0.20
Solvent R-1 0.10
Solvent R-4 0.05
Polymer A 2 0.03
The 4th layer (the ultraviolet absorber layer 1.)
Gelatin 0.80
Anti-pollutant KB-1 0.10
Ultraviolet absorber UV-1 0.20
Ultraviolet absorber UV-2 0.08
Solvent R-1 0.15
Solvent R-3 0.03
Solvent R-4 0.12
Layer 5 (sense red beds)
Magenta-sensitive emulsion (SR) silver 0.17
Gelatin 0.90
Cyan coupler B1 0.37
Ultraviolet absorber UV-1 0.10
Solvent R-1 0.25
Solvent R-3 0.10
Polymer A 2 0.06
Layer 6 (the ultraviolet absorber layer 2.)
Gelatin 0.55
Anti-pollutant KB-1 0.03
Ultraviolet absorber UV-1 0.16
Ultraviolet absorber UV-2 0.04
Solvent R-1 0.09
Solvent R-3 0.02
Solvent R-4 0.05
Layer 7 (sealer)
Gelatin 0.80
Surfactant J-1 0.22
Hardener H-1 0.12
Blue-sensitive emulsion SB-1 preparation
In 1 liter of 4% aqueous gelatin solution, add 3g sodium chloride, then to wherein adding 130 milligrams of sulfide compounds.Keeping under 65 ℃ of conditions and the strong agitation, the sodium-chloride water solution of the 2.0M of the 2.0M silver nitrate aqueous solution of adding 1mol and 1mol is settled out high silver chloride emulsion in the aqueous solution of gained; During silver halide particle forms,, between distance particle center 0～70%, add radium chloride sodium complex 1.0*10 in silver
-8Mol/molAg between distance particle center 75～80%, adds 1.0*10
-7The six cyano group potassium ruthenate compounds of mol/molAg in 90% position, distance particle center, add 0.0015mol potassium iodide compound, between distance particle center 90～95%, add (5-methylthiazol)-5 potassium hexachloroiridate compounds, consumption 5.0*10
-6Mol/molAg; Adopt sedimentation or ultrafiltration to carry out desalting processing then, add down 80 gram gelatin, the PH of this emulsion is adjusted to 5.2～5.4 at 45 ℃, the PCI value is adjusted to 1.3～1.4, observes from electron microscopic image, and this particle is a Cubic Emulsion, its particle diameter is 0.65 μ m, and coefficient of alteration is 0.09; Add stabilizing agent W4 and sensitizer sodium thiosulfate 1.0*10 down at 60 ℃
-6Mol/molAg, gold potassium chloride 1.0*10
-6Mol/molAg carries out best chemical sensitization, adds the blue sensitizing dye Y-2 of sense then and carries out spectral sensitization, further adds W2 compound and potassium bromide solution.
The coating of employing fashion of extrusion, the plastic-coated that above-mentioned each layer is applied to gel subization has on the poly paper support, and drying obtains color photographic paper color photo paper, according to the RA-4 technology washing processing of standard, asks for various photographic properties, in the results are shown in Table.
Embodiment 2
On embodiment 1 basis:
Feel blue strata compound A3 0.03
Blue-sensitive emulsion SB-2 silver 0.25
Green layer polymer A 3 0.03
Sense red beds polymer A 3 0.06
Blue-sensitive emulsion SB-2 preparation
In 1 liter of 4% aqueous gelatin solution, add 3g sodium chloride, then to wherein adding 130 milligrams of sulfide compounds.Keeping under 65 ℃ of conditions and the strong agitation, the sodium-chloride water solution of the 2.0M of the 2.0M silver nitrate aqueous solution of adding 1mol and 1mol is settled out high silver chloride emulsion in the aqueous solution of gained; During silver halide particle forms,, between distance particle center 0～70%, add radium chloride sodium complex 1.0*10 in silver
-6Mol/molAg between distance particle center 75～80%, adds 1.0*10
-7The six cyano group potassium ruthenate compounds of mol/molAg in 90% position, distance particle center, add 0.003mol potassium iodide compound, between distance particle center 90～95%, add (5-methylthiazol)-5 potassium hexachloroiridate compounds, consumption 5.0*10
-6Mol/molAg; Adopt sedimentation or ultrafiltration to carry out desalting processing then, add down 80 gram gelatin, the PH of this emulsion is adjusted to 5.2～5.4 at 45 ℃, the PCI value is adjusted to 1.3～1.4, observes from electron microscopic image, and this particle is a Cubic Emulsion, its particle diameter is 0.65 μ m, and coefficient of alteration is 0.09; Add stabilizing agent W4 and sensitizer sodium thiosulfate 1.0*10 down at 60 ℃
-6Mol/molAg, gold potassium chloride 1.0*10
-6Mol/molAg carries out best chemical sensitization, adds the blue sensitizing dye Y-2 of sense then and carries out spectral sensitization, further adds W2 compound and potassium bromide solution.
The coating of employing fashion of extrusion, the plastic-coated that above-mentioned each layer is applied to gel subization has on the poly paper support, and drying obtains color photographic paper color photo paper, according to the RA-4 technology washing processing of standard, asks for various photographic properties, in the results are shown in Table.
Embodiment 3
On embodiment 1 basis:
Feel blue strata compound A2 0.03
Blue-sensitive emulsion SB-3 silver 0.25
Green layer polymer A 2 0.03
Sense red beds polymer A 2 0.12
Blue-sensitive emulsion SB-3 preparation
In 1 liter of 4% aqueous gelatin solution, add 3g sodium chloride, then to wherein adding 130 milligrams of sulfide compounds.Keeping under 65 ℃ of conditions and the strong agitation, the sodium-chloride water solution of the 2.0M of the 2.0M silver nitrate aqueous solution of adding 1mol and 1mol is settled out high silver chloride emulsion in the aqueous solution of gained; During silver halide particle forms,, between distance particle center 0～70%, add radium chloride sodium complex 1.0*10 in silver
-8Mol/molAg between distance particle center 80～85%, adds 1.0*10
-7The six cyano group potassium ruthenate compounds of mol/molAg in 90% position, distance particle center, add 0.0015mol potassium iodide compound, between distance particle center 90～95%, add (5-methylthiazol)-5 potassium hexachloroiridate compounds, consumption 5.0*10
-6Mol/molAg; Adopt sedimentation or ultrafiltration to carry out desalting processing then, add down 80 gram gelatin, the PH of this emulsion is adjusted to 5.2～5.4 at 45 ℃, the PCI value is adjusted to 1.3～1.4, observes from electron microscopic image, and this particle is a Cubic Emulsion, its particle diameter is 0.65 μ m, and coefficient of alteration is 0.09; Add stabilizing agent W4 and sensitizer sodium thiosulfate 1.0*10 down at 60 ℃
-6Mol/molAg, gold potassium chloride 1.0*10
-6Mol/molAg carries out best chemical sensitization, adds the blue sensitizing dye Y-2 of sense then and carries out spectral sensitization, further adds W2 compound and potassium bromide solution.
The coating of employing fashion of extrusion, the plastic-coated that above-mentioned each layer is applied to gel subization has on the poly paper support, and drying obtains color photographic paper color photo paper, according to the RA-4 technology washing processing of standard, asks for various photographic properties, in the results are shown in Table.
Embodiment 4
On embodiment 1 basis:
Feel blue strata compound A2 0.06
Blue-sensitive emulsion SB-4 silver 0.25
Green layer polymer A 2 0.06
Sense red beds polymer A 2 0.06
Blue-sensitive emulsion SB-4 preparation
In 1 liter of 4% aqueous gelatin solution, add 3g sodium chloride, then to wherein adding 130 milligrams of sulfide compounds.Keeping under 65 ℃ of conditions and the strong agitation, the sodium-chloride water solution of the 2.0M of the 2.0M silver nitrate aqueous solution of adding 1mol and 1mol is settled out high silver chloride emulsion in the aqueous solution of gained; During silver halide particle forms,, between distance particle center 0～70%, add radium chloride sodium complex 1.0*10 in silver
-8Mol/molAg in 90% position, distance particle center, adds 0.0015mol potassium iodide compound, between distance particle center 90～95%, adds (5-methylthiazol)-5 potassium hexachloroiridate compounds, consumption 5.0*10
-6Mol/molAg between distance particle center 96～98%, adds 1.0*10
-7The six cyano group potassium ruthenate compounds of mol/molAg; Adopt sedimentation or ultrafiltration to carry out desalting processing then, add down 80 gram gelatin, the PH of this emulsion is adjusted to 5.2～5.4 at 45 ℃, the PCI value is adjusted to 1.3～1.4, observes from electron microscopic image, and this particle is a Cubic Emulsion, its particle diameter is 0.65 μ m, and coefficient of alteration is 0.09; Add stabilizing agent W4 and sensitizer sodium thiosulfate 1.0*10 down at 60 ℃
-6Mol/molAg, gold potassium chloride 1.0*10
-6Mol/molAg carries out best chemical sensitization, adds the blue sensitizing dye Y-2 of sense then and carries out spectral sensitization, further adds W2 compound and potassium bromide solution.
The coating of employing fashion of extrusion, the plastic-coated that above-mentioned each layer is applied to gel subization has on the poly paper support, and drying obtains color photographic paper color photo paper, according to the RA-4 technology washing processing of standard, asks for various photographic properties, in the results are shown in Table.
Embodiment 5
On embodiment 1 basis:
Feel blue strata compound A2 0.04
Blue-sensitive emulsion SB-5 silver 0.25
Green layer polymer A 2 0.04
Sense red beds polymer A 2 0.08
Blue-sensitive emulsion SB-5 preparation
In 1 liter of 4% aqueous gelatin solution, add 3g sodium chloride, then to wherein adding 130 milligrams of sulfide compounds.Keeping under 65 ℃ of conditions and the strong agitation, the sodium-chloride water solution of the 2.0M of the 2.0M silver nitrate aqueous solution of adding 1mol and 1mol is settled out high silver chloride emulsion in the aqueous solution of gained; During silver halide particle forms,, between distance particle center 0～70%, add radium chloride sodium complex 1.0*10 in silver
-8Mol/molAg in 90% position, distance particle center, adds 0.001mol potassium iodide compound, between distance particle center 90～95%, adds (5-methylthiazol)-5 potassium hexachloroiridate compounds, consumption 5.0*10
-6Mol/molAg between distance particle center 97～100%, adds 1.0*10
-7The six cyano group potassium ruthenate compounds of mol/molAg; Adopt sedimentation or ultrafiltration to carry out desalting processing then, add down 80 gram gelatin, the PH of this emulsion is adjusted to 5.2～5.4 at 45 ℃, the PCI value is adjusted to 1.3～1.4, observes from electron microscopic image, and this particle is a Cubic Emulsion, its particle diameter is 0.65 μ m, and coefficient of alteration is 0.09; Add stabilizing agent W4 and sensitizer sodium thiosulfate 1.0*10 down at 60 ℃
-6Mol/molAg, gold potassium chloride 1.0*10
-6Mol/molAg carries out best chemical sensitization, adds the blue sensitizing dye Y-2 of sense then and carries out spectral sensitization, further adds W2 compound and potassium bromide solution.
The coating of employing fashion of extrusion, the plastic-coated that above-mentioned each layer is applied to gel subization has on the poly paper support, and drying obtains color photographic paper color photo paper, according to the RA-4 technology washing processing of standard, asks for various photographic properties, in the results are shown in Table.
Embodiment 6
On embodiment 5 bases:
Feel blue strata compound A2 0.04
Blue-sensitive emulsion SB-6 silver 0.25
Green layer polymer A 2 0.04
Sense red beds polymer A 2 0.08
Blue-sensitive emulsion SB-6 preparation
In 1 liter of 4% aqueous gelatin solution, add 3g sodium chloride, then to wherein adding 130 milligrams of sulfide compounds.Keeping under 65 ℃ of conditions and the strong agitation, the sodium-chloride water solution of the 2.0M of the 2.0M silver nitrate aqueous solution of adding 1mol and 1mol is settled out high silver chloride emulsion in the aqueous solution of gained; During silver halide particle forms,, between distance particle center 0～70%, add radium chloride sodium complex 1.0*10 in silver
-8Mol/molAg in 90% position, distance particle center, adds 0.002mol potassium iodide compound, between distance particle center 90～95%, adds (5-methylthiazol)-5 potassium hexachloroiridate compounds, consumption 5.0*10
-6Mol/molAg between distance particle center 96～98%, adds 5.0*10
-6The six cyano group potassium ruthenate compounds of mol/molAg; Adopt sedimentation or ultrafiltration to carry out desalting processing then, add down 80 gram gelatin, the PH of this emulsion is adjusted to 5.2～5.4 at 45 ℃, the PCI value is adjusted to 1.3～1.4, observes from electron microscopic image, and this particle is a Cubic Emulsion, its particle diameter is 0.65 μ m, and coefficient of alteration is 0.09; Add stabilizing agent W4 and sensitizer sodium thiosulfate 1.0*10 down at 60 ℃
-6Mol/molAg, gold potassium chloride 1.0*10
-6Mol/molAg carries out best chemical sensitization, adds the blue sensitizing dye Y-2 of sense then and carries out spectral sensitization, further adds W2 compound and potassium bromide solution.
The coating of employing fashion of extrusion, the plastic-coated that above-mentioned each layer is applied to gel subization has on the poly paper support, and drying obtains color photographic paper color photo paper, according to the RA-4 technology washing processing of standard, asks for various photographic properties, in the results are shown in Table.
Embodiment 7
On embodiment 5 bases:
Feel blue strata compound A2 0.04
Blue-sensitive emulsion SB-7 silver 0.25
Green layer polymer A 2 0.04
Sense red beds polymer A 2 0.08
Blue-sensitive emulsion SB-7 preparation
In 1 liter of 4% aqueous gelatin solution, add 3g sodium chloride, then to wherein adding 130 milligrams of sulfide compounds.Keeping under 65 ℃ of conditions and the strong agitation, the sodium-chloride water solution of the 2.0M of the 2.0M silver nitrate aqueous solution of adding 1mol and 1mol is settled out high silver chloride emulsion in the aqueous solution of gained; During silver halide particle forms,, between distance particle center 0～70%, add radium chloride sodium complex 1.0*10 in silver
-8Mol/molAg in 90% position, distance particle center, adds 0.002mol potassium iodide compound, between distance particle center 90～95%, adds (5-methylthiazol)-5 potassium hexachloroiridate compounds, consumption 5.0*10
-8Mol/molAg between distance particle center 96～98%, adds 5.0*10
-6The six cyano group potassium ruthenate compounds of mol/molAg; Adopt sedimentation or ultrafiltration to carry out desalting processing then, add down 80 gram gelatin, the PH of this emulsion is adjusted to 5.2～5.4 at 45 ℃, the PCI value is adjusted to 1.3～1.4, observes from electron microscopic image, and this particle is a Cubic Emulsion, its particle diameter is 0.65 μ m, and coefficient of alteration is 0.09; Add stabilizing agent W4 and sensitizer sodium thiosulfate 1.0*10 down at 60 ℃
-6Mol/molAg, gold potassium chloride 1.0*10
-6Mol/molAg carries out best chemical sensitization, adds the blue sensitizing dye Y-2 of sense then and carries out spectral sensitization, further adds W2 compound and potassium bromide solution.
The coating of employing fashion of extrusion, the plastic-coated that above-mentioned each layer is applied to gel subization has on the poly paper support, and drying obtains color photographic paper color photo paper, according to the RA-4 technology washing processing of standard, asks for various photographic properties, in the results are shown in Table.
The blue or green leuco dye production rate of table 1 test data table
Cyan leuco dye production rate acquiring method in the table 1: foregoing invention sample and contrast sample are exposed with Japanese JIS sensitometer respectively, adopt the PH correctives to adjust the pH value of bleach-fixing liquid, carry out colour development then, float fixed, stable, dry washing processing and obtain the print that blue or green density value is D1 (about 2.10), in 5% potassium ferricyanide solution, soaked 1 minute, behind the washing and drying, test sample density D 2, then latent blue or green production rate=(D2-D1)/D2*100%.Numerical value is lower, proves that blue or green leuco dye growing amount is littler.
As can be seen from Table 1, blue in sense, sense is green, the sense red beds adds polymer A and can obviously reduce blue or green leuco dye production rate, special effect is more obvious in the lower bleach-fixing liquid of pH value, thereby improved color photographic paper color photo paper low PH is floated the flushing stability of deciding the rapid processing soup.
The blue layer of table 2 sense rapid development performance test data table
Test data acquiring method in the table 2: foregoing invention sample and contrast sample are gone up the classification exposure at xenon lamp sensitometer (Chinese Lekai Film Co's manufacturing), and by the color filter of 480nm, the time shutter is 10 during exposure
-7Second, carry out 45 seconds, 25 seconds colour development then respectively, float surely, through after stable, the drying, measure the colour density of each print, determine minimum density, light sensitivity, maximal density.Minimum density is the colour density of unexposed area; Light sensitivity is to make colour density multiply by 100 again than the inverse of the high 0.6 necessary exposure of minimum color density; Maximal density is the high density point of colour density and required exposure amount log characteristic curve; The light sensitivity difference is that the light sensitivity that processing in 45 seconds obtains deducts the light sensitivity that processing in 25 seconds obtains; The maximal density difference is that the maximum density values that processing in 45 seconds obtains deducts the maximum density values that processing in 25 seconds obtains; Light sensitivity, maximal density difference are littler, and interpret sample rapid development ability is stronger.
As can be seen from Table 2, the blue layer of the sense of sample of the present invention emulsion is with the obvious advantage aspect the rapid development ability, helps improving color photographic paper color photo paper and adapts to the stability of getting processing technology express developed.
Claims (8)
1. silver halides colourful photographic paper, it comprises the imaging layer of support and autochromy silver halide, comprise the blue layer of silver halide sense of one deck yellowly at least, at least the silver halide green layer of one deck finished product look, at least one deck becomes the silver halide sense red beds of cyan, at least one deck hydrophilic colloid layer of quality not is characterized in that:
A. the polymkeric substance that contains general formula A at three sense chromatographs, wherein sense consumption blue, green layer is respectively 0.03～0.07 gram/m
2, sense red beds consumption is 0.06～0.12 gram/m
2,
Among the general formula A, R
1Be C
1～C
4Alkyl; R
2Be H or C
1～C
4Alkyl;
B. the content of silver chloride is 97mol% or more in the silver emulsion of the blue layer of sense, and the content of silver iodide is 0～0.3mol%, and has the noble metal complexes phase in silver in the position at 95%～100% place, distance chlorosulfonylation silver particle center.
2. silver halides colourful photographic paper according to claim 1 is characterized in that, described noble metal complexes is the noble metal complexes phase of cyano-containing ligand mutually.
3. silver halides colourful photographic paper according to claim 1 is characterized in that, the silver halide particle in the described sense chromatograph contains at least 97% silver chloride, and also contains two or more noble metal complexes phase.
4. according to the silver halides colourful photographic paper of claim 3, it is characterized in that contain the iridium complex compound phase that has thiazole or substituted thiazole ligand in the silver halide particle in the described sense chromatograph, consumption is 1.0*10
-5～1.0*10
-9Mol/molAg.
5. according to claim 1,2,3 or 4 described silver halides colourful photographic papers, it is characterized in that, in the blue layer of the described sense silver halide particle, the content of silver iodide is 0.10～0.3%mol, and have the noble metal complexes phase in silver in the position at 95%～98% place, distance chlorosulfonylation silver particle center, its consumption is 1.0*10
-4～1.0*10
-8Mol/molAg.
6. according to the described silver halides colourful photographic paper of claim 5, it is characterized in that, contain formula B colour coupler or formula B and formula C colour coupler in the described sense red beds:
Among the formula B, R is for containing C
10～C
20Groups;
Among the formula C, R
1, R
2Be the aralkyl group.
7. according to the described silver halides colourful photographic paper of claim 5, it is characterized in that the blue layer of described sense contains the colour coupler of formula D:
Among the formula D, R is the C that contains hexatomic ring
20～C
30Groups.
8. according to the described silver halides colourful photographic paper of claim 5, it is characterized in that described green layer contains colour coupler E and anti-fading agent F:
Among the formula E, R
1Be hydrogen atom, methyl or butyl; R
2Be C
1～C
5Alkyl; R
3Be bag C
10～C
20Long chain alkyl group or contain aryl or sulfur-bearing, nitrogen five yuan, the C of hexa-member heterocycle
10～C
20Long chain alkyl group;
Among the formula F, R
4For hydroxyl, phenoxy group or contain sulfonic group and the hexatomic ring of nitrogen-atoms; R
5Be hydrogen atom, C
10～C
20Alkyl, hydroxyl or aryl.
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| CNA2007101853571A CN101178536A (en) | 2007-12-11 | 2007-12-11 | Silver halides colourful photographic paper |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108625223A (en) * | 2018-04-13 | 2018-10-09 | 保定市乐凯化学有限公司 | A kind of colour paper water-soluble anti-fading agent and preparation method thereof |
| CN112708019A (en) * | 2019-10-25 | 2021-04-27 | 乐凯化学材料有限公司 | Water-soluble color stabilizer for color photographic paper and preparation method thereof |
-
2007
- 2007-12-11 CN CNA2007101853571A patent/CN101178536A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108625223A (en) * | 2018-04-13 | 2018-10-09 | 保定市乐凯化学有限公司 | A kind of colour paper water-soluble anti-fading agent and preparation method thereof |
| CN108625223B (en) * | 2018-04-13 | 2020-09-11 | 保定市乐凯化学有限公司 | Water-soluble fading-resistant agent for color photographic paper and preparation method thereof |
| CN112708019A (en) * | 2019-10-25 | 2021-04-27 | 乐凯化学材料有限公司 | Water-soluble color stabilizer for color photographic paper and preparation method thereof |
| CN112708019B (en) * | 2019-10-25 | 2024-04-30 | 乐凯化学材料有限公司 | Water-soluble color stabilizer for color photographic paper and preparation method thereof |
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