CN101419394A - High-sensitivity light-sensitive thermal imaging material emulsion, reparation method and application thereof - Google Patents
High-sensitivity light-sensitive thermal imaging material emulsion, reparation method and application thereof Download PDFInfo
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- CN101419394A CN101419394A CNA2007101761724A CN200710176172A CN101419394A CN 101419394 A CN101419394 A CN 101419394A CN A2007101761724 A CNA2007101761724 A CN A2007101761724A CN 200710176172 A CN200710176172 A CN 200710176172A CN 101419394 A CN101419394 A CN 101419394A
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Abstract
The invention belongs to the technical field of photothermographic materials, and provides a high-sensitivity emulsion used in the photothermographic materials. The emulsion takes a mixture of silver tetraazaindene and other organic sliver salts as a sliver source, takes silver chlorobromide, sliver iodobromide and the like as a photosensitizer, and contains a binder, a developer and a surfactant. The high-sensitivity emulsion used in the photothermographic materials contains no anti-fogging agent, has relatively simple components, high sensitivity and little fog, and can be taken as a photosensitive coating of the photothermographic (PTG) materials.
Description
Technical field
The invention belongs to the light-sensitive thermal imaging material technical field, particularly with the silver-colored ISO light-sensitive thermal imaging material emulsion that mixes with other organic silver salts as silver-colored source of four benzazoles, and the preparation method and the purposes of this ISO light-sensitive thermal imaging material emulsion.
Background technology
Light-sensitive thermal imaging material (PTG) grows up on traditional silver halide image forming material basis, it is to be coated with the special photographic layer of one deck on polyester film base, and it is made up of the organic silver salts of non-photosensitivity, ultra-fine photosensitive silver halide particles, toner, antifoggant, stabilizing agent, spectral sensitizer and bonding agent etc.After exposure, on silver halide particle, generate latent image (this point is identical with the traditional silver halide photographic material), in thermal development process subsequently, the non-photosensitivity organic silver salts of latent image centers catalysis coexistence and the redox reaction between the weak reductant form visible black-and-white image.The PTG material has had development rapidly at last decade, its more traditional silver halide imaging material has not only been saved a large amount of noble metal silver, and it is easy and simple to handle, directly heating just can obtain image after exposing, do not need traditional photographic fixing step, reduce the discharging of waste liquid, thereby reduced environmental pollution.Light-sensitive thermal imaging material is because its unique advantage can be applied to medical diagnosis, aviation shooting etc.
Organic silver salts is the main silver-colored source of PTG material, different with silver halide, the silver source visible region do not have photosensitivity and must be after thermal treatment can with other component stable existences, many patents in silver-colored source and document about PTG all have report, for example US patent 4260677, US patent0 057 515, and US patent 6,573 033, US patent 4 835 272, US patent4 775 613 etc.Summarize and to get up to have following three kinds: the silver carboxylate class mainly is the silver carboxylate of carbon atom quantity 10～30, and wherein the most frequently used have silver stearate, mountain Yu acid silver, perhaps both potpourris.Another kind is the silver salt of silver acetylide or acetylene-derivative.The third is to contain-the organic monoacid part of NH-heterocycle and the complex of silver formation, and mainly part has imidazoles, benzimidazole, pyrazoles, triazole, benzotriazole, tetrazolium etc.Contain-the organic silver complex of NH-heterocycle compares with silver carboxylate, has certain advantage.For example benzotriazole silver (AgBZT) thermal stability is better than silver carboxylate, do not decompose with interior at 300 ℃, and it is reported that silver carboxylate is owing to reasons such as the existence of carboxylic acid free radical or lattice imperfections, just begin to decompose at 150 ℃, simultaneously owing to the insensitivity of benzotriazole silver, so have higher light stability to visible light.Reports such as United States Patent (USP) 6649332,6 790 569 are used for colored PTG system with AgBZT, have obtained effect preferably.But benzotriazole silver is used for the PTG system and also has certain defective.Because benzotriazole silver generates benzotriazole with the reductive agent reaction, reduce the pH value of system on the one hand, be subjected to certain inhibition thereby make to develop, benzotriazole silver is a kind of special stable polymer on the other hand, and the silver-colored source as the PTG material is unfavorable for Ag
+Transmission, therefore need higher development temperature, about 150 ℃, developing powder is common problem slowly.Therefore press for and address these problems, can reduce development temperature, improve maximal density, improve light sensitivity etc.
Summary of the invention
Defectives such as one of purpose of the present invention is to overcome above-mentioned-NH-class silver salt development temperature height, and density is little, and light sensitivity is low provide the ISO light-sensitive thermal imaging material emulsion; This ISO light-sensitive thermal imaging material emulsion is a photosensitizer with chlorine silver bromide, bromo-iodide etc., and a kind of organic mixed salt is silver-colored source.This light-sensitive thermal imaging material emulsion does not add any antifoggant, and component is simple relatively, and light sensitivity height and photographic fog are less.
Two of purpose of the present invention provides the organic mixed salt that is used to prepare the ISO light-sensitive thermal imaging material emulsion.
Three of purpose of the present invention provides the preparation method of ISO light-sensitive thermal imaging material emulsion.
Four of purpose of the present invention provides the preparation method of two organic mixed salts of purpose.
Five of purpose of the present invention provides the purposes of ISO light-sensitive thermal imaging material emulsion.
ISO light-sensitive thermal imaging material emulsion of the present invention comprises photosensitizer, organic mixed salt, hydrophobic nature bonding agent or water-soluble binder, developer and surfactant; Wherein the molal quantity of the photosensitizer in the emulsion is 0.1%～40%mol of organic mixed salt, the quality of hydrophobic nature bonding agent or water-soluble binder is 0.1～2 times of organic mixed salt, the molal quantity of developer is 1～50%mol of organic mixed salt, and the quality of surfactant is 0～1% of organic mixed salt.
Described photosensitizer is original position or the synthetic silver emulsion crystallite of dystopy, and the synthetic silver emulsion crystallite of described original position comprises silver bromide, silver chloride, silver iodide, chlorine silver bromide, bromo-iodide or silver chloroiodobromide etc.Preferred photosensitizer is emulsions such as chlorine silver bromide, bromo-iodide or silver chloroiodobromide.The synthetic silver emulsion crystallite of described dystopy comprises the microcrystal grain of different-shape structures such as cube, octahedron, T-particle, sandwich construction particle or nucleocapsid emulsion.
Described organic mixed salt is by any one the potpourri in any one and the second kind of organic silver salts compound in first kind of organic silver salts compound; Wherein second kind of organic silver salts occupy total silver amount in the machine mixed salt mole fraction be 1%～50%.
The part of described first kind of organic silver salts compound can be selected from the derivant of tetrazolium or tetrazolium, the derivant of triazole or triazole, and a kind of in the derivant of imidazoles or imidazoles, central atom is all silver atoms.
The concrete example of the derivant of described tetrazolium includes but not limited to: 5-ethyl-1H-tetrazolium or 5-amino-1H-tetrazolium etc.
The concrete example of the derivant of described triazole includes but not limited to: benzotriazole, methylbenzotrazole, 1H-1,2,4-triazole, 3-amino-1,2,4-triazole, 5,6-dimethyl-benzotriazole or 5-chloro-benzotriazole etc.
The concrete example of the derivant of described imidazoles includes but not limited to: benzimidazole, 5-methyl-benzimidazole or 2-methyl-5-nitro-benzimidazole etc.
First kind of organic silver salts compound preferred exemplary comprises benzotriazole, methylbenzotrazole, 1H-1,2, and the silver salt of 4-triazole or 5-chloro-benzotriazole etc.
Second kind of organic silver salts compound described in the present invention is to be part with the hydroxyl indenes, and silver is the compound of central atom.Concrete ligand structure formula example is as follows:
Wherein R is hydrogen atom, methyl, normal-butyl, phenyl or trifluoromethyl etc.
Second kind of organic silver salts compound be 4-hydroxyl-6-methyl isophthalic acid preferably, and 3,3a, 7-four benzazoles (TAI), 4-hydroxyl-6-normal-butyl-1,3,3a, the silver salt of 7-four benzazoles or 4-hydroxyl four benzazoles etc.
Described hydrophobic nature bonding agent is polyvinyl butyral (PVB), polyvinyl formal, polymethacrylate, polyacrylate or styrene-butadiene rubber; Described water-soluble binder is polyvinyl alcohol (PVA), modified butyl benzene emulsion, polyglycol, polyvinylpyrrolidone, polymethylacrylic acid, acrylic acid aqueous latex or the styrene-butadiene aqueous latex (SRB) etc. after gelatin, polyvinyl alcohol (PVA) (PVA), the modification, more than the weight percent concentration of each binder substance be 1%～50%.
Described developer is the derivant of phenolic compound, phenolic compound or the organic acid compound of phenolic hydroxy group,
Wherein, described phenolic compound has following structure:
The derivant of described phenolic compound has following structure:
Wherein, R is hydrogen atom, C
1～C
4Alkyl or methoxyl electron donating group;
The organic acid compound of described phenolic hydroxy group has following structure:
Described surfactant is that weight percent concentration is 1 ‰～10% isooctyl phenol polyoxyethylene ether, hexadecanol polyoxyethylene ether, nonylphenol glycol ether, isooctyl phenol polyoxyethylene ether sulfonic acid diethanolamine salt, octyl group succinic acid glyceride sylvite, butene dioic acid di-isooctyl sodium sulfonate, neopelex, N, the aqueous solution or the ethanolic solution of N-dimethyl lauryl amine acetate or polyoxyethylene pentaerythritol phosphate etc.
The preparation method of ISO light-sensitive thermal imaging material emulsion of the present invention is: under the condition of darkroom lucifuge, with organic mixed salt, molal quantity is the halogenide of organic mixed salt 0.1%～40%mol, quality is the water-soluble binder of 0.1～2 times of organic mixed salt, through the bowl mill ball milling after 0.5～3 hour, form the dispersion liquid of homogeneous, adding surfactant and the molal quantity that quality is organic mixed salt 0～1% then is the developer of organic mixed salt 1～50%mol, evenly disperses;
Described halogenide is ammonium bromide, potassium iodide, sodium chloride etc. or their any mixture.Described halogenide can obtain described photosensitizer (the silver emulsion crystallite that original position is synthetic) behind ball milling.
Or
Under the condition of darkroom lucifuge, with organic mixed salt, quality is the water-soluble binder of 0.1～2 times of organic mixed salt, through the bowl mill ball milling after 0.5～3 hour, form the dispersion liquid of homogeneous, add the photosensitizer that molal quantity is organic mixed salt 0.1%～40%mol then, surfactant and the molal quantity that quality is organic mixed salt 0～1% is the developer of organic mixed salt 1～50%mol, evenly disperse;
Or
Under the condition of darkroom lucifuge, with organic mixed salt, quality is that the hydrophobic nature bonding agent and the molal quantity of 0.1～2 times of organic mixed salt is the photosensitizer of organic mixed salt 0.1%～40%mol, quality is the surfactant of organic mixed salt 0～1%, through ultrasonic echography 0.5～3 hour, be uniformly dispersed, add the developer that molal quantity is organic mixed salt 1～50%mol then, evenly disperse.
Organic mixed salt described in the present invention can be prepared as follows: with in first kind of organic silver salts compound (having part and center silver atoms) any one with second kind of organic silver salts compound (having hydroxyl indenyl ligand and silver-colored central atom) in any one carry out the bowl mill ball milling and mix, make described organic mixed salt, wherein the silver in second kind of organic silver salts occupy total silver amount in the machine mixed salt mole fraction 1%～50%; Or
In a container that high-speed stirring apparatus is housed, can add 3～7 premium on currency in advance, add 0.01～1 kilogram of any one part in second kind of organic silver salts then, be heated to 40～90 ℃, constant temperature stirs, use the inorganic base adjust pH then between 5～7, liquor argenti nitratis ophthalmicus is added in the reactor under constant speed react; And then add 0.05～1 kilogram of any one part in first kind of organic silver salts, and continue to drip liquor argenti nitratis ophthalmicus, wherein the concentration of liquor argenti nitratis ophthalmicus is 0.5～3 mol, consumption is 1～3 liter, suction filtration, washing, drying obtains white powder, and organic mixed salt preparation is finished.Drying at room temperature is standby; Or
Any one part in any one and the second kind of organic silver salts in first kind of organic silver salts compound (having part and center silver atoms) is directly made through the bowl mill ball milling; Wherein any one part of second kind of organic silver salts occupy in the machine mixed salt total silver amount mole fraction 1%～50%.
Described inorganic base is NaOH, potassium hydroxide or sodium carbonate etc.; Its strength of fluid is 0.1～1 mol.
ISO light-sensitive thermal imaging material emulsion of the present invention can be used as the light sensitive layer of photothermographic (PTG) material.The emulsion that is about to make is with 0.3～0.7kg/m
2Consumption coat uniformly on the water white polyester film base, guarantee that the silver amount of every polyester film base coating equates that drying at room temperature makes the PTG film then.Use the PTG film that emulsion of the present invention makes, not only can reduce development temperature, and increase under the little situation, increase development density and improve light sensitivity at photographic fog.
Find through experiment, add the PTG material that second kind of organic silver salts forms organic mixed salt among the present invention, not only can reduce development temperature, and increase under the little situation, increase development density and improve light sensitivity at photographic fog.And with first kind of single organic silver salts PTG material that is silver-colored source, the development temperature height, development density is little, and light sensitivity is low.Find to use different photosensitizers simultaneously, the light sensitivity difference, it is lower to use AgBr to make the photosensitizer light sensitivity separately, uses the more independent AgBr of AgI to be height separately, and uses AgBrI to be the photosensitizer best results, and light sensitivity is the highest.Characteristics of the present invention are to be silver-colored source with above-mentioned organic mixed salt, are photosensitizer with the bromo-iodide, and the light sensitivity of PTG material can reach optimum value.
From following concrete experimental result as can be seen, the PTG film development temperature that only contains first kind of organic silver salts is higher, light sensitivity is lower, and be that the PTG film in silver-colored source develops at a lower temperature and just can reach higher development density and higher light sensitivity with organic mixed salt, photographic fog increases little simultaneously.It is standard that following examples light sensitivity adds 0.1 density place with photographic fog, is 100 with the light sensitivity of embodiment 1 original position AgBZT (benzotriazole silver)-AgBr system, and other is all relative sensitivity.
Table 1. print a, a ' and a " the thermal development result relatively
The thermal development result's of table 2. print b and print a comparison
The thermal development result's of table 3. print c and print a comparison
The thermal development result's of table 4. print d and print b print c comparison
The thermal development result's of table 5. print d ' and print b ' print c ' comparison
Table 6. print d " with print b " print c " and thermal development result's comparison
Embodiment
Comparative example 1
In a container that high-speed stirring apparatus is housed, add 5 premium on currency in advance, 0.21 kilogram of benzotriazole, be heated to 60 ℃, constant temperature stirs, and uses certain density sodium hydroxide solution adjust pH then about 8.0, with 1 liter of 0.3 kilogram of silver nitrate wiring solution-forming, under constant speed, add the reactor internal reaction, after reaction finishes, suction filtration, wash 3 times, drying obtains white powder at last, and benzotriazole silvery is finished fully.Drying at room temperature is standby.
In one 2 liters ball grinder, accurately take by weighing 0.024 kilogram of benzotriazole silver, add 0.001 kilogram of ammonium bromide, add 50 zirconia ball milling pearls then, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.4 gram pyrogallic acid, 0.5 ml concn is the isooctylphenol polyoxyethylene groups ether ethanolic solution of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.6kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print a, 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity, the gained result is as shown in table 1.
Comparative example 2
The preparation of benzotriazole silver is with comparative example 1.
In one 2 liters ball grinder, accurately take by weighing 0.024 kilogram of benzotriazole silver, add 0.0018 kilogram of potassium iodide, add 50 zirconia ball milling pearls then, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.4 gram pyrogallic acid, 0.5 ml concn is the isooctylphenol polyoxyethylene groups ether ethanolic solution of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.6kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print a ', 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity, the gained result is as shown in table 1.
Comparative example 3
The preparation of benzotriazole silver is with comparative example 1.
In one 2 liters ball grinder, accurately take by weighing 0.024 kilogram of benzotriazole silver, add 0.0018 kilogram of potassium iodide, add 50 zirconia ball milling pearls then, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.4 gram pyrogallic acid, 0.5 ml concn is the isooctylphenol polyoxyethylene groups ether ethanolic solution of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.6kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print a ", 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity, the gained result is as shown in table 1.
Embodiment 1
In a container that high-speed stirring apparatus is housed, add 5 premium on currency in advance, 0.21 kilogram of benzotriazole, be heated to 60 ℃, constant temperature stirs, and uses certain density sodium hydroxide solution adjust pH then about 8.0, with 1 liter of 0.3 kilogram of silver nitrate wiring solution-forming, under constant speed, add the reactor internal reaction, after reaction finishes, suction filtration, wash 3 times, drying obtains white powder at last, and benzotriazole silvery is finished fully.Drying at room temperature is standby.
In a container that high-speed stirring apparatus is housed, add 5 premium on currency in advance, 0.134 kilogram of 4-hydroxyl-6-methyl-1,3,3a, 7-four benzazole sodium salts are heated to 60 ℃, and constant temperature stirs, use certain density sodium hydroxide solution adjust pH then about 7.0, with 1 liter of 0.132 kilogram of silver nitrate wiring solution-forming, under constant speed, add the reactor internal reaction, after reaction finishes, suction filtration, wash 3 times, drying obtains white powder at last, 4-hydroxyl-6-methyl-1,3,3a, 7-four benzazole silvery are finished fully.Drying at room temperature is standby.
In one 2 liters ball grinder, accurately take by weighing 0.022 kilogram of benzotriazole silver, 0.002 kilogram 4-hydroxyl-6-methyl isophthalic acid, 3,3a, 7-four benzazole silver form mixed salt (note is made mixed salt one), add 0.001 kilogram of ammonium bromide, add 50 zirconia ball milling pearls then, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.4 gram pyrogallic acid, 0.5 ml concn is the aqueous solution of the neopelex of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.6kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print b, 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity, the gained result is as shown in table 2.
Embodiment 2
Benzotriazole silver and 4-hydroxyl-6-methyl isophthalic acid, 3,3a, the preparation of 7-four benzazole silver is with embodiment 1.
In one 2 liters ball grinder, accurately take by weighing 0.022 kilogram of benzotriazole silver, 0.002 kilogram 4-hydroxyl-6-methyl isophthalic acid, 3,3a, 7-four benzazole silver, form mixed salt (note is made mixed salt one), add 0.001 kilogram of ammonium bromide, 0.0012 kilogram of potassium iodide adds 50 zirconia ball milling pearls then, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.4 gram pyrogallic acid, 0.5 ml concn is the hexadecanol polyoxyethylene ether ethanolic solution of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.6kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print b ', 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity, the gained result is as shown in table 5.
Embodiment 3
In a container that high-speed stirring apparatus is housed, add 5 premium on currency in advance, 0.0134 kilogram of 4-hydroxyl-6-methyl-1,3,3a, 7-four benzazole sodium salts are heated to 60 ℃, and constant temperature stirs, use certain density sodium hydroxide solution adjust pH then about 7.0, with 1 liter of 0.15 kilogram of silver nitrate wiring solution-forming, under constant speed, add the reactor internal reaction, after reaction a period of time, before liquor argenti nitratis ophthalmicus drips, add 0.0945 kilogram of benzotriazole, continue to drip liquor argenti nitratis ophthalmicus, after reaction finishes, suction filtration, wash 3 times, drying obtains white powder at last, benzotriazole silver and 4-hydroxyl-6-methyl-1,3,3a, 7-four benzazoles silver mixed salts (note is done mixed salt two) preparation is finished.Drying at room temperature is standby.
In one 2 liters ball grinder, accurately take by weighing 0.024 kilogram of mixed salt two, add 0.001 kilogram of ammonium bromide, add 50 zirconia ball milling pearls then, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.4 gram pyrogallic acid, 0.5 ml concn is the isooctylphenol polyoxyethylene groups ether ethanolic solution of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.6kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print c, 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity, the gained result is as shown in table 3.
Embodiment 4
The preparation of mixed salt two is with embodiment 3.
Accurately take by weighing 0.024 kilogram of mixed salt two in one 2 liters ball grinder, add 0.001 kilogram of ammonium bromide, 0.0012 kilogram of potassium iodide adds 50 zirconia ball milling pearls then, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.4 gram pyrogallic acid, 0.5 ml concn is the isooctylphenol polyoxyethylene groups ether ethanolic solution of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.6kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print c ', 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity, the gained result is as shown in table 5.
Embodiment 5
The preparation of mixed salt two is with embodiment 3.
In one 2 liters ball grinder, accurately take by weighing 0.024 kilogram of mixed salt two, add 0.0018 kilogram of potassium iodide, add 50 zirconia ball milling pearls then, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.4 gram pyrogallic acid, 0.5 ml concn is the isooctylphenol polyoxyethylene groups ether ethanolic solution of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.6kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print c ", 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity, the gained result is as shown in table 6.
Embodiment 6
The preparation of benzotriazole silver is with comparative example 1.
In one 2 liters ball grinder, accurately take by weighing 0.024 kilogram of benzotriazole silver, 0.001 kilogram 4-hydroxyl-6-methyl-1,3,3a, 7-four benzazoles form mixed salt (note is made mixed salt three), add 0.001 kilogram of ammonium bromide, add 50 zirconia ball milling pearls then, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.4 gram pyrogallic acid, 0.5 ml concn is the isooctylphenol polyoxyethylene groups ether ethanolic solution of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.6kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print d, 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity, the gained result is as shown in table 4.
Embodiment 7
The preparation of benzotriazole silver is with comparative example 1.
In one 2 liters ball grinder, accurately take by weighing 0.024 kilogram of benzotriazole silver, 0.001 kilogram 4-hydroxyl-6-methyl-1,3,3a, 7-four benzazoles, form mixed salt three, add 0.001 kilogram of ammonium bromide, 0.0012 kilogram of potassium iodide adds 50 zirconia ball milling pearls then, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.4 gram pyrogallic acid, 0.5 ml concn is the isooctylphenol polyoxyethylene groups ether ethanolic solution of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.6kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print d ', 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity, the gained result is as shown in table 5.
Embodiment 8
The preparation of benzotriazole silver is with comparative example 1.
In one 2 liters ball grinder, accurately take by weighing 0.024 kilogram of benzotriazole silver, 0.001 kilogram 4-hydroxyl-6-methyl-1,3,3a, 7-four benzazoles form mixed salt three, add 0.0018 kilogram of potassium iodide, add 50 zirconia ball milling pearls then, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.4 gram pyrogallic acid, 0.5 ml concn is the isooctylphenol polyoxyethylene groups ether ethanolic solution of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.6kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print d ", 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity, the gained result is as shown in table 6.
Embodiment 9
In a container that high-speed stirring apparatus is housed, add 5 premium on currency in advance, 0.067 kilogram of methylbenzotrazole is heated to 60 ℃, constant temperature stirs, use certain density sodium hydroxide solution adjust pH then about 8.0, with 0.5 liter of adding reactor internal reaction under constant speed of liquor argenti nitratis ophthalmicus of 1 mol, after reaction finishes, suction filtration, wash 3 times, obtain white powder, methylbenzotrazole silvery is finished fully.Drying at room temperature is standby.
In a container that high-speed stirring apparatus is housed, add 5 premium on currency in advance, 0.134 kilogram of 4-hydroxyl-6-normal-butyl-1,3,3a, 7-four benzazole sodium salts are heated to 90 ℃, and constant temperature stirs, use certain density sodium hydroxide solution adjust pH then about 6.0, with 1 liter of 0.132 kilogram of silver nitrate wiring solution-forming, under constant speed, add the reactor internal reaction, after reaction finishes, suction filtration, wash 3 times, drying obtains white powder at last, 4-hydroxyl-6-normal-butyl-1,3,3a, 7-four benzazole silvery are finished fully.Drying at room temperature is standby.
In one 2 liters ball grinder, accurately take by weighing 0.022 kilogram of methylbenzotrazole silver, 0.011 kilogram of 4-hydroxyl-6-normal-butyl-1,3,3a, 7-four benzazole silver add 50 zirconia ball milling pearls, the polyvinyl alcohol water solution that to add 0.96 kilogram of concentration again be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 36 gram silver bromide emulsions, 1.6 gram catechols, 1.0 ml concns are the polyoxyethylene pentaerythritol phosphate ethanolic solution of 5wt%, are uniformly dispersed, and make the PTG material emulsion.
With emulsion with 0.7kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print, 5500K white light exposure 10 seconds, 120 ℃ were developed 30 seconds, test density calculates relative sensitivity.
Embodiment 10
In a container that high-speed stirring apparatus is housed, add 5 premium on currency in advance, 0.5 kilogram of 1H-1,2, the 4-triazole is heated to 60 ℃, constant temperature stirs, and uses certain density sodium hydroxide solution adjust pH then about 8.0, with 2.5 liters of 1.2 kilograms of silver nitrate wiring solution-formings, under constant speed, add the reactor internal reaction, after reaction finishes, suction filtration, wash 3 times, drying obtains white powder at last, 1H-1,2,4-triazole silvery is finished fully.Drying at room temperature is standby.
In one 2 liters ball grinder, accurately take by weighing 0.024 kilogram of 1H-1,2,4-triazole silver, 0.001 kilogram 4-hydroxyl-6-methyl isophthalic acid, 3,3a, 7-four benzazoles, form mixed salt, add 0.0005 kilogram of ammonium bromide again, 0.0006 kilogram of potassium iodide adds 50 zirconia ball milling pearls, the polyvinyl alcohol water solution that to add 0.48 kilogram of concentration then be 5wt%, ball milling 2 hours.Take out 0.3 kilogram dispersion liquid after ball milling finishes, add 0.1 gram pyrogallic acid, 0.1 ml concn is the isooctylphenol polyoxyethylene groups ether ethanolic solution of 5wt%, is uniformly dispersed, and makes the PTG material emulsion.
With emulsion with 0.7kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print, 5500K white light exposure 120 seconds, 150 ℃ were developed 30 seconds, test density calculates relative sensitivity.
Embodiment 11
In a container that high-speed stirring apparatus is housed, add 5 premium on currency in advance, 0.1 kilogram of 4-hydroxyl-6-methyl isophthalic acid, 3,3a, 7-four benzazole sodium salts, be heated to 40 ℃, constant temperature stirs, and is 5 with certain density sodium hydroxide solution adjust pH then, with 2.5 liters of 1.3 kilograms of silver nitrate wiring solution-formings, under constant speed, add the reactor internal reaction, after reaction a period of time, before liquor argenti nitratis ophthalmicus drips, add 0.8 kilogram of benzimidazole, continue to drip liquor argenti nitratis ophthalmicus, after question response is complete, suction filtration, wash 3 times, drying obtains white powder at last, benzimidazole silver and 4-hydroxyl-6-methyl isophthalic acid, 3,3a, the mixed salt preparation of 7-four benzazole silver is finished.Drying at room temperature is standby.
In a beaker, accurately take by weighing 0.0024 kilogram of benzimidazole silver and 4-hydroxyl-6-methyl isophthalic acid, 3,3a, the mixed salt of 7-four benzazole silver, the ethanolic solution that to add 0.024 kilogram of concentration again be the 5wt% polyvinyl butyral, ultrasonic dispersion 1 hour, 0.02 kilogram of dispersion liquid is taken out in the ultrasonic back that finishes, add 0.9 gram silver bromide emulsion, 0.05 gram gallic acid, be uniformly dispersed, make the PTG material emulsion.
With emulsion with 0.3kg/m
2Consumption evenly coat on the water white polyester film base, drying at room temperature makes print, white light exposure 10 seconds, 120 ℃ were developed 30 seconds, test density calculates relative sensitivity.
Claims (10)
1. ISO light-sensitive thermal imaging material emulsion, it is characterized in that: described ISO light-sensitive thermal imaging material emulsion comprises photosensitizer, organic mixed salt, hydrophobic nature bonding agent or water-soluble binder, developer and surfactant; Wherein the molal quantity of the photosensitizer in the emulsion is 0.1%～40%mol of organic mixed salt, the quality of hydrophobic nature bonding agent or water-soluble binder is 0.1～2 times of organic mixed salt, the molal quantity of developer is 1～50%mol of organic mixed salt, and the quality of surfactant is 0～1% of organic mixed salt;
Described organic mixed salt is by any one the potpourri in any one and the second kind of organic silver salts compound in first kind of organic silver salts compound; Wherein the silver in second kind of organic silver salts occupy total silver amount in the machine mixed salt mole fraction 1%～50%;
The part of described first kind of organic silver salts compound is selected from the derivant of tetrazolium or tetrazolium, the derivant of triazole or triazole, and a kind of in the derivant of imidazoles or imidazoles, central atom is all silver atoms;
Described second kind of organic silver salts compound is to be part with the hydroxyl indenes, and silver is the compound of central atom.
2. ISO light-sensitive thermal imaging material emulsion according to claim 1, it is characterized in that: described photosensitizer is original position or the synthetic silver emulsion crystallite of dystopy, and the synthetic silver emulsion crystallite of described original position is silver bromide, silver chloride, silver iodide, chlorine silver bromide, bromo-iodide or silver chloroiodobromide; The synthetic silver emulsion crystallite of described dystopy is the microcrystal grain of cube, octahedron, T-particle, sandwich construction particle or nucleocapsid emulsion structure.
3. ISO light-sensitive thermal imaging material emulsion according to claim 1 is characterized in that: described hydrophobic nature bonding agent is polyvinyl butyral, polyvinyl formal, polymethacrylate, polyacrylate or styrene-butadiene rubber; Described water-soluble binder is polyvinyl alcohol (PVA), modified butyl benzene emulsion, polyglycol, polyvinylpyrrolidone, polymethylacrylic acid, acrylic acid aqueous latex or the styrene-butadiene aqueous latex after gelatin, polyvinyl alcohol (PVA), the modification.
4. ISO light-sensitive thermal imaging material emulsion according to claim 1 is characterized in that: described developer is the derivant of phenolic compound, phenolic compound or the organic acid compound of phenolic hydroxy group,
Wherein, described phenolic compound has following structure:
The derivant of described phenolic compound has following structure:
Wherein, R is hydrogen atom, C
1～C
4Alkyl or methoxyl electron donating group;
The organic acid compound of described phenolic hydroxy group has following structure:
5. organic mixed salt for preparing each described ISO light-sensitive thermal imaging material emulsion of claim 1～4 is characterized in that: described organic mixed salt is by any one the potpourri in any one and the second kind of organic silver salts compound in first kind of organic silver salts compound; Wherein the silver in second kind of organic silver salts occupy total silver amount in the machine mixed salt mole fraction 1%～50%;
The part of described first kind of organic silver salts compound is selected from the derivant of tetrazolium or tetrazolium, the derivant of triazole or triazole, and a kind of in the derivant of imidazoles or imidazoles, central atom is all silver atoms;
Described second kind of organic silver salts compound is to be part with the hydroxyl indenes, and silver is the compound of central atom.
6. organic mixed salt according to claim 5 is characterized in that: the derivant of described tetrazolium is 5-ethyl-1H-tetrazolium or 5-amino-1H-tetrazolium;
The derivant of described triazole is benzotriazole, methylbenzotrazole, 1H-1,2, and 4-triazole, 3-amino-1,2,4-triazole, 5,6-dimethyl-benzotriazole or 5-chloro-benzotriazole;
The derivant of described imidazoles is benzimidazole, 5-methyl-benzimidazole or 2-methyl-5-nitro-benzimidazole.
7. organic mixed salt according to claim 5 is characterized in that: the ligand structure formula of described second kind of organic silver salts compound is:
Wherein R is hydrogen atom, methyl, normal-butyl, phenyl or trifluoromethyl.
8. preparation method according to each described ISO light-sensitive thermal imaging material emulsion of claim 1～4, it is characterized in that: under the condition of darkroom lucifuge, with organic mixed salt, molal quantity is the halogenide of organic mixed salt 0.1%～40%mol, quality is the water-soluble binder of 0.1～2 times of organic mixed salt, behind the bowl mill ball milling, form the dispersion liquid of homogeneous, adding surfactant and the molal quantity that quality is organic mixed salt 0～1% then is the developer of organic mixed salt 1～50%mol, evenly disperses; Or
Under the condition of darkroom lucifuge, with organic mixed salt, quality is the water-soluble binder of 0.1～2 times of organic mixed salt, behind the bowl mill ball milling, form the dispersion liquid of homogeneous, add the photosensitizer that molal quantity is organic mixed salt 0.1%～40%mol then, surfactant and the molal quantity that quality is organic mixed salt 0～1% is the developer of organic mixed salt 1～50%mol, evenly disperse; Or
Under the condition of darkroom lucifuge, with organic mixed salt, quality is that the hydrophobic nature bonding agent and the molal quantity of 0.1～2 times of organic mixed salt is the photosensitizer of organic mixed salt 0.1%～40%mol, quality is the surfactant of organic mixed salt 0～1%, through ultrasonic echography, be uniformly dispersed, add the developer that molal quantity is organic mixed salt 1～50%mol then, evenly disperse.
9. method according to claim 8 is characterized in that, described organic mixed salt prepares by the following method:
With in first kind of organic silver salts compound any one with second kind of organic silver salts compound in any one carry out the bowl mill ball milling and mix, make described organic mixed salt, wherein the silver in second kind of organic silver salts occupy total silver amount in the machine mixed salt mole fraction 1%～50%; Or
In a container that stirring apparatus is housed, add entry in advance, add 0.01～1 kilogram of any one part in second kind of organic silver salts then, be heated to 40～90 ℃, constant temperature stirs, use the inorganic base adjust pH then between 5～7, liquor argenti nitratis ophthalmicus is added in the reactor under constant speed react; And then add 0.05～1 kilogram of any one part in first kind of organic silver salts, and continue to drip liquor argenti nitratis ophthalmicus, wherein the concentration of liquor argenti nitratis ophthalmicus is 0.5～3 mol, consumption is 1～3 liter, suction filtration, washing, drying obtains white powder, and organic mixed salt preparation is finished; Or
Any one part in any one and the second kind of organic silver salts in first kind of organic silver salts compound is directly made through the bowl mill ball milling; Wherein any one part of second kind of organic silver salts occupy in the machine mixed salt total silver amount mole fraction 1%～50%.
10. purposes according to each described ISO light-sensitive thermal imaging material emulsion of claim 1～4 is characterized in that: this described ISO light-sensitive thermal imaging material emulsion is as the light sensitive layer material of light-sensitive thermal imaging material film.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104093280A (en) * | 2014-07-21 | 2014-10-08 | 南京瑞盈环保科技有限公司 | Method for preparing high-precision electronic circuit |
| CN108715693A (en) * | 2018-06-29 | 2018-10-30 | 南方科技大学 | A kind of photochemistry removes oxygen to protect the medium and methods and applications of the triplet excited state of photosensitizer |
| CN114853017A (en) * | 2022-04-06 | 2022-08-05 | 湖州师范学院 | Silver-carbon composite temperature-sensitive material and preparation method and application thereof |
-
2007
- 2007-10-22 CN CNA2007101761724A patent/CN101419394A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104093280A (en) * | 2014-07-21 | 2014-10-08 | 南京瑞盈环保科技有限公司 | Method for preparing high-precision electronic circuit |
| CN104093280B (en) * | 2014-07-21 | 2017-01-18 | 南京瑞盈环保科技有限公司 | Method for preparing high-precision electronic circuit |
| CN108715693A (en) * | 2018-06-29 | 2018-10-30 | 南方科技大学 | A kind of photochemistry removes oxygen to protect the medium and methods and applications of the triplet excited state of photosensitizer |
| CN108715693B (en) * | 2018-06-29 | 2020-08-25 | 南方科技大学 | Medium for protecting triplet excited state of photosensitizer by removing oxygen photochemically, and method and application thereof |
| CN114853017A (en) * | 2022-04-06 | 2022-08-05 | 湖州师范学院 | Silver-carbon composite temperature-sensitive material and preparation method and application thereof |
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