CN112882335A - Silver-containing thermosensitive imaging layer, thermosensitive printing medical film and preparation method thereof - Google Patents

Silver-containing thermosensitive imaging layer, thermosensitive printing medical film and preparation method thereof Download PDF

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Publication number
CN112882335A
CN112882335A CN202110024454.2A CN202110024454A CN112882335A CN 112882335 A CN112882335 A CN 112882335A CN 202110024454 A CN202110024454 A CN 202110024454A CN 112882335 A CN112882335 A CN 112882335A
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China
Prior art keywords
silver
imaging layer
amount
reducing agent
film
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CN202110024454.2A
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Chinese (zh)
Inventor
李万迎
常聪慧
高超
江晓利
桑大力
马少勋
徐义
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China Lucky Group Corp
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China Lucky Group Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49809—Organic silver compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3372—Macromolecular compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49827—Reducing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging

Abstract

The invention discloses a silver-containing thermal imaging layer, a thermal printing medical film and a preparation method thereof, wherein the silver-containing thermal imaging layer comprises the following components: the organic silver toner comprises organic silver, a binder, a reducing agent, a stabilizer, a toner and a cross-linking agent, wherein the addition amount of the reducing agent is 0.45 g-1 g, the addition amount of the stabilizer is 0.18 g-0.4 g, and the addition amount of the toner is 0.08 g-0.3 g based on 1g of the organic silver. Thus, the silver-containing heat-sensitive imaging layer can be used for coating silver with low amount (calculated by silver, the coating amount is 0.5 g/m)2～0.8g/m2) The film which has the same performance as the existing high-silver coating product is prepared on the basis, and the use requirement is met, so that the cost of the film is reduced to a great extent.

Description

Silver-containing thermosensitive imaging layer, thermosensitive printing medical film and preparation method thereof
Technical Field
The invention belongs to the technical field of imaging materials, and particularly relates to a silver-containing thermosensitive imaging layer, a thermosensitive printing medical film and a preparation method thereof.
Background
Thermosensitive imaging materials based on long-chain silver carboxylates are the main medical image output hard copy materials in the medical imaging field today, and are important carriers of medical images. Two technical routes currently exist for this imaging material: photothermographic and direct thermal imaging. The two technologies are widely applied in the field of medical imaging, the imaging principle of the two technologies is thermal reduction of organic silver, the difference is that the photothermal reduction of the organic silver is carried out under the catalytic action of a silver halide photosensitive center, the factor influencing the image contrast is the photosensitive degree difference of the silver halide under different light intensities, the direct thermal imaging technology is that the organic silver is reduced at different temperatures, and the factor influencing the image contrast is the temperature difference.
The main factor influencing the overall quality of the direct thermal imaging silver salt film is the performance of the film, the main performance is the high density (Dmax), and when the high density is within a certain range, the overall quality of the film can be ensured to be at a better level, and the accuracy of the doctor in judging the state of an illness is improved.
The existing direct thermal imaging silver salt film products on the market are only owned by the Agfa company. In the practical application process, the film meets the diagnosis requirement when the large density is more than or equal to 3.1, the application effect is optimal, and the overall quality is excellent. In order to ensure that the large density reaches the standard, the coating silver amount of the existing product is about 1.0 g/square meter, and the cost of the film is high due to the high price of metal silver.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to provide a silver-containing thermal imaging layer with which a low coating amount of silver (in terms of silver, the coating amount is 0.5 g/m) can be used, a thermal printing medical film, and a method for producing the same2～0.8g/m2) The film which has the same performance as the existing high-silver coating product is prepared on the basis, and the use requirement is met, so that the cost of the film is reduced to a great extent.
In one aspect, the present invention provides a silver-containing thermal imaging layer. According to an embodiment of the present invention, the silver-containing thermal imaging layer comprises: organic silver, a binder, a reducing agent, a stabilizer, a toner and a crosslinking agent,
wherein the addition amount of the reducing agent is 0.45g to 1g, the addition amount of the stabilizer is 0.18g to 0.4g, and the addition amount of the toner is 0.08g to 0.3g, based on 1g of the organic silver.
According to the silver-containing thermal imaging layer provided by the embodiment of the invention, the imaging layer can be obtained by adjusting the using amount of the reducing agent, the stabilizing agent and the toner to be matched with the using amount of the organic silver, and the low coating silver amount (the coating weight is 0.5g/m in terms of silver) can be used2～0.8g/m2) The film which has the same performance as the existing high-silver coating product is prepared on the basis, and the use requirement is met, so that the cost of the film is reduced to a great extent.
In addition, the silver-containing thermal imaging layer according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the organic silver is a long chain organic silver, preferably at least one of silver eicosanoate, silver docosanoate and silver tetracosanoate.
In some embodiments of the invention, the reducing agent is a phenolic reducing agent, preferably at least one of a phenolic reducing agent and a naphthol reducing agent, more preferably a polyhydric phenolic reducing agent, and most preferably at least one of 3, 4-dihydroxybenzonitrile and 3, 4-dihydroxybenzophenone.
In some embodiments of the present invention, the reducing agent is a combination of 3, 4-dihydroxybenzonitrile and 3, 4-dihydroxybenzophenone, wherein the amount of the 3, 4-dihydroxybenzonitrile added is 0.4g to 0.8g and the amount of the 3, 4-dihydroxybenzophenone added is 0.05g to 0.2g, based on 1g of the organic silver. Therefore, the sample can be prevented from being yellowed by the visible light while the sample density is ensured to meet the use requirement.
In some embodiments of the invention, the stabilizer comprises at least one of tetrachlorophthalic acid and azelaic acid.
In some embodiments of the invention, the stabilizer is a combination of tetrachlorophthalic acid and azelaic acid, wherein the tetrachlorophthalic acid is added in an amount of 0.08 to 0.2g and the azelaic acid is added in an amount of 0.1 to 0.2g, based on 1g of the organic silver. Thereby, it is possible to prevent a large density reduction of the film while securing the stability of the film.
In some embodiments of the present invention, the toner comprises at least one of casalam and acesulfame k.
In some embodiments of the present invention, the toner is a combination of casalam and acesulfame k, wherein the amount of the casalam added is 0.05g to 0.2g and the amount of the acesulfame k added is 0.03g to 0.1g based on 1g of the organic silver. Thus, it is possible to prevent the film from becoming reddish or yellowish in color and increasing the feeling of fatigue when viewing the film.
In some embodiments of the present invention, the binder is added in an amount of 2g to 4g and the crosslinking agent is added in an amount of 0.4g to 0.7g, based on 1g of the organic silver.
In some embodiments of the present invention, the adhesive comprises at least one of PVB and epoxy.
In some embodiments of the invention, the crosslinking agent comprises at least one of MDI and IPDI.
In a second aspect of the invention, a method of making a thermally printed medical film is provided. According to an embodiment of the invention, the method comprises: and drying the heat-sensitive imaging layer after the heat-sensitive imaging layer is applied on the base film so as to obtain the heat-sensitive printing medical film, wherein the heat-sensitive imaging layer is the silver-containing heat-sensitive imaging layer. Thus, by using the above-mentioned silver-containing heat-sensitive image-forming layer, a low coating amount of silver (in terms of silver, the coating amount is 0.5 g/m)2～0.8g/m2) The film which has the same performance as the existing high-silver coating product is prepared on the basis, and the use requirement is met, so that the cost of the film is reduced to a great extent.
In some embodiments of the invention, based on 1m2The base film, the silver-containing thermal imaging layer in terms of silverThe amount of the additive (B) is 0.5 to 0.8 g.
In a third aspect of the invention, a thermal printing medical film is provided. According to the embodiment of the invention, the thermal printing medical film is prepared by adopting the method. Thus, the film was coated with a low amount of silver (in terms of silver, the coating amount was 0.5 g/m)2～0.8g/m2) On the basis, the performance of the coating is equivalent to that of the existing high-silver coating product, and the use requirement is met, so that the cost of the film is reduced to a great extent.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following detailed description of the embodiments of the present invention is intended to be illustrative, and not to be construed as limiting the invention.
In one aspect of the invention, a silver-containing thermal imaging layer is provided. According to an embodiment of the present invention, the silver-containing thermal imaging layer comprises: the organic silver toner comprises organic silver, a binder, a reducing agent, a stabilizer, a toner and a cross-linking agent, wherein the addition amount of the reducing agent is 0.45 g-1 g, the addition amount of the stabilizer is 0.18 g-0.4 g, and the addition amount of the toner is 0.08 g-0.3 g based on 1g of the organic silver.
The inventor finds that the thermal printing medical film development process comprises the steps that the stabilizer is firstly complexed with the organic silver to form a complex, the reducing agent attacks the organic silver under the carrying of the toner, the complex further generates oxidation reduction reaction to generate silver atoms, the silver atoms are stacked into silver atom clusters, and the final density of the film has a great relationship with the stacking state and the average particle size of the silver atom clusters. Therefore, in the process, the types and the amounts of the reducing agent, the stabilizer and the toner have different influences on the final stacking state of the silver atomic clusters, and a certain dynamic balance exists among the reducing agent, the stabilizer and the toner, and the dynamic balance has non-uniqueness. Thus, by adjusting the dosage of the reducing agent, the stabilizer and the toner to be matched with the dosage of the organic silver, a new dynamic balance is establishedThat is, the imaging layer can be coated with low silver coating amount (calculated by silver, the coating amount is 0.5 g/m)2～0.8g/m2) The film which has the same performance as the existing high-silver coating product is prepared on the basis, the use requirement is met, and the film cost is reduced to a great extent.
Further, the organic silver in the imaging layer is a long-chain organic silver, preferably at least one of silver eicosanoate, silver docosanoate and silver tetracosanoate, more preferably silver docosanoate. Silver behenate can be prepared by methods commercially available or in the prior art, for example, the method disclosed in patent CN 1006292168.
Further, the reducing agent in the image forming layer is a phenol reducing agent, preferably at least one of a phenol reducing agent and a naphthol reducing agent, more preferably a polyhydric phenol reducing agent, and most preferably at least one of 3, 4-dihydroxybenzonitrile and 3, 4-dihydroxybenzophenone. According to a specific embodiment of the present invention, the reducing agent is a combination of 3, 4-dihydroxybenzonitrile and 3, 4-dihydroxybenzophenone, and the amount of the 3, 4-dihydroxybenzonitrile added is 0.4g to 0.8g, and the amount of the 3, 4-dihydroxybenzophenone added is 0.05g to 0.2g, based on 1g of the organic silver. The inventor finds that ideal reduction effect cannot be achieved by using any reducing agent alone, 3, 4-dihydroxybenzonitrile is used as a main reducing agent and 3, 4-dihydroxybenzophenone is used as an auxiliary reducing agent in the combined reducing agent, the auxiliary reducing agent assists the main reducing agent to complete reduction reaction, the film density can be further improved, the requirement of the film for high density cannot be met due to too low addition amount of any reducing agent, and unnecessary waste can be caused due to too high addition amount, so that waste can be avoided by using the combined reducing agent formed by the method on the basis of meeting the requirement of the film for high density.
Further, the stabilizer in the imaging layer includes at least one of tetrachlorophthalic acid and azelaic acid; preferably, the organic silver is a combination of tetrachlorophthalic acid and azelaic acid, wherein the tetrachlorophthalic acid is added in an amount of 0.08 to 0.2g and the azelaic acid is added in an amount of 0.1 to 0.2g, based on 1g of the organic silver. The inventor finds that the two stabilizers have different complexing rates with silver ions, one of the two stabilizers cannot achieve an ideal complexing state when used alone, and different complexing states can be obtained by adjusting the dosage of the two stabilizers, so that the purpose of screening the complexing state required by the product is achieved, and the complexing state of the organic silver and the stabilizer meeting the application requirement cannot be obtained when the dosage of any one of the two stabilizers is too high or too low. Thus, the desired complexation state of the product can be achieved with the combination stabilizer of the compositions of the present application.
Furthermore, the toner in the imaging layer is selected from organic matters which can have stronger complexing ability with silver ions, and preferably comprises at least one of casalam and acesulfame potassium; more preferably a combination of casalam and acesulfame-k, wherein the amount of the casalam is 0.05g to 0.2g and the amount of the acesulfame-k is 0.03g to 0.1g based on 1g of the organic silver. The inventors have found that the migration rates of the carbazepine and the acesulfame potassium in the binder after combination with the reducing agent are greatly different due to the difference in steric hindrance, and the migration rates satisfying the imaging requirements of the film can be obtained by adjusting the amounts and combinations thereof, thereby ensuring that the film has a high density and other properties such as the color tone of the swatch within a desired range.
In the imaging layer, the addition amount of the binder is 2 to 4g and the addition amount of the crosslinking agent is 0.4 to 0.7g based on 1g of the organic silver. The inventors have found that the binder provides reaction sites in an amount that directly affects the migration of the reducing agent, stabilizer, toner during development, and the cross-linking agent adjusts the final state of the binder in an amount that directly affects the migration rate of the reducing agent, stabilizer, toner during development. If the amount of the adhesive is too low, the migration process is too short, although the use requirement is met by large density, other application properties such as color tone are obviously deteriorated, and the use requirement of the film cannot be met, and if the amount of the adhesive is too high, the migration process is too long, oxidation-reduction reaction and the final stacking state of silver clusters are influenced, so that the use requirement cannot be met by large density; meanwhile, if the dosage of the cross-linking agent is too low, the coating is not compact enough, the migration rate of the reducing agent, the stabilizing agent and the toner in the adhesive is too fast, although the high density can meet the requirement, other application properties such as color tone are obviously deteriorated, and the use requirement of the film cannot be met, and if the dosage of the cross-linking agent is too high, the coating is too compact, the migration rate of the reducing agent, the stabilizing agent and the toner in the adhesive is too slow, so that the oxidation-reduction reaction and the final stacking state of silver clusters are influenced, and the high density cannot meet the use requirement. And the adhesive comprises at least one of PVB and an epoxy; the crosslinking agent includes at least one of MDI and IPDI.
In a second aspect of the invention, a method of making a thermally printed medical film is provided. According to an embodiment of the invention, the method comprises: and drying the heat-sensitive imaging layer after the heat-sensitive imaging layer is applied on the base film so as to obtain the heat-sensitive printing medical film, wherein the heat-sensitive imaging layer is the silver-containing heat-sensitive imaging layer. Thus, by using the above-mentioned silver-containing heat-sensitive image-forming layer, a low coating amount of silver (in terms of silver, the coating amount is 0.5 g/m)2～0.8g/m2) The film which has the same performance as the existing high-silver coating product is prepared on the basis, and the use requirement is met, so that the cost of the film is reduced to a great extent. Preferably, the base film is a PET film base, a photographic paper base, based on 1m2The base film is characterized in that the application amount of the silver-containing thermosensitive imaging layer is 0.5-0.8 g in terms of silver. Therefore, the film cost can be reduced on the basis of ensuring the film quality. It should be noted that the features and advantages described above for the silver-containing thermal imaging layer are also applicable to the method for preparing the thermal printing medical film, and are not described in detail herein.
In a third aspect of the invention, a thermal printing medical film is provided. According to the embodiment of the invention, the thermal printing medical film is prepared by adopting the method. Thus, the film was coated with a low amount of silver (in terms of silver, the coating amount was 0.5 g/m)2～0.8g/m2) On the basis, the performance of the coating is equivalent to that of the existing high-silver coating product, and the use requirement is met, so that the cost of the film is reduced to a great extent. It is noted that the foregoing is directed to the preparation of thermal printingThe features and advantages described for the method of medical film apply equally to the thermal print medical film and are not described in detail herein.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
Preparation of imaging layer coating liquid: dispersing 1g of silver behenate powder in 10g of PVB solution with the solid content of 20 wt% to obtain 12g of dispersion liquid A, and mixing the dispersion liquid A, 0.6g of 3, 4-dihydroxybenzonitrile, 0.1g of 3, 4-dihydroxybenzophenone, 0.1g of kazalan, 0.05g of acesulfame potassium, 0.1g of tetrachlorophthalic acid, 0.15g of azelaic acid and 0.4g of cross-linking agent MDI under stirring to obtain an imaging layer coating liquid B;
coating an imaging layer: and (3) coating the imaging layer coating liquid B on a PET (polyethylene terephthalate) sheet base, and naturally drying to obtain an imaging layer sample C, wherein the coating silver amount is 0.6 g/square meter.
Coating a protective layer: mixing PVA, silicone oil dispersion liquid, zinc stearate dispersion liquid, polysilicic acid and boric acid to obtain a protective layer coating liquid, and coating the protective layer coating liquid on the imaging layer sample wafer C to obtain a film D.
Example 2
Preparation of imaging layer coating liquid: dispersing 1g of silver behenate powder in 15g of PVB solution with the solid content of 20 wt% to obtain 12g of dispersion liquid A, and mixing the dispersion liquid A, 0.4g of 3, 4-dihydroxybenzonitrile, 0.05g of 3, 4-dihydroxybenzophenone, 0.05g of kazalan, 0.03g of acesulfame potassium, 0.08g of tetrachlorophthalic acid, 0.1g of azelaic acid and 0.5g of cross-linking agent MDI under stirring to obtain an imaging layer coating liquid B;
coating an imaging layer: and (3) coating the imaging layer coating liquid B on a PET (polyethylene terephthalate) sheet base, and naturally drying to obtain an imaging layer sample C, wherein the coating silver amount is 0.5 g/square meter.
Coating a protective layer: mixing PVA, silicone oil dispersion liquid, zinc stearate dispersion liquid, polysilicic acid and boric acid to obtain a protective layer coating liquid, and coating the protective layer coating liquid on the imaging layer sample wafer C to obtain a film D.
Example 3
Preparation of imaging layer coating liquid: dispersing 1g of silver behenate powder in 20g of PVB solution with the solid content of 20 wt% to obtain 12g of dispersion liquid A, and mixing the dispersion liquid A, 0.8g of 3, 4-dihydroxybenzonitrile, 0.2g of 3, 4-dihydroxybenzophenone, 0.2g of kazalan, 0.1g of acesulfame potassium, 0.2g of tetrachlorophthalic acid, 0.2g of azelaic acid and 0.6g of cross-linking agent MDI under stirring to obtain an imaging layer coating liquid B;
coating an imaging layer: and (3) coating the imaging layer coating liquid B on a PET (polyethylene terephthalate) sheet base, and naturally drying to obtain an imaging layer sample C, wherein the coating silver amount is 0.8 g/square meter.
Coating a protective layer: mixing PVA, silicone oil dispersion liquid, zinc stearate dispersion liquid, polysilicic acid and boric acid to obtain a protective layer coating liquid, and coating the protective layer coating liquid on the imaging layer sample wafer C to obtain a film D.
Example 4
Preparation of imaging layer coating liquid: dispersing 1g of silver behenate powder in 17g of PVB solution with the solid content of 20 wt% to obtain 12g of dispersion liquid A, and mixing the dispersion liquid A, 0.4g of 3, 4-dihydroxybenzonitrile, 0.05g of 3, 4-dihydroxybenzophenone, 0.2g of kazalan, 0.1g of acesulfame potassium, 0.08g of tetrachlorophthalic acid, 0.1g of azelaic acid and 0.8g of cross-linking agent MDI under stirring to obtain an imaging layer coating liquid B;
coating an imaging layer: and (3) coating the imaging layer coating liquid B on a PET (polyethylene terephthalate) sheet base, and naturally drying to obtain an imaging layer sample C, wherein the coating silver amount is 0.7 g/square meter.
Coating a protective layer: mixing PVA, silicone oil dispersion liquid, zinc stearate dispersion liquid, polysilicic acid and boric acid to obtain a protective layer coating liquid, and coating the protective layer coating liquid on the imaging layer sample wafer C to obtain a film D.
Example 5
The organic silver was silver eicosanoate, the adhesive was epoxy resin, the crosslinking agent was IPDI, and the rest was the same as in example 1.
Example 6
The organic silver is silver tetracosanate, the adhesive is epoxy resin, the cross-linking agent is IPDI, and the rest is the same as the embodiment 1.
Comparative example 1
Preparation of imaging layer coating liquid: dispersing 1g of silver behenate powder in a PVB solution to obtain 12g of dispersion A, and mixing the dispersion A, 0.6g of 3, 4-dihydroxybenzonitrile, 0.1g of 3, 4-dihydroxybenzophenone, 0.1g of carbazol, 0.05g of acesulfame potassium, 0.1g of tetrachlorophthalic acid, 0.15g of azelaic acid and 0.5g of crosslinking agent under stirring to obtain an imaging layer coating liquid B;
coating an imaging layer: and (3) coating the imaging layer coating liquid B on a PET (polyethylene terephthalate) sheet base, and naturally drying to obtain an imaging layer sample C, wherein the coating silver amount is 1.0 g/square meter.
Coating a protective layer: mixing PVA, silicone oil dispersion liquid, zinc stearate dispersion liquid, polysilicic acid and boric acid to obtain a protective layer coating liquid, and coating the protective layer coating liquid on the imaging layer sample wafer C to obtain a film D.
Comparative example 2
Preparation of imaging layer coating liquid: dispersing 1g of silver behenate powder in a PVB solution to obtain 12g of dispersion A, and mixing the dispersion A, 0.6g of 3, 4-dihydroxybenzonitrile, 0.1g of 3, 4-dihydroxybenzophenone, 0.1g of carbazol, 0.05g of acesulfame potassium, 0.1g of tetrachlorophthalic acid, 0.15g of azelaic acid and 0.6g of crosslinking agent under stirring to obtain an imaging layer coating liquid B;
coating an imaging layer: and (3) coating the imaging layer coating liquid B on a PET (polyethylene terephthalate) sheet base, and naturally drying to obtain an imaging layer sample C, wherein the coating silver amount is 0.45 g/square meter.
Coating a protective layer: mixing PVA, silicone oil dispersion liquid, zinc stearate dispersion liquid, polysilicic acid and boric acid to obtain a protective layer coating liquid, and coating the protective layer coating liquid on the imaging layer sample wafer C to obtain a film D.
Evaluation:
1. the large density of the film D obtained in examples 1 to 6 and comparative examples 1 to 2 was evaluated:
2. the large density test method comprises the following steps:
(1) test conditions
The samples were post-processed by equilibrating at a temperature of 25 ℃. + -. 5 ℃ and a relative humidity of 50%. + -. 10% for at least 30 minutes.
(2) Sampling of the sample
After the sample is balanced, the sample is taken, and the film is taken from the unopened packaging box as a test piece.
(3) Test piece printing
The photographic paper is printed by a Fuji DryPix3000 camera to form 24-level density gray scale, and the 24-level density gray scale is read on a densitometer to form a 24-level gray scale characteristic curve.
(4) Measurement of density
The density is the national standard visual diffuse reflection density, the geometric condition of the density measurement is in accordance with the regulation of GB/T11500, the spectral condition of the density measurement is in accordance with the regulation of GB/T11501, and the maximum density value on the 24-level gray scale characteristic curve is in accordance with the large density Dmax.
The bulk density tests of the films obtained in examples 1 to 6 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1
Figure BDA0002889897010000071
Figure BDA0002889897010000081
As can be seen from the data in Table 1, the thermal imaging silver salt digital medical films prepared by using low silver content in examples 1-6 have the same performance as the direct thermal imaging silver salt digital medical films prepared by using the existing silver coating amount comparative example 1 and the existing Agfa products, and meet the use requirements, and on the basis of the performance, the coating silver amount is continuously reduced, and the contrast and the large density are lost to different degrees, so that the quality of the films is seriously reduced, and the diagnosis requirements cannot be met. From this, this application when guaranteeing performance greatly reduced the coating silver volume of film, reduced manufacturing cost to a great extent.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A silver-containing thermal imaging layer, comprising: organic silver, a binder, a reducing agent, a stabilizer, a toner and a crosslinking agent,
wherein the addition amount of the reducing agent is 0.45g to 1g, the addition amount of the stabilizer is 0.18g to 0.4g, and the addition amount of the toner is 0.08g to 0.3g, based on 1g of the organic silver.
2. The silver-containing thermal imaging layer of claim 1, wherein the organic silver is a long chain organic silver, preferably at least one of silver eicosanoate, silver docosanoate, and silver tetracosanoate, more preferably silver docosanoate.
3. The silver-containing thermographic layer of claim 1 wherein the reducing agent is a phenolic reducing agent, preferably at least one of a phenolic reducing agent and a naphthol reducing agent, more preferably a polyhydric phenolic reducing agent, most preferably at least one of 3, 4-dihydroxybenzonitrile and 3, 4-dihydroxybenzophenone;
optionally, the reducing agent is a combination of 3, 4-dihydroxybenzonitrile and 3, 4-dihydroxybenzophenone, wherein the addition amount of the 3, 4-dihydroxybenzonitrile is 0.4g to 0.8g and the addition amount of the 3, 4-dihydroxybenzophenone is 0.05g to 0.2g based on 1g of the organic silver.
4. The silver-containing thermographic layer of claim 1 wherein the stabilizer comprises at least one of tetrachlorophthalic acid and azelaic acid;
preferably, the stabilizer is a combination of tetrachlorophthalic acid and azelaic acid, wherein the tetrachlorophthalic acid is added in an amount of 0.08 to 0.2g and the azelaic acid is added in an amount of 0.1 to 0.2g, based on 1g of the organic silver.
5. The silver-containing thermographic layer of claim 1 wherein the toner comprises at least one of casalam and acesulfame k;
preferably, the toner is a combination of casselan and acesulfame potassium, wherein the addition amount of the casselan is 0.05g to 0.2g and the addition amount of the acesulfame potassium is 0.03g to 0.1g based on 1g of the organic silver.
6. The silver-containing thermal imaging layer of claim 1, wherein the binder is added in an amount of 2g to 4g and the crosslinking agent is added in an amount of 0.4g to 0.7g, based on 1g of the organic silver.
7. The silver-containing thermal imaging layer of claim 1 or 6, wherein the binder comprises at least one of PVB and an epoxy resin;
optionally, the crosslinking agent comprises at least one of MDI and IPDI.
8. A method of making a thermally printed medical film, comprising: drying the heat-sensitive imaging layer after applying the heat-sensitive imaging layer on the base film so as to obtain a heat-sensitive printing medical film,
wherein the thermal imaging layer is the silver-containing thermal imaging layer of any one of claims 1-7.
9. The method of claim 8, wherein the method is based on 1m2The base film is characterized in that the application amount of the silver-containing thermosensitive imaging layer is 0.5-0.8 g in terms of silver.
10. A thermally printed medical film, wherein the thermally printed medical film is prepared by the method of claim 8 or 9.
CN202110024454.2A 2021-01-08 2021-01-08 Silver-containing thermosensitive imaging layer, thermosensitive printing medical film and preparation method thereof Pending CN112882335A (en)

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