CN112882335B - 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 PDFInfo
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 105
- 239000004332 silver Substances 0.000 title claims abstract description 100
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000003384 imaging method Methods 0.000 title description 51
- 238000007639 printing Methods 0.000 title description 2
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 38
- 238000001931 thermography Methods 0.000 claims abstract description 33
- 239000003381 stabilizer Substances 0.000 claims abstract description 25
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 238000007651 thermal printing Methods 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 19
- ARWCZKJISXFBGI-UHFFFAOYSA-N (3,4-dihydroxyphenyl)-phenylmethanone Chemical compound C1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 ARWCZKJISXFBGI-UHFFFAOYSA-N 0.000 claims description 15
- NUWHYWYSMAPBHK-UHFFFAOYSA-N 3,4-dihydroxybenzonitrile Chemical compound OC1=CC=C(C#N)C=C1O NUWHYWYSMAPBHK-UHFFFAOYSA-N 0.000 claims description 15
- WBZFUFAFFUEMEI-UHFFFAOYSA-M Acesulfame k Chemical compound [K+].CC1=CC(=O)[N-]S(=O)(=O)O1 WBZFUFAFFUEMEI-UHFFFAOYSA-M 0.000 claims description 15
- 229960004998 acesulfame potassium Drugs 0.000 claims description 15
- 235000010358 acesulfame potassium Nutrition 0.000 claims description 15
- 239000000619 acesulfame-K Substances 0.000 claims description 15
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 claims description 14
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 4
- LPYHADGLCYWDNC-UHFFFAOYSA-M silver;tetracosanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCCCC([O-])=O LPYHADGLCYWDNC-UHFFFAOYSA-M 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 77
- 238000000576 coating method Methods 0.000 abstract description 77
- 239000010410 layer Substances 0.000 description 63
- 239000006185 dispersion Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- 239000011241 protective layer Substances 0.000 description 18
- 238000013508 migration Methods 0.000 description 8
- 230000005012 migration Effects 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 7
- -1 silver carboxylates Chemical class 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 238000010668 complexation reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004533 oil dispersion Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000003378 silver Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001739 density measurement Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 241001479434 Agfa Species 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002059 diagnostic imaging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- OHGHHPYRRURLHR-UHFFFAOYSA-M silver;tetradecanoate Chemical group [Ag+].CCCCCCCCCCCCCC([O-])=O OHGHHPYRRURLHR-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
技术领域Technical Field
本发明属于成像材料技术领域,具体涉及一种含银热敏成像层、热敏打印医疗胶片及其制备方法。The invention belongs to the technical field of imaging materials, and in particular relates to a silver-containing thermal imaging layer, a thermal printing medical film and a preparation method thereof.
背景技术Background technique
基于长链羧酸银的热敏成像材料是当今医学成像领域的主要的医学图像输出硬拷贝材料,是医学图像的重要载体。该成像材料目前存在两种技术路线:光敏热成像和直接热成像。两种技术都在医用影像领域得到广泛的应用,这两种技术的成像原理均是有机银的热还原,存在的差异是光敏热成像技术是有机银在卤化银感光中心的催化作用下发生热还原,影响图像对比度的因素是不同光强度下卤化银的感光程度差异,而直接热成像技术是有机银在不同温度下进行还原,影响图像对比度的因素是温度差异。Thermosensitive imaging materials based on long-chain silver carboxylates are the main medical image output hard copy materials in the field of medical imaging today, and are important carriers of medical images. There are currently two technical routes for this imaging material: photothermal imaging and direct thermal imaging. Both technologies have been widely used in the field of medical imaging. The imaging principles of these two technologies are the thermal reduction of organic silver. The difference is that in photothermal imaging technology, organic silver is thermally reduced under the catalytic action of silver halide photosensitive centers, and the factor affecting image contrast is the difference in the photosensitivity of silver halide under different light intensities, while in direct thermal imaging technology, organic silver is reduced at different temperatures, and the factor affecting image contrast is the temperature difference.
影响直接热成像银盐胶片整体质量最主要的因素为胶片的性能,最主要性能为大密度(Dmax),当大密度在某一范围内时,可保证胶片整体质量处于较优的水平,提升医生判断病情的准确率。The most important factor affecting the overall quality of direct thermal imaging silver halide film is the performance of the film, and the most important performance is the maximum density (Dmax). When the maximum density is within a certain range, the overall quality of the film can be guaranteed to be at a better level, thereby improving the accuracy of doctors' diagnosis of the disease.
市场上现有的直接热成像银盐胶片产品仅为Agfa公司所有。实际应用过程中发现,其大密度≥3.1时,胶片满足诊断需求,应用效果最佳,整体质量优良。为保证大密度达标,现有产品的涂布银量约1.0g/㎡,而由于金属银的价格昂贵,导致胶片成本居高不下。The current direct thermal imaging silver halide film products on the market are only owned by Agfa. In actual application, it is found that when the maximum density is ≥3.1, the film meets the diagnostic requirements, has the best application effect, and has excellent overall quality. In order to ensure that the maximum density meets the standard, the coating amount of the existing products is about 1.0g/㎡, and due to the high price of metallic silver, the cost of the film remains high.
发明内容Summary of the invention
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。为此,本发明的一个目的在于提出一种含银热敏成像层、热敏打印医疗胶片及其制备方法,采用该含银热敏成像层可以在使用低涂布银量(以银计,其涂布量为0.5g/m2~0.8g/m2)的基础上制备得到与现有高银量涂布产品性能相当的胶片,满足使用需求,从而很大程度上降低了胶片的成本。The present invention aims to solve at least one of the technical problems in the related art to a certain extent. To this end, one object of the present invention is to provide a silver-containing thermal imaging layer, a thermal printing medical film and a preparation method thereof, wherein the silver-containing thermal imaging layer can be used to prepare a film having performance equivalent to that of existing high-silver-content coated products on the basis of using a low coating amount of silver (the coating amount is 0.5 g/m 2 to 0.8 g/m 2 in terms of silver), thereby meeting the use requirements and thus greatly reducing the cost of the film.
在本发明的一个方面,本发明提成了一种含银热敏成像层。根据本发明的实施例,所述含银热敏成像层包括:有机银、粘合剂、还原剂、稳定剂和调色剂和交联剂,In one aspect of the present invention, 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 cross-linking agent,
其中,基于1g所述有机银,所述还原剂的添加量为0.45g~1g,所述稳定剂的添加量为0.18g~0.4g,所述调色剂的添加量为0.08g~0.3g。Wherein, based on 1g of the organic silver, the added amount of the reducing agent is 0.45g to 1g, the added amount of the stabilizer is 0.18g to 0.4g, and the added amount of the toner is 0.08g to 0.3g.
根据本发明实施例的含银热敏成像层,通过调整还原剂、稳定剂和调色剂用量与有机银用量相匹配,得到成像层可以在使用低涂布银量(以银计,其涂布量为0.5g/m2~0.8g/m2)的基础上制备得到与现有高银量涂布产品性能相当的胶片,满足使用需求,从而很大程度上降低了胶片的成本。According to the silver-containing thermal imaging layer of the embodiment of the present invention, by adjusting the amount of reducing agent, stabilizer and toner to match the amount of organic silver, the imaging layer can be prepared on the basis of using a low coating silver amount (the coating amount is 0.5g/ m2 to 0.8g/ m2 in terms of silver) to obtain a film with performance equivalent to that of existing high-silver coating products, thereby meeting the use requirements and greatly reducing the cost of the film.
另外,根据本发明上述实施例的含银热敏成像层还可以具有如下附加的技术特征: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:
在本发明的一些实施例中,所述有机银为长链有机银,优选二十烷酸银、二十二烷酸银和二十四烷酸银中的至少之一。In some embodiments of the present invention, the organic silver is a long-chain organic silver, preferably at least one of silver eicosanoate, silver docosanoate and silver tetracosanoate.
在本发明的一些实施例中,所述还原剂为酚类还原剂,优选苯酚类还原剂和萘酚类还原剂中的至少之一,更优选多羟基酚类还原剂,最优选3,4-二羟基苯甲腈和3,4-二羟基二苯甲酮中的至少之一。In some embodiments of the present 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 polyhydroxyphenol reducing agent, and most preferably at least one of 3,4-dihydroxybenzonitrile and 3,4-dihydroxybenzophenone.
在本发明的一些实施例中,所述还原剂为3,4-二羟基苯甲腈和3,4-二羟基二苯甲酮的组合,其中,基于1g所述有机银,所述3,4-二羟基苯甲腈的添加量为0.4g~0.8g,所述3,4-二羟基二苯甲酮的添加量为0.05g~0.2g。由此,可以在保证样品密度满足使用要求的同时避免样品见光黄变。In some embodiments of the present invention, the reducing agent is a combination of 3,4-dihydroxybenzonitrile and 3,4-dihydroxybenzophenone, wherein, based on 1g of the organic silver, the amount of 3,4-dihydroxybenzonitrile added is 0.4g to 0.8g, and the amount of 3,4-dihydroxybenzophenone added is 0.05g to 0.2g. Thus, the sample can be prevented from yellowing when exposed to light while ensuring that the sample density meets the use requirements.
在本发明的一些实施例中,所述稳定剂包括四氯邻苯二甲酸和壬二酸中的至少之一。In some embodiments of the present invention, the stabilizer includes at least one of tetrachlorophthalic acid and azelaic acid.
在本发明的一些实施例中,所述稳定剂为四氯邻苯二甲酸和壬二酸的组合,其中,基于1g所述有机银,所述四氯邻苯二甲酸的添加量为0.08g~0.2g,所述壬二酸的添加量为0.1g~0.2g。由此,可以在保证胶片稳定性的同时避免胶片大密度降低。In some embodiments of the present invention, the stabilizer is a combination of tetrachlorophthalic acid and azelaic acid, wherein, based on 1g of the organic silver, the amount of tetrachlorophthalic acid added is 0.08g to 0.2g, and the amount of azelaic acid added is 0.1g to 0.2g. Thus, the film stability can be ensured while avoiding the reduction of the film density.
在本发明的一些实施例中,所述调色剂包括卡沙仑和安赛蜜中的至少之一。In some embodiments of the present invention, the toner includes at least one of casalan and acesulfame potassium.
在本发明的一些实施例中,所述调色剂为卡沙仑和安赛蜜的组合,其中,基于1g所述有机银,所述卡沙仑的添加量为0.05g~0.2g,所述安赛蜜的添加量为0.03g~0.1g。由此,可以避免胶片出现色调发红或发黄而增加观看胶片的疲劳感。In some embodiments of the present invention, the toner is a combination of casalan and acesulfame potassium, wherein, based on 1g of the organic silver, the amount of casalan added is 0.05g to 0.2g, and the amount of acesulfame potassium added is 0.03g to 0.1g. Thus, the film can be prevented from having a reddish or yellowish hue and increasing the fatigue of watching the film.
在本发明的一些实施例中,基于1g所述有机银,所述粘合剂的添加量为2g~4g,所述交联剂的添加量为0.4g~0.7g。In some embodiments of the present invention, based on 1 g of the organic silver, the added amount of the binder is 2 g to 4 g, and the added amount of the cross-linking agent is 0.4 g to 0.7 g.
在本发明的一些实施例中,所述粘合剂包括PVB和环氧树脂中的至少之一。In some embodiments of the present invention, the adhesive includes at least one of PVB and epoxy resin.
在本发明的一些实施例中,所述交联剂包括MDI和IPDI中的至少之一。In some embodiments of the present invention, the cross-linking agent includes at least one of MDI and IPDI.
在本发明的第二个方面,本发明提出了一种制备热敏打印医疗胶片的方法。根据本发明的实施例,所述方法包括:将热敏成像层施加在基膜上后进行干燥,以便得到热敏打印医疗胶片,其中,所述热敏成像层为上述的含银热敏成像层。由此,通过使用上述的含银热敏成像层可以在使用低涂布银量(以银计,其涂布量为0.5g/m2~0.8g/m2)的基础上制备得到与现有高银量涂布产品性能相当的胶片,满足使用需求,从而很大程度上降低了胶片的成本。In the second aspect of the present invention, the present invention proposes a method for preparing a thermal printing medical film. According to an embodiment of the present invention, the method comprises: applying a thermal imaging layer on a base film and then drying it to obtain a thermal printing medical film, wherein the thermal imaging layer is the above-mentioned silver-containing thermal imaging layer. Thus, by using the above-mentioned silver-containing thermal imaging layer, a film having performance equivalent to that of existing high-silver-content coated products can be prepared on the basis of using a low coating silver amount (in terms of silver, the coating amount is 0.5g/ m2 to 0.8g/ m2 ), meeting the use requirements, thereby greatly reducing the cost of the film.
在本发明的一些实施例中,基于1m2的所述基膜,以银计,所述含银热敏成像层的施加量为0.5~0.8g。In some embodiments of the present invention, the silver-containing thermal imaging layer is applied in an amount of 0.5 to 0.8 g in terms of silver based on 1 m 2 of the base film.
在本发明的第三个方面,本发明提出了一种热敏打印医疗胶片。根据本发明的实施例,所述热敏打印医疗胶片采用上述的方法制备得到。由此,该胶片在使用低涂布银量(以银计,其涂布量为0.5g/m2~0.8g/m2)的基础上与现有高银量涂布产品性能相当,满足使用需求,从而很大程度上降低了胶片的成本。In the third aspect of the present invention, a thermal printing medical film is provided. According to an embodiment of the present invention, the thermal printing medical film is prepared by the above method. Therefore, the film has the same performance as the existing high silver coating products on the basis of using a low silver coating amount (the coating amount is 0.5g/ m2 to 0.8g/ m2 in terms of silver), meets the use requirements, and thus greatly reduces the cost of the film.
本发明的附加方面和优点将在下面的描述中部分给出,部分将从下面的描述中变得明显,或通过本发明的实践了解到。Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention.
具体实施方式Detailed ways
下面详细描述本发明的实施例,旨在用于解释本发明,而不能理解为对本发明的限制。The embodiments of the present invention are described in detail below, which are intended to explain the present invention but are not to be construed as limiting the present invention.
在本发明的一个方面,本发明提出了一种含银热敏成像层。根据本发明的实施例,该含银热敏成像层包括:有机银、粘合剂、还原剂、稳定剂和调色剂和交联剂,其中,基于1g所述有机银,所述还原剂的添加量为0.45g~1g,所述稳定剂的添加量为0.18g~0.4g,所述调色剂的添加量为0.08g~0.3g。In one aspect of the present invention, 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 cross-linking agent, wherein, based on 1g of the organic silver, the adding amount of the reducing agent is 0.45g to 1g, the adding amount of the stabilizer is 0.18g to 0.4g, and the adding amount of the toner is 0.08g to 0.3g.
发明人发现,本发明所述热敏打印医疗胶片显影过程为,稳定剂首先与有机银络合形成络合物,还原剂在调色剂的携带下“进攻”该络合物“抢夺”有机银,进而发生氧化还原反应产生银原子,银原子堆积为银原子簇,胶片最终密度与银原子簇的堆积状态及平均粒径有很大的关系。因此在该过程中,还原剂、稳定剂、调色剂的种类及用量对于银原子簇最终的堆积状态均有不同程度的影响,且三者之间存在一定程度上的动态平衡,且这种动态平衡具有不唯一性。由此通过调整还原剂、稳定剂和调色剂用量与有机银用量相匹配,建立新的动态平衡,即可达到成像层在使用低涂布银量(以银计,其涂布量为0.5g/m2~0.8g/m2)的基础上制备得到与现有高银量涂布产品性能相当的胶片,满足使用需求,从而很大程度上降低胶片成本的目的。The inventors found that the development process of the thermal printing medical film of the present invention is that the stabilizer first forms a complex with organic silver, and the reducing agent "attacks" the complex under the support of the toner to "rob" the organic silver, and then an oxidation-reduction reaction occurs to produce silver atoms, and the silver atoms are accumulated into silver atom clusters. The final density of the film has a great relationship with the accumulation state and average particle size of the silver atom clusters. Therefore, in this process, the type and amount of the reducing agent, stabilizer, and toner have different degrees of influence on the final accumulation state of the silver atom clusters, and there is a certain degree of dynamic balance between the three, and this dynamic balance is not unique. Therefore, by adjusting the amount of reducing agent, stabilizer and toner to match the amount of organic silver, a new dynamic balance is established, and the imaging layer can be prepared on the basis of using a low coating silver amount (in terms of silver, the coating amount is 0.5g/ m2 ~0.8g/ m2 ) to obtain a film with performance equivalent to the existing high silver coating product, which meets the use requirements and thus greatly reduces the cost of the film.
进一步地,上述成像层中有机银为长链有机银,优选二十烷酸银、二十二烷酸银和二十四烷酸银中的至少之一,更优选二十二烷酸银。需要说明的是,二十二烷酸银可以采用市售或现有技术中方法制备得到,例如可以参考专利CN1006292168中的方法制备得到。Furthermore, the organic silver in the imaging layer is a long-chain organic silver, preferably at least one of silver eicosanoate, silver behenate and silver tetracosanoate, more preferably silver behenate. It should be noted that silver behenate can be prepared by commercially available methods or methods in the prior art, for example, it can be prepared by referring to the method in patent CN1006292168.
进一步地,上述成像层中还原剂为酚类还原剂,优选苯酚类还原剂和萘酚类还原剂中的至少之一,更优选多羟基酚类还原剂,最优选3,4-二羟基苯甲腈和3,4-二羟基二苯甲酮中的至少之一。根据本发明的一个具体实施例,还原剂为3,4-二羟基苯甲腈和3,4-二羟基二苯甲酮的组合,并且基于1g所述有机银,所述3,4-二羟基苯甲腈的添加量为0.4g~0.8g,所述3,4-二羟基二苯甲酮的添加量为0.05g~0.2g。发明人发现,单独使用任何其中一种还原剂均无法达到理想的还原效果,而本申请的组合还原剂中3,4-二羟基苯甲腈为主还原剂,3,4-二羟基二苯甲酮为助还原剂,该助还原剂协助主还原剂完成还原反应,可进一步提升胶片密度,而其中任何一种添加量过低均无法满足胶片对大密度的需求,添加量过高又会造成不必要的浪费,由此,采用本申请组成的组合还原剂可以在满足胶片对大密度的需求基础上避免浪费。Further, the reducing agent in the imaging layer is a phenolic reducing agent, preferably at least one of a phenolic reducing agent and a naphthol reducing agent, more preferably a polyhydroxyphenolic 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 based on 1g of the organic silver, 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. The inventors have found that the ideal reduction effect cannot be achieved by using any one of the reducing agents alone. In the combined reducing agent of the present application, 3,4-dihydroxybenzonitrile is the main reducing agent and 3,4-dihydroxybenzophenone is the auxiliary reducing agent. The auxiliary reducing agent assists the main reducing agent in completing the reduction reaction, which can further improve the film density. If the addition amount of any one of the reducing agents is too low, it cannot meet the film's demand for high density, and if the addition amount is too high, it will cause unnecessary waste. Therefore, the combined reducing agent composed of the present application can avoid waste on the basis of meeting the film's demand for high density.
进一步地,上述成像层中稳定剂包括四氯邻苯二甲酸和壬二酸中的至少之一;优选为四氯邻苯二甲酸和壬二酸的组合,其中,基于1g所述有机银,所述四氯邻苯二甲酸的添加量为0.08g~0.2g,所述壬二酸的添加量为0.1g~0.2g。发明人发现,该两种稳定剂与银离子络合速率不同,单独使用其中一种稳定剂,无法达到理想中的络合状态,通过调整二者的用量,可以得到不同络合状态,从而达到对本产品所需的络合状态进行筛选的目的,而其中任何一种稳定剂用量过高或过低,均无法得到满足应用需求的稳定剂与有机银的络合状态。由此,采用本申请的组成的组合稳定剂可以达到本产品所需的络合状态。Furthermore, the stabilizer in the imaging layer includes at least one of tetrachlorophthalic acid and azelaic acid; preferably, it is a combination of tetrachlorophthalic acid and azelaic acid, wherein, based on 1g of the organic silver, the amount of the tetrachlorophthalic acid added is 0.08g to 0.2g, and the amount of the azelaic acid added is 0.1g to 0.2g. The inventors found that the two stabilizers have different complexation rates with silver ions, and the ideal complexation state cannot be achieved by using only one of the stabilizers. By adjusting the dosage of the two, different complexation states can be obtained, thereby achieving the purpose of screening the complexation state required for this product. If the dosage of any one of the stabilizers is too high or too low, the complexation state of the stabilizer and the organic silver that meets the application requirements cannot be obtained. Therefore, the combined stabilizer of the composition of the present application can achieve the complexation state required for this product.
进一步地,上述成像层中调色剂选用可以与银离子有较强络合能力的有机物,优选包括卡沙仑和安赛蜜中的至少之一;更优选为卡沙仑和安赛蜜的组合,其中,基于1g所述有机银,所述卡沙仑的添加量为0.05g~0.2g,所述安赛蜜的添加量为0.03g~0.1g。发明人发现,由于空间位阻的差异,卡沙仑与安赛蜜在与还原剂结合后,在粘合剂中的迁移速率有较大的差异,通过对其用量及组合的调整,可以得到满足胶片成像需求的迁移速率,从而保证胶片大密度及其它诸如样片色调的性能在所需范围内。Furthermore, the toner in the imaging layer is selected from organic substances that have strong complexing ability with silver ions, preferably including at least one of casalan and acesulfame potassium; more preferably, it is a combination of casalan and acesulfame potassium, wherein, based on 1g of the organic silver, the amount of casalan added is 0.05g to 0.2g, and the amount of acesulfame potassium added is 0.03g to 0.1g. The inventors have found that due to the difference in steric hindrance, the migration rates of casalan and acesulfame potassium in the adhesive are greatly different after combining with the reducing agent. By adjusting the amount and combination thereof, the migration rate that meets the film imaging requirements can be obtained, thereby ensuring that the film's high density and other properties such as the color tone of the sample are within the required range.
进一步地,上述成像层中,基于1g所述有机银,所述粘合剂的添加量为2g~4g,所述交联剂的添加量为0.4g~0.7g。发明人发现,粘合剂提供反应场所,其用量多少直接影响还原剂、稳定剂、调色剂在显影过程中的迁移程,交联剂调整粘合剂的最终状态,其用量多少直接影响还原剂、稳定剂、调色剂在显影过程中的迁移速率。而若粘合剂用量太低迁移程太短,虽大密度满足使用需求,但其它应用性能如色调出现明显的恶化,无法满足胶片使用需求,而若粘合剂用量过高,迁移程过长,影响氧化还原反应及银原子簇的最终堆积状态,导致大密度无法满足使用需求;同时若交联剂用量太低,涂层不够致密,还原剂、稳定剂、调色剂在粘合剂中的迁移速率过快,虽大密度可满足需求,但其它应用性能如色调出现明显的恶化,无法满足胶片使用需求,而若交联剂用量太高,涂层过于致密,还原剂、稳定剂、调色剂在粘合剂中的迁移速率过慢,影响氧化还原反应及银原子簇的最终堆积状态,导致大密度无法满足使用需求。并且所述粘合剂包括PVB和环氧树脂中的至少之一;所述交联剂包括MDI和IPDI中的至少之一。Furthermore, in the imaging layer, based on 1g of the organic silver, the amount of the binder added is 2g to 4g, and the amount of the crosslinker added is 0.4g to 0.7g. The inventors found that the binder provides a reaction site, and its amount directly affects the migration of the reducing agent, stabilizer, and toner during the development process, and the crosslinker adjusts the final state of the binder, and its amount directly affects the migration rate of the reducing agent, stabilizer, and toner during the development process. If the amount of adhesive is too low and the migration distance is too short, although the high density meets the use requirements, other application properties such as color tone will be significantly deteriorated and cannot meet the use requirements of the film. If the amount of adhesive is too high, the migration distance will be too long, which will affect the redox reaction and the final stacking state of the silver atom clusters, resulting in a high density that cannot meet the use requirements; at the same time, if the amount of cross-linking agent is too low, the coating is not dense enough, and the migration rate of the reducing agent, stabilizer, and toner in the adhesive is too fast. Although the high density can meet the requirements, other application properties such as color tone will be significantly deteriorated and cannot meet the use requirements of the film. If the amount of cross-linking agent is too high, the coating is too dense, and the migration rate of the reducing agent, stabilizer, and toner in the adhesive is too slow, which will affect the redox reaction and the final stacking state of the silver atom clusters, resulting in a high density that cannot meet the use requirements. And the adhesive includes at least one of PVB and epoxy resin; the cross-linking agent includes at least one of MDI and IPDI.
在本发明的第二个方面,本发明提出了一种制备热敏打印医疗胶片的方法。根据本发明的实施例,所述方法包括:将热敏成像层施加在基膜上后进行干燥,以便得到热敏打印医疗胶片,其中,所述热敏成像层为上述的含银热敏成像层。由此,通过使用上述的含银热敏成像层可以在使用低涂布银量(以银计,其涂布量为0.5g/m2~0.8g/m2)的基础上制备得到与现有高银量涂布产品性能相当的胶片,满足使用需求,从而很大程度上降低了胶片的成本。优选地,基膜为PET片基、相纸纸基,基于1m2的所述基膜,以银计,所述含银热敏成像层的施加量为0.5~0.8g。由此,可以在保证胶片质量的基础上降低胶片成本。需要说明的是,上述针对含银热敏成像层所描述的特征和优点同样适用于该制备热敏打印医疗胶片的方法,此处不再赘述。In the second aspect of the present invention, the present invention proposes a method for preparing a thermal printing medical film. According to an embodiment of the present invention, the method comprises: applying a thermal imaging layer on a base film and then drying it to obtain a thermal printing medical film, wherein the thermal imaging layer is the above-mentioned silver-containing thermal imaging layer. Thus, by using the above-mentioned silver-containing thermal imaging layer, a film with performance equivalent to that of existing high-silver-content coated products can be prepared on the basis of using a low coating silver amount (in terms of silver, the coating amount is 0.5g/ m2 to 0.8g/ m2 ), meeting the use requirements, thereby greatly reducing the cost of the film. Preferably, the base film is a PET film base or a photographic paper base, and based on 1m2 of the base film, the application amount of the silver-containing thermal imaging layer is 0.5 to 0.8g in terms of silver. Thus, the cost of the film can be reduced while ensuring the quality of the film. 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 will not be repeated here.
在本发明的第三个方面,本发明提出了一种热敏打印医疗胶片。根据本发明的实施例,所述热敏打印医疗胶片采用上述的方法制备得到。由此,该胶片在使用低涂布银量(以银计,其涂布量为0.5g/m2~0.8g/m2)的基础上与现有高银量涂布产品性能相当,满足使用需求,从而很大程度上降低了胶片的成本。需要说明的是,上述针对制备热敏打印医疗胶片的方法所描述的特征和优点同样适用于该热敏打印医疗胶片,此处不再赘述。In the third aspect of the present invention, the present invention proposes a thermal printing medical film. According to an embodiment of the present invention, the thermal printing medical film is prepared by the above method. As a result, the film has the same performance as the existing high silver coating products on the basis of using a low coating silver amount (in terms of silver, the coating amount is 0.5g/ m2 to 0.8g/ m2 ), meets the use requirements, and thus greatly reduces the cost of the film. It should be noted that the features and advantages described above for the method for preparing thermal printing medical film are also applicable to the thermal printing medical film, and will not be repeated here.
下面详细描述本发明的实施例,需要说明的是下面描述的实施例是示例性的,仅用于解释本发明,而不能理解为对本发明的限制。另外,如果没有明确说明,在下面的实施例中所采用的所有试剂均为市场上可以购得的,或者可以按照本文或已知的方法合成的,对于没有列出的反应条件,也均为本领域技术人员容易获得的。The embodiments of the present invention are described in detail below. It should be noted that the embodiments described below are exemplary and are only used to explain the present invention, and cannot be interpreted as limiting the present invention. In addition, if not explicitly stated, all reagents used in the following embodiments are commercially available, or can be synthesized according to this article or known methods, and the reaction conditions not listed are also easily available to those skilled in the art.
实施例1Example 1
成像层涂布液的制备:将1g山嵛酸银粉末在10g固含量20wt%的PVB溶液中进行分散得到11g分散液A,在搅拌状态下将分散液A、0.6g 3,4-二羟基苯甲腈、0.1g3,4-二羟基二苯甲酮、0.1g卡沙仑、0.05g安赛蜜、0.1g四氯邻苯二甲酸、0.15g壬二酸、0.4g的交联剂MDI混合,得到成像层涂布液B;Preparation of imaging layer coating liquid: 1 g of silver behenate powder was dispersed in 10 g of PVB solution with a solid content of 20 wt% to obtain 11 g of dispersion A, and dispersion A, 0.6 g of 3,4-dihydroxybenzonitrile, 0.1 g of 3,4-dihydroxybenzophenone, 0.1 g of casalan, 0.05 g of acesulfame potassium, 0.1 g of tetrachlorophthalic acid, 0.15 g of azelaic acid, and 0.4 g of a crosslinking agent MDI were mixed under stirring to obtain imaging layer coating liquid B;
成像层涂布:将成像层涂布液B涂布到PET片基上,自然干燥得到成像层样片C,涂布银量0.6g/㎡。Imaging layer coating: coating the imaging layer coating liquid B onto the PET film base and drying naturally to obtain the imaging layer sample C, with a coating silver amount of 0.6 g/㎡.
保护层涂布:将PVA、硅油分散液、硬脂酸锌分散液、聚硅酸、硼酸进行混合,得到保护层涂布液,将该保护层涂布液涂布到成像层样片C上,得到胶片D。Protective layer coating: PVA, silicone oil dispersion, zinc stearate dispersion, polysilicic acid and boric acid are mixed to obtain a protective layer coating solution, and the protective layer coating solution is coated on the imaging layer sample C to obtain film D.
实施例2Example 2
成像层涂布液的制备:将1g山嵛酸银粉末在15g固含量20wt%PVB溶液中进行分散得到16g分散液A,在搅拌状态下将分散液A、0.4g 3,4-二羟基苯甲腈、0.05g3,4-二羟基二苯甲酮、0.05g卡沙仑、0.03g安赛蜜、0.08g四氯邻苯二甲酸、0.1g壬二酸、0.5g的交联剂MDI混合,得到成像层涂布液B;Preparation of imaging layer coating liquid: 1 g of silver behenate powder was dispersed in 15 g of PVB solution with a solid content of 20 wt % to obtain 16 g of dispersion A, and dispersion A, 0.4 g of 3,4-dihydroxybenzonitrile, 0.05 g of 3,4-dihydroxybenzophenone, 0.05 g of casalan, 0.03 g of acesulfame potassium, 0.08 g of tetrachlorophthalic acid, 0.1 g of azelaic acid, and 0.5 g of crosslinking agent MDI were mixed under stirring to obtain imaging layer coating liquid B;
成像层涂布:将成像层涂布液B涂布到PET片基上,自然干燥得到成像层样片C,涂布银量0.5g/㎡。Imaging layer coating: coating the imaging layer coating liquid B onto the PET film base and drying naturally to obtain the imaging layer sample C, with a coating amount of silver of 0.5 g/㎡.
保护层涂布:将PVA、硅油分散液、硬脂酸锌分散液、聚硅酸、硼酸进行混合,得到保护层涂布液,将该保护层涂布液涂布到成像层样片C上,得到胶片D。Protective layer coating: PVA, silicone oil dispersion, zinc stearate dispersion, polysilicic acid and boric acid are mixed to obtain a protective layer coating solution, and the protective layer coating solution is coated on the imaging layer sample C to obtain film D.
实施例3Example 3
成像层涂布液的制备:将1g山嵛酸银粉末在20g固含量20wt%PVB溶液中进行分散得到21g分散液A,在搅拌状态下将分散液A、0.8g 3,4-二羟基苯甲腈、0.2g3,4-二羟基二苯甲酮、0.2g卡沙仑、0.1g安赛蜜、0.2g四氯邻苯二甲酸、0.2g壬二酸、0.6g的交联剂MDI混合,得到成像层涂布液B;Preparation of imaging layer coating liquid: 1 g of silver behenate powder was dispersed in 20 g of PVB solution with a solid content of 20 wt % to obtain 21 g of dispersion A, and dispersion A, 0.8 g of 3,4-dihydroxybenzonitrile, 0.2 g of 3,4-dihydroxybenzophenone, 0.2 g of casalan, 0.1 g of acesulfame potassium, 0.2 g of tetrachlorophthalic acid, 0.2 g of azelaic acid, and 0.6 g of crosslinking agent MDI were mixed under stirring to obtain imaging layer coating liquid B;
成像层涂布:将成像层涂布液B涂布到PET片基上,自然干燥得到成像层样片C,涂布银量0.8g/㎡。Imaging layer coating: coating the imaging layer coating liquid B onto the PET film base and drying naturally to obtain the imaging layer sample C, with a coating silver amount of 0.8 g/㎡.
保护层涂布:将PVA、硅油分散液、硬脂酸锌分散液、聚硅酸、硼酸进行混合,得到保护层涂布液,将该保护层涂布液涂布到成像层样片C上,得到胶片D。Protective layer coating: PVA, silicone oil dispersion, zinc stearate dispersion, polysilicic acid and boric acid are mixed to obtain a protective layer coating solution, and the protective layer coating solution is coated on the imaging layer sample C to obtain film D.
实施例4Example 4
成像层涂布液的制备:将1g山嵛酸银粉末在17g固含量20wt%PVB溶液中进行分散得到18g分散液A,在搅拌状态下将分散液A、0.4g 3,4-二羟基苯甲腈、0.05g3,4-二羟基二苯甲酮、0.2g卡沙仑、0.1g安赛蜜、0.08g四氯邻苯二甲酸、0.1g壬二酸、0.8g的交联剂MDI混合,得到成像层涂布液B;Preparation of imaging layer coating liquid: 1 g of silver behenate powder was dispersed in 17 g of PVB solution with a solid content of 20 wt% to obtain 18 g of dispersion A, and dispersion A, 0.4 g of 3,4-dihydroxybenzonitrile, 0.05 g of 3,4-dihydroxybenzophenone, 0.2 g of casalan, 0.1 g of acesulfame potassium, 0.08 g of tetrachlorophthalic acid, 0.1 g of azelaic acid, and 0.8 g of crosslinking agent MDI were mixed under stirring to obtain imaging layer coating liquid B;
成像层涂布:将成像层涂布液B涂布到PET片基上,自然干燥得到成像层样片C,涂布银量0.7g/㎡。Imaging layer coating: coating the imaging layer coating liquid B onto the PET film base and drying naturally to obtain the imaging layer sample C, with a coating silver amount of 0.7 g/㎡.
保护层涂布:将PVA、硅油分散液、硬脂酸锌分散液、聚硅酸、硼酸进行混合,得到保护层涂布液,将该保护层涂布液涂布到成像层样片C上,得到胶片D。Protective layer coating: PVA, silicone oil dispersion, zinc stearate dispersion, polysilicic acid and boric acid are mixed to obtain a protective layer coating solution, and the protective layer coating solution is coated on the imaging layer sample C to obtain film D.
实施例5Example 5
其有机银采用二十烷酸银,粘合剂采用环氧树脂,交联剂采用IPDI,其余同于实施例1。The organic silver is silver eicosanoate, the adhesive is epoxy resin, the cross-linking agent is IPDI, and the rest is the same as in Example 1.
实施例6Example 6
其有机银采用二十四烷酸银,粘合剂采用环氧树脂,交联剂采用IPDI,其余同于实施例1。The organic silver is silver tetradecanoate, the adhesive is epoxy resin, the cross-linking agent is IPDI, and the rest is the same as in Example 1.
对比例1Comparative Example 1
成像层涂布液的制备:将1g山嵛酸银粉末在PVB溶液中进行分散得到12g分散液A,在搅拌状态下将分散液A、0.6g 3,4-二羟基苯甲腈、0.1g3,4-二羟基二苯甲酮、0.1g卡沙仑、0.05g安赛蜜、0.1g四氯邻苯二甲酸、0.15g壬二酸、0.5g的交联剂混合,得到成像层涂布液B;Preparation of imaging layer coating liquid: 1 g of silver behenate powder was dispersed in PVB solution to obtain 12 g of dispersion A, and dispersion A, 0.6 g of 3,4-dihydroxybenzonitrile, 0.1 g of 3,4-dihydroxybenzophenone, 0.1 g of casalan, 0.05 g of acesulfame potassium, 0.1 g of tetrachlorophthalic acid, 0.15 g of azelaic acid, and 0.5 g of a cross-linking agent were mixed under stirring to obtain imaging layer coating liquid B;
成像层涂布:将成像层涂布液B涂布到PET片基上,自然干燥得到成像层样片C,涂布银量1.0g/㎡。Imaging layer coating: coating the imaging layer coating liquid B onto the PET film base and drying naturally to obtain the imaging layer sample C, with a coating amount of silver of 1.0 g/㎡.
保护层涂布:将PVA、硅油分散液、硬脂酸锌分散液、聚硅酸、硼酸进行混合,得到保护层涂布液,将该保护层涂布液涂布到成像层样片C上,得到胶片D。Protective layer coating: PVA, silicone oil dispersion, zinc stearate dispersion, polysilicic acid and boric acid are mixed to obtain a protective layer coating solution, and the protective layer coating solution is coated on the imaging layer sample C to obtain film D.
对比例2Comparative Example 2
成像层涂布液的制备:将1g山嵛酸银粉末在PVB溶液中进行分散得到12g分散液A,在搅拌状态下将分散液A、0.6g 3,4-二羟基苯甲腈、0.1g3,4-二羟基二苯甲酮、0.1g卡沙仑、0.05g安赛蜜、0.1g四氯邻苯二甲酸、0.15g壬二酸、0.6g的交联剂混合,得到成像层涂布液B;Preparation of imaging layer coating liquid: 1 g of silver behenate powder was dispersed in PVB solution to obtain 12 g of dispersion A, and dispersion A, 0.6 g of 3,4-dihydroxybenzonitrile, 0.1 g of 3,4-dihydroxybenzophenone, 0.1 g of casalan, 0.05 g of acesulfame potassium, 0.1 g of tetrachlorophthalic acid, 0.15 g of azelaic acid, and 0.6 g of a cross-linking agent were mixed under stirring to obtain imaging layer coating liquid B;
成像层涂布:将成像层涂布液B涂布到PET片基上,自然干燥得到成像层样片C,涂布银量0.45g/㎡。Imaging layer coating: coating the imaging layer coating liquid B onto the PET film base and drying naturally to obtain the imaging layer sample C, with a coating amount of 0.45 g/㎡ of silver.
保护层涂布:将PVA、硅油分散液、硬脂酸锌分散液、聚硅酸、硼酸进行混合,得到保护层涂布液,将该保护层涂布液涂布到成像层样片C上,得到胶片D。Protective layer coating: PVA, silicone oil dispersion, zinc stearate dispersion, polysilicic acid and boric acid are mixed to obtain a protective layer coating solution, and the protective layer coating solution is coated on the imaging layer sample C to obtain film D.
评价:evaluate:
1、对实施例1-6和对比例1-2得到胶片D的大密度进行评价:1. Evaluate the high density of film D obtained in Examples 1-6 and Comparative Examples 1-2:
2、大密度测试方法:2. High density test method:
(1)、试验条件(1) Test conditions
样品需在温度25℃±5℃和相对湿度50%±10%条件下至少平衡30分钟后加工。The samples must be equilibrated at a temperature of 25°C ± 5°C and a relative humidity of 50% ± 10% for at least 30 minutes before processing.
(2)、取样(2) Sampling
样品达到平衡后取样,从未开封的包装盒内任取胶片,作为试片。After the sample reaches equilibrium, take a sample and take any film from the unopened package as a test piece.
(3)、试片打印(3) Test piece printing
用富士DryPix3000相机打印相纸,形成24级密度灰阶,将24级密度灰阶在密度计上读取后形成一条24级灰阶特性曲线。Use Fuji DryPix3000 camera to print photo paper to form 24 levels of density grayscale. After reading the 24 levels of density grayscale on the densitometer, a 24-level grayscale characteristic curve is formed.
(4)、密度测量(4) Density measurement
密度应为国家标准视觉漫反射密度,密度测量的几何条件应符合GB/T11500的规定,密度测量的光谱条件应符合GB/T11501的规定,在24级灰阶特性曲线上密度最大值对应大密度Dmax。The density should be the national standard visual diffuse reflection density. The geometric conditions for density measurement should comply with the provisions of GB/T11500. The spectral conditions for density measurement should comply with the provisions of GB/T11501. The maximum density value corresponds to the maximum density Dmax on the 24-level grayscale characteristic curve.
实施例1-6和对比例1-2得到胶片的大密度测试如表1所示。The high density test results of the films obtained in Examples 1-6 and Comparative Examples 1-2 are shown in Table 1.
表1Table 1
由表1数据可知,实施例1-6使用低银量制备的热成像银盐数字医疗胶片,与现有涂布银量对比例1和Agfa现有产品的直接热成像银盐数字医疗胶片性能相当,满足使用需求,在此基础上继续降低涂布银量,反差及大密度均有不同程度的损失,导致胶片质量严重下降,无法满足诊断需求。由此,本申请在保证性能的同时大大降低了胶片的涂布银量,在很大程度上降低了生产成本。As can be seen from the data in Table 1, the thermal imaging silver salt digital medical film prepared with low silver content in Examples 1-6 has comparable performance to the direct thermal imaging silver salt digital medical film of the existing coated silver content comparative example 1 and Agfa's existing products, meeting the use requirements. On this basis, if the coated silver content is further reduced, the contrast and high density will be lost to varying degrees, resulting in a serious decline in film quality and failure to meet diagnostic requirements. Therefore, the present application greatly reduces the coated silver content of the film while ensuring performance, thereby greatly reducing production costs.
在本说明书的描述中,参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外,在不相互矛盾的情况下,本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.
尽管上面已经示出和描述了本发明的实施例,可以理解的是,上述实施例是示例性的,不能理解为对本发明的限制,本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.
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