CN112859506A - Thermal black-white photographic paper - Google Patents
Thermal black-white photographic paper Download PDFInfo
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- CN112859506A CN112859506A CN202110026179.8A CN202110026179A CN112859506A CN 112859506 A CN112859506 A CN 112859506A CN 202110026179 A CN202110026179 A CN 202110026179A CN 112859506 A CN112859506 A CN 112859506A
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- China
- Prior art keywords
- photographic paper
- optionally
- white photographic
- silver
- thermal black
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- 238000003384 imaging method Methods 0.000 claims abstract description 80
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052709 silver Inorganic materials 0.000 claims abstract description 37
- 239000004332 silver Substances 0.000 claims abstract description 36
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 21
- 239000000194 fatty acid Substances 0.000 claims abstract description 21
- 229930195729 fatty acid Natural products 0.000 claims abstract description 21
- -1 alkyl fatty acid Chemical class 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 64
- 239000011241 protective layer Substances 0.000 claims description 34
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 15
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000006234 thermal black Substances 0.000 claims description 9
- 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 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 230000035945 sensitivity Effects 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- NUWHYWYSMAPBHK-UHFFFAOYSA-N 3,4-dihydroxybenzonitrile Chemical compound OC1=CC=C(C#N)C=C1O NUWHYWYSMAPBHK-UHFFFAOYSA-N 0.000 claims description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 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
- 239000000203 mixture Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 3
- LPYHADGLCYWDNC-UHFFFAOYSA-M silver;tetracosanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCCCC([O-])=O LPYHADGLCYWDNC-UHFFFAOYSA-M 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004971 Cross linker Substances 0.000 claims description 2
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 claims 1
- 229960000623 carbamazepine Drugs 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 description 44
- 239000011248 coating agent Substances 0.000 description 40
- 238000000576 coating method Methods 0.000 description 40
- 239000006185 dispersion Substances 0.000 description 18
- 238000001035 drying Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- CYFHLEMYBPQRGN-UHFFFAOYSA-N ditetradecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCC CYFHLEMYBPQRGN-UHFFFAOYSA-N 0.000 description 8
- KRIXEEBVZRZHOS-UHFFFAOYSA-N tetradecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCOP(O)(O)=O KRIXEEBVZRZHOS-UHFFFAOYSA-N 0.000 description 8
- 238000012795 verification Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011835 investigation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001739 density measurement Methods 0.000 description 4
- 239000011092 plastic-coated paper Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- NUWHYWYSMAPBHK-ARERNSRJSA-N 3,4-dihydroxybenzonitrile Chemical group OC1=CC=C([13C]#[15N])C=C1O NUWHYWYSMAPBHK-ARERNSRJSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002508 contact lithography Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
The invention provides a thermosensitive black-and-white photographic paper. The heat-sensitive black-and-white photographic paper comprises: a substrate layer; and an image-forming layer comprising silver long-chain alkyl fatty acid and a reducing agent. The thermosensitive black-and-white photographic paper has the advantages of simple structure, excellent imaging texture, simple and rapid imaging process, high resolution of formed images, clear layers and good stability, does not generate harmful substances in the imaging process, is safe, environment-friendly and pollution-free, can meet the imaging requirements of multiple fields, and has good commercial prospect.
Description
Technical Field
The invention relates to the technical field of imaging, in particular to thermosensitive black-and-white photographic paper.
Background
In the related art, conventional black and white paper (black white paper) is an output consumable for black and white photo output, which can be used for contact printing (soft photosensitive paper) and amplification (silver bromide and silver bromide paper). However, the above-mentioned photographic paper needs to be washed during use, and the application process is cumbersome, and has certain requirements for technology, and it will cause great pollution to the environment during washing.
Thus, the related art of the existing black and white photographic paper still needs to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a method for forming an image with a simple structure, excellent image quality, simple and fast imaging process, high resolution of the formed image, clear gradation, good stability, no harmful substance generated during the imaging process, safety, environmental protection, no pollution, and capability of meeting the imaging requirements of multiple fields or having good commercial prospects.
In one aspect of the present invention, the present invention provides a thermal black and white photographic paper. According to an embodiment of the present invention, the thermal black and white photographic paper comprises: a substrate layer; and an image-forming layer comprising silver long-chain alkyl fatty acid and a reducing agent. The inventor finds that the thermosensitive black-and-white photographic paper has the advantages of simple structure, excellent imaging texture, simple and rapid imaging process, high resolution, clear layers and good stability of the formed image, does not generate harmful substances in the imaging process, is safe, environment-friendly and pollution-free, can meet the imaging requirements of multiple fields, and has good commercial prospect.
According to an embodiment of the present invention, the long-chain alkyl fatty acid silver has a crystal length of 4 to 10 μm.
According to an embodiment of the present invention, the long-chain alkyl fatty acid silver has a crystal length of 6 to 8 μm.
According to an embodiment of the present invention, the number of carbon atoms in the silver long-chain alkyl fatty acid is greater than or equal to 18.
According to an embodiment of the invention, the long chain alkyl fatty acid silver comprises at least one of silver eicosanoate, silver docosanoate or silver tetracosanoate.
According to an embodiment of the invention, the silver long-chain alkyl fatty acid is silver behenate.
According to an embodiment of the present invention, the silver in the imaging layer has a basis weight of 0.3g/m2～0.6g/m2。
According to an embodiment of the present invention, the silver in the imaging layer has a basis weight of 0.4g/m2～0.5g/m2。
According to an embodiment of the invention, the reducing agent comprises phenol.
According to an embodiment of the present invention, the phenol comprises at least one of a monohydric phenol or a polyhydric phenol.
According to an embodiment of the present invention, the monohydric phenol comprises at least one of phenol or naphthol.
According to an embodiment of the present invention, the polyhydric phenol comprises 3, 4-dihydroxybenzonitrile.
According to an embodiment of the present invention, the imaging layer further comprises at least one of a stabilizer, a toner, a first binder, and a first crosslinker.
According to an embodiment of the invention, the stabilizer comprises an organic polyacid.
According to an embodiment of the present invention, the organic polyacid comprises at least one of azelaic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, or tetrachlorophthalic acid.
According to an embodiment of the present invention, the organic polyacid is at least one of azelaic acid or tetrachlorophthalic acid.
According to an embodiment of the present invention, the toner comprises a mixture of a toner and a non-ionic surfactant.
According to an embodiment of the present invention, the first adhesive comprises polyvinyl butyral.
According to an embodiment of the present invention, the polyvinyl butyral comprises at least one of B76, B79, or B98.
According to an embodiment of the present invention, the polyvinyl butyral is B79.
According to an embodiment of the invention, the first cross-linking agent comprises an isocyanate.
According to an embodiment of the invention, the isocyanate comprises at least one of isophorone diisocyanate or diphenylmethane diisocyanate.
According to an embodiment of the present invention, the thermal black-and-white photographic paper further comprises: a protective layer disposed on a surface of the imaging layer distal from the substrate layer.
According to an embodiment of the invention, the protective layer comprises at least one of a lubricant, a second binder and a second cross-linking agent.
According to an embodiment of the invention, the lubricant comprises an organic phosphate.
According to an embodiment of the invention, the organic phosphate comprises a long chain fatty alcohol phosphate.
According to an embodiment of the present invention, the long chain fatty alcohol phosphate ester comprises at least one of monotetradecyl phosphate and ditetradecyl phosphate.
According to an embodiment of the invention, the long-chain fatty alcohol phosphate is a mixture of mono-and ditetradecyl phosphate.
According to an embodiment of the invention, the second binder comprises polyvinyl alcohol.
According to an embodiment of the present invention, the polyvinyl alcohol includes at least one of polyvinyl alcohol 224 and polyvinyl alcohol 1130.
According to an embodiment of the present invention, the polyvinyl alcohol is polyvinyl alcohol 1130.
According to an embodiment of the present invention, the second crosslinking agent comprises at least one of butyraldehyde, glyoxal, boric acid, or ethyl orthosilicate.
According to an embodiment of the invention, the second cross-linking agent is ethyl orthosilicate.
According to an embodiment of the invention, the thickness of the protective layer is 2 μm to 4 μm.
According to an embodiment of the present invention, the thermal black-and-white photographic paper satisfies at least one of the following conditions: density of fog D0Not more than 0.04; the contrast gamma is not greater than 2.45; the sensitivity S is not less than 10; maximum density DmaxNot less than 1.66.
Drawings
Fig. 1 shows a schematic cross-sectional structure of a thermal black-and-white photographic paper according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view of a thermal black-and-white photographic paper according to another embodiment of the present invention.
Reference numerals:
10: thermal black-and-white photographic paper 100: substrate layer 200: imaging layer 300: protective layer
Detailed Description
It should be noted that the following description of the embodiments of the present invention is merely exemplary in nature and is in no way intended to limit the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the present invention, the present invention provides a thermal black and white photographic paper. Referring to fig. 1, the thermal black-and-white photographic paper 10 according to an embodiment of the present invention includes: a substrate layer 100; and an imaging layer 200, the imaging layer 200 comprising a long chain alkyl fatty acid silver and a reducing agent. The inventor finds that the thermosensitive black-and-white photographic paper 10 is simple in structure, excellent in imaging texture, simple and rapid in imaging process, high in resolution, clear in level, good in stability of formed images, safe, environment-friendly and pollution-free, cannot generate harmful substances in the imaging process, can meet imaging requirements of multiple fields, and is good in commercial prospect.
Specifically, according to the embodiment of the present invention, the image formation of the thermal black-and-white photographic paper 10 uses long-chain alkyl fatty acid silver, which reacts with a reducing agent after being heated to generate reduced silver, and the silver atoms can be piled into large and small silver atom clusters, and the specific principle is as follows: AgB + reducing agent Ag + HBe + RO, where B is a long chain alkyl fatty acid radical, the resulting reduction product is Ag, which can form an image, and HBe and RO are both oxidation products of the above reaction.
According to an embodiment of the present invention, the crystal length of the long-chain alkyl fatty acid silver may be 4 μm to 10 μm, specifically, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or the like, and further, the crystal length of the long-chain alkyl fatty acid silver may be 6 μm to 8 μm. Thus, the crystal length of the long-chain alkyl fatty acid silver is not too short and the activity is too strong, which results in too high haze of the thermal black-and-white photographic paper 10 during imaging; the density of the thermal black-and-white photographic paper 10 can not meet the requirement when the thermal black-and-white photographic paper is imaged because of too long and too weak activity, and further, the imaging texture of the thermal black-and-white photographic paper 10 can be more excellent, and the formed image has higher resolution, clearer gradation and better stability.
According to an embodiment of the present invention, the number of carbon atoms in the silver long-chain alkyl fatty acid is greater than or equal to 18. Specifically, in some specific embodiments of the present invention, the long-chain alkyl fatty acid silver may include silver eicosanoate, silver docosanoate, silver tetracosanoate, or the like. After a great deal of thorough investigation and experimental verification, the inventor finds that when the long-chain alkyl fatty acid silver is the silver behenate, the imaging texture of the thermosensitive black-and-white photographic paper 10 can be optimal, the resolution of the formed image is optimal, the level is optimal, and the stability is optimal.
According to embodiments of the present invention, the basis weight of silver in the imaging layer 200 may be 0.3g/m2～0.6g/m2Specifically, in some embodiments of the present invention, the basis weight of the silver in the imaging layer 200 may be 0.3g/m2、0.4g/m2、0.5g/m2Or 0.6g/m2Etc., further, the silver in the imaging layer 200 may have a basis weight of 0.4g/m2～0.5g/m2. Therefore, the unit weight of silver in the image forming layer 200 is not too low, which results in that the density of the thermal black-and-white photographic paper 10 is too low during image forming, and the image forming requirement cannot be met; it is not too high to cause unnecessary waste, and further, the image quality of the thermal black and white photographic paper 10 is more excellent, the resolution of the formed image is higher, the gradation is clearer, and the stability is better.
According to an embodiment of the present invention, the reducing agent may include phenol, and specifically, it may be either monohydric phenol or polyhydric phenol. Specifically, in some embodiments of the present invention, the reducing agent may be phenol, naphthol, or 3, 4-dihydroxybenzonitrile, among others. After a great deal of thorough investigation and experimental verification, the inventor finds that when the reducing agent is 3, 4-dihydroxybenzonitrile, the imaging texture of the thermosensitive black-and-white photographic paper 10 can be optimal, the resolution of the formed image is optimal, the level is optimal, the stability is optimal, and the imaging is simpler and quicker.
Further, in other embodiments of the present invention, a stabilizer, a toner, a first binder or a first cross-linking agent, etc. may be further included in the image-forming layer 200. Specifically, the stabilizer may include an organic polybasic acid, and the organic polybasic acid may include azelaic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, or the like. After a great deal of thorough examination and experimental verification, the inventor finds that when the stabilizer is azelaic acid or tetrachlorophthalic acid, the imaging texture of the thermosensitive black-and-white photographic paper 10 can be optimal, the resolution of the formed image is optimal, the gradation is optimal, and the stability is optimal. Specifically, the toner may include casalam, whereby the material source is wide, readily available, and low cost. In particular, the first binder may include polyvinyl butyral (PVB), which may include B76, B79, B98, or the like. After extensive and thorough examination and experimental verification, the inventor finds that when the first adhesive is B79, the best adhesion effect can be achieved. Specifically, the first crosslinking agent may include isocyanate, which may include B76, B79, B98, or the like. After extensive and intensive investigation and experimental verification, the inventors found that when the first crosslinking agent is at least one of isophorone diisocyanate (IPDI) or diphenylmethane diisocyanate (MDI), the crosslinking effect can be optimized.
Still further, in other embodiments of the present invention, referring to fig. 2, the thermal black-and-white photographic paper 10 may further include: a protective layer 300, the protective layer 300 being disposed on a surface of the imaging layer 200 remote from the substrate layer 100. Thus, the imaging layer 200 described above may be protected during imaging.
According to an embodiment of the present invention, still further, the protective layer may include a lubricant, a second binder or a second crosslinking agent, or the like. In particular, the lubricant may include an organophosphate ester, which may include a long chain fatty alcohol phosphate ester, which may yet further include at least one of a monotetradecyl phosphate and a ditetradecyl phosphate. After extensive and intensive investigation and experimental verification, the inventors found that the lubricating effect can be optimized when the lubricant is a mixture of mono-tetradecyl phosphate and di-tetradecyl phosphate. Specifically, the second binder may include polyvinyl alcohol (PVA), which may include at least one of polyvinyl alcohol 224 and polyvinyl alcohol 1130. After extensive and thorough examination and experimental verification, the inventor finds that when the second adhesive is polyvinyl alcohol EP1130, the best adhesion effect can be achieved. Specifically, the second crosslinking agent may include butyraldehyde, glyoxal, boric acid, or ethyl orthosilicate, and the like. After a great deal of thorough investigation and experimental verification, the inventor finds that when the second crosslinking agent is tetraethoxysilane, the crosslinking effect can be optimal.
In addition, according to an embodiment of the present invention, the thickness of the protective layer 300 may be 2 μm to 4 μm. Specifically, in some embodiments of the present invention, the thickness of the protective layer 300 may be 2 μm, 3 μm, or 4 μm, etc. Therefore, the thickness of the protective layer 300 is not too thin to protect the thermal black-and-white photographic paper 10 during image formation; the thermal black-and-white photographic paper 10 is not too thick to affect the thermal conductivity during the imaging process, so that the imaging density cannot meet the requirements, and further, the thickness of the protective layer 300 can make the imaging texture of the thermal black-and-white photographic paper 10 more excellent, and the formed image has higher resolution, clearer gradation and better stability.
According to the embodiment of the present invention, it can be understood by those skilled in the art that the thermal black-and-white photographic paper of the present invention can satisfy at least one of the following conditions: density of fog D0Not more than 0.04, specifically, may be 0.03 or 0.04, etc.; contrast gamma is not greater than 2.45, in particularAnd may be 2.45, 2.4, 2.3, etc.; the sensitivity S is not less than 10, specifically, may be 10, 10.5, 11, 12, or the like; maximum density DmaxNot less than 1.66, specifically, 1.77, 1.70, 1.68, 1.66, or the like may be mentioned. Therefore, the thermosensitive black-and-white photographic paper 10 is simple in structure, excellent in imaging texture, simple and rapid in imaging process, high in resolution, clear in level and good in stability of formed images, does not generate harmful substances in the imaging process, is safe, environment-friendly and pollution-free, can meet imaging requirements of multiple fields, and is good in commercial prospect.
According to an embodiment of the present invention, further, the thermosensitive black-and-white photographic paper may be prepared by: (1) preparing an imaging layer coating liquid: dispersing long-chain alkyl fatty acid silver in a first adhesive to obtain a prefabricated dispersion liquid, and then slowly adding the first adhesive, a reducing agent, a stabilizing agent, a toner and a first cross-linking agent into the prefabricated dispersion liquid under a stirring state to obtain an imaging layer coating liquid; (2) forming an imaging layer: coating the imaging layer coating liquid on a substrate layer, controlling the unit weight of silver in the imaging layer to be in a required range, and naturally drying to obtain an imaging layer; (3) preparing a protective layer coating liquid: adding the second adhesive into water under the stirring state, and then slowly adding the lubricant and the second cross-linking agent to obtain a protective layer coating liquid; (4) forming a protective layer: and coating the protective layer coating liquid on an imaging layer, and drying to obtain the thermosensitive black-and-white photographic paper. Therefore, the method is simple and convenient to operate, easy to realize and easy for industrial production, and the thermosensitive black-and-white photographic paper can be effectively prepared.
The following describes embodiments of the present invention in detail.
Example 1
(1) Preparing an imaging layer coating liquid: dispersing silver behenate in PVB 79 to obtain a pre-dispersion liquid, taking 40g of the pre-dispersion liquid, and slowly adding 50g of PVB 79 with the mass concentration of 20%, 1.0g of 3, 4-dihydroxybenzonitrile, 0.1g of azelaic acid, 0.05g of Casalaren and 1.5g of MDI into the pre-dispersion liquid under stirring to obtain an imaging layer coating liquid;
(2) is formed intoImaging layer: coating the imaging layer coating liquid on a plastic-coated paper base, and controlling the unit weight of silver in the imaging layer to be 0.4g/m2Naturally drying to obtain an imaging layer;
(3) preparing a protective layer coating liquid: 400g of 4.5% PVA EP1130 was added to 300g of pure water while stirring, and then 10g of an aqueous dispersion of monotetradecyl phosphate and ditetradecyl phosphate (5% by mass) and 20g of ethyl orthosilicate were slowly added to obtain a resist coating liquid;
(4) forming a protective layer: and coating the protective layer coating liquid on an imaging layer, and drying to obtain the thermosensitive black-and-white photographic paper, wherein the thickness of the protective layer is 2 μm.
The photographic properties of the thermal black and white photographic paper were tested and are detailed in table 1.
Example 2
(1) Preparing an imaging layer coating liquid: dispersing silver behenate in PVB 79 to obtain a pre-dispersion liquid, taking 40g of the pre-dispersion liquid, and then slowly adding 50g of PVB 79 with the mass concentration of 20%, 1.0g of 3, 4-dihydroxybenzonitrile, 0.1g of tetrachlorophthalic acid, 0.05g of carbazalen and 1.5g of IPDI to the pre-dispersion liquid under stirring to obtain an imaging layer coating liquid;
(2) forming an imaging layer: coating the imaging layer coating liquid on a plastic-coated paper base, and controlling the unit weight of silver in the imaging layer to be 0.5g/m2Naturally drying to obtain an imaging layer;
(3) preparing a protective layer coating liquid: 400g of 4.5% PVA EP1130 was added to 300g of pure water while stirring, and then 10g of an aqueous dispersion of monotetradecyl phosphate and ditetradecyl phosphate (5% by mass) and 20g of ethyl orthosilicate were slowly added to obtain a resist coating liquid;
(4) forming a protective layer: and coating the protective layer coating liquid on an imaging layer, and drying to obtain the thermosensitive black-and-white photographic paper, wherein the thickness of the protective layer is 4 microns.
The photographic properties of the thermal black and white photographic paper were tested and are detailed in table 1.
Example 3
(1) Preparing an imaging layer coating liquid: dispersing silver behenate in PVB 79 to obtain a pre-dispersion liquid, taking 40g of the pre-dispersion liquid, and then slowly adding 50g of PVB 79 with the mass concentration of 20%, 1.0g of 3, 4-dihydroxybenzonitrile, 0.1g of tetrachlorophthalic acid, 0.05g of carbazalen and 1.5g of MDI to the pre-dispersion liquid under stirring to obtain an imaging layer coating liquid;
(2) forming an imaging layer: coating the imaging layer coating liquid on a plastic-coated paper base, and controlling the unit weight of silver in the imaging layer to be 0.45g/m2Naturally drying to obtain an imaging layer;
(3) preparing a protective layer coating liquid: 400g of 4.5% PVA EP1130 was added to 300g of pure water while stirring, and then 10g of an aqueous dispersion of monotetradecyl phosphate and ditetradecyl phosphate (5% by mass) and 20g of ethyl orthosilicate were slowly added to obtain a resist coating liquid;
(4) forming a protective layer: and coating the protective layer coating liquid on an imaging layer, and drying to obtain the thermosensitive black-and-white photographic paper, wherein the thickness of the protective layer is 3 μm.
The photographic properties of the thermal black and white photographic paper were tested and are detailed in table 1.
Example 4
(1) Preparing an imaging layer coating liquid: dispersing silver behenate in PVB 79 to obtain a pre-dispersion liquid, taking 40g of the pre-dispersion liquid, and then slowly adding 50g of PVB 79 with the mass concentration of 20%, 1.0g of 3, 4-dihydroxybenzonitrile, 0.1g of azelaic acid, 0.05g of Casalaren and 1.5g of IPDI into the pre-dispersion liquid under stirring to obtain an imaging layer coating liquid;
(2) forming an imaging layer: coating the imaging layer coating liquid on a plastic-coated paper base, and controlling the unit weight of silver in the imaging layer to be 0.4g/m2Naturally drying to obtain an imaging layer;
(3) preparing a protective layer coating liquid: 400g of 4.5% PVA EP1130 was added to 300g of pure water while stirring, and then 10g of an aqueous dispersion of monotetradecyl phosphate and ditetradecyl phosphate (5% by mass) and 20g of ethyl orthosilicate were slowly added to obtain a resist coating liquid;
(4) forming a protective layer: and coating the protective layer coating liquid on an imaging layer, and drying to obtain the thermosensitive black-and-white photographic paper, wherein the thickness of the protective layer is 4 microns.
The photographic properties of the thermal black and white photographic paper were tested and are detailed in table 1.
TABLE 1 photographic Properties of the thermosensitive black-and-white photographic papers of examples 1 to 4
| Density of fog D0 | Contrast gamma | Sensitivity S | Maximum density Dmax | |
| Example 1 | 0.03 | 2.45 | 10 | 1.70 |
| Example 2 | 0.04 | 2.4 | 10.5 | 1.66 |
| Example 3 | 0.03 | 2.3 | 11 | 1.68 |
| Example 4 | 0.03 | 2.4 | 12 | 1.77 |
As can be seen from the data in Table 1, the fog density D of the thermal black-and-white photographic paper0Contrast gamma, sensitivity S, maximum density DmaxThe method has the advantages of good uniformity, excellent imaging texture, high resolution of the formed image, clear level and good stability, and can meet the imaging requirements of multiple fields.
The performance test method comprises the following steps:
part 2 was measured according to Q/LK 10322.7-2012, GB/T11500 photographic density: geometry of transmission Density section 3 of GB/T11501 photographic Density measurement: spectral conditions and a spectrodensitometer X-Rite310 was used for the test, the procedure was as follows:
(1) the test conditions are as follows: the temperature-sensitive black-and-white photographic paper is balanced for 30 minutes under the conditions that the temperature is 25 +/-5 ℃ and the relative humidity is 50% +/-10%;
(2) sampling: sampling the balanced thermosensitive black-and-white photographic paper as a test piece.
(3) Printing a test piece: the thermal black-and-white 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) Density measurement: the density is national standard visual diffuse reflection density, the geometric condition of the density measurement is in accordance with the regulation of GB11500, the spectral condition of the density measurement is in accordance with the regulation of GB11501, wherein,
density of fog D0Subtracting the optical density value of the used substrate layer from the optical density value of the unprocessed test piece;
the contrast gamma is the slope value of the straight line part on the gray scale characteristic curve obtained by a gamma ruler;
the sensitivity S is determined by subtracting the initial level of the sensitivity curve from 24 on the gray scale characteristic curve, and determining the coordinate as the fog density D0The corresponding (daylight) value at the +1.00 point is the sensitivity S;
maximum density DmaxIs the maximum density on the 24-level gray scale characteristic.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
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 thermal black and white photographic paper, comprising:
a substrate layer; and
an imaging layer comprising silver long chain alkyl fatty acid and a reducing agent.
2. The thermal black-and-white photographic paper as claimed in claim 1, wherein the crystal length of the silver long-chain alkyl fatty acid is 4 to 10 μm, preferably 6 to 8 μm.
3. The thermal black-and-white photographic paper as claimed in claim 1, wherein the number of carbon atoms in the silver long-chain alkyl fatty acid is 18 or more,
optionally, the long chain alkyl fatty acid silver comprises at least one of silver eicosanoate, silver docosanoate, or silver tetracosanoate, preferably silver docosanoate.
4. The thermal black-and-white photographic paper as claimed in claim 1, wherein the silver in the image-forming layer has a basis weight of 0.3g/m2～0.6g/m2Preferably 0.4g/m2～0.5g/m2。
5. The thermal black-and-white photographic paper as claimed in claim 1, wherein the reducing agent comprises phenol,
optionally, the phenol comprises at least one of a monohydric phenol or a polyhydric phenol,
optionally, the monohydric phenol comprises at least one of phenol or naphthol,
optionally, the polyhydric phenol comprises 3, 4-dihydroxybenzonitrile.
6. The thermal black-and-white photographic paper of claim 1, wherein the image-forming layer further comprises at least one of a stabilizer, a toner, a first binder, and a first cross-linking agent,
optionally, the stabilizer comprises an organic polyacid,
optionally, the organic polyacid comprises at least one of azelaic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, or tetrachlorophthalic acid, preferably at least one of azelaic acid or tetrachlorophthalic acid,
optionally, the hueing agent comprises a mixture of carbazepine,
optionally, the first binder comprises polyvinyl butyral,
optionally, the polyvinyl butyral comprises at least one of B76, B79, or B98, preferably B79,
optionally, the first crosslinker comprises an isocyanate,
optionally, the isocyanate comprises at least one of isophorone diisocyanate or diphenylmethane diisocyanate.
7. The thermal black-and-white photographic paper as claimed in claim 1, further comprising:
a protective layer disposed on a surface of the imaging layer distal from the substrate layer.
8. The thermal black-and-white photographic paper of claim 7, wherein the protective layer comprises at least one of a lubricant, a second binder, and a second crosslinking agent,
optionally, the lubricant comprises an organic phosphate ester,
optionally, the organic phosphate ester comprises a long chain fatty alcohol phosphate ester,
optionally, the long-chain fatty alcohol phosphate ester comprises at least one of mono-tetradecyl phosphate ester and ditetradecyl phosphate ester, preferably a mixture of mono-tetradecyl phosphate ester and ditetradecyl phosphate ester,
optionally, the second binder comprises polyvinyl alcohol,
optionally, the polyvinyl alcohol comprises at least one of polyvinyl alcohol 224 and polyvinyl alcohol 1130, preferably polyvinyl alcohol 1130,
optionally, the second crosslinking agent comprises at least one of butyraldehyde, glyoxal, boric acid, or ethyl orthosilicate, preferably ethyl orthosilicate.
9. The thermal black-and-white photographic paper as claimed in claim 7, wherein the protective layer has a thickness of 2 to 4 μm.
10. The thermal black-and-white photographic paper as claimed in claim 1, wherein at least one of the following conditions is satisfied:
density of fog D0Not more than 0.04;
the contrast gamma is not greater than 2.45;
the sensitivity S is not less than 10;
maximum density DmaxNot less than 1.66.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0754969A2 (en) * | 1995-07-18 | 1997-01-22 | Agfa-Gevaert N.V. | Process for producing an aqueous suspension of particles containing a substantially light-insensitive silver salt of an organic carboxylic acid for production of (photo)thermographic materials |
| CN1219684A (en) * | 1997-12-08 | 1999-06-16 | 富士摄影胶片株式会社 | Thermographic recording elements |
| EP0962812A1 (en) * | 1998-06-03 | 1999-12-08 | Fuji Photo Film Co., Ltd. | Aqueous dispersion of fatty acid silver salt particles, method for redispersing fatty acid silver salt particles, photothermographic light-sensitive material, and method for producing the same |
| JP2001163889A (en) * | 1999-12-07 | 2001-06-19 | Fuji Photo Film Co Ltd | Method for producing fatty acid silver salt particle and heat developing image recording material |
| US6472138B1 (en) * | 1999-09-28 | 2002-10-29 | Fuji Photo Film Co., Ltd. | Black and white photothermographic material and method for fabricating thereof |
| US20060046214A1 (en) * | 2004-08-25 | 2006-03-02 | Eastman Kodak Company | Photothermographic materials with reduced development time |
| CN1746767A (en) * | 2005-09-30 | 2006-03-15 | 中国乐凯胶片集团公司 | Production of fatty acid silver salt for photosensitive heat display imaging material |
| CN101750870A (en) * | 2008-12-17 | 2010-06-23 | 中国科学院理化技术研究所 | Application of nicotinic acid compound as toner in direct thermal imaging material |
| CN109096095A (en) * | 2018-08-23 | 2018-12-28 | 中国乐凯集团有限公司 | A kind of long-chain fat acid silver salt crystallite preparation method and applications |
| CN111471508A (en) * | 2020-05-09 | 2020-07-31 | 中国乐凯集团有限公司 | Lubricant and preparation method thereof, direct thermal imaging material and preparation method thereof |
-
2021
- 2021-01-08 CN CN202110026179.8A patent/CN112859506B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0754969A2 (en) * | 1995-07-18 | 1997-01-22 | Agfa-Gevaert N.V. | Process for producing an aqueous suspension of particles containing a substantially light-insensitive silver salt of an organic carboxylic acid for production of (photo)thermographic materials |
| CN1219684A (en) * | 1997-12-08 | 1999-06-16 | 富士摄影胶片株式会社 | Thermographic recording elements |
| EP0962812A1 (en) * | 1998-06-03 | 1999-12-08 | Fuji Photo Film Co., Ltd. | Aqueous dispersion of fatty acid silver salt particles, method for redispersing fatty acid silver salt particles, photothermographic light-sensitive material, and method for producing the same |
| US6472138B1 (en) * | 1999-09-28 | 2002-10-29 | Fuji Photo Film Co., Ltd. | Black and white photothermographic material and method for fabricating thereof |
| JP2001163889A (en) * | 1999-12-07 | 2001-06-19 | Fuji Photo Film Co Ltd | Method for producing fatty acid silver salt particle and heat developing image recording material |
| US20060046214A1 (en) * | 2004-08-25 | 2006-03-02 | Eastman Kodak Company | Photothermographic materials with reduced development time |
| CN1746767A (en) * | 2005-09-30 | 2006-03-15 | 中国乐凯胶片集团公司 | Production of fatty acid silver salt for photosensitive heat display imaging material |
| CN101750870A (en) * | 2008-12-17 | 2010-06-23 | 中国科学院理化技术研究所 | Application of nicotinic acid compound as toner in direct thermal imaging material |
| CN109096095A (en) * | 2018-08-23 | 2018-12-28 | 中国乐凯集团有限公司 | A kind of long-chain fat acid silver salt crystallite preparation method and applications |
| CN111471508A (en) * | 2020-05-09 | 2020-07-31 | 中国乐凯集团有限公司 | Lubricant and preparation method thereof, direct thermal imaging material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 常聪慧等: "银盐直接热成像体系还原剂和调色剂研究", 信息记录材料, vol. 16, no. 4, pages 8 - 9 * |
| 李万迎等: "直接热成像银盐胶片色调优化研究", 信息记录材料, vol. 20, no. 9, pages 8 - 9 * |
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