CN103072396A - 4-hydroxy-4'isopropoxydiphenyl sulfone temperature-sensitive developer dispersion liquid and transparent temperature-sensitive record material - Google Patents
4-hydroxy-4'isopropoxydiphenyl sulfone temperature-sensitive developer dispersion liquid and transparent temperature-sensitive record material Download PDFInfo
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- 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
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
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- 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
- B41M5/3375—Non-macromolecular compounds
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Abstract
The invention relates to a 4-hydroxy-4'isopropoxydiphenyl sulfone temperature-sensitive developer dispersion liquid and a transparent temperature-sensitive record material, the dispersion liquid can be obtained by performing wet type crushing on 4-hydroxy-4'isopropoxydiphenyl sulfone temperature-sensitive developer through existence of a dispersion protective agent, the dispersion protective agent selects from sodium naphthalenesulfonate, relative to 100 mass fraction of temperature-sensitive developer, the dispersion protective agent is 0.05-2 mass parts; the average particle size of the temperature-sensitive developer after dispersing is 0.2-0.8 micrometers, and the particle size distribution is less than 15%. The dispersion liquid has good stability, and can effectively solves the problem that the temperature-sensitive developer enables easy hydration effect generation to generate crystallization in the processes of grinding and storing, and the industrialization period production requirement can be satisfied; the temperature-sensitive record material has fine particles, high temperature-sensitive degree, low haze and good transparency, and the image quality can satisfy the medical diagnosis requirement.
Description
Technical field
The present invention relates to the 4-hydroxyl-4 for thermal recording medium
,Isopropoxy diphenyl sulphone (DPS) thermosensitive color development agent dispersing liquid and the transparent thermal recording medium that uses this thermosensitive color development agent dispersing liquid to prepare.
Background technology
Thermal recording medium is flexible because of its layout, image quality is high, speed is fast, low price, recording equipment simple and maintenance side more, the advantage such as recording process noiselessness, it is not only as facsimile machine, the output recording materials of POS machine, label machine, and can be used as the diagnosis of the radioscopic images such as CR, DR and use, magnetic resonance imaging (MRI), the output recording materials of the Medical Devices such as X ray computer tomography (CT) use, and have also avoided the conventional silver halide film technologies must use noble silver to be the shortcoming of raw material and preparation use procedure complexity simultaneously.
The image output recording materials of Medical Devices require the image of output need have good definition, abundant image level, higher maximal density and lower photographic fog etc. as medical image diagnosis use.These require not only to be subject to the printhead properties influence of thermal printer, and are more closely related with the characteristic of thermal recording medium itself.In order to guarantee that picture quality can satisfy the medical diagnosis requirement, thermal recording medium need have fine and smooth particle, higher sensible heat ability, lower mist degree and the good transparency.
4-hydroxyl-4
,Isopropoxy diphenyl sulphone (DPS) (D-8) is the temperature-sensitive developer of present industrial extensive use, and its advantage is that the thermo-sensitive material that makes is highly sensitive, and the retention of image is good.
Application number is that the Chinese patent of CN200580008385.5 discloses 4-hydroxyl-4, isopropoxy sulfone developer dispersion, case of wet attrition method and thermal recording material, there is following defective in this patent scheme: the average grain diameter of (1) dispersion liquid is large, dispersion liquid is unstable, deposits the needs that can't satisfy the production of industrialization cycle in the process because of the growth of crystallization; (2) the color development density of thermal recording material is low, mist degree is large, opaque.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of 4-hydroxyl-4
,Isopropoxy diphenyl sulphone (DPS) thermosensitive color development agent dispersing liquid, this dispersion liquid has preferably color developing.
Another technical problem that the present invention will solve provides a kind of transparent thermal recording medium.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of 4-hydroxyl-4
,Isopropoxy diphenyl sulphone (DPS) thermosensitive color development agent dispersing liquid, it is by case of wet attrition 4-hydroxyl-4 in the presence of dispersion is protectant
,Isopropoxy diphenyl sulphone (DPS) thermosensitive color development agent and obtaining, described dispersion protective agent is selected from naphthalene sulfonic acids isopropyl ester sodium salt, and with respect to the thermosensitive color development agent of 100 mass parts, disperseing protective agent is 0.05～2 mass parts; Average grain diameter after described thermosensitive color development agent disperses is 0.2～0.8 micron, and size distribution is less than 15%.
In the above-mentioned dispersion liquid, with respect to the thermosensitive color development agent of 100 mass parts, disperseing protective agent is 0.1～1 mass parts.
In the above-mentioned dispersion liquid, the average grain diameter after described thermosensitive color development agent disperses is 0.3～0.5 micron, and size distribution is less than 8%.
In the above-mentioned dispersion liquid, the content of the thermosensitive color development agent in the described dispersion liquid is greater than 25 quality %.
A kind of transparent thermal recording medium; it comprises transparent support; be positioned at thermo-responsive imaging layer and the protective layer of support one side; be positioned at the backing layer of the another side of support, described thermo-responsive imaging layer is dry formation of heat sensitive recording layer coating composition comprise temperature-sensitive microcapsules and above-mentioned thermosensitive color development agent dispersing liquid by applying at support.
In the above-mentioned thermal recording medium, described thermal recording medium haze value is less than 50%, and preferred 40%.
Compared with prior art, the present invention is by to disperseing protectant selection, and the control of the dispersion particle diameter by adjusting consumption proportion between thermosensitive color development agent and the dispersion protective agent and thermosensitive color development agent, efficiently solve the crystallization that the thermosensitive color development agent very easily occurs in aquation occurs in grinding and storage process, particularly when below the abrasive grains particle diameter to 1 of thermosensitive color development agent micron, deposit the serious crystallization situation that occurs in the process at process of lapping or after grinding, satisfied the needs of production cycle; Thermal recording medium has fine and smooth particle, higher temperature-sensitive sensitivity, and lower mist degree and the good transparency, picture quality can satisfy the medical diagnosis requirement.
The specific embodiment
Among the present invention, dispersion liquid is case of wet attrition 4-hydroxyl-4 in the presence of dispersion is protectant
,Isopropoxy diphenyl sulphone (DPS) thermosensitive color development agent and obtaining disperses protective agent to be selected from naphthalene sulfonic acids isopropyl ester sodium salt.Dispersant when naphthalene sulfonic acids isopropyl ester sodium salt disperses as the thermosensitive color development agent uses, it can be adsorbed onto thermosensitive color development agent particle surface well when grinding distribution, after the particle surface absorption of thermosensitive color development agent, form electric double layer, do not assemble because of electrostatic repulsion between the thermosensitive color development agent particle, and be difficult for being got off from the particle surface desorb by external force, and then prevented thermosensitive color development agent crystalline hydrate.The time that naphthalene sulfonic acids isopropyl ester sodium salt adds can be at thermosensitive color development agent 4-hydroxyl-4
,Before the wet lapping of isopropoxy diphenyl sulphone (DPS), in the process of lapping or grind and once to add after finishing, also can be before grinding, in the process of lapping, grind finish after repeatedly part add, preferably before grinding, once add.With respect to the thermosensitive color development agent of 100 mass parts, disperseing protective agent is 0.05～2 mass parts, preferred 0.1～1 mass parts.When disperseing protectant consumption to be lower than 0.05 mass parts, can not suppress well the crystalline hydrate of thermosensitive color development agent; When the consumption of dispersant is higher than 2 mass parts, can increase on the cost.
Dispersion liquid obtains by case of wet attrition, and wet lapping equipment can be selected from vertical grinding machine, basket type sand mill, and horizontal sand mill, bar type sand mill etc. are from the preferred horizontal sand mill in industrial production efficiency angle aspect.Preferred case of wet attrition 4-hydroxyl-4 to the dispersion liquid
,The isopropoxy diphenyl sulphone (DPS) average grain diameter be 0.2～0.8 micron, size distribution is less than 15%, the average grain diameter of preferred thermosensitive color development agent is 0.3～0.5 micron, size distribution is less than 8%.When particle diameter during less than 0.2 micron, be prone to crystalline hydrate, and suitability for industrialized production need to consume a large amount of energy and time, uneconomical; When particle diameter during greater than 0.8 micron, the sensitivity of thermal recording medium reduces, mist degree increases, and particle is thick, and picture quality can not satisfy the medical diagnosis requirement.
Transparent thermal recording medium provided by the invention; comprise transparent support; be positioned at thermo-responsive imaging layer and the protective layer of support one side; be positioned at the backing layer of the another side of support, described thermo-responsive imaging layer is dry formation of heat sensitive recording layer coating composition comprise temperature-sensitive microcapsules and above-mentioned thermosensitive color development agent dispersing liquid by applying at support.
The support that is used as thermal recording medium should have Heat stability is good, Shi Buhui produces deformation and stretching, hygroscopicity is little, shrinkage factor is low, flatness is high being heated, it can be the transparent supports such as PET, PBT, transparent PP, thickness 100-250um, the preferred thick PET of 175um.
Thermo-responsive imaging layer is dry formation of heat sensitive recording layer coating composition comprise temperature-sensitive microcapsules and above-mentioned thermosensitive color development agent dispersing liquid by applying at support.
Contain colourless heat sensitive dye precursor in the temperature-sensitive microcapsules, it is disclosed method preparation in the Chinese patent of CN1843767A that the preparation of temperature-sensitive microcapsules can be adopted publication number.
For improving the sensible heat ability of thermal recording medium, can also add the temperature-sensitive sensitizer in the temperature-sensitive thermographic layer, the temperature-sensitive sensitizer can use with colourless heat sensitive dye and be coated in the microcapsules, also can use with the thermosensitive color development agent.The sensitizer consumption is not particularly limited, as long as can satisfy specific instructions for use.Temperature-sensitive sensitizer commonly used, for example: bis ethane, 2-benzyl naphthyl ether, 1,2-two-(3-phenoxy group) ethane, 4-benzylbiphenyl etc.
For improving the film-strength of the thermographic layer that forms, can also add adhesive in the temperature-sensitive thermographic layer, adhesive is coated in the microcapsules to use with colourless heat sensitive dye, also can use with the thermosensitive color development agent.Adhesive can be natural, also can be artificial synthetic.Such as: the natural polymer subclasses such as various gelatine, hide glue, casein, starch, modified starch, alginic acid; The cellulose derivatives such as hydroxyethylcellulose; The polyvinyl alcohols such as carboxy-modified polyvinyl alcohol; The high polymer classes such as polyacrylic acid.These adhesives can be used alone or be used in combination of two or more.
Protective layer Main Ingredients and Appearance of the present invention is adhesive and each analog assistant.Being water-soluble polymer or water-soluble emulsion as the adhesive that uses in the protective layer, can be the polyvinyl alcohol of complete alcoholysis or partial alcoholysis, the water-soluble binders such as the ammonium salt copolymer of phenylethylene/maleic anhydride, aqueous polyurethane emulsion.Each analog assistant comprises such as crosslinking agent, release agent and lubricant, ultraviolet absorber.The adhesive that uses in the protective layer and each analog assistant all are commercially available known products.
The present invention is at the backing layer that is coated with of support another side, and the preferred gelatin of the adhesive in the backing layer has certain film-strength in order to guarantee gelatin coating, also adds crosslinking agent, and crosslinking agent can be glyoxal, trichloro-triazine class or vinyl sulfone(RemzaolHuo Xingranliaodehuoxingjituan) class etc.Backing layer has prevent adhesion, also can reduce coefficient of friction, also ultraviolet absorber should be arranged simultaneously, to guarantee to form the photostability of image.In addition, be sticked together in order to prevent recording materials, in backing layer, can also add the material with prevent adhesion effect, such as: cataloid, polymethyl methacrylate near-spherical particle etc.
Thermal recording medium of the present invention can adopt any mode to be coated with, and preferably uses sloping flow coat cloth, slope stream extrusion coated or the curtain coating method that falls.
Below enumerate specific embodiment and further specify thermal recording medium of the present invention, but the invention is not restricted to these examples, in addition, " part " in the example and " % " represent respectively " mass parts " and " mass percent " if not otherwise specified.In addition, the average grain diameter of leuco dye microcapsules and thermosensitive color development agent and distribution of particles are all measured with MALVERN ZETASIZER 3000HS laser light scattering Particle Size Analyzer.
(1) preparation of leuco dye microcapsules A
6 parts ODB-2 (Shandong Rui Kang refines), 0.8 part GN-2(Tokyo are changed into), 1 part of gram CK-16(Wenzhou dragon wins), 0.8 part of beta-methylnaphthalene, 24 parts ethyl acetate join in the dissolving pan, stir, after the heating for dissolving, when being cooled to 55 ℃, add 10 parts XDI and trimethylolpropane tris addition polymer D-110N(Mitsui chemistry) and 3 parts IPDI (German Degussa), stir, obtain oil phase.
Be 4.5% PVA2488 polyvinyl alcohol water solution with 80 parts of concentration, 6 parts of 7# surfactants (Chinese Lekai Film Group Co's production) join dispersion pot, stir, and obtain water.
Above-mentioned oil phase is slowly joined in the aqueous phase solution, use simultaneously high speed shear to stir with 5600 rev/mins speed and disperseed 7 minutes, obtaining average grain diameter is the oil-in-water dispersion emulsion of 0.35um; Add 30 parts of deionized waters in scattered emulsion, then 1.2 parts of TEPAs under 600 rev/mins mixing speed, in 55 ℃ of lower reactions 3 hours, obtain the leuco dye microcapsules A of average grain diameter 0.36um, for subsequent use.
(2) preparation of leuco dye microcapsules B
6 parts ODB-2,1 part GN-2,0.5 part of gram Y-1(Beijing are become the space chemical industry), 0.8 part of beta-methylnaphthalene, 24 parts ethyl acetate join in the dissolving pan, stir, after the heating for dissolving, when being cooled to 55 ℃, the IPDI that adds 10 parts XDI and trimethylolpropane tris addition polymer D-110N and 3 parts, stir, obtain oil phase.
Be 4.5% PVA2488 polyvinyl alcohol water solution with 80 parts of concentration, 6 parts of 7# surfactants join dispersion pot, stir, and obtain water.
Above-mentioned oil phase is slowly joined in the aqueous phase solution, use simultaneously high speed shear to stir with 5600 rev/mins speed and disperseed 7 minutes, obtaining average grain diameter is the oil-in-water dispersion emulsion of 0.35um; Add 30 parts of deionized waters in scattered emulsion, then 1.2 parts of TEPAs under 600 rev/mins mixing speed, in 55 ℃ of lower reactions 3 hours, obtain the leuco dye microcapsules B of average grain diameter 0.36um, for subsequent use.
(3) preparation of protective layer coating solution
Various additives are being appointed full and uniform mixing in the reactor according to consumption listed in the table 1 with stirring, layer coating fluid that be protected, for subsequent use.
Table 1 protective layer coating solution list of ingredients
| Name of material | Concentration (%) | Consumption (part) |
| PVA 2488 aqueous solution | 4.5 | 600 |
| The PVA dispersion liquid of zinc stearate | 10 | 60 |
| Silicone oil and PVA dispersion liquid | 5 | 30 |
| The PVA dispersion liquid of ultraviolet absorber | 6 | 30 |
| Boric acid | 2 | 60 |
| Ludox | 25 | 20 |
| Styrene-maleic acid ammonium salt copolymer | 5 | 180 |
| Fluorine surfactant | 8 | 10 |
| Glutaraldehyde | 50 | 5 |
Embodiment 1
1. the preparation of developer dispersion
Be 4.5%PVA1788 polyvinyl alcohol water solution, 35 parts 4-hydroxyl-4 with 64 parts of concentration
,Isopropoxy diphenyl sulphone (DPS) (Shouguang Citroen zx pharmacy purity 99.53%) joins in the reactor, the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution that add again 0.7 part, stirred 1 hour, using SWZ50-1 horizontal sand mill (Chongqing Red Flag Chemical Mechine Co., Ltd.) recirculation system sand to be milled to the particle average grain diameter is 0.40 micron again, size distribution is 8% simultaneously, thermosensitive color development agent content 35%.Under 20 ± 5 ℃ of conditions, airtightly deposit after 14 days microscopic examination and do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
In reactor, add 25 parts leuco dye microcapsules A, 25 parts leuco dye microcapsules B, developer dispersion, 5 parts zinc salicylate type resin color-developing agent emulsion (40%), 3 parts styrene-butadiene latex (45%) and 2 parts the sodium dodecyl sulfate solution (10%) of 20 parts of said method preparations, stir evenly mixed, namely obtain thermographic layer coating fluid, for subsequent use.
3. the preparation of transparent thermal recording medium
After heat sensitive recording layer coating composition obtained above and protective layer coating solution left standstill froth breaking, use the extrusion coated mode, with the coating weight of thermographic layer, protective layer respectively 80,25ml/m
2Be coated with at density PET support, at the another side coating backing layer of PET support, and fully dry, obtain transparent thermal recording medium.Survey its performance.
Embodiment 2
1. the preparation of developer dispersion
Be 4.5% PVA1788 polyvinyl alcohol water solution, 35 parts 4-hydroxyl-4 with 64 parts of concentration
,The isopropoxy diphenyl sulphone (DPS) joins in the reactor, stir, infiltrate 1 hour, when being milled to the particle average grain diameter and being 1.00 ± 0.20 microns with the sand mill recirculation system sand, the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution that add 0.7 part, continuing sand milling to particle average grain diameter is 0.40 micron, and size distribution is 13% simultaneously, thermosensitive color development agent content 35%.Under 20 ± 5 ℃ of conditions, airtightly deposit after 14 days microscopic examination and do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
In reactor, add 25 parts leuco dye microcapsules A, 25 parts leuco dye microcapsules B, developer dispersion, 5 parts zinc salicylate type resin color-developing agent emulsion (40%), 3 parts styrene-butadiene latex (45%) and 2 parts the sodium dodecyl sulfate solution (10%) of 20 parts of said method preparations, stir evenly mixed, namely obtain thermographic layer coating fluid, for subsequent use.
3. the preparation of transparent thermal recording medium
After heat sensitive recording layer coating composition obtained above and protective layer coating solution left standstill froth breaking, use the extrusion coated mode, with the coating weight of thermographic layer, protective layer respectively 80,25ml/m
2Be coated with at density PET support, at the another side coating backing layer of PET support, and fully dry, obtain transparent thermal recording medium.Survey its performance.
Embodiment 3
1. the preparation of developer dispersion
Be 4.5% PVA1788 polyvinyl alcohol water solution, 25 parts 4-hydroxyl-4 with 74 parts of concentration
,The isopropoxy diphenyl sulphone (DPS) joins in the reactor, stirs, and adds 0.0625 part the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution again, infiltrates 1 hour, and sand milling to particle average grain diameter is 0.80 micron, and size distribution is 10% simultaneously, thermosensitive color development agent content 25%.Under 20 ± 5 ℃ of conditions, airtightly deposit after 14 days microscopic examination and do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
In reactor, add 25 parts leuco dye microcapsules A, 25 parts leuco dye microcapsules B, developer dispersion, 5 parts zinc salicylate type resin color-developing agent emulsion (40%), 3 parts styrene-butadiene latex (45%) and 2 parts the sodium dodecyl sulfate solution (10%) of 28 parts of said method preparations, stir evenly mixed, namely obtain thermographic layer coating fluid, for subsequent use.
3. the preparation of transparent thermal recording medium
After heat sensitive recording layer coating composition obtained above and protective layer coating solution left standstill froth breaking, use the extrusion coated mode, with the coating weight of thermographic layer, protective layer respectively 88,25ml/m
2Be coated with at density PET support, at the another side coating backing layer of PET support, and fully dry, obtain transparent thermal recording medium.Survey its performance.
Embodiment 4
1. the preparation of developer dispersion
Be 4.5% PVA1788 polyvinyl alcohol water solution, 35 parts 4-hydroxyl-4 with 61.5 parts of concentration
,The isopropoxy diphenyl sulphone (DPS) joins in the reactor, stirs, and adds 3.5 parts the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution again, infiltrates 1 hour, and sand milling to particle average grain diameter is 0.20 micron, and size distribution is 5% simultaneously, thermosensitive color development agent content 35%.Under 20 ± 5 ℃ of conditions, airtightly deposit after 14 days microscopic examination and do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
In reactor, add 25 parts leuco dye microcapsules A, 25 parts leuco dye microcapsules B, developer dispersion, 5 parts zinc salicylate type resin color-developing agent emulsion (40%), 3 parts styrene-butadiene latex (45%) and 2 parts the sodium dodecyl sulfate solution (10%) of 20 parts of said method preparations, stir evenly mixed, namely obtain thermographic layer coating fluid, for subsequent use.
3. the preparation of transparent thermal recording medium
After heat sensitive recording layer coating composition obtained above and protective layer coating solution left standstill froth breaking, use the extrusion coated mode, with the coating weight of thermographic layer, protective layer respectively 80,25ml/m
2Be coated with at density PET support, at the another side coating backing layer of PET support, and fully dry, obtain transparent thermal recording medium.Survey its performance.
Embodiment 5
1. the preparation of developer dispersion
Be 4.5% PVA1788 polyvinyl alcohol water solution, 25 parts of 4-hydroxyls-4 with 64 parts of concentration
,Isopropoxy diphenyl sulphone (DPS) and 10 parts of benzyl p-hydroxybenzoates (the Panjin ancient cooking vessel is inferior) and 0.625 part the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution join in the reactor, stir, infiltrate 1 hour, being milled to the particle average grain diameter with the sand mill recirculation system sand again is 0.30 micron, size distribution is 3% simultaneously, thermosensitive color development agent content 35%.Under 20 ± 5 ℃ of conditions, airtightly deposit after 14 days microscopic examination and do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
In reactor, add 25 parts leuco dye microcapsules A, 25 parts leuco dye microcapsules B, developer dispersion, 5 parts zinc salicylate type resin color-developing agent emulsion (40%), 3 parts styrene-butadiene latex (45%) and 2 parts the sodium dodecyl sulfate solution (10%) of 20 parts of said method preparations, stir evenly mixed, namely obtain thermographic layer coating fluid, for subsequent use.
3. the preparation of transparent thermal recording medium
After heat sensitive recording layer coating composition obtained above and protective layer coating solution left standstill froth breaking, use the extrusion coated mode, with the coating weight of thermographic layer, protective layer respectively 80,25ml/m
2Be coated with at density PET support, at the another side coating backing layer of PET support, and fully dry, obtain transparent thermal recording medium.Survey its performance.
Embodiment 6
1. the preparation of developer dispersion
Be 4.5% PVA1788 polyvinyl alcohol water solution, 31.5 parts of 4-hydroxyls-4 with 64 parts of concentration
,Isopropoxy diphenyl sulphone (DPS) and 3.5 parts of BON(Shouguang Citroen zx pharmacy) when joining in 300 liters the reactor, add again 0.63 part of naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution, stir, infiltrate 1 hour, being milled to the particle average grain diameter with the sand mill recirculation system sand again is 0.50 micron, size distribution is 7% simultaneously, thermosensitive color development agent content 35%.Under 20 ± 5 ℃ of conditions, airtightly deposit after 14 days microscopic examination and do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
In reactor, add 25 parts leuco dye microcapsules A, 25 parts leuco dye microcapsules B, developer dispersion, 5 parts zinc salicylate type resin color-developing agent emulsion (40%), 3 parts styrene-butadiene latex (45%) and 2 parts the sodium dodecyl sulfate solution (10%) of 20 parts of said method preparations, stir evenly mixed, namely obtain thermographic layer coating fluid, for subsequent use.
3. the preparation of transparent thermal recording medium
After heat sensitive recording layer coating composition obtained above and protective layer coating solution left standstill froth breaking, use the extrusion coated mode, with the coating weight of thermographic layer, protective layer respectively 80,25ml/m
2Be coated with at density PET support, at the another side coating backing layer of PET support, and fully dry, obtain transparent thermal recording medium.Survey its performance.
Comparative example 1
1. the preparation of developer dispersion
Be 4.5% PVA1788 polyvinyl alcohol water solution, 35 parts of 4-hydroxyls-4 with 65 parts of concentration
,The isopropoxy diphenyl sulphone (DPS) joins in the reactor, stirs, and adds 0.05 part the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution again, infiltrates 1 hour, and being milled to the particle average grain diameter with the sand mill recirculation system sand again is 0.40 micron, thermosensitive color development agent content 35%.Under 20 ± 5 ℃ of conditions, airtightly deposit after 14 days microscopic examination and find to have seldom to measure crystallization.For subsequent use.
2. the preparation of heat sensitive recording layer coating composition
In reactor, add 25 parts leuco dye microcapsules A, 25 parts leuco dye microcapsules B, developer dispersion, 5 parts zinc salicylate type resin color-developing agent emulsion (40%), 3 parts styrene-butadiene latex (45%) and 2 parts the sodium dodecyl sulfate solution (10%) of 20 parts of said method preparations, stir evenly mixed, namely obtain thermographic layer coating fluid, for subsequent use.
3. the preparation of transparent thermal recording medium
After heat sensitive recording layer coating composition obtained above and protective layer coating solution left standstill froth breaking, use the extrusion coated mode, with the coating weight of thermographic layer, protective layer respectively 80,25ml/m
2Be coated with at density PET support, at the another side coating backing layer of PET support, and fully dry, obtain transparent thermal recording medium.Survey its performance.
Comparative example 2
1. the preparation of developer dispersion
Be 4.5% PVA1788 polyvinyl alcohol water solution, 35 parts of 4-hydroxyls-4 with 65 parts of concentration
,The isopropoxy diphenyl sulphone (DPS) joins in the reactor, stirs to infiltrate 1 hour, and being milled to the particle average grain diameter with the sand mill recirculation system sand again is 0.40 micron.Under 20 ± 5 ℃ of conditions, thermosensitive color development agent content 35% is airtightly deposited after 14 days microscopic examination and is found have mass crystallization to separate out, shown in illustration 1.For subsequent use.
2. the preparation of heat sensitive recording layer coating composition
In reactor, add 25 parts leuco dye microcapsules A, 25 parts leuco dye microcapsules B, developer dispersion, 5 parts zinc salicylate type resin color-developing agent emulsion (40%), 3 parts styrene-butadiene latex (45%) and 2 parts the sodium dodecyl sulfate solution (10%) of 20 parts of said method preparations, stir evenly mixed, namely obtain thermographic layer coating fluid, for subsequent use.
3. the preparation of transparent thermal recording medium
After heat sensitive recording layer coating composition obtained above and protective layer coating solution left standstill froth breaking, use the extrusion coated mode, with the coating weight of thermographic layer, protective layer respectively 80,25ml/m
2Be coated with at density PET support, at the another side coating backing layer of PET support, and fully dry, obtain transparent thermal recording medium.Survey its performance.
Table 2: the test data table of each embodiment
| ? | Density (the 1st grade) | Density (the 8th grade) | Density (the 16th grade) | Haze value % |
| Embodiment 1 | 0.15 | 1.02 | 3.32 | 39.2 |
| Embodiment 2 | 0.15 | 0.96 | 3.27 | 39.4 |
| Embodiment 3 | 0.14 | 0.83 | 3.01 | 46.8 |
| Embodiment 4 | 0.14 | 1.36 | 3.35 | 36.5 |
| Embodiment 5 | 0.14 | 1.33 | 3.15 | 37.2 |
| Embodiment 6 | 0.14 | 1.15 | 3.31 | 37.9 |
| Comparative example 1 | 0.15 | 0.98 | 2.95 | 43.7 |
| Comparative example 2 | 0.15 | 0.67 | 2.77 | 65.2 |
In the table, the method for testing of properties is as follows:
1. haze value
Measure the film haze value with NDH-2000 type haze meter transmissometer (Japanese electric look),
2. density value
After printing 16 grades of density GTGs, uses by LUCKY DRY IMAGER DryMate-1000 dry image forming instrument X-Rite 310T type densitometer test density value.
In the table 2, the 1st grade is minimum density, and the Fog density of film has been described; The 8th grade is intermediate density, is the density area that actual use is often used, and has reflected the temperature-sensitive sensitivity of film; The 16th grade of density of printing when being dry image forming instrument maximum temperature is the maximum color development density value of film.The permeability of haze value reflection film, it is worth, and more the novel gelatin foil transparency is better.
Claims (7)
1. 4-hydroxyl-4
,Isopropoxy diphenyl sulphone (DPS) thermosensitive color development agent dispersing liquid, it is by case of wet attrition 4-hydroxyl-4 in the presence of dispersion is protectant
,Isopropoxy diphenyl sulphone (DPS) thermosensitive color development agent and obtaining is characterized in that described dispersion protective agent is selected from naphthalene sulfonic acids isopropyl ester sodium salt, and with respect to the thermosensitive color development agent of 100 mass parts, disperseing protective agent is 0.05～2 mass parts; Average grain diameter after described thermosensitive color development agent disperses is 0.2～0.8 micron, and size distribution is less than 15%.
2. described dispersion liquid according to claim 1 is characterized in that, with respect to the thermosensitive color development agent of 100 mass parts, disperseing protective agent is 0.1～1 mass parts.
3. described dispersion liquid according to claim 1 and 2 is characterized in that, the average grain diameter after described thermosensitive color development agent disperses is 0.3～0.5 micron, and size distribution is less than 8%.
4. described dispersion liquid according to claim 3 is characterized in that, the thermosensitive color development agent content in the described dispersion liquid is greater than 25 quality %.
5. transparent thermal recording medium; comprise transparent support; be positioned at thermo-responsive imaging layer and the protective layer of support one side; be positioned at the backing layer of the another side of support; it is characterized in that, described thermo-responsive imaging layer is that the heat sensitive recording layer coating composition that comprises temperature-sensitive microcapsules and the described thermosensitive color development agent dispersing liquid of claim 1～4 is dry to be formed by applying at support.
6. require as requested 5 described thermal recording mediums, it is characterized in that, described thermal recording medium haze value is less than 50%.
7. require as requested 6 described thermal recording mediums, it is characterized in that, described thermal recording medium haze value is less than 40%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104985943A (en) * | 2015-08-13 | 2015-10-21 | 新乡市瑞丰新材料股份有限公司 | Color developing agent special for inner coating of membrane transfer machine and preparation method thereof |
| CN106004143A (en) * | 2015-08-03 | 2016-10-12 | 理光感热技术（无锡）有限公司 | Transparent thermal sensitive recording material |
| JP2018513794A (en) * | 2015-03-23 | 2018-05-31 | パピエルファブリーク・アウグスト・ケーラー・エスエー | Thermal recording material |
| CN110079172A (en) * | 2019-05-15 | 2019-08-02 | 南阳九鼎材料科技股份有限公司 | A kind of preparation process of salicylic acid isooctyl ester lotion |
| CN111511565A (en) * | 2017-12-27 | 2020-08-07 | 花王株式会社 | Gravure printing method |
| CN111619258A (en) * | 2020-05-29 | 2020-09-04 | 乐凯医疗科技有限公司 | Thermosensitive recording material and preparation method thereof |
| CN112009129A (en) * | 2020-08-31 | 2020-12-01 | 广东鼎孚新材料科技有限公司 | Plastic substrate thermal sensitive paper |
| CN115820052A (en) * | 2022-11-29 | 2023-03-21 | 上海席亚高分子材料有限公司 | High-transparency pressure-sensitive color development layer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56148589A (en) * | 1980-04-22 | 1981-11-18 | Konishiroku Photo Ind Co Ltd | Heat-sensitive recording material |
| JP2008246875A (en) * | 2007-03-30 | 2008-10-16 | Oji Paper Co Ltd | Manufacturing method for dispersion liquid for heat-sensitive recording material |
| US20100130356A1 (en) * | 2008-11-21 | 2010-05-27 | Appleton Papers Inc. | Thermally-responsive record material |
| CN102574409A (en) * | 2009-10-14 | 2012-07-11 | 王子制纸株式会社 | Heat-sensitive recording material |
-
2012
- 2012-11-12 CN CN201210449826.7A patent/CN103072396B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56148589A (en) * | 1980-04-22 | 1981-11-18 | Konishiroku Photo Ind Co Ltd | Heat-sensitive recording material |
| JP2008246875A (en) * | 2007-03-30 | 2008-10-16 | Oji Paper Co Ltd | Manufacturing method for dispersion liquid for heat-sensitive recording material |
| US20100130356A1 (en) * | 2008-11-21 | 2010-05-27 | Appleton Papers Inc. | Thermally-responsive record material |
| WO2010059194A2 (en) * | 2008-11-21 | 2010-05-27 | Appleton Papers Inc. | Thermally-responsive record material |
| CN102574409A (en) * | 2009-10-14 | 2012-07-11 | 王子制纸株式会社 | Heat-sensitive recording material |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018513794A (en) * | 2015-03-23 | 2018-05-31 | パピエルファブリーク・アウグスト・ケーラー・エスエー | Thermal recording material |
| CN106004143A (en) * | 2015-08-03 | 2016-10-12 | 理光感热技术（无锡）有限公司 | Transparent thermal sensitive recording material |
| CN106004143B (en) * | 2015-08-03 | 2018-09-21 | 理光感热技术（无锡）有限公司 | Transparent thermal recording medium |
| CN104985943A (en) * | 2015-08-13 | 2015-10-21 | 新乡市瑞丰新材料股份有限公司 | Color developing agent special for inner coating of membrane transfer machine and preparation method thereof |
| CN104985943B (en) * | 2015-08-13 | 2017-02-08 | 新乡市瑞丰新材料股份有限公司 | Color developing agent special for inner coating of membrane transfer machine and preparation method thereof |
| CN111511565A (en) * | 2017-12-27 | 2020-08-07 | 花王株式会社 | Gravure printing method |
| CN111511565B (en) * | 2017-12-27 | 2021-11-26 | 花王株式会社 | Gravure printing method |
| US11254828B2 (en) | 2017-12-27 | 2022-02-22 | Kao Corporation | Gravure printing method |
| CN110079172A (en) * | 2019-05-15 | 2019-08-02 | 南阳九鼎材料科技股份有限公司 | A kind of preparation process of salicylic acid isooctyl ester lotion |
| CN111619258A (en) * | 2020-05-29 | 2020-09-04 | 乐凯医疗科技有限公司 | Thermosensitive recording material and preparation method thereof |
| CN111619258B (en) * | 2020-05-29 | 2021-10-19 | 乐凯医疗科技有限公司 | Thermosensitive recording material and preparation method thereof |
| CN112009129A (en) * | 2020-08-31 | 2020-12-01 | 广东鼎孚新材料科技有限公司 | Plastic substrate thermal sensitive paper |
| CN112009129B (en) * | 2020-08-31 | 2022-04-26 | 广东鼎孚新材料科技有限公司 | Plastic substrate thermal sensitive paper |
| CN115820052A (en) * | 2022-11-29 | 2023-03-21 | 上海席亚高分子材料有限公司 | High-transparency pressure-sensitive color development layer and preparation method thereof |
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