Detailed description of the invention
In the present invention, dispersion liquid is case of wet attrition 4-hydroxyl-4 under the protectant existence of dispersion
,isopropoxy diphenyl sulphone (DPS) temperature-sensitive developer and obtaining, dispersion protective agent is selected from naphthalene sulfonic acids isopropyl ester sodium salt.Dispersant when naphthalene sulfonic acids isopropyl ester sodium salt disperses as temperature-sensitive developer uses, it can be adsorbed onto temperature-sensitive developer particle surface well when grinding distribution, electric double layer is formed after the particle surface absorption of temperature-sensitive developer, do not assemble because of electrostatic repulsion between temperature-sensitive developer particle, and not easily got off from particle surface desorb by external force, and then prevent temperature-sensitive developer crystalline hydrate.The time that naphthalene sulfonic acids isopropyl ester sodium salt adds can at temperature-sensitive developer 4-hydroxyl-4
,before the wet lapping of isopropoxy diphenyl sulphone (DPS), once add in process of lapping or after having ground, also can before the milling, in process of lapping, ground after repeatedly part add, preferably once add before the milling.Relative to the temperature-sensitive developer of 100 mass parts, dispersion protective agent is 0.05 ~ 2 mass parts, preferably 0.1 ~ 1 mass parts.When disperseing protectant consumption lower than 0.05 mass parts, the crystalline hydrate of temperature-sensitive developer can not be suppressed well; When the consumption of dispersant is higher than 2 mass parts, cost can increase.
Dispersion liquid is obtained 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., from the preferred horizontal sand mill in industrial production efficiency angle aspect.4-hydroxyl-4 in preferred case of wet attrition to dispersion liquid
,isopropoxy diphenyl sulphone (DPS) average grain diameter be 0.2 ~ 0.8 micron, size distribution is less than 15%, and the average grain diameter of preferred temperature-sensitive developer is 0.3 ~ 0.5 micron, and size distribution is less than 8%.When particle diameter is less than 0.2 micron, easily occur crystalline hydrate, and suitability for industrialized production needs to consume a large amount of energy and time, uneconomical; When particle diameter is greater than 0.8 micron, the sensitivity of thermal recording medium reduces, mist degree increases, and particle is thick, and picture quality can not meet 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 comprises the heat sensitive recording layer coating composition drying of temperature-sensitive microcapsules and above-mentioned thermosensitive color development agent dispersing liquid by coating on support and formed.
The support being used as thermal recording medium should having Heat stability is good, can not produce deformation and stretching when being heated, hygroscopicity is little, shrinkage factor is low, flatness is high, it can be the transparent supports such as PET, PBT, transparent PP, thickness 100-250um, the PET that preferred 175um is thick.
Thermo-responsive imaging layer comprises the heat sensitive recording layer coating composition drying of temperature-sensitive microcapsules and above-mentioned thermosensitive color development agent dispersing liquid by coating on support and formed.
Containing colourless heat sensitive dye precursor in temperature-sensitive microcapsules, the preparation of temperature-sensitive microcapsules can adopt publication number to be method preparation disclosed in the Chinese patent of CN1843767A.
For improving the sensible heat ability of thermal recording medium, can also add temperature-sensitive sensitizer in temperature-sensitive thermographic layer, temperature-sensitive sensitizer can use and be coated in microcapsules together with colourless heat sensitive dye, also can use together with temperature-sensitive developer.Sensitizer consumption is not particularly limited, as long as can meet specific instructions for use.Conventional temperature-sensitive sensitizer, such as: bis ethane, 2-benzyl naphthyl ether, 1,2-bis--(3-phenoxy group) ethane, 4-benzylbiphenyl etc.
For improving the film-strength of the thermographic layer formed, can also add adhesive in temperature-sensitive thermographic layer, adhesive is coated in microcapsules to use together with colourless heat sensitive dye, also can use together with temperature-sensitive developer.Adhesive can be natural, also can be Prof. Du Yucang.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 one or are 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 used in protective layer, can be the polyvinyl alcohol of complete alcoholysis or partial alcoholysis, the water-soluble binder such as ammonium salt copolymer, aqueous polyurethane emulsion of phenylethylene/maleic anhydride.Each analog assistant comprises as crosslinking agent, release agent and lubricant, ultraviolet absorber.The adhesive used in protective layer and each analog assistant are all commercially available known products.
The present invention is coated with backing layer support another side, the preferred gelatin of the adhesive in backing layer, in order to ensure that gelatin coating has certain film-strength, also adds crosslinking agent, and crosslinking agent can be glyoxal, trichloro-triazine class or vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) class etc.Backing layer has and prevents adhesion and can reduce coefficient of friction, also should have ultraviolet absorber simultaneously, to ensure the photostability forming image.In addition, in order to prevent recording materials to be sticked together, the material with the effect of preventing adhesion can also be added in backing layer, such as: cataloid, polymethyl methacrylate near-spherical particle etc.
Thermal recording medium of the present invention can be adopted and be coated with in any way, preferably uses slope flow coat cloth, slope stream extrusion coated or dropping curtain coating method.
Below enumerate specific embodiment and further illustrate thermal recording medium of the present invention, but the invention is not restricted to these examples, in addition, " part " and " % " in example if not otherwise specified, represents " mass parts " and " mass percent " respectively.In addition, the average grain diameter of leuco dye microcapsules and temperature-sensitive developer and distribution of particles all use MALVERN ZETASIZER 3000HS laser diffraction particle size analysis-e/or determining.
(1) preparation of leuco dye microcapsules A
The ODB-2 of 6 parts (Shandong Rui Kang refines), the GN-2(Tokyo of 0.8 part are changed into), 1 part of gram of CK-16(Wenzhou dragon victory), 0.8 part of beta-methylnaphthalene, the ethyl acetate of 24 parts joins in dissolving pan, stir, after heating for dissolving, when being cooled to 55 DEG C, add the XDI of 10 parts and trimethylolpropane tris addition polymer D-110N(Mitsui chemistry) and the IPDI (German Degussa) of 3 parts, stir, obtain oil phase.
By the PVA2488 polyvinyl alcohol water solution that 80 parts of concentration are 4.5%, 6 parts of 7# surfactants (Chinese Lekai Film Group Co's production) join dispersion pot, stir, obtain aqueous phase.
Above-mentioned oil phase is slowly joined in aqueous phase solution, uses high shear agitation with the Rate Dispersion 7 minutes of 5600 revs/min simultaneously, obtain the oil-in-water dispersion emulsion that average grain diameter is 0.35um; In scattered emulsion, add 30 parts of deionized waters, 1.2 parts of TEPAs, then under the mixing speed of 600 revs/min, react 3 hours at 55 DEG C, obtain the leuco dye microcapsules A of average grain diameter 0.36um, for subsequent use.
(2) preparation of leuco dye microcapsules B
The ODB-2 of 6 parts, the GN-2 of 1 part, 0.5 part of gram of Y-1(Beijing are become space chemical industry), 0.8 part of beta-methylnaphthalene, the ethyl acetate of 24 parts joins in dissolving pan, stir, after heating for dissolving, when being cooled to 55 DEG C, add the XDI of 10 parts and the IPDI of trimethylolpropane tris addition polymer D-110N and 3 part, stir, obtain oil phase.
By the PVA2488 polyvinyl alcohol water solution that 80 parts of concentration are 4.5%, 6 parts of 7# surfactants join dispersion pot, stir, obtain aqueous phase.
Above-mentioned oil phase is slowly joined in aqueous phase solution, uses high shear agitation with the Rate Dispersion 7 minutes of 5600 revs/min simultaneously, obtain the oil-in-water dispersion emulsion that average grain diameter is 0.35um; In scattered emulsion, add 30 parts of deionized waters, 1.2 parts of TEPAs, then under the mixing speed of 600 revs/min, react 3 hours at 55 DEG C, obtain the leuco dye microcapsules B of average grain diameter 0.36um, for subsequent use.
(3) preparation of protective layer coating solution
Various additive is being appointed with stirring in reactor full and uniform mixed according to consumption listed in table 1, is obtaining protective layer coating solution, 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, the 4-hydroxyl-4 of 35 parts by 64 parts of concentration
,isopropoxy diphenyl sulphone (DPS) (Shouguang Citroen zx pharmacy purity 99.53%) joins in reactor, add the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution of 0.7 part again, stir 1 hour, using SWZ50-1 horizontal sand mill (Chongqing Red Flag Chemical Mechine Co., Ltd.) recirculation system sand to be milled to mean particle size is again 0.40 micron, size distribution is 8% simultaneously, thermosensitive color development agent content 35%.Under 20 ± 5 DEG C of conditions, airtight deposit 14 days after microscopic examination do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
Add the leuco dye microcapsules A of 25 parts, the leuco dye microcapsules B of 25 parts in the reactor, the sodium dodecyl sulfate solution (10%) of developer dispersion prepared by 20 parts of said methods, salicylic acid zinc-type resin color-developing agent emulsion (40%) of 5 parts, the styrene-butadiene latex (45%) of 3 parts and 2 parts, stirring is mixed evenly, namely thermographic layer coating fluid is obtained, 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 are left standstill froth breaking, use extrusion coated mode, with the coating weight of thermographic layer, protective layer difference 80,25ml/m
2density PET support is coated with, 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 the PVA1788 polyvinyl alcohol water solution of 4.5%, the 4-hydroxyl-4 of 35 parts by 64 parts of concentration
,isopropoxy diphenyl sulphone (DPS) joins in reactor, stir, infiltrate 1 hour, when with sand mill recirculation system sand, to be milled to mean particle size be 1.00 ± 0.20 microns, add the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution of 0.7 part, continuing sand milling to mean particle size is 0.40 micron, and size distribution is 13% simultaneously, thermosensitive color development agent content 35%.Under 20 ± 5 DEG C of conditions, airtight deposit 14 days after microscopic examination do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
Add the leuco dye microcapsules A of 25 parts, the leuco dye microcapsules B of 25 parts in the reactor, the sodium dodecyl sulfate solution (10%) of developer dispersion prepared by 20 parts of said methods, salicylic acid zinc-type resin color-developing agent emulsion (40%) of 5 parts, the styrene-butadiene latex (45%) of 3 parts and 2 parts, stirring is mixed evenly, namely thermographic layer coating fluid is obtained, 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 are left standstill froth breaking, use extrusion coated mode, with the coating weight of thermographic layer, protective layer difference 80,25ml/m
2density PET support is coated with, 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 the PVA1788 polyvinyl alcohol water solution of 4.5%, the 4-hydroxyl-4 of 25 parts by 74 parts of concentration
,isopropoxy diphenyl sulphone (DPS) joins in reactor, and stir, then add the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution of 0.0625 part, infiltrate 1 hour, sand milling to mean particle size is 0.80 micron, and size distribution is 10% simultaneously, thermosensitive color development agent content 25%.Under 20 ± 5 DEG C of conditions, airtight deposit 14 days after microscopic examination do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
Add the leuco dye microcapsules A of 25 parts, the leuco dye microcapsules B of 25 parts in the reactor, the sodium dodecyl sulfate solution (10%) of developer dispersion prepared by 28 parts of said methods, salicylic acid zinc-type resin color-developing agent emulsion (40%) of 5 parts, the styrene-butadiene latex (45%) of 3 parts and 2 parts, stirring is mixed evenly, namely thermographic layer coating fluid is obtained, 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 are left standstill froth breaking, use extrusion coated mode, with the coating weight of thermographic layer, protective layer difference 88,25ml/m
2density PET support is coated with, 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 the PVA1788 polyvinyl alcohol water solution of 4.5%, the 4-hydroxyl-4 of 35 parts by 61.5 parts of concentration
,isopropoxy diphenyl sulphone (DPS) joins in reactor, and stir, then add the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution of 3.5 parts, infiltrate 1 hour, sand milling to mean particle size is 0.20 micron, and size distribution is 5% simultaneously, thermosensitive color development agent content 35%.Under 20 ± 5 DEG C of conditions, airtight deposit 14 days after microscopic examination do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
Add the leuco dye microcapsules A of 25 parts, the leuco dye microcapsules B of 25 parts in the reactor, the sodium dodecyl sulfate solution (10%) of developer dispersion prepared by 20 parts of said methods, salicylic acid zinc-type resin color-developing agent emulsion (40%) of 5 parts, the styrene-butadiene latex (45%) of 3 parts and 2 parts, stirring is mixed evenly, namely thermographic layer coating fluid is obtained, 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 are left standstill froth breaking, use extrusion coated mode, with the coating weight of thermographic layer, protective layer difference 80,25ml/m
2density PET support is coated with, 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 PVA1788 polyvinyl alcohol water solution, 25 parts of 4-hydroxyls-4 of 4.5% by 64 parts of concentration
,isopropoxy diphenyl sulphone (DPS) and 10 parts of benzyl p-hydroxybenzoates (Panjin ancient cooking vessel is sub-) and the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution of 0.625 part join in reactor, stir, infiltrate 1 hour, being milled to mean particle size with sand mill recirculation system sand is again 0.30 micron, size distribution is 3% simultaneously, thermosensitive color development agent content 35%.Under 20 ± 5 DEG C of conditions, airtight deposit 14 days after microscopic examination do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
Add the leuco dye microcapsules A of 25 parts, the leuco dye microcapsules B of 25 parts in the reactor, the sodium dodecyl sulfate solution (10%) of developer dispersion prepared by 20 parts of said methods, salicylic acid zinc-type resin color-developing agent emulsion (40%) of 5 parts, the styrene-butadiene latex (45%) of 3 parts and 2 parts, stirring is mixed evenly, namely thermographic layer coating fluid is obtained, 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 are left standstill froth breaking, use extrusion coated mode, with the coating weight of thermographic layer, protective layer difference 80,25ml/m
2density PET support is coated with, 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 PVA1788 polyvinyl alcohol water solution, 31.5 parts of 4-hydroxyls-4 of 4.5% by 64 parts of concentration
,isopropoxy diphenyl sulphone (DPS) and 3.5 parts of BON(Shouguang Citroen zx pharmacy) when joining in the reactor of 300 liters, add 0.63 part of naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution again, stir, infiltrate 1 hour, being milled to mean particle size with sand mill recirculation system sand is again 0.50 micron, size distribution is 7% simultaneously, thermosensitive color development agent content 35%.Under 20 ± 5 DEG C of conditions, airtight deposit 14 days after microscopic examination do not find crystallization, for subsequent use.
2. the preparation of heat sensitive recording layer coating composition
Add the leuco dye microcapsules A of 25 parts, the leuco dye microcapsules B of 25 parts in the reactor, the sodium dodecyl sulfate solution (10%) of developer dispersion prepared by 20 parts of said methods, salicylic acid zinc-type resin color-developing agent emulsion (40%) of 5 parts, the styrene-butadiene latex (45%) of 3 parts and 2 parts, stirring is mixed evenly, namely thermographic layer coating fluid is obtained, 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 are left standstill froth breaking, use extrusion coated mode, with the coating weight of thermographic layer, protective layer difference 80,25ml/m
2density PET support is coated with, 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 PVA1788 polyvinyl alcohol water solution, 35 parts of 4-hydroxyls-4 of 4.5% by 65 parts of concentration
,isopropoxy diphenyl sulphone (DPS) joins in reactor, stirs, then adds the naphthalene sulfonic acids isopropyl ester sodium salt 200 grams per liter aqueous solution of 0.05 part, infiltrate 1 hour, then to be milled to mean particle size with sand mill recirculation system sand be 0.40 micron, thermosensitive color development agent content 35%.Under 20 ± 5 DEG C of conditions, airtight deposit 14 days after microscopic examination find that there is and seldom measure crystallization.For subsequent use.
2. the preparation of heat sensitive recording layer coating composition
Add the leuco dye microcapsules A of 25 parts, the leuco dye microcapsules B of 25 parts in the reactor, the sodium dodecyl sulfate solution (10%) of developer dispersion prepared by 20 parts of said methods, salicylic acid zinc-type resin color-developing agent emulsion (40%) of 5 parts, the styrene-butadiene latex (45%) of 3 parts and 2 parts, stirring is mixed evenly, namely thermographic layer coating fluid is obtained, 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 are left standstill froth breaking, use extrusion coated mode, with the coating weight of thermographic layer, protective layer difference 80,25ml/m
2density PET support is coated with, 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 PVA1788 polyvinyl alcohol water solution, 35 parts of 4-hydroxyls-4 of 4.5% by 65 parts of concentration
,isopropoxy diphenyl sulphone (DPS) joins in reactor, stirs infiltration 1 hour, then to be milled to mean particle size with sand mill recirculation system sand be 0.40 micron.Under 20 ± 5 DEG C of conditions, thermosensitive color development agent content 35%, airtight deposit 14 days after microscopic examination find that there is mass crystallization separate out, as shown in illustration 1.For subsequent use.
2. the preparation of heat sensitive recording layer coating composition
Add the leuco dye microcapsules A of 25 parts, the leuco dye microcapsules B of 25 parts in the reactor, the sodium dodecyl sulfate solution (10%) of developer dispersion prepared by 20 parts of said methods, salicylic acid zinc-type resin color-developing agent emulsion (40%) of 5 parts, the styrene-butadiene latex (45%) of 3 parts and 2 parts, stirring is mixed evenly, namely thermographic layer coating fluid is obtained, 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 are left standstill froth breaking, use extrusion coated mode, with the coating weight of thermographic layer, protective layer difference 80,25ml/m
2density PET support is coated with, 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 table, the method for testing of properties is as follows:
1. haze value
Film haze value is measured with NDH-2000 type haze meter transmissometer (Japanese electric look),
2. density value
X-Rite 310T type densitometer test density value is used after LUCKY DRY IMAGER DryMate-1000 dry image forming instrument prints 16 grades of density GTGs.
In table 2, the 1st grade is minimum density, describes the most Fog density of film; 8th grade is intermediate density, is the density area that actual use is often used, and reflects the heat sensitivity of film; The 16th grade of density for printing during dry image forming instrument maximum temperature is the maximum color development density value of film.The permeability of haze value reflection film, its value more novel gelatin foil transparency is better.