CN111619258B - Thermosensitive recording material and preparation method thereof - Google Patents
Thermosensitive recording material and preparation method thereof Download PDFInfo
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- CN111619258B CN111619258B CN202010476464.5A CN202010476464A CN111619258B CN 111619258 B CN111619258 B CN 111619258B CN 202010476464 A CN202010476464 A CN 202010476464A CN 111619258 B CN111619258 B CN 111619258B
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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
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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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
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
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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
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
The invention relates to a thermosensitive recording material and a preparation method thereof, wherein the thermosensitive recording material comprises a support body, a thermosensitive imaging layer on the support body and a protective layer on the thermosensitive imaging layer, the thermosensitive imaging layer is prepared by curing a thermosensitive coating liquid, and the thermosensitive coating liquid is prepared from a dye dispersion liquid A, a developer dispersion liquid B, a polyvinyl alcohol aqueous solution mixture C, a polyvinyl alcohol aqueous solution, a gamma-glycidyl ether propyl trimethoxy silane stock solution and a fluorine surfactant. The invention uses gamma-glycidyl ether propyl trimethoxy silane, thereby avoiding the coating defect generated by directly coating the thermal sensitive imaging layer on the support; the invention improves the adhesiveness between the thermosensitive imaging layer and the support, makes it possible to dispense with the primer layer, greatly reduces the production cost, improves the production efficiency and simplifies the production process.
Description
Technical Field
The invention relates to the technical field of recording materials, in particular to a thermosensitive recording material.
Background
In recent years, with the diversification of information and the expansion of demand, recording materials applied to different fields have been developed and put into practical use in the field of information recording. As a thermosensitive recording material, a recording image is formed mainly by a chemical reaction of an electron-donating leuco dye and a color developer of an electron-accepting compound in a high-temperature molten state. Such thermosensitive recording materials have significant advantages, making recording devices used therefor simple and compact in structure, high in reliability, inexpensive, and free from routine maintenance. For these reasons, it has been widely used as a recording material for various fields such as electronic computers, facsimile machines, ticket vending machines, scientific computers, CAD printers, plotters, and CRT-based medical inspection printers.
The thermosensitive recording materials disclosed in chinese patents CN201510277560.6, CN201510562582.7, CN201110021891.5, CN01802667.2, CN201080046540.3 and CN200680030922.0 achieve the improvement of the thermosensitive performance of the recording materials by introducing an undercoat layer between the thermosensitive imaging layer and the support, and the undercoat layer is designed with one, two or more layers, and the coating method can be single-layer coating, double-layer coating or multi-layer coating. This is disadvantageous in terms of mass production stability and increases the running cost. The bottom coating layer is coated on the supporting body, so that the connection between the coating liquid on the bottom coating layer and the supporting body is mainly realized, the adhesion performance of the upper layer coating liquid and the supporting body is improved, the upper layer coating liquid is promoted to be better spread on the supporting body, and the coating defects are reduced. Thus, there are problems such as high demand for the undercoat layer coating liquid, 100% absence of coating defects after coating, or the appearance of the upper layer coating; the introduction of the bottom coating liquid also brings potential risks to the quality stability of the end product. The prior primer coating has the defect of overlarge surface resistance after being coated and dried, and brings fatal damage to the processing and the use of subsequent products.
Disclosure of Invention
The invention aims to provide a thermosensitive recording material and a preparation method thereof, which do not need a bottom coating, have low fog density, stable color development and excellent coating fastness and simultaneously have the characteristics of stable apparent quality.
The invention aims to solve the problems by the following technical scheme:
a thermosensitive recording material comprises a support, a thermosensitive imaging layer on the support and a protective layer on the thermosensitive imaging layer, wherein the thermosensitive imaging layer is prepared by curing a thermosensitive coating liquid, and the thermosensitive coating liquid comprises the following components in parts by mass:
in the thermosensitive recording material, the polyvinyl alcohol aqueous solution mixture C is prepared from the following components in parts by mass:
30-60% of polyvinyl alcohol aqueous solution (solid content is 3%)
Silicon dioxide dispersion (solid content 25%) 0.8-6.0
Boric acid (20g/l) 4.0-20.0.
In the thermosensitive recording material, the dye dispersion liquid A is prepared from the following components in parts by mass:
15 parts of 3-phenylamino-3-methyl-6-dibutylaminofluoran
25 parts of polyvinyl alcohol aqueous solution (10% solid content, mass percentage concentration, the same applies below)
60 parts of deionized water;
dispersing the above components with a sand mill until the volume average particle size of the obtained mixture is less than 1.0 μm to obtain the dye dispersion A.
In the thermosensitive recording material, the developer dispersion liquid B is prepared from the following components in parts by mass:
25 parts of 4-hydroxy-4' -isopropoxydiphenyl sulfone
25 parts of polyvinyl alcohol aqueous solution (10% solid content)
50 portions of deionized water
Dispersing the above components with sand mill until the volume average particle diameter of the obtained mixture is less than 1.0 μm to obtain developer dispersion liquid B.
The polymerization degree of the polyvinyl alcohol is 1300-2400, and the alcoholysis degree is greater than or equal to 86% and less than or equal to 98%.
When the thermosensitive coating liquid is prepared, the polyvinyl alcohol aqueous solution mixture C, the dye dispersion liquid A and the color developing agent dispersion liquid B are uniformly mixed, and then the polyvinyl alcohol aqueous solution is added.
Advantageous effects
1. The thermosensitive recording material uses gamma-glycidyl ether propyl trimethoxy silane, thereby avoiding the coating defects generated by directly coating a thermosensitive imaging layer on a support, such as edge shrinkage, streaking, coating removal and the like; meanwhile, the same polyvinyl alcohol, silicon dioxide dispersion liquid and boric acid are used in the thermosensitive imaging layer as those in the protective layer, namely the same polyvinyl alcohol, silicon dioxide dispersion liquid and boric acid are also used in the protective layer, so that the adhesion between the thermosensitive imaging layer and the support is improved, and the situation that an undercoating layer is not needed is possible.
2. The thermosensitive recording material does not contain a base coat, greatly reduces the production cost, improves the production efficiency and simplifies the production process.
3. The thermosensitive imaging layer and the protective layer in the thermosensitive recording material disclosed by the invention use the same raw materials, so that the potential risk of side reaction caused by various materials is reduced, the types of the raw materials in the formula are reduced, and the coating formula is simple, the operation is convenient and fast, and the operation cost is low.
4. The raw materials used in the thermosensitive recording material of the present invention are commonly used materials and are inexpensive and readily available.
Detailed Description
The present invention provides a thermosensitive recording material having a support, a thermosensitive image-forming layer on the support, and a protective layer on the thermosensitive image-forming layer. The thermosensitive imaging layer contains gamma-glycidyl ether propyl trimethoxy silane; the thermosensitive imaging layer contains the same raw materials of polyvinyl alcohol, silicon dioxide dispersion liquid and boric acid as those in the protective layer.
The support used as the thermosensitive recording material has good thermal stability, can not generate deformation and stretching when being heated, has small hygroscopicity and high flatness, can be a polyethylene film (PE), a polypropylene film (PP), a polyvinyl chloride film (PVC), a polyester film (PET), a polystyrene film (PS), a polyvinylidene chloride film (PVDC) and other transparent supports, can be added with color master batches to form different colors, can also be directly used without adding the color master batches, and selects the PET with the thickness of 80-300 micrometers and the density of 0.16-0.24; PET with a thickness of 175 microns and a density of 0.20 is preferred.
The thermosensitive imaging layer is prepared by coating a coating solution containing a leuco dye, a developer, a polyvinyl alcohol silica dispersion and boric acid on one side of the support having the under layer, and is easily compatible with other components.
Leuco dyes
The leuco dye can be selected from fluoran type, such as 2-phenylamino-3-methyl-6-diethylaminofluoran, 2-phenylamino-3-methyl-6-dibutylaminofluoran, 2- (2-4-dimethylanilino) -3-methyl-6-diethylaminofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-cyclohexylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-cyclopentylamino) -6-methyl-7-anilinofluoran, 2-phenylamino-3-methyl-6-diethylaminofluoran, 2-diethylamino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-cyclopentylamino) -6-methyl-7-anilinofluoran, 3-dibutylamino-7-o-fluoroanilino (fluoran), 3-diethylamino-7- (3, 4-dichloroanilino) fluoran and the like, preferably 2-phenylamino-3-methyl-6-diethylaminofluoran; triarylmethane type, including 3, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1, 2-dimethylaminoindol-3-yl) phthalide, 3-bis (1, 2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide, etc.; as the spiro compound type, there are 3-methyl spirodibenzopyran, 3-ethyl spirodibenzopyran, 3, 3 ' -dichloro spironaphthopyran, 3-benzyl spirodibenzopyran, 3-propyl spirodibenzopyran, 1, 3, 3-trimethyl-6-nitro-8 ' -methoxyspiro (indoline-2, 2 ' -benzopyran), and the like.
These leuco dye compounds may be used alone or in combination.
As the developer usable in combination, alpha-naphthol, beta-naphthol, p-octylphenol, 4-tert-octylphenol, p-tert-butylphenol, 3-diallyl-4, 4' -dihydroxydiphenyl sulfone, 4-hydroxy-4-isopropoxydiphenyl sulfone, 4-hydroxy-4-methoxydiphenyl sulfone, 4-hydroxy-4-ethoxydiphenyl sulfone, 4-hydroxy-4-butoxydiphenyl sulfone, benzyl p-hydroxybenzoate, dibenzyl 4-hydroxyphthalite, dimethyl 4-hydroxyphthalite, zinc 1-acetoxy-2-naphthoate, zinc 2-acetoxy-1-naphthoate, zinc 2-acetoxy-3-naphthoate, zinc p-octylphenol, 4-hydroxy-4-isopropoxydiphenyl sulfone, 4-hydroxy-4-methoxydiphenyl sulfone, zinc 1-acetoxy-2-naphthoate, zinc 2-acetoxy-1-naphthoate, zinc 2-acetoxy-3-naphthoate, zinc, 2, 4-diphenylsulfonylphenol, 4-benzenesulfonylphenol, 2, 4, 6-triphenylsulfonylphenol, or the like. These color developers may be used alone or in combination.
In order to further improve the heat-sensitive ability of the heat-sensitive recording material, a heat-sensitive sensitizer may be added to the heat-sensitive image-forming layer, and the sensitizer may be dispersed by milling together with the colorless heat-sensitive dye precursor, the developer, or the developer alone. Commonly used heat-sensitive sensitizers, for example: bis-ethane, 2-benzylnaphthyl ether, 1, 2-bis- (3-phenoxy) ethane, 4-benzylbiphenyl, benzyl paraben, and the like.
The binder in the thermal sensitive imaging layer of the present invention may be starch and its derivatives, carboxylated styrene-butadiene latex, methoxy cellulose, carboxymethyl cellulose, acrylamide-acrylate copolymer, styrene-butadiene copolymer, polyacrylate, polybutylmethacrylate, polyvinyl alcohol, and the like. Wherein the polyvinyl alcohol can be a fully alcoholyzed, intermediately alcoholyzed, partially alcoholyzed, or modified polyvinyl alcohol; the polymerization degree of the used polyvinyl alcohol is generally 1000-3000; the binder may be used alone or in combination of different types. The polyvinyl alcohol which is partially alcoholyzed and has a polymer of 1300-2400 is preferentially used as the binder in the aspects of use effect and application cost.
The function auxiliary agent in the thermosensitive imaging layer has the functions of improving the transparency of the thermosensitive imaging layer after coating and drying and simultaneously enhancing the adhesion of the coating and a support. The functional assistant is mainly silicon dioxide dispersion liquid and boric acid. The silica dispersion is not particularly limited in use and may be suitably selected from existing products according to the purpose. Examples of the dispersion include an alcohol-based silica dispersion, a ketone-based silica dispersion, an ester-based silica dispersion, an ether-based silica dispersion, a hydrocarbon-based silica dispersion, an acyl-based silica dispersion, a silica dispersion having a volume average particle diameter of 10 to 50 nm, an alkaline silica dispersion, a neutral silica dispersion, an acidic silica dispersion, and a modified silica dispersion. Not limited to the above types, any ones capable of achieving the object may be used. The volume average particle size is less than 10 nanometers, and the cost is obviously increased; the volume average particle size is more than 80 nanometers, and the transparency of the coating is reduced; a large number of experiments prove that the silicon dioxide dispersion liquid with the volume average particle diameter of 20-35 nanometers and the pH value of 8.0-10.0 is preferable. Boric acid solution is required to be added for preparing the thermosensitive imaging layer, and the boric acid solution is added as little as possible under the condition that the fastness of the dry coating reaches the standard (the coating does not fall off after being folded for more than or equal to 9 times). The excessive boric acid solution causes the viscosity of the image forming layer coating liquid to become high and easily introduces coating streaks, de-coating, and the like during the coating process.
Adding polyvinyl alcohol, silicon dioxide dispersion liquid and boric acid in the thermosensitive imaging layer in a manner that a part of polyvinyl alcohol, silicon dioxide dispersion liquid and boric acid are premixed in advance and placed for 1-3 hours, and then adding the rest of polyvinyl alcohol into the thermosensitive imaging layer coating liquid; or all polyvinyl alcohol, silicon dioxide dispersion liquid and boric acid are mixed and then added into the coating liquid of the thermosensitive imaging layer; or adding the particle polyvinyl alcohol into the silicon dioxide dispersion liquid and the boric acid in proportion in the dissolving process to prepare a premix; or premixing a part of polyvinyl alcohol and boric acid, and adding the silicon dioxide dispersion liquid when preparing the thermosensitive imaging layer coating liquid; or premixing a part of polyvinyl alcohol and silicon dioxide dispersion liquid, and adding boric acid when preparing the thermosensitive imaging layer; the first feeding mode is optimized according to stable controllability and practical effect of production.
Other types of functional aids such as surfactants, leveling agents, lubricants may be further added to the thermosensitive image forming layer as the case may be, without hindering the low fog density, image preservation excellence of the thermosensitive recording material. The surfactant includes alkali metal salts of sulfosuccinic acids, fluorosurfactants, sulfonates, and the like; the flatting agent comprises silicone oil, polydimethylsiloxane, polyether polyester modified organic siloxane, alkyl modified organic siloxane, end group modified organic silicon, fluorine modified acrylic resin and the like; the lubricant is selected from higher fatty acid or its metal salt, higher fatty acid amide, higher fatty acid ester, animal wax, vegetable wax, polyethylene wax, etc.
The thermal imaging layer can be prepared by respectively grinding and dispersing the leuco dye and the color developing agent with the binder resin and other components by a dispersion machine, a ball mill or a sand mill until the average diameter of dispersed particles is less than or equal to 1 mu m, mixing the obtained dispersion with polyvinyl alcohol, silicon dioxide dispersion, boric acid and other auxiliary agents, coating the mixture on PET with the thickness of 160-200 microns and the density of 0.20 by means of slide extrusion coating, wire rod coating, strip seam coating, curtain coating, air knife coating, scraper coating and the like, and drying the mixture to finally form the thermal imaging layer.
Protective layer
The main components of the protective layer of the invention are various additives and adhesives. The binder used in the protective layer is a water-soluble polymer resin, and may be a fully alcoholyzed, intermediately alcoholyzed, partially alcoholyzed or modified polyvinyl alcohol. The various auxiliary agents comprise a cross-linking agent, a lubricating agent, an ultraviolet-proof absorbent, a flatting agent, a surfactant, an antistatic agent and the like. The crosslinking agent should be capable of forming a crosslinking reaction with the polyvinyl alcohol described above, such as: paraformaldehyde compounds such as glyoxal, glutaraldehyde; silane coupling agents, water-soluble primary polycondensates such as boric acid, borax, urea-formaldehyde, etc., layered silicates, nano-dioxides, nano-calcium carbonate, etc.; the lubricant is higher fatty acid or its metal salt, higher fatty acid amide, higher fatty acid ester, animal wax, vegetable wax, polyethylene wax, etc.; the flatting agent comprises silicone oil, polydimethylsiloxane, polyether polyester modified organic siloxane, alkyl modified organic siloxane, end group modified organic silicon, fluorine modified acrylic resin and the like; the surfactant includes alkali metal salts of sulfosuccinic acids, fluorosurfactants, sulfonates, and the like; the ultraviolet light absorption-imitating agent and the antistatic agent are not particularly limited herein.
The protective layer may also contain filler assistant, which may be calcium carbonate, magnesium carbonate, kaolin, bentonite, aluminum hydroxide, calcined kaolin, non-calcined kaolin, clay, titanium dioxide, or other inorganic material, or polymethyl methacrylate microsphere, or other organic material. The silica dispersion is preferable, and the silica dispersion is added to the protective layer so that the protective layer has good heat resistance and erasure resistance in actual use, and in order to improve the transparency of the recording material, the silica dispersion is selected so that the volume average particle diameter is 10 to 50 nm or less, the pH is 3.0 to 9.5, preferably 20 to 35 nm, and the pH is 8.0 to 10.0. The amount of the silica dispersion is required so as not to impair the low fog density and storage stability of the heat-sensitive recording material of the present invention.
The adhesive and various auxiliaries used in the protective layer are commercially available products. Mixing various required additives, adhesives or filling additives, coating the mixture on the thermosensitive imaging layer by means of slide extrusion coating, wire rod coating, strip seam coating, curtain coating, air knife coating, scraper coating and the like, drying and finally forming a protective layer.
The present invention will be described in further detail with reference to specific examples.
Example 1
Preparation of thermosensitive recording Material
(1) Preparation of dye Dispersion A
The following components were dispersed with a sand mill until the volume average particle diameter of the resultant mixture was <1.0 μm, to thereby prepare a dye dispersion liquid (liquid a).
4-phenylamino-3-methyl-6-dibutylaminofluoran 15g
25g of a 10% polyvinyl alcohol aqueous solution
Deionized water 60g
(2) Preparation of developer Dispersion B
The following components were dispersed with a sand mill until the volume average particle diameter of the resultant mixture was <1.0 μm, to thereby prepare a developer dispersion liquid (liquid B).
4-hydroxy-4' -isopropoxydiphenyl sulfone 25g
25g of a 10% polyvinyl alcohol aqueous solution
50g of deionized water
(3) Preparation of polyvinyl alcohol aqueous solution mixture C
The following components are uniformly mixed, stirred for 10-30min at room temperature by using a mechanical stirrer (type IKA RW20) at 80-200(r/min), and then placed for 1-3 h.
40g of a 3% by mass aqueous solution of polyvinyl alcohol (degree of alcoholysis: 88%, degree of polymerization: 1700)
Silica dispersion (volume average particle diameter 25 nm, pH 9.2) 4g
Boric acid 2% by mass aqueous solution 12g
(4) Preparation of coating liquid
The following components were mixed to prepare a thermosensitive imaging layer coating liquid.
(5) Preparation of protective layer coating liquid
The following components were mixed to prepare a coating liquid for a storage layer
And then, using a PET sheet base with a thickness of 160-200 μm and a density of 0.20 for a support, coating the coating liquid for the thermosensitive imaging layer on the support, and drying to form the thermosensitive imaging layer. A protective layer is then applied directly over the dried thermographic layer using the same method. After drying, the thermosensitive recording material of example 1 was finally prepared.
Example 2
Preparation of thermosensitive recording Material
The components of the heat-sensitive imaging layer coating liquid in example 1 were adjusted as follows:
the thermosensitive recording materials in examples were prepared in the same manner as in example 1, except that.
Example 3
Preparation of thermosensitive recording Material
The components of the heat-sensitive imaging layer coating liquid in example 1 were adjusted as follows:
the thermosensitive recording material of example 3 was prepared in the same manner as in example 1 except that.
Example 4
Preparation of thermosensitive recording Material
The components of the heat-sensitive imaging layer coating liquid in example 1 were adjusted as follows:
the thermosensitive recording material of example 4 was prepared in the same manner as in example 1 except that.
Example 5
Preparation of thermosensitive recording Material
The components of the heat-sensitive imaging layer coating liquid in example 1 were adjusted as follows:
the thermosensitive recording material of example 5 was prepared in the same manner as in example 1 except that.
Example 6
Preparation of thermosensitive recording Material
A thermosensitive recording material of example 6 was prepared in the same manner as in example 1, except that the amount of polyvinyl alcohol used in the preparation of the blend C described in example 1 was adjusted from 40g to 60 g.
Example 7
Preparation of thermosensitive recording Material
A thermosensitive recording material of example 7 was prepared in the same manner as in example 1, except that the amount of γ -glycidoxypropyltrimethoxysilane used in example 1 was adjusted from 0.6g to 0.3 g.
Example 8
Preparation of thermosensitive recording Material
A thermosensitive recording material of example 8 was prepared in the same manner as in example 1, except that the amount of γ -glycidoxypropyltrimethoxysilane used in example 1 was adjusted from 0.6g to 2.5 g.
Comparative example 1
Preparation of thermosensitive recording Material
A thermosensitive recording material of comparative example 1 was prepared in the same manner as in example 1, except that the thermosensitive imaging layer mixture C described in example 1 was separately added in place of the polyvinyl alcohol, the silica dispersion liquid, and the boric acid.
Comparative example 2
Preparation of thermosensitive recording Material
A thermosensitive recording material of comparative example 2 was prepared in the same manner as in example 1, except that boric acid was removed from the thermosensitive imaging layer mixture C described in example 1 while boric acid was added at the time of preparing the thermosensitive imaging layer coating liquid.
Comparative example 3
Preparation of thermosensitive recording Material
A thermosensitive recording material of comparative example 3 was prepared in the same manner as in example 1, except that the silica dispersion in the thermosensitive imaging layer mixture C described in example 1 was removed and at the same time the silica dispersion was added at the time of preparing the thermosensitive imaging layer coating liquid.
Comparative example 4
Preparation of thermosensitive recording Material
A thermosensitive recording material of comparative example 4 was prepared in the same manner as in example 1, except that the thermosensitive imaging layer described in example 1 was removed with γ -glycidoxypropyltrimethoxysilane.
Comparative example 5
Preparation of thermosensitive recording Material
A thermosensitive recording material of comparative example 5 was prepared in the same manner as in example 1, using a primer-coated PET instead of the non-primer-coated PET used in example 1.
Rating the test results
Testing and grading the obtained thermosensitive recording material, printing a 21-gray-scale density sheet by using a Lekei DryMate 320 dry imager, and establishing density values under different gray scales; recording the minimum density corresponding to gray scale (i.e. deducting the density of substrate as the density of coating).
The influence on the stability is defined as the difference between the densities before and after the 21 gray scale is printed by a Lekei DryMate 320 dry imager under different temperatures and humidity, then the sum is summed, the average value is obtained, and then the square root of the arithmetic number is obtained. Selecting the temperature conditions of (1)25 ℃ and 50% relative humidity, standing for 1h, and testing the gray scale density; (2) testing the gray scale density after the mixture is placed for 1 hour at the temperature of 35 ℃ and the relative humidity of 60 percent; (3) the gray-scale density was measured after standing at 35 ℃ and 70% relative humidity for 1 h. The calculation formula is as follows:
the image coating fastness was defined as that the obtained thermosensitive recording material was printed with the same image with a lekside DryMate 320 dry imager, folded in half at the same position several times, and the coating was observed to peel off.
Apparent smoothness of thermal imaging layer coating is defined as the apparent quality of the image layer during application of the coating solution to the thermal imaging layer and after drying.
TABLE 1 test data for each example and comparative example
| Appearance of Heat sensitive imaging layer | Density of coating | Image stabilization | Fastness stability of heat-sensitive coating | |
| Example 1 | Superior food | 0.04 | 0.688 | Folded in half 12 times |
| Example 2 | Superior food | 0.03 | 0.686 | Folded in half 11 times |
| Example 3 | Superior food | 0.04 | 0.765 | Folded in half 11 times |
| Example 4 | Good wine | 0.05 | 0.822 | Folded in half 9 times |
| Example 5 | Good wine | 0.03 | 0.745 | Folded in half 12 times |
| Example 6 | Superior food | 0.05 | 0.712 | Folded in half 13 times |
| Example 7 | Good wine | 0.04 | 0.731 | Folded in half 11 times |
| Example 8 | Good wine | 0.05 | 0.691 | Folded in half 12 times |
| Comparative example 1 | Superior food | 0.04 | 0.697 | Folded in half 8 times |
| Comparative example 2 | Good wine | 0.04 | 0.721 | Folded in half 7 times |
| Comparative example 3 | Good wine | 0.04 | 0.755 | Folded in half 6 times |
| Comparative example 4 | Poor (strip road, not wet) | 0.04 | 0.689 | Folded in half 11 times |
| Comparative example 5 | Good wine | 0.06 | 0.982 | Folded in half 7 times |
Description of the drawings: (1) appearance of the thermosensitive imaging layer: the appearance defect is avoided; the good is that the number of dots with the average grain diameter less than or equal to 0.5mm is not more than 5;
(2) and the fastness stability of the heat-sensitive coating: the folding times are more than or equal to 9 times (the coating does not fall off), and the coating is qualified.
Claims (5)
1. A thermosensitive recording material, comprising a support, a thermosensitive imaging layer on the support, and a protective layer on the thermosensitive imaging layer, wherein the thermosensitive imaging layer is prepared by curing a thermosensitive coating liquid, and the thermosensitive coating liquid comprises the following components in parts by mass:
dye dispersion liquid A280-
Developer dispersion B275-
Polyvinyl alcohol aqueous solution mixture C37-80
42-84% of polyvinyl alcohol aqueous solution (solid content is 10%)
Gamma-glycidol ether propyl trimethoxy silane stock solution 1.2-5.6
0.5-3.0% of fluorine surfactant (solid content is 8%);
the polyvinyl alcohol aqueous solution mixture C is prepared from the following components in parts by weight:
30-60% of polyvinyl alcohol aqueous solution (solid content is 3%)
Silicon dioxide dispersion (solid content 25%) 0.8-6.0
Boric acid (20g/l) 4.0-20.0;
the protective layer contains the same raw materials of polyvinyl alcohol, silicon dioxide dispersion liquid and boric acid as those in the thermosensitive imaging layer.
2. A thermosensitive recording material according to claim 1, characterized in that the dye dispersion a is made of the following components in parts by mass:
phenylamino-3-methyl-6-dibutylaminofluoran 15 parts
25 parts of polyvinyl alcohol aqueous solution (10% solid content)
60 parts of deionized water;
dispersing the components by using a sand mill until the volume average particle size of the obtained mixture is less than 1.0 mu m to obtain the dye dispersion liquid A.
3. A thermosensitive recording material according to claim 1, wherein the developer dispersion liquid B is made of the following components in parts by mass:
4-hydroxy-4，25 parts of-isopropoxydiphenyl sulfone
25 parts of polyvinyl alcohol aqueous solution (10% solid content)
50 portions of deionized water
Dispersing the above components with sand mill until the volume average particle diameter of the obtained mixture is less than 1.0 μm to obtain developer dispersion liquid B.
4. A thermosensitive recording material according to claim 1, wherein the degree of polymerization of the polyvinyl alcohol is 1300 to 2400, and the degree of alcoholysis is 86% or more and 98% or less.
5. A thermosensitive recording material according to claim 4, wherein, in preparing the thermosensitive coating liquid, the polyvinyl alcohol aqueous solution mixture C is mixed uniformly with the dye dispersion A and the developer dispersion B, and then the polyvinyl alcohol aqueous solution is added.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010476464.5A CN111619258B (en) | 2020-05-29 | 2020-05-29 | Thermosensitive recording material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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