CN111038136A - Backing-paper-free thermosensitive recording material - Google Patents
Backing-paper-free thermosensitive recording material Download PDFInfo
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- CN111038136A CN111038136A CN201911319229.0A CN201911319229A CN111038136A CN 111038136 A CN111038136 A CN 111038136A CN 201911319229 A CN201911319229 A CN 201911319229A CN 111038136 A CN111038136 A CN 111038136A
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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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
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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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F2003/0257—Multilayer
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- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
The invention discloses a backing-paper-free thermosensitive recording material, which sequentially comprises a multifunctional protective layer, a thermosensitive information recording layer, a base material and an adhesive layer from bottom to top, wherein the thermosensitive information recording layer and the multifunctional protective layer are formed by coating a thermosensitive information recording layer and a multifunctional protective layer coating liquid on the base material and drying, and the adhesive layer is coated on the other surface of the base material; the multifunctional protective layer coating liquid comprises modified polyvinyl alcohol resin and a plurality of silicon dispersion liquids. Compared with the traditional backing-free paper label, the invention omits the step of coating a special silicone oil stripping layer on the protective layer, simplifies the production process and has higher application value.
Description
The technical field is as follows:
the invention relates to the technical field of printing, in particular to a thermal label recording material.
Technical background:
the label without the backing paper has no backing paper, so that compared with the traditional adhesive label, the label without the backing paper has the advantages of energy saving and consumption reduction, and accords with the ideal requirements of energy saving and environmental protection.
Because of the particularity of the temperature sensitivity of the heat-sensitive coating, most of the existing backing-paper-free label technologies are to coat a silicone oil layer on heat-sensitive paper with a protective layer, and then carry out cold curing through UV curing, wherein a large amount of nitrogen needs to be filled into a UV curing device during curing to prevent oxygen from reacting with silicone oil (see Chinese patent document CN 106297550A). The existing production process is complicated and has large loss. Therefore, research on new thermal label materials is a problem to be solved urgently in the industry.
The invention content is as follows:
the invention aims to overcome the defects of the prior art and provide a backing-free thermal recording material which has the functions of ensuring the safety, water resistance and smooth printing of recorded information and is easy to peel off from a bonding layer on the back surface of the thermal recording material so as to form the backing-free thermal recording material. Compared with the traditional backing-paper-free label, the production process is simplified, and the label has a higher practical value.
In order to achieve the purpose, the invention adopts the following technical scheme:
a kind of no bottom paper heat-sensitive recording material, the said recording material is from the bottom to the upper multi-functional protective layer, heat-sensitive information recording layer, substrate and bond coat sequentially, said heat-sensitive information recording layer and multi-functional protective layer are dried and formed by coating heat-sensitive information recording layer and multi-functional protective layer coating liquid on the substrate, coat the bond coat on another side of the substrate; the multifunctional protective layer coating liquid comprises modified polyvinyl alcohol resin and a plurality of silicon dispersion liquids; the multifunctional protective layer coating liquid is prepared from the following components in parts by mass:
the above mentioned non-backing paper thermal sensitive recording material, the formulation of the said multiple silicon dispersion liquid is:
oil phase:
additive:
silica sol (20%) 5-10
5-10% of silane coupling agent (100%);
slowly adding the oil phase into the water phase stirred at a high speed, dispersing for 1 hour at a high speed, and then adding the additive to prepare various silicon dispersion liquids.
The backing-paper-free thermosensitive recording material comprises the following components in parts by mass:
in the above base-paper-free thermosensitive recording material, the hydroxyl silicone oil: silica sol: the ratio of silane coupling agent is 1:1: 1.
The above backing-free thermal recording material, wherein the silicone oil has a dry weight of 0.3 to 1.7g/m2Preferably 0.6 to 1.0g/m2。
The above-mentioned backing-less thermal recording material, wherein the polyvinyl alcohol resin has a dry weight of 0.6 to 2.0g/m2Preferably 1.0 to 1.5g/m2。
In the base-paper-free thermosensitive recording material, the adhesive layer is made of transparent water-based adhesive or transparent hot melt adhesive, and the coating weight is 10-30g/m2。
Advantageous effects
The invention has the following characteristics: (1) the multifunctional protective layer is adopted, so that the use of glassine is abandoned, the cost is reduced, and the waste base paper is prevented from polluting the environment; (2) the multifunctional protective layer has the functions of protection and release, because the organic silicon oil, the silica sol, the silane coupling agent and the polyvinyl alcohol are cooperated to form a compact coating, not only can complete thermosensitive continuous printing, but also can contact with the adhesive in the bonding layer to effectively release, and has the functions of printing protection and release. The invention simplifies the production process, reduces the cost and has greater practical value.
Drawings
FIG. 1 is a schematic cross-sectional view of the structure of the present invention.
In the drawings, the reference numerals denote: (ii) a 1. An adhesive layer; 2. a substrate; 3. a thermosensitive information recording layer; 4. a multifunctional protective layer.
Detailed Description
The surface of the backing-free thermal recording material is provided with a multifunctional protective layer, and the multifunctional protective layer has a waterproof function of protecting recorded information, ensures smooth printing of a thermal printer, and is easy to peel off from a bonding layer on the back of the thermal recording material to form the backing-free thermal recording material.
The invention coats a thermosensitive imaging layer and a multifunctional protective layer on one surface of a base material in sequence, coats an adhesive layer on the other surface of the base material, and directly contacts and rolls the adhesive layer (inner side) and the multifunctional protective layer (outer side) after coating to prepare a scroll-shaped product.
The thermosensitive imaging layer is formed by coating thermosensitive imaging coating liquid containing thermosensitive dye dispersion liquid, thermosensitive color developing agent dispersion liquid, adhesive and other coating auxiliaries on one surface of a base material corona and fully drying the thermosensitive imaging coating liquid in a drying process.
The thermosensitive dye is a colorless thermosensitive dye precursor for thermosensitive materials, and the colorless thermosensitive dye precursor may be black, red, blue, cyan, etc. after color development. The thermosensitive dye precursor may be fluorans such as 2-phenylamino-3-methyl-6-diethylaminofluoran, 2-phenylamino-3-methyl-6-dibutylamino fluoran, 2- (2-4-xylidino) -3-methyl-6-diethylaminofluoran, etc., also employable are phthalides such as 6-dimethylamino-3, 3-bis (4-dimethylaminophenyl) phthalide, 3-bis (1-butyl-2-methylindol-3-yl) phthalide, 3-bis (4-diethylamino-2-ethoxyphenyl) -4-phthalide and the like. The leuco thermosensitive dye precursor may be encapsulated in microcapsules dispersed in an aqueous solution; or adding the colorless thermosensitive dye precursor into the adhesive aqueous solution, and dispersing in a wet grinding mode, wherein the average particle size of the dispersed particles is less than 0.6 micrometer, thereby preparing the thermosensitive dye dispersion.
The heat-sensitive color developing agent is solid acid color developing agent, and can be 2,4 '-dihydroxy diphenyl sulfone, 4' -dihydroxy diphenyl sulfone, diallyl dihydroxy diphenyl sulfone, 4-hydroxy-4 '-isopropoxy diphenyl sulfone, 4' - [1, 3-phenyl bis (1-methyl-ethylidene) ] bisphenyl cyanate ester, etc. The melting point is preferably 80-190 ℃, and the heat-sensitive color developing agent dispersion liquid is prepared by dispersing 4-hydroxy-4' -isopropoxy diphenyl sulfone according to the mode of Chinese patent document CN 201210449826. In order to further improve the heat-sensitive capability 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 or the heat-sensitive developer. The amount of sensitizer used is not particularly limited as long as it satisfies the specific use requirements. The thermal sensitizer can be selected from bis-ethane, 2-benzyl naphthyl ether, 1, 2-di- (3-phenoxy) ethane, 4-benzyl biphenyl, etc.
The binder in the heat-sensitive imaging layer of the present invention serves to protect the heat-sensitive dye particles and the heat-sensitive developer particles from aggregation and facilitate coating of a coating solution to form a film, and the binder may be a water-soluble resin such as fully saponified or partially saponified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, an alkali salt of a styrene-maleic anhydride copolymer, an alkali salt of an ethylene-acrylic acid copolymer, and an alkali salt of a styrene-acrylic acid copolymer. Among them, at least one or more polyvinyl alcohols having an alcoholysis degree of 85% or more are preferably used in combination.
The adhesive in the multifunctional protective layer of the invention is used for film forming and crosslinking, and the used adhesive is modified polyvinyl alcohol such as acetoacetyl modified, diacetone modified, carboxylic acid modified, silicon modified and the like, wherein the carboxylic acid modified polyvinyl alcohol resin is preferred.
The silane coupling agent used by the silicon dispersion liquid in the multifunctional protective layer is commonly bis- [3- (triethoxysilyl) -propyl ] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl ] -disulfide, gamma-aminopropyltriethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidyl ether oxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriisopropoxysilane and the like, can be used alone or in a mixed way.
The silica sol used by the various silica dispersions in the multifunctional protective layer is a dispersion of nano silica particles in water or a solvent, the silica sol particles are 10 to 30 nanometers, the silica sol is used as a cross-linking agent in the multifunctional protective layer, and the optimal ratio of the silica sol to the silane coupling agent is 1: 1.
The organic silicone oil used by the silicon dispersion liquid in the multifunctional protective layer can be methyl silicone oil or hydroxyl silicone oil. The common methyl silicone oil also has good release effect when being applied to the system, but the methyl silicone oil is easy to adhere to the adhesive layer because of poor fastness of the methyl silicone oil and the coating, and the residual adhesive force of the adhesive layer is influenced. The organic silicone oil in the invention is preferably hydroxyl silicone oil, the hydroxyl silicone oil has the general performance of methyl silicone oil and the reactivity of hydroxyl, and the hydroxyl can react with a cross-linking agent coupling agent and the like in a system, thereby improving the fastness of the silicone oil in a coating. Among them, hydroxyl silicone oils having a viscosity of 500-1000 mPas are more preferable.
The organic silicon oil, the silica sol, the silane coupling agent and the polyvinyl alcohol in the multifunctional protective layer cooperate to form a compact coating, so that the multifunctional protective layer can achieve the effects of thermosensitive continuous printing, effective release by contacting with an adhesive in the bonding layer, and printing protection and release functions.
The invention aims to further improve the printing adaptability between the thermal head and the recording material and prolong the service life of the thermal head, and can add other additives, including lubricant and filler additives, as lubricating additives, zinc stearate, stearic acid amide, polyethylene wax, paraffin and the like. These adjuvants are added in the form of an aqueous dispersion or emulsion in which the particles have an average particle size of less than 0.8 μm. In addition, other auxiliary agents such as UV absorbent, antistatic agent and the like can be added into the protective layer.
The multifunctional protective layer of the invention has the following final effects: (1) the adhesive layer is in contact with the protective layer, has certain viscosity, is convenient to peel when in use, and ensures effective adhesion and peeling of the material; (2) the protective layer further improves the water resistance of the recording material; (3) the protective layer can enable the thermosensitive layer to be capable of effectively heating and coloring to achieve the use density index, and meanwhile, the thermosensitive layer is not scratched to influence imaging.
The formula of the coating liquid of the thermosensitive imaging layer suitable for the invention is as follows:
the formula of the multifunctional protective layer coating liquid suitable for the invention is as follows:
the formula of the various silicon dispersion liquids of the thermosensitive recording material is as follows:
oil phase:
5-10 parts of hydroxyl silicone oil (100 percent)
Ethyl acetate 5 parts
Water phase:
40 parts of polyvinyl alcohol resin solution (10%)
40 parts of deionized water
Sodium dodecyl sulfate solution (10%) 1 part
Additive:
5-10 parts of silica sol (20 percent)
5-10 parts of silane coupling agent (100 percent)
The invention coats adhesive on the other side of the transparent base material and then takes up the transparent base material into a roll shape. The adhesive is preferably environmental-friendly pollution-free water-based adhesive or hot melt adhesive.
The coating mode of the imaging layer, the protective layer and the adhesive layer can adopt one or more combination modes of slide extrusion coating, slot coating, curtain coating, knife coating, micro-gravure coating, wire rod coating or roller coating.
The present invention is further illustrated by the following specific examples, which are not intended to be exhaustive or to limit the invention to the precise forms disclosed.
In addition, the thermal printing adopts an ATLANTEK Model 400 thermal reaction tester; testing the density with an X-Rite310T (or X-Rite400) densitometer; the machine test is carried out by using a bottomless paper printing electronic scale of Shanghai temple SM-120 (LL).
Example 1
Base material
The present invention uses a 50 μm thick transparent PET (produced by Lekei).
Preparation of Heat-sensitive imaging layer E
25 parts of 10% PVA217 (Nippon Coli) aqueous solution, 13 parts of ODB-2 (Shandong Ruikang refinement), 2 parts of 2-naphthol benzyl ether (Wuhan Haishan technology) 59 parts of deionized water are added into a reaction kettle, stirred, 1 part of 200g/L of sodium isopropyl naphthalenesulfonate aqueous solution is added, the mixture is soaked for 1 hour, and then a SWZ50-1 horizontal sand mill (Chongqing Hongqi chemical machinery Co., Ltd.) is used for circularly sanding until the average particle size of particles is 0.60 micrometer, so that the thermosensitive dye dispersion liquid A with the solid content of 17.7% is obtained.
Adding 24 parts of 10.0% PVA217 aqueous solution, 29 parts of deionized water and 24 parts of 4-hydroxy-4' -isopropoxydiphenyl sulfone (Aolandada ALD-2000 purity 99.26%) into a reaction kettle, stirring, adding 3 parts of 200g/L sodium naphthalene sulfonate isopropyl salt aqueous solution, soaking for 1 hour, and circularly sanding by using a SWZ50-1 horizontal sand mill until the average particle size of particles is 0.30 micron to obtain the heat-sensitive developer dispersion liquid B with the solid content of 33.75%.
Adding 30 parts of thermosensitive dye dispersion liquid A (17.7%) prepared by the method, 40 parts of thermosensitive color developing agent dispersion liquid B (33.75%) prepared by the method, 20 parts of styrene-butadiene latex (45%) and 1.5 parts of sodium dodecyl sulfate solution (10%) into a reactor, stirring and uniformly mixing until the total amount of deionized water reaches 100 parts to obtain a thermosensitive imaging layer coating liquid, and fully drying at 21-25 ℃ on one surface of corona PET (polyethylene terephthalate) by adopting a wire rod coating mode through a drying process to obtain the thermosensitive imaging layer coating liquid with the attachment amount of 8g/m2Thermal imaging layer E. In order to improve the transparency of the coating, the amount of the styrene-butadiene latex can be increased by 20 to 25 percent.
Preparation of various silicon dispersions DS1
An oil phase was prepared by uniformly mixing 5 parts of a hydroxy silicone oil (viscosity 800mpa · s, the same applies hereinafter) and 5 parts of ethyl acetate. An aqueous phase was prepared by uniformly mixing 40 parts of 10% aqueous PVA224 solution, 40 parts of deionized water, and 1 part of sodium lauryl sulfate solution (10%). And slowly adding the oil phase into the water phase stirred at a high speed, dispersing for 1 hour at a high speed, adding a mixed solution of 5 parts of silica sol and 5 parts of silane coupling agent KH570 (Nanjing Chuangcentury chemical auxiliary agent Co., Ltd.), and uniformly stirring to obtain various silicon dispersion solutions DS1 for later use.
Preparation of multifunctional protective layer P1
Adding 30 parts of modified polyvinyl alcohol RS-2117 (Coly, the same below) solution (10 percent), 10 parts of boric acid aqueous solution (2 percent), 5 parts of zinc stearate dispersion liquid (10 percent) and 30 parts of the various silicon dispersion liquids DS1 into a reactor, supplementing 100 parts of deionized water to the total amount, stirring and mixing uniformly to obtain multifunctional protective layer coating liquid P1, coating the multifunctional protective layer coating liquid on the thermosensitive imaging layer E in a wire rod coating mode, and fully drying the multifunctional protective layer coating liquid in a drying process to obtain the protective layer with the dry weight of 3.0g/m2A thermosensitive recording layer EP 1.
Preparation of adhesive layer A
Melting the hot melt adhesive at the temperature of more than 150 ℃, preserving heat in a heat preservation groove, coating the adhesive on the surface of release paper with the coating weight of 25g/m2, cooling through a cooling roller, transferring the hot melt adhesive to the back of a thermosensitive recording layer EP1, peeling the release paper, and contacting and rolling the adhesive layer A (inner side) with the EP1 (outer side).
Example 2
The base material, the thermal imaging layer, and the adhesive layer were formulated and operated as in example 1.
Preparation of various silicon dispersions DS2
7.5 parts of hydroxyl silicone oil and 5 parts of ethyl acetate are uniformly mixed to prepare an oil phase. An aqueous phase was prepared by uniformly mixing 40 parts of 10% aqueous PVA224 solution, 40 parts of deionized water, and 1 part of sodium lauryl sulfate solution (10%). And slowly adding the oil phase into the high-speed stirred water phase, dispersing for 1 hour at a high speed, adding a mixed solution of 7.5 parts of silica sol and 7.5 parts of silane coupling agent KH570, and uniformly stirring to obtain various silicon dispersion solutions DS2 for later use.
Preparation of multifunctional protective layer P2
Adding 30 parts of modified polyvinyl alcohol RS-2117 solution (10%), 10 parts of boric acid aqueous solution (2%), 5 parts of zinc stearate dispersion (10%) and 30 parts of the various silicon dispersions DS2 into a reactor, supplementing deionized water to 100 parts of the total amount, stirring and uniformly mixing to obtain multifunctional protective layer coating liquid P2, coating the multifunctional protective layer coating liquid on a thermosensitive imaging layer E in a wire rod coating mode, and fully drying in a drying process to obtain a protective layer with the dry weight of 3.5g/m2A thermosensitive recording layer EP 2.
Example 3
The base material, the thermal imaging layer, and the adhesive layer were formulated and operated as in example 1.
Preparation of various silicon dispersions DS3
10 parts of hydroxyl silicone oil and 5 parts of ethyl acetate are uniformly mixed to prepare an oil phase. An aqueous phase was prepared by uniformly mixing 40 parts of 10% aqueous PVA224 solution, 40 parts of deionized water, and 1 part of sodium lauryl sulfate solution (10%). And slowly adding the oil phase into the high-speed stirred water phase, dispersing for 1 hour at a high speed, adding a mixed solution of 10 parts of silica sol and 10 parts of a silane coupling agent KH570, and uniformly stirring to obtain various silicon dispersion solutions DS3 for later use.
Preparation of multifunctional protective layer P3
Adding 30 parts of modified polyvinyl alcohol RS-2117 solution (10%), 10 parts of boric acid aqueous solution (2%), 5 parts of zinc stearate dispersion (10%) and 30 parts of the various silicon dispersions DS3 into a reactor, supplementing deionized water to 100 parts of the total amount, stirring and uniformly mixing to obtain multifunctional protective layer coating liquid P3, coating the multifunctional protective layer coating liquid on a thermosensitive imaging layer E in a wire rod coating mode, and fully drying in a drying process to obtain a protective layer with the dry weight of 4.0g/m2A thermosensitive recording layer EP 3.
Example 4
The base material, the thermal imaging layer, and the adhesive layer were formulated and operated as in example 1.
Preparation of multifunctional protective layer P4
Adding 20 parts of modified polyvinyl alcohol RS-2117 solution (10%), 10 parts of boric acid aqueous solution (2%), 5 parts of zinc stearate dispersion (10%), 20 parts of the various silicon dispersions DS2 into a reactor, supplementing deionized water to 100 parts of the total amount, stirring and uniformly mixing to obtain multifunctional protective layer coating liquid P4, coating the multifunctional protective layer coating liquid on a thermosensitive imaging layer E in a wire rod coating mode, and fully drying the multifunctional protective layer coating liquid in a drying process to obtain a protective layer with the dry weight of 2.5g/m2A thermosensitive recording layer EP 4.
Example 5
The base material, the thermal imaging layer, and the adhesive layer were formulated and operated as in example 1.
Preparation of multifunctional protective layer P5
Adding 40 parts of modified polyvinyl alcohol RS-2117 solution (10%), 10 parts of boric acid aqueous solution (2%), 5 parts of zinc stearate dispersion liquid (10%), 40 parts of the various silicon dispersion liquids DS2 into a reactor, supplementing deionized water to 100 parts of the total amount, stirring and uniformly mixing to obtain multifunctional protective layer coating liquid P5, coating the multifunctional protective layer coating liquid on a thermosensitive imaging layer E in a wire rod coating mode, and fully drying the multifunctional protective layer coating liquid in a drying process to obtain a protective layer with the dry weight of 4.5g/m2A thermosensitive recording layer EP 5.
Example 6
The base material, the thermal imaging layer, and the adhesive layer were formulated and operated as in example 1.
Preparation of multifunctional protective layer P6
Adding 20 parts of modified polyvinyl alcohol RS-2117 solution (10%), 10 parts of boric acid aqueous solution (2%), 5 parts of zinc stearate dispersion (10%), 20 parts of the various silicon dispersions DS1 into a reactor, supplementing deionized water to 100 parts of the total amount, stirring and uniformly mixing to obtain multifunctional protective layer coating liquid P6, coating the multifunctional protective layer coating liquid on a thermosensitive imaging layer E in a wire rod coating mode, and fully drying the multifunctional protective layer coating liquid in a drying process to obtain a protective layer with the dry weight of 2.0g/m2A thermosensitive recording layer EP 6.
Example 7
The base material, the thermal imaging layer, and the adhesive layer were formulated and operated as in example 1.
Preparation of multifunctional protective layer P7
Adding 40 parts of modified polyvinyl alcohol RS-2117 solution (10%), 10 parts of boric acid aqueous solution (2%), 5 parts of zinc stearate dispersion liquid (10%), and 40 parts of the various silicon dispersion liquids DS3 into a reactor, supplementing the total amount of deionized water to 100 parts, stirring and uniformly mixing to obtain multifunctional protective layer coating liquid P7, coating the multifunctional protective layer coating liquid on a thermosensitive imaging layer E in a wire rod coating mode, and fully drying the multifunctional protective layer coating liquid in a drying process to obtain a protective layer with the dry weight of 5.5g/m2A thermosensitive recording layer EP 7.
Example 8
The formulation and operation of the thermographic layer, multifunctional protective layer and adhesive layer were the same as in example 1. The substrate was changed to white PP synthetic paper having a thickness of 50 μm to obtain a heat-sensitive recording layer EP 8.
Comparative example 1
The base material, the thermal sensitive imaging layer, the multifunctional protective layer and the adhesive layer were formulated and operated as in example 6 to obtain a multifunctional protective layer having a dry weight of 1.5g/m2EP 9.
Comparative example 2
The base material, the thermal sensitive imaging layer, the multifunctional protective layer and the adhesive layer were formulated and operated as in example 7 to obtain a multifunctional protective layer having a dry weight of 6.0g/m2EP 10.
Comparative example 3
The base material, the thermal imaging layer, and the adhesive layer were formulated and operated as in example 1.
Preparation of multifunctional protective layer P9
Adding 30 parts of common polyvinyl alcohol PVA217 solution (10%), 10 parts of boric acid aqueous solution (2%), 5 parts of zinc stearate dispersion liquid (10%), and 30 parts of the various silicon dispersion liquids DS2 into a reactor, adding deionized water to 100 parts of the total amount, stirring and uniformly mixing to obtain multifunctional protective layer coating liquid P9, coating the multifunctional protective layer coating liquid on a thermosensitive imaging layer E in a wire rod coating mode, and fully drying the multifunctional protective layer coating liquid in a drying process to obtain a protective layer with the dry weight of 3.5g/m2A thermosensitive recording layer EP 11.
Comparative example 4
The base material, the thermal imaging layer, and the adhesive layer were formulated and operated as in example 1.
Preparation of various silicon dispersions DS4
And 7.5 parts of methyl silicone oil and 5 parts of ethyl acetate are uniformly mixed to prepare an oil phase. An aqueous phase was prepared by uniformly mixing 40 parts of 10% aqueous PVA224 solution, 40 parts of deionized water, and 1 part of sodium lauryl sulfate solution (10%). And slowly adding the oil phase into the high-speed stirred water phase, dispersing for 1 hour at a high speed, adding a mixed solution of 7.5 parts of silica sol and 7.5 parts of silane coupling agent KH570, and uniformly stirring to obtain various silicon dispersion solutions DS4 for later use.
Preparation of multifunctional protective layer P10
Adding 30 parts of modified polyvinyl alcohol RS-2117 solution (10%), 10 parts of boric acid aqueous solution (2%), 5 parts of zinc stearate dispersion (10%) and 30 parts of the various silicon dispersions DS4 into a reactor, supplementing deionized water to 100 parts of the total amount, stirring and uniformly mixing to obtain multifunctional protective layer coating liquid P10, coating the multifunctional protective layer coating liquid on a thermosensitive imaging layer E in a wire rod coating mode, and fully drying in a drying process to obtain a protective layer with the dry weight of 3.5g/m2A thermosensitive recording layer EP 12.
The backing-less thermal recording materials prepared in examples 1 to 8 and comparative examples 1 to 4 were evaluated for various characteristics in the following manner. The results are shown in the following table
(one) color development Density test:
the coating is heat-sensitiveContinuously aging the heat-sensitive recording material with the dried image layer and multifunctional protective layer at 23 + -2 deg.C for 7 days, cutting into strips with width of 100mm and length of 500mm, printing 10 dynamic reaction blocks under high energy level by ATLANTEK model 400 thermal reaction tester, and continuously printing 10 strips of the above recording material with maximum energy density of 29.99mj/mm2The transmission density in the M state (or the reflection density in the X-Rite400 state) was measured by X-Rite310T, and the obtained value was the color development density of the thermosensitive recording material.
(II) water resistance test:
after the thermosensitive recording material coated with the thermosensitive imaging layer and the multifunctional protective layer is dried, the thermosensitive recording material is cured for 7 days at the room temperature of 23 +/-2 ℃, cut into strips, completely immersed in deionized water, soaked for 4 hours at the room temperature, the surface state is observed, and then the surfaces are taken out and strongly rubbed by fingers for 10 times to test the water resistance degree of the protective layer.
Evaluation criteria for Water resistance:
a: the water is in a water drop shape on the surface of the coating, the surface of the coating is smooth and has no substance which is erased and falls off, and the water resistance is excellent.
B: the appearance is not changed, the surface of the coating is smooth, the coating is not erased to drop substances, and the water resistance is good.
C: the coating is foamed, the surface of the coating is melted and easily wiped off, and the water resistance is poor.
(III) Printer test
The thermosensitive information recording material was cut into rolls having a width of 60mm, and printed by a printer-ready electronic scale at temple of Shanghai.
And (4) testing standard:
a: the reel sample wafer can be normally disengaged, and the printing is smooth;
b: the reel coupons cannot be released and the printer cannot be printed.
(IV) adhesion test
The printed 60mm by 60mm label was applied to the uncoated PET clear film, pressed gently with a cell phone, and then the label was peeled off with a hand.
And (4) testing standard:
a: the glue is not easy to tear, and 20-50% of glue falls off;
b: the glue is not easy to tear, and less than 20 percent of glue falls off;
c: easy to tear and has no glue falling off.
Results of the Table test
| Color density | Water resistance | Printing machine | Adhesive force | |
| Example 1 | 1.56 | A | A | A |
| Example 2 | 1.45 | A | A | A |
| Example 3 | 1.38 | A | A | A |
| Example 4 | 1.76 | B | A | A |
| Example 5 | 1.29 | A | A | B |
| Example 6 | 1.80 | B | A | A |
| Example 7 | 1.20 | A | A | B |
| Example 8 | 2.50 (reflection) | A | A | A |
| Comparative example 1 | 1.85 | C | B | A |
| Comparative example 2 | 1.10 | A | A | B |
| Comparative example 3 | 1.40 | C | B | C |
| Comparative example 4 | 1.46 | A | A | C |
Claims (7)
1. A backing-paper-free thermosensitive recording material is characterized in that the recording material sequentially comprises a multifunctional protective layer, a thermosensitive information recording layer, a base material and an adhesive layer from bottom to top, wherein the thermosensitive information recording layer and the multifunctional protective layer are formed by coating the thermosensitive information recording layer and the multifunctional protective layer coating liquid on the base material and drying, and the adhesive layer is coated on the other surface of the base material; the multifunctional protective layer coating liquid comprises modified polyvinyl alcohol resin and a plurality of silicon dispersion liquids; the multifunctional protective layer coating liquid is prepared from the following components in parts by mass:
the balance is adjusted to 100 parts by deionized water.
2. The backing-free thermal recording material according to claim 1, wherein the plurality of silicon dispersions are formulated as:
oil phase:
hydroxyl silicone oil (100%) 5-10
Ethyl acetate 5
Water phase:
polyvinyl alcohol resin solution (10%) 40
Deionized water 40
Sodium dodecyl sulfate solution (10%) 1
Additive:
silica sol (20%) 5-10
Silane coupling agent (100%) 5-10
Slowly adding the oil phase into the water phase stirred at a high speed, dispersing for 1 hour at a high speed, and then adding the additive to prepare various silicon dispersion liquids.
3. The backing-free thermosensitive recording material according to claim 1, wherein the thermosensitive imaging layer coating liquid is prepared from the following components in parts by mass:
the balance is adjusted to 100 parts by deionized water.
4. The backing-free thermal recording material according to claim 1, wherein the hydroxyl silicone oil: silica sol: the ratio of silane coupling agent is 1:1: 1.
5. The backing-free thermal recording material according to claim 1, wherein the silicone oil has a dry weight of 0.3 to 1.7g/m2Preferably 0.6 to 1.0g/m2。
6. The backing-free thermosensitive recording material according to claim 1, wherein the modified polyvinyl alcohol resin has a dry weight of 0.6 to 2.0g/m2Preferably 1.0 to 1.5g/m2。
7. The backing-less thermal recording of claim 1The material is characterized in that the adhesive layer is transparent water-based adhesive or transparent hot melt adhesive, and the coating weight is 10-30g/m2。
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Cited By (1)
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| 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 |
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