CN111038136B - Backing-paper-free thermosensitive recording material - Google Patents
Backing-paper-free thermosensitive recording material Download PDFInfo
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- CN111038136B CN111038136B CN201911319229.0A CN201911319229A CN111038136B CN 111038136 B CN111038136 B CN 111038136B CN 201911319229 A CN201911319229 A CN 201911319229A CN 111038136 B CN111038136 B CN 111038136B
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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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- Engineering & Computer Science (AREA)
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- 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
Technical Field
The invention relates to the technical field of printing, in particular to a thermal label recording material.
Technical Field
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.
Disclosure of Invention
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:
20-40 parts of modified polyvinyl alcohol resin solution with mass concentration of 10%
10 parts of 2 mass% aqueous solution of boric acid crosslinking agent
5 parts of zinc stearate dispersion liquid with mass concentration of 10 percent
20-40 parts of various silicon dispersion liquids with mass concentration of 10%
The balance is adjusted to 100 parts by deionized water;
the formula of the silicon dispersion liquid comprises the following components:
oil phase:
5-10 parts of hydroxyl silicone oil with mass concentration of 100%
Ethyl acetate 5 parts
Water phase:
40 parts of modified polyvinyl alcohol resin solution with mass concentration of 10%
40 parts of deionized water
1 part of sodium dodecyl sulfate solution with mass concentration of 10 percent
Additive:
5-10 parts of silica sol with mass concentration of 20%
5-10 parts of silane coupling agent with mass concentration of 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 an additive to prepare various silicon dispersion liquids;
the viscosity of the hydroxyl silicone oil is 500-1000 mPas.
The backing-paper-free thermosensitive recording material is prepared from the following components in parts by mass:
30 parts of thermosensitive dye dispersion liquid with mass concentration of 18%
40 parts of 34 mass% thermosensitive color developer dispersion liquid
20 parts of styrene-butadiene latex with mass concentration of 45%
1.5 parts of sodium dodecyl sulfate solution with mass concentration of 10%
The balance is adjusted to 100 parts by deionized water.
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-mentioned backing-free thermal recording material, wherein the hydroxyl silicone oil has a dry weight of 0.3 to 1.7 g/m2Preferably 0.6 to 1.0 g/m2。
In the above-mentioned backing-less thermal recording material, the modified polyvinyl alcohol resin has a dry weight of 0.6 to 2.0 g/m2Preferably 1.0 to 1.5 g/m2。
The adhesive layer is transparent aqueous adhesive or transparent hot melt adhesive, and the coating weight is 10-30 g/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 modified polyvinyl alcohol act synergistically together to form a compact coating, not only can complete thermosensitive continuous printing, but also can contact 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: 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 heat sensitive information recording layer and a multifunctional protective layer on one side of a base material in sequence, coats an adhesive layer on the other side 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 information recording layer is prepared by coating thermosensitive imaging coating liquid containing thermosensitive dye dispersion liquid, thermosensitive color developing agent dispersion liquid, adhesive and other coating auxiliary agents on one corona surface of a base material, and fully drying the 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-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-dibutylaminofluoran, 2- (2-4-dimethylanilino) -3-methyl-6-diethylaminofluoran, and the like, 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 ability of the heat-sensitive recording material, a heat-sensitive sensitizer may be added to the heat-sensitive information recording 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 information recording layer of the present invention functions to protect the heat-sensitive dye particles and the heat-sensitive developer particles from aggregation and is advantageous for coating with 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 of modified 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 agents used by various silicon dispersion liquids in the multifunctional protective layer are as follows: bis- [3- (triethoxysilyl) -propyl ] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl ] -disulfide, gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, gamma-methacryloyloxypropyltrimethoxysilane, gamma-methacryloyloxypropyltriisopropoxysilane, and the like. Can be used alone or in combination. The silane coupling agent has the main function of crosslinking the resin in the protective layer and the inorganic functional auxiliary agent, so that the water-resistant effect of the coating is improved, and meanwhile, the silane coupling agent can permeate into the thermosensitive information recording layer to perform crosslinking reaction with the adhesive in the imaging layer, so that the coating becomes more compact, and the fastness and the protective effect of the coating are further improved.
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 bonding layer due to poor fastness of the coating, so that the residual adhesive force of the bonding 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 modified polyvinyl alcohol in the multifunctional protective layer cooperatively act to form a compact coating, so that the multifunctional protective layer can achieve thermosensitive continuous printing, can contact with an adhesive in the bonding layer to effectively release, and has 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 coating liquid for the thermosensitive information recording layer suitable for the present invention has the following formula:
30 portions of heat-sensitive dye dispersion liquid (17.7 percent)
40 parts of heat-sensitive color developing agent dispersion liquid (33.75 percent)
20 portions of styrene-butadiene latex (45 percent)
Sodium dodecyl sulfate solution (10%) 1.5 parts
The balance is adjusted to 100 parts by deionized water.
The formula of the multifunctional protective layer coating liquid suitable for the invention is as follows:
20-40 parts of modified polyvinyl alcohol resin solution (10 percent)
10 portions of aqueous solution (2%) of boric acid crosslinking agent
5 portions of zinc stearate dispersion liquid (10 percent)
20-40 parts of various silicon dispersion liquids (10 percent)
The balance is adjusted to 100 parts by deionized water.
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 modified polyvinyl alcohol resin solution (10 percent)
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 imaging, protective and adhesive layers of the present invention may be applied by any one or more of a variety of combinations including slide extrusion coating, slot coating, curtain coating, knife coating, microgravure coating, wire bar coating or roll 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-Rite 400) 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 thermosensitive information-recording 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 200 g/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 200 g/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 information recording layer coating liquid, and fully drying the thermosensitive information recording layer coating liquid on one surface of corona PET (polyethylene terephthalate) at 21-25 ℃ in a wire rod coating mode to obtain the thermosensitive information recording layer coating liquid with the attachment amount of 8g/m2The thermosensitive information recording layer E of (1). 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 800 mpa · 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 information recording 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 3.0 g/m2A thermosensitive recording layer EP 1.
Preparation of adhesive layer A
Melting the hot melt adhesive at the temperature of more than 150 ℃, keeping the temperature 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 heat-sensitive recording layer EP1, peeling the release paper, and then contacting and rolling the adhesive layer A (inner side) with the EP1 (outer side).
Example 2
The base material, the thermosensitive information recording layer, the adhesive layer formulation and the operation were the same 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 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 DS2 into a reactor, supplementing the mixture to 100 parts of the total amount by using deionized water, stirring and mixing uniformly to obtain the multifunctional protective layer coatingThe liquid distribution P2 was coated on the thermosensitive information recording layer E by wire rod coating, and dried sufficiently to give a protective layer having a dry weight of 3.5 g/m2A thermosensitive recording layer EP 2.
Example 3
The base material, the thermosensitive information recording layer, the adhesive layer formulation and the operation were the same 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 information recording 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 4.0 g/m2A thermosensitive recording layer EP 3.
Example 4
The base material, the thermosensitive information recording layer, the adhesive layer formulation and the operation were the same 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%) and 20 parts of the various silicon dispersions 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 P4, coating the multifunctional protective layer coating liquid on a thermosensitive information recording 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 2.5 g/m2A thermosensitive recording layer EP 4.
Example 5
The base material, the thermosensitive information recording layer, the adhesive layer formulation and the operation were the same 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 (10%), 40 parts of the various silicon dispersions 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 P5, coating the multifunctional protective layer coating liquid on a thermosensitive information recording 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 4.5 g/m2A thermosensitive recording layer EP 5.
Example 6
The base material, the thermosensitive information recording layer, the adhesive layer formulation and the operation were the same 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%) and 20 parts of the various silicon dispersions DS1 into a reactor, adding 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 information recording 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 2.0 g/m2A thermosensitive recording layer EP 6.
Example 7
The base material, the thermosensitive information recording layer, the adhesive layer formulation and the operation were the same 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 (10%) and 40 parts of the various silicon dispersions 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 information recording 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 5.5 g/m2A thermosensitive recording layer EP 7.
Example 8
The formulation and operation of the thermosensitive information recording layer, the multifunctional protective layer and the adhesive layer were the same as those of 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 thermosensitive information recording layer, the multifunctional protective layer, the adhesive layer were formulated and operated in the same manner as in example 6 to obtain a multifunctional protective layer having a dry weight of 1.5 g/m2EP 9.
Comparative example 2
The base material, the thermosensitive information recording layer, the multifunctional protective layer, the adhesive layer were formulated and operated in the same manner as in example 7 to obtain a multifunctional protective layer having a dry weight of 6.0 g/m2EP 10.
Comparative example 3
The base material, the thermosensitive information recording layer, the adhesive layer formulation and the operation were the same 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 a multifunctional protective layer coating liquid P9, coating the multifunctional protective layer coating liquid on a thermosensitive information recording 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 3.5 g/m2A thermosensitive recording layer EP 11.
Comparative example 4
The base material, the thermosensitive information recording layer, the adhesive layer formulation and the operation were the same 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 information recording 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 3.5 g/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 table below.
(one) color development Density test:
continuously aging the heat-sensitive recording material coated with the heat-sensitive information recording layer and the 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-mentioned strip-shaped recording material with highest 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:
the heat-sensitive recording material coated with the heat-sensitive information recording layer and the multifunctional protective layer after drying is cured for 7 days at the room temperature of 23 +/-2 ℃, cut into strips, completely immersed in deionized water, immersed for 4 hours at the room temperature, observed for the surface state, taken out, and then the surface is strongly rubbed with fingers for 10 times to test the water resistance 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) machine testing after printing:
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 testing:
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
Claims (6)
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:
20-40 parts of modified polyvinyl alcohol resin solution with mass concentration of 10%
10 parts of 2 mass% aqueous solution of boric acid crosslinking agent
5 parts of zinc stearate dispersion liquid with mass concentration of 10 percent
20-40 parts of various silicon dispersion liquids with mass concentration of 10%
The balance is adjusted to 100 parts by deionized water;
the formula of the silicon dispersion liquid comprises the following components:
oil phase:
5-10 parts of hydroxyl silicone oil with mass concentration of 100%
Ethyl acetate 5 parts
Water phase:
40 parts of modified polyvinyl alcohol resin solution with mass concentration of 10%
40 parts of deionized water
1 part of sodium dodecyl sulfate solution with mass concentration of 10 percent
Additive:
5-10 parts of silica sol with mass concentration of 20%
5-10 parts of silane coupling agent with mass concentration of 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 an additive to prepare various silicon dispersion liquids;
the viscosity of the hydroxyl silicone oil is 500-1000 mPas.
2. The backing-free thermosensitive recording material according to claim 1, wherein the thermosensitive information recording layer coating liquid is prepared from the following components in parts by mass:
30 parts of thermosensitive dye dispersion liquid with mass concentration of 18%
40 parts of 34 mass% thermosensitive color developer dispersion liquid
20 parts of styrene-butadiene latex with mass concentration of 45%
1.5 parts of sodium dodecyl sulfate solution with mass concentration of 10%
The balance is adjusted to 100 parts by deionized water.
3. 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.
4. The backing-free thermal recording material according to claim 1, wherein the hydroxy silicone oil has a dry weight of 0.3 to 1.7 g/m2。
5. The backing-free thermosensitive recording material according to claim 1, wherein the modified polyvinyl alcohol resin has a dry weight of 0.6 to 2.0 g/m2。
6. The backing-free thermosensitive recording material according to claim 1, wherein the adhesive layer is a transparent aqueous adhesive or a transparent hot-melt adhesive and is applied in an amount of 10 to 30 g/m2。
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