CN115056586A - Novel flame-retardant printing medium - Google Patents

Novel flame-retardant printing medium Download PDF

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Publication number
CN115056586A
CN115056586A CN202210880099.3A CN202210880099A CN115056586A CN 115056586 A CN115056586 A CN 115056586A CN 202210880099 A CN202210880099 A CN 202210880099A CN 115056586 A CN115056586 A CN 115056586A
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layer
flame retardant
receiving layer
retardant
ink
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CN202210880099.3A
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CN115056586B (en
Inventor
荆柏华
杜云舒
王冰心
仇发鑫
王民清
马天凤
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Shandong Jiayu Weaving Co ltd
Weifang Jiaming New Material Co ltd
Weifang Jiacheng Digital Supplies Co ltd
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Shandong Jiayu Weaving Co ltd
Weifang Jiaming New Material Co ltd
Weifang Jiacheng Digital Supplies Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506Intermediate layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5227Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants

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  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

The application discloses novel fire-retardant print media belongs to print media technical field. The printing medium includes: a base layer; a glue bottom layer disposed over the base layer; the flame-retardant layer is arranged above the rubber bottom layer and comprises, by weight, 40-70 parts of thermoplastic polymer and 30-60 parts of flame retardant, and the ink receiving layer is arranged above the flame-retardant layer. The flame retardant in the flame retardant layer can be uniformly mixed with the thermoplastic polymer, the annular phosphorus flame retardant can play a good flame retardant effect, O, H contained in the flame retardant system forms a carbonization layer in the dehydration process to isolate oxygen and meet the flame retardant requirement, and the flame retardant does not generate harmful substances and meets the environment protection requirement.

Description

Novel flame-retardant printing medium
Technical Field
The application relates to a novel flame-retardant printing medium, and belongs to the technical field of printing media.
Background
In recent years, inkjet advertising materials have found increasing use, including home furnishings, store promotions, and other indoor and outdoor advertising.
The halogen-free flame-retardant system adopted by the traditional flame-retardant printing medium can not meet the requirement that the Limiting Oxygen Index (LOI) is more than or equal to 32 percent basically, but can meet the bromine antimony type flame-retardant system with the LOI more than or equal to 32 percent, heavy metal in the used antimony trioxide exceeds the standard, smoke dust and harmful gas are generated in the combustion process, the diffusion speed of the harmful gas is high, the toxicity level of the generated smoke dust is more than or equal to ZA2 level, and therefore the environment-friendly requirement can not be met, and the development of the printing medium which can meet the flame-retardant requirement and is beneficial to environment protection is urgently needed.
Disclosure of Invention
In order to solve the problems, a novel flame-retardant printing medium is provided, in a flame-retardant layer of the printing medium, a flame retardant can be uniformly mixed with a thermoplastic polymer, a cyclic phosphorus flame retardant can play a good flame-retardant effect, O, H contained in a flame retardant system forms a carbonization layer in a dehydration process to isolate oxygen, the flame retardance is further improved, the requirement that the LOI is not less than 32% is met, and the flame retardant does not generate harmful substances and meets the requirement of environmental protection.
According to one aspect of the present application, there is provided a novel flame retardant printing medium comprising:
a base layer;
a glue bottom layer disposed over the base layer;
the flame-retardant layer is arranged above the rubber bottom layer and comprises 40-70 parts by weight of thermoplastic polymer and 30-60 parts by weight of flame retardant, and the molecular structural formula of the flame retardant is shown as a formula I and/or a formula II:
Figure BDA0003763912450000021
wherein R is 1 And R 2 Each independently selected from substituted or unsubstituted C 1 -C 6 Alkyl radical, C 3 -C 5 Any one of cycloalkyl and substituted or unsubstituted phenyl, R 3 And R 4 Each independently selected from substituted or unsubstituted C 1 -C 8 Alkyl radical, C 5 -C 7 Any one of cycloalkyl and substituted or unsubstituted phenyl, R 5 And R 6 Each independently selected from substituted or unsubstituted C 1 -C 8 Alkyl radical, C 5 -C 7 Any one of cycloalkyl, substituted or unsubstituted phenyl:
an ink receiving layer disposed above the flame retardant layer.
In the flame-retardant layer, 30-60 parts of flame retardant is added, in the range, the flame retardant and the thermoplastic polymer are uniformly dispersed, the formed flame-retardant layer is compact, when the flame retardant is lower than 30 parts, the flame-retardant effect of the flame-retardant layer can be reduced, and the flame-retardant requirement of a printing medium can not be met.
The printing ink receiving layer has an electric double layer structure, the flame retardant contains more hydroxyl groups, and the electronegativity of the flame retardant layer can be increased, so that positrons of the printing ink receiving layer are firmly adsorbed on the flame retardant layer, and the stability of the electric double layer structure in the printing ink receiving layer is improved.
The flame retardant is of an annular structure, has a stable structure, can improve the heat resistance of the flame retardant, contains C-P bonds capable of absorbing heat to play a role in flame retardance, contains four hydroxyl groups with good water solubility, and can improve the compatibility and mixing uniformity of the flame retardant and a thermoplastic polymer through the action of hydrogen bonds when being mixed with the thermoplastic polymer, so that the flame retardant can be uniformly dispersed in a flame retardant layer, prevent agglomeration, improve the compactness of the flame retardant layer, is easy to dry when being used in a printing medium, and has a simple production process; meanwhile, the hydroxyl can provide H, O elements for the dehydration and carbonization step in the flame retardant treatment, so that a carbonization layer is formed, oxygen is isolated, the spread of fire is prevented, and the flame retardant capability is further improved.
Optionally, the flame retardant is selected from a mixture of formula I and formula II, the weight ratio of the flame retardant of formula I to the flame retardant of formula II being (5-7): 1.
the flame retardant comprises a structure shown in formula I and a structure shown in formula II, and the reason is that: compared with the structure of formula I, the structure of formula II is small in annular structure, can fill in the gap between the structure of formula I to reduce this fire-retardant layer and coating in the hole behind the bottom layer of gluing, make all fire retardants can adsorb on the basement, improve fire-retardant layer and glue the cohesiveness on bottom layer and printing ink receiving layer. The weight ratio can ensure the flame-retardant effect of the flame retardant and simultaneously improve the mixing uniformity of the flame retardant and the thermoplastic polymer so as to achieve the optimal flame-retardant effect.
Alternatively, the R is 1 And R 2 Each independently selected from substituted or unsubstituted C 1 -C 4 Alkyl radical, C 3 -C 5 Any one of cycloalkyl radicals, R 3 And R 4 Each independently selected from substituted or unsubstituted C 4 -C 7 Alkyl radical, C 5 -C 7 Any one of cycloalkyl radicals, R 5 And R 6 Each independently selected from substituted or unsubstituted C 4 -C 7 Alkyl radical, C 5 -C 7 Any one of cycloalkyl groups.
Alternatively, the R is 1 And R 2 Each independently selected from hydroxy substituted C 1 -C 4 Alkyl radical, R 3 And R 4 Each independently selected from unsubstituted C 4 Alkyl or C 6 Cycloalkyl radical, R 5 And R 6 Each independently selected from unsubstituted C 4 Alkyl or C 6 A cycloalkyl group.
R 1 And R 2 The hydroxyl-substituted alkyl is adopted to further increase the content of hydroxyl in the flame retardant, further improve the dispersion uniformity of the flame retardant in the thermoplastic polymer and the flame retardant property of the flame retardant, and the hydroxyl-substituted C is adopted 1 -C 4 Alkyl radicals compared with unsubstituted C 1 -C 4 Alkyl, the flame retardant performance is improved by at least 10 percent.
Optionally, the basis weight of the flame retardant layer is from 15gsm to 25 gsm; the larger the basis weight of the flame-retardant layer is, the better the flame-retardant effect is, but further increase in basis weight leads to increase in cost.
The thickness of the flame retardant layer is 40-80um, preferably 40-60um, more preferably 50 um.
Optionally, the thermoplastic polymer is selected from at least one of polyurethane, polyacrylate, polymethacrylate, styrene butadiene copolymer, polyvinyl alcohol, polystyrene, polyvinyl acetate.
Optionally, the preparation method of the flame retardant comprises the following steps:
weighing a first monomer, dissolving the first monomer in a solvent, adding a second monomer, stirring for 4 hours at the temperature of 20-40 ℃, filtering, washing and drying to obtain the flame retardant, wherein the molar ratio of the first monomer to the second monomer is 1: (0.9-1.1);
the first monomer is selected from at least one of tert-butyl phosphine, isobutyl phosphine, isooctyl phosphine, cyclohexyl phosphine and phenyl phosphine;
the second monomer is at least one of glyoxal, malondialdehyde, succinaldehyde, hydroxy malondialdehyde, hydroxy-1, 4-succinaldehyde, 2-hydroxy adipaldehyde, 2-cyclopropyl malondialdehyde, 3-methylglutaraldehyde, 2-phenylpropanedialdehyde, cyclohexane-1, 4-dicarboxaldehyde, 2-bromomalondialdehyde and 2-chloropropanedialdehyde.
The second monomer is selected in a slight excess amount, which is advantageous for flame retarding to form a cyclic structure, and if it is out of the above range, formation of the cyclic flame retardant is inhibited, and the obtained flame retardant contains a linear compound and many impurities.
Optionally, the molar ratio of the first monomer to the second monomer is 1: (1-1.05).
Optionally, the first monomer is selected from at least one of tert-butyl phosphine, isobutyl phosphine, cyclohexyl phosphine;
the second monomer is at least one of glyoxal, malondialdehyde, succinaldehyde, hydroxy malondialdehyde, hydroxy-1, 4-succinaldehyde and 2-hydroxy adipaldehyde.
Optionally, the solvent is selected from any one or more of water, methanol, ethanol, isopropanol, dichloromethane, chloroform, tetrahydrofuran, benzene, toluene, xylene, diethyl ether, and ethylene oxide.
Optionally, the ink-receiving layer comprises a first ink-receiving layer disposed above the flame-retardant layer and a second ink-receiving layer disposed above the first ink-receiving layer.
The existing printing media all contain an ink receiving layer, which means that the ink receiving layer only has an electric double layer, and the model of the electric double layer structure has low stability and is not enough to generate a surface with the lowest surface potential energy, namely, a uniform and flat surface cannot be obtained, so that the phenomena of ink color bleeding, aggregation, shrinkage and the like are caused in the printing process, the printed image has the problems of scratch resistance, stretching white marks and the like, and the defects seriously block the high-quality image output and the rapid development of the printing industry.
When ink is deposited onto the ink-receiving layer, the gloss of the surface of the ink-receiving layer and the compatibility and absorption of the ink by the pore structure within the ink-receiving layer affect the quality of the image. Generally, the more uniform the gloss of the surface of the ink-receiving layer, the more uniform the wettability of the ink on the surface of the ink-receiving layer, and the better the spread. The more regular the pore structure inside the ink receiving layer, the better the wicking effect.
The first ink-receiving layer comprises within it a first double-layer structure of a first ink-receiving layer, which in turn comprises a first sliding surface and a first spreading layer, and the second ink-receiving layer comprises a second double-layer structure of a second ink-receiving layer, which in turn comprises a second sliding surface and a second spreading layer.
In the double-ink receiving layer adopted by the application, when the liquid first receiving layer coating is contacted with the flame retardant layer, the flame retardant layer adsorbs certain charged particles in the first ink receiving layer coating to form a first sliding surface with charges on an interface where the flame retardant layer is contacted with the first ink receiving layer coating, a first double-electric-layer structure is formed by the flame retardant layer and counter ions flowing in the first ink receiving layer coating, liquid of the first ink receiving layer coating is evaporated from the surface of a medium along with drying, a first diffusion layer of the first double-electric-layer structure becomes smaller and smaller, finally, a binder, a pigment, an additive and other functional additive components are left in the first ink receiving layer to form the dried first ink receiving layer, and the first double-electric-layer structure with a certain thickness is maintained in the dried first ink receiving layer.
When the liquid second receiving layer paint is contacted with the first ink receiving layer, a second double-electrical-layer structure can be formed in the second receiving layer paint due to the influence of the first double-electrical-layer structure in the first ink receiving layer paint, in the drying process of the second receiving layer paint, the first double-electrical-layer structure in the first ink receiving layer influences the change of the second double-electrical-layer structure in the second ink receiving layer through electrostatic interaction, and under the interaction of attraction and repulsion, the components of a binder, a pigment, an additive and other functional additives in the second ink receiving layer are arranged and combined according to the principle of lowest energy, so that a regular internal pore structure and a surface with lower surface potential energy are formed. Thereby solving the problems of ink color bleeding, aggregation and shrinkage, and further presenting high-quality images.
Alternatively, the basis weight of the ink receiving layer is 10gsm to 16gsm, a uniformly covered surface cannot be formed if the basis weight is lower than 10gsm, and the cost is increased and the industrial production is not facilitated if the basis weight is higher than 16gsm, the basis weight of the first ink receiving layer is 5gsm to 8gsm, and the basis weight of the second ink receiving layer is 5gsm to 8 gsm.
Optionally, the thickness of the ink receiving layer is 5 to 10um, the thickness of the first ink receiving layer is 2.5 to 5um, and the thickness of the second ink receiving layer is 2.5 to 5 um.
Optionally, the ink receiving layer consists of 50-70 parts of hydrogel material, 10-40 parts of flame retardant and 0.1-1 part of functional additive; the functional additive is selected from any one or more of fillers, fixing agents, release agents, optical agents, coloring agents and rheology modifiers. The hydrogel material includes a material that is hydrophilic and capable of absorbing moisture, helping to improve the recoatability of the ink-receiving layer. The hydrogel may comprise any one or more of thermoplastic polyurethane, polyvinyl alcohol, ethylene vinyl alcohol copolymer, ethylene vinyl acetate, absorbent salts.
The flame retardant is added into the ink receiving layer, so that the flame retardant effect can be further improved, and the flame retardant is a water-based flame retardant, can be uniformly dispersed in the ink receiving layer and does not influence the electric double layer structure in the ink receiving layer. 10-40 parts of flame retardant, which can not only ensure the flame retardant effect, but also can not influence the formability of the ink receiving layer and can improve the film forming property of the ink receiving layer.
Preferably, the functional additive is selected from any one or more of polyethylene, polyethylene oxide, polyacrylamide, polyolefin, cellulose-based polymer, silica, alumina titanium dioxide, calcium carbonate, optical brightener, dye, pigment, fixing agent, mold release agent, optical agent, rheology regulator, colorant fixing agent.
Alternatively, the ink-receiving layer coating may be applied by slot die coating, roll coating, feed curtain coating, knife coating, bar coating, air knife coating, gravure coating, air brush coating, or combinations thereof. The coating may be dried after completion by convection, conduction, atmospheric conditions, or a combination thereof.
Optionally, the thickness of the substrate layer is 120-.
The substrate layer may provide support for other layers and contribute to the overall properties of the media, including stiffness, haze, brightness, thickness, and elasticity.
Optionally, the subbing layer is polyacrylic acid latex and water, wherein the weight ratio of the polyacrylic acid latex to the water is 1: 4;
the thickness of the bottom glue layer is 15-25um, and the basis weight of the bottom glue layer is 5-8 gsm.
The glue bottom layer can cover the pores of the substrate layer, block the infiltration of the flame-retardant layer, provide soft hand feeling for the comprehensive properties of the medium, cover cloth marks due to the fact that the glue bottom layer is too thick, and are not beneficial to re-coating and feeding.
Benefits of the present application include, but are not limited to:
1. according to the utility model provides a novel fire-retardant print media, during the fire retardant can form fire-retardant layer with thermoplastic polymer misce bene, annular phosphorus type fire retardant can play better flame retardant efficiency, and O, H that contains in the fire retardant system forms the carbonization zone at the dehydration in-process, completely cuts off oxygen, further improves the fire retardance.
2. According to the novel flame-retardant printing medium, the uniformity of the surface glossiness is improved by the double ink receiving layers, so that the internal pore structure of the ink receiving layers is more regular, the capillary action is better, the problems of ink color bleeding, aggregation and shrinkage are solved, and a high-quality image is presented.
3. According to the novel flame-retardant printing medium, the flame retardant on the flame-retardant layer can enable the first double-electric-layer structure of the first ink receiving layer to be more stable, so that the cohesiveness of the flame-retardant layer and the first ink receiving layer is improved, and the phenomenon of delamination of the printing medium is avoided.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
fig. 1 is a cross-sectional view of a novel flame-retardant print medium according to an embodiment of the present application.
Fig. 2 is an explanatory diagram of a first ink-receiving layer and a second ink-receiving layer according to an embodiment of the present application.
List of parts and reference numerals:
100. a print medium; 101. a base layer; 102. a glue bottom layer; 103. a flame retardant layer; 104. a first ink-receiving layer; 105. a second ink-receiving layer; 503. a first double-electrical layer; 504. a first sliding surface; 505. a first diffusion layer; 506. a second dual electrical layer; 507. a second sliding surface; 508. a second diffusion layer.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Example 1
The present embodiment relates to a novel flame retardant printing medium 100, and referring to fig. 1-2, the printing medium 100 includes: a base layer 101; a glue bottom layer 102, the glue bottom layer 102 being disposed above the base layer 101; the flame-retardant layer 103 is arranged above the glue bottom layer 102, and the flame-retardant layer 103 comprises 40-70 parts by weight of thermoplastic polymer and 30-60 parts by weight of flame retardant, wherein the molecular structural formula of the flame retardant is shown as formula I and/or formula II:
Figure BDA0003763912450000081
wherein R is 1 And R 2 Each independently selected from substituted or unsubstituted C 1 -C 6 Alkyl radical, C 3 -C 5 Any one of cycloalkyl and substituted or unsubstituted phenyl, R 3 And R 4 Each independently selected from substituted or unsubstituted C 1 -C 8 Alkyl radical, C 5 -C 7 Any one of cycloalkyl and substituted or unsubstituted phenyl, R 5 And R 6 Each independently selected from substituted or unsubstituted C 1 -C 8 Alkyl radical, C 5 -C 7 Any one of cycloalkyl, substituted or unsubstituted phenyl: an ink receiving layer disposed above the flame retardant layer 103.
In one embodiment, the ink-receiving layer includes a first ink-receiving layer 104 and a second ink-receiving layer 105, the first ink-receiving layer 104 is disposed above the flame retardant layer 103, and the second ink-receiving layer 105 is disposed above the first ink-receiving layer 104.
The first ink receiving layer 104 internally comprises a first double-layer 503 structure of the first ink receiving layer 104, the first double-layer 503 structure further comprises a first sliding surface 504 and a first diffusion layer 505, the second ink receiving layer 105 comprises a second double-layer 506 structure of the second ink receiving layer 105, the second double-layer 506 structure further comprises a second sliding surface 507 and a second diffusion layer 508.
In the dual ink receiving layers employed in the present application, when the first receiving layer coating material in a liquid state is brought into contact with the flame retardant layer 103, the adsorption of certain charged particles in the coating of the first ink receiving layer 104 by the flame retardant layer 103 forms a charged first sliding surface 504 at the interface where the flame retardant layer 103 is in contact with the coating of the first ink receiving layer 104, forming a first diffusion layer 505 with counter ions flowing in the coating of the first ink receiving layer 104, the first slip surface 504 and the first diffusion layer 505 forming a first bilayer 503 structure, the liquid of the coating of the first ink receiving layer 104 evaporating from the surface of the medium as drying progresses, the first diffusion layer 505 of the first bilayer 503 structure becoming smaller and smaller, and finally the first ink receiving layer leaving the binder, pigment, additives and other functional additive components to form a dried first ink receiving layer 104, and a first bilayer 503 structure is maintained at a certain thickness in the dried first ink receiving layer.
When the liquid second receiving layer coating material comes into contact with the first ink receiving layer 104, a second double electrical layer 506 structure is formed in the second receiving layer coating material due to the influence of the structure of the first double electrical layer 503 in the first ink receiving layer 104, the second double electrical layer 506 structure including a second sliding surface 507 and a second diffusion layer 508. During the drying process of the second receiving layer paint, the first double-electric layer 503 in the first ink receiving layer influences the change of the structure of the second double-electric layer 506 in the second ink receiving layer through electrostatic interaction, and under the interaction of attraction and repulsion, the binder, pigment, additive and other functional additive components in the second ink receiving layer are arranged and combined according to the principle of lowest energy, so that a regular internal pore structure and a surface with lower surface potential energy are formed. Thereby solving the problems of ink color bleeding, aggregation and shrinkage, and further presenting high-quality images.
Example 2: synthesis of flame retardant
Flame retardant 1#
Weighing and dissolving isobutylphosphine in tetrahydrofuran, adding a glyoxal aqueous solution, stirring for 4 hours at 25 ℃, filtering, washing and drying to obtain a flame retardant 1#, wherein the molar ratio of the isobutylphosphine to the glyoxal is 1: 1.05, and the structural formula of the flame retardant 1# is a structure shown in a formula I.
Flame retardant No. 2
Weighing cyclohexylphosphine, dissolving the cyclohexylphosphine in dichloromethane, adding a glyoxal water solution, stirring for 4 hours at 25 ℃, filtering, washing and drying to obtain a flame retardant 2#, wherein the molar ratio of the cyclohexylphosphine to the glyoxal is 1: 1.1, the structural formula of the flame retardant 2# is a structure shown in a formula I.
Flame retardant No. 3
Weighing isobutyl phosphine, dissolving the isobutyl phosphine in tetrahydrofuran, adding a butanedialdehyde aqueous solution, stirring for 4 hours at 25 ℃, filtering, washing and drying to obtain a flame retardant No. 3, wherein the molar ratio of the isobutyl phosphine to the butanedialdehyde is 1: 1.05, the structural formula of the flame retardant 3# is a structure shown in a formula II.
Flame retardant 4#
Weighing phenyl phosphine, dissolving the phenyl phosphine in tetrahydrofuran, adding a butanedialdehyde water solution, stirring for 4 hours at 25 ℃, filtering, washing and drying to obtain a flame retardant No. 4, wherein the molar ratio of the phenyl phosphine to the butanedialdehyde is 1: 0.9, the structural formula of the flame retardant 4# is a structure shown in a formula II.
Flame retardant No. 5
Weighing and dissolving isobutylphosphine in tetrahydrofuran, adding a hydroxypropanedialdehyde water solution, stirring for 4 hours at 25 ℃, filtering, washing and drying to obtain a flame retardant No. 5, wherein the molar ratio of the isobutylphosphine to the hydroxypropanedialdehyde is 1: 1.05, the structural formula of the flame retardant 5# is a structure shown in a formula II.
Flame retardant 6#
Weighing isobutyl phosphine, dissolving the isobutyl phosphine in tetrahydrofuran, adding a trichloromethane solution of cyclohexane-1, 4-dicarboxaldehyde, stirring for 4 hours at 25 ℃, filtering, washing and drying to obtain a flame retardant No. 6, wherein the molar ratio of the isobutyl phosphine to the cyclohexane-1, 4-dicarboxaldehyde is 1: 1.05, the structural formula of the flame retardant 6# is a structure shown in a formula II.
Example 3: preparation of novel flame-retardant printing medium
Print Medium 1#
(1) Base layer: adopting chemical fiber cloth, cotton cloth and polyester cotton cloth to shape to obtain a base layer with the thickness of 120um and the basis weight of 100 gsm;
(2) glue bottom layer: coating polyacrylic acid latex and water in a weight ratio of 1:4 on a substrate layer, and drying to obtain a glue bottom layer with a thickness of 15um and a basis weight of 5 gsm;
(3) a flame-retardant layer: mixing 40 parts of polyacrylate and 30 parts of flame retardant No. 2 to obtain a flame-retardant coating, coating the flame-retardant coating on a glue bottom layer, and drying to obtain a flame-retardant layer with the thickness of 40um and the basis weight of 15 gsm;
(4) ink-receiving layer: adopting 70 parts of polyvinyl alcohol hydrogel, 40 parts of flame retardant No. 4, 0.2 part of silica and 0.3 part of rheology regulator to obtain an ink receiving layer coating, coating the ink receiving layer coating on the flame retardant layer, and drying to obtain an ink receiving layer with the thickness of 5um and the basis weight of 10gsm, namely preparing the printing medium No. 1.
Print Medium 2#
(1) Base layer: adopting chemical fiber cloth, cotton cloth and polyester cotton cloth to shape to obtain a base layer with the thickness of 130um and the basis weight of 110 gsm;
(2) glue bottom layer: coating a mixture of polyacrylic acid latex and water in a weight ratio of 1:4 on a substrate layer, and drying to obtain a glue bottom layer with the thickness of 20um and the basis weight of 6 gsm;
(3) a flame-retardant layer: mixing 60 parts of polyacrylate and 48 parts of flame retardant No. 3 to obtain a flame-retardant coating, coating the flame-retardant coating on a glue bottom layer, and drying to obtain a flame-retardant layer with the thickness of 50um and the basis weight of 20 gsm;
(4) ink-receiving layer: 60 parts of polyvinyl alcohol hydrogel, 24 parts of flame retardant 1#, 0.2 part of silica and 0.3 part of rheology regulator are adopted to obtain an ink receiving layer coating, the ink receiving layer coating is coated on the flame retardant layer and dried to obtain an ink receiving layer with the thickness of 8um and the basis weight of 14gsm, and the printing medium 2# is prepared.
Print Medium 3#
(1) Base layer: adopting chemical fiber cloth, cotton cloth and polyester cotton cloth to shape to obtain a base layer with the thickness of 150um and the basis weight of 150 gsm;
(2) glue bottom layer: coating a mixture of polyacrylic acid latex and water in a weight ratio of 1:4 on a substrate layer, and drying to obtain a glue bottom layer with the thickness of 25um and the basis weight of 8 gsm;
(3) a flame-retardant layer: mixing 70 parts of polyacrylate and 60 parts of flame retardant No. 6 to obtain a flame-retardant coating, coating the flame-retardant coating on a glue bottom layer, and drying to obtain a flame-retardant layer with the thickness of 80um and the basis weight of 25 gsm;
(4) ink-receiving layer: and (3) obtaining an ink receiving layer coating by adopting 50 parts of polyvinyl alcohol hydrogel, 0.2 part of silica and 0.3 part of rheology regulator, coating the ink receiving layer coating on the flame-retardant layer, and drying to obtain an ink receiving layer with the thickness of 10um and the basis weight of 16gsm, namely preparing the printing medium.
Print media 4#
(1)(2): same as print medium # 2;
(3) a flame-retardant layer: mixing 60 parts of polyacrylate, 40 parts of flame retardant No. 5 and 8 parts of flame retardant No. 1 to obtain a flame-retardant coating, coating the flame-retardant coating on a glue bottom layer, and drying to obtain a flame-retardant layer with the thickness of 50um and the basis weight of 20 gsm;
(4) the same as printing medium 2#, printing medium 4# was prepared.
Print media 5#
(1)(2): same as print medium # 2;
(3) a flame-retardant layer: mixing 60 parts of polyacrylate, 41.15 parts of flame retardant No. 5 and 6.85 parts of flame retardant No. 1 to obtain a flame-retardant coating, coating the flame-retardant coating on a glue bottom layer, and drying to obtain a flame-retardant layer with the thickness of 50um and the basis weight of 20 gsm;
(4) the same as the printing medium No. 2, namely the printing medium No. 5 is prepared.
Print media 6#
(1)(2): same as print medium # 2;
(3) a flame-retardant layer: mixing 60 parts of polyacrylate, 42 parts of flame retardant 5# and 6 parts of flame retardant 1# to obtain a flame-retardant coating, coating the flame-retardant coating on a glue bottom layer, and drying to obtain a flame-retardant layer with the thickness of 50 mu m and the basis weight of 20 gsm;
(4) the same as the print medium No. 2, print medium No. 6 was obtained.
Print media 7#
(1)(2)(3): same as print media # 5;
(4) ink-receiving layer: 60 parts of polyvinyl alcohol hydrogel, 20.57 parts of flame retardant No. 5, 3.43 parts of flame retardant No. 1, 0.2 part of silica and 0.3 part of rheology modifier are adopted to obtain an ink receiving layer coating, the ink receiving layer coating is coated on the flame retardant layer and dried to obtain an ink receiving layer with the thickness of 8 mu m and the basis weight of 14gsm, and the printing medium No. 7 is prepared.
Print media 8#
(1)(2)(3): same as print media # 5;
(4) ink-receiving layer: 60 parts of polyvinyl alcohol hydrogel, 20.57 parts of flame retardant 5#, 3.43 parts of flame retardant 1#, 0.2 part of silica and 0.3 part of rheology regulator are adopted to obtain an ink receiving layer coating, the ink receiving layer coating is coated on the flame retardant layer and dried to obtain a first ink receiving layer with the thickness of 4um and the basis weight of 7gsm, the ink receiving layer coating is continuously coated on the first ink receiving layer, and a second ink receiving layer with the thickness of 4um and the basis weight of 7gsm is obtained by drying, so that the printing medium 8 #.
Print media 9#
(1) Base layer: adopting chemical fiber cloth, cotton cloth and polyester cotton cloth to shape to obtain a base layer with the thickness of 120um and the basis weight of 100 gsm;
(2) (3) and (4) the same as the printing medium No. 2, namely, the printing medium No. 9 was prepared.
Print Medium 10#
(1) Base layer: same as print medium # 2;
(2) glue bottom layer: coating a mixture of polyacrylic acid latex and water in a weight ratio of 1:3 on a substrate layer, and drying to obtain a glue bottom layer with the thickness of 20um and the basis weight of 7 gsm;
(3) (4) the same as the printing medium No. 2, namely, the printing medium No. 10 was prepared.
Comparative printing Medium D1#
(1)(2): same as print medium # 2;
(3) a flame-retardant layer: mixing 60 parts of polyacrylate, 12 parts of antimony trioxide flame retardant and 36 parts of decabromodiphenylethane flame retardant to obtain a flame-retardant coating, coating the flame-retardant coating on the bottom rubber layer, and drying to obtain a flame-retardant layer with the thickness of 50um and the basis weight of 20 gsm;
(4) the same as printing medium # 2, comparative printing medium D1# was prepared.
Comparative printing Medium D2#
(1)(2)(3): same as print medium # 2;
(4) ink-receiving layer: 60 parts of polyvinyl alcohol hydrogel, 6 parts of antimony trioxide flame retardant, 18 parts of decabromodiphenylethane flame retardant, 0.2 part of silica and 0.3 part of rheology modifier are adopted to obtain an ink receiving layer coating, the ink receiving layer coating is coated on the flame retardant layer and dried to obtain an ink receiving layer with the thickness of 8 mu m and the basis weight of 14gsm, and then the comparative printing medium D2# is prepared.
Test example 1: water solubility test
A5060 flame retardant of Sandoflam company and the flame retardant No. 1-6 are adopted to carry out a water solubility test, 10 parts of flame retardant is added into 100 parts of water at 25 ℃, the dissolution performance of the flame retardant is observed after the mixture is stirred for 10min, and the test results are shown in Table 1
Table 1: phosphorus content and Water solubility test results
Sample(s) Solubility S (g/100g water) Water solubility Phosphorus content (%)
Flame retardant 1# 5.98 Soluble in water 20.95
Flame retardant 1# 5.48 Soluble in water 15.05
Flame retardant 1# 5.39 Soluble in water 17.61
Flame retardant 1# 5.31 Soluble in water 15.81
Flame retardant 1# 5.76 Soluble in water 15.66
Flame retardant 1# 5.24 Soluble in water 13.48
Commercially available flame retardant 5060 0.008 Is difficult to dissolve 17.89
As can be seen from Table 1, the selected flame retardant has high water solubility among the cyclic phosphorus flame retardants with close phosphorus content, while the conventional cyclic phosphorus flame retardants in the market are hardly soluble in water. The reason is that the flame retardant contains four hydroxyl groups, and the flame retardant can be well combined with water through hydrogen bond action to be uniformly dispersed, so that the flame retardant and the water-based curing agent can have better compatibility, and the prepared fireproof coating material is more uniform and stable in the use process.
Test example 2: surface roughness test
R457 was measured using a whiteness color meter and Gloss (60 ℃ C.) was measured using a micro-TRI-Gloss instrument in Germany for printing media No. 1-10 # and comparative printing media D1# -D2#, and the test results are shown in Table 2.
TABLE 2
Figure BDA0003763912450000141
Figure BDA0003763912450000151
The larger R457 in Table 2 proves that the stronger the reflection capability of the printing medium to light with a 457nm wavelength, and the higher the reflection effect of light is improved compared with the ink receiving layer of one layer by the first ink receiving layer and the second ink receiving layer adopted in the application. The smaller the Gloss (60 °) value in table 2 indicates that the object surface is closer to a mirror surface, demonstrating that the first ink-receiving layer and the second ink-receiving layer can form a more regular surface, i.e., the surface potential is lower, in the present application.
Test example 3: printing test
Print tests were performed on print media # 1-10 # and comparative print media # D1-D2 # on an HP Latex 360 printer, equipped with HP Latex designated as an HP 831B ink cartridge. The conditions of the printer are set as follows: the hot zone temperature was 60 ℃, the cure zone temperature was 116 ℃ and the air flow was 4%, and the image quality was determined using either the color gamut or ink bleed using the standard Hewlett-Packard procedure. The parameters for print image quality are shown in table 3:
TABLE 3
Sample (I) Gamut KOD L*min Color bleeding Aggregation Scratch resistance
Print Medium 1# 75096 2.2 2.7 3.5 3.5 3
Print Medium 2# 76584 2.4 2.3 4 4.5 4
Print Medium 3# 75596 2.3 2.6 3.5 3.5 3.5
Print media 4# 77065 2.4 2.1 4.5 4.5 4.5
Print media 5# 77540 2.5 2.0 5 4.5 4.5
Print media 6# 76580 2.4 2.2 4.5 4.5 4.5
Print media 7# 77890 2.6 1.9 5 5 4.5
Print media 8# 78105 2.7 1.8 5 5 5
Print media 9# 76029 2.4 2.4 4 4 4
Print Medium 10# 75926 2.3 2.5 3.5 4 3.5
Comparative printing Medium D1# 72738 2.0 3.0 2.5 2.5 2.5
Comparative printing Medium D2# 73598 2.1 2.7 3 3 3
Bleed, aggregation, scratch resistance are evaluated in table 3 by the following scores: 5-no defects; slight defects are observed within 4-1 m; easily visible defects within 3-1 m, at an acceptable level; many defects can be seen within 2-1 m, at an unacceptable level; and 1-serious defect. As can be seen from the data in table 3, the first and second ink-receiving layers in this application exhibit a wider color gamut, higher black color light density and more accurate resolution than the single ink-receiving layer.
Test example 4: flame retardancy test
The print media No. 1-10 # and comparative print media D1-D2 # were subjected to flame retardant testing according to the methods specified in national standards GB/T5455 and GB/T5454, French NF P92, and U.S. NFPA701, with the results shown in Table 4:
TABLE 4
Figure BDA0003763912450000161
Figure BDA0003763912450000171
According to the burning length, the afterflame time, the smoldering time, the maximum oxygen index, the flame spread speed and the dripping afterflame time in the table 4, compared with other bromine antimony flame retardants, the flame retardant in the application can exert a better flame retardant effect, and the flame retardant performance of the printing medium with the double ink receiving layers containing the same flame retardant material is higher than that of the printing medium with the single ink receiving layer.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. A novel flame retardant print media, comprising:
a base layer;
a glue bottom layer disposed over the base layer;
the flame-retardant layer is arranged above the rubber bottom layer and comprises 40-70 parts by weight of thermoplastic polymer and 30-60 parts by weight of flame retardant, and the molecular structural formula of the flame retardant is shown as a formula I and/or a formula II:
Figure FDA0003763912440000011
wherein R is 1 And R 2 Each independently selected from substituted or unsubstituted C 1 -C 6 Alkyl radical, C 3 -C 5 Any one of cycloalkyl and substituted or unsubstituted phenyl, R 3 And R 4 Each independently selected from substituted or unsubstituted C 1 -C 8 Alkyl radical, C 5 -C 7 Any one of cycloalkyl and substituted or unsubstituted phenyl, R 5 And R 6 Each independently selected from substituted or unsubstituted C 1 -C 8 Alkyl radical, C 5 -C 7 Any one of cycloalkyl, substituted or unsubstituted phenyl:
an ink receiving layer disposed above the flame retardant layer.
2. The novel flame retardant print media of claim 1, wherein the flame retardant layer has a basis weight of 15gsm to 25 gsm;
the thickness of the flame-retardant layer is 40-80 um.
3. The novel flame retardant print medium of claim 1, wherein the thermoplastic polymer is selected from at least one of polyurethane, polyacrylate, polymethacrylate, styrene butadiene copolymer, polyvinyl alcohol, polystyrene, polyvinyl acetate.
4. The novel flame retardant printing medium according to claim 1, wherein the preparation method of the flame retardant comprises the following steps:
weighing a first monomer, dissolving the first monomer in a solvent, adding a second monomer, stirring for 4 hours at the temperature of 20-40 ℃, filtering, washing and drying to obtain the flame retardant, wherein the molar ratio of the first monomer to the second monomer is 1: (0.9-1.1);
the first monomer is selected from at least one of tert-butyl phosphine, isobutyl phosphine, isooctyl phosphine, cyclohexyl phosphine and phenyl phosphine;
the second monomer is at least one selected from glyoxal, malondialdehyde, succinaldehyde, hydroxy-malondialdehyde, hydroxy-1, 4-succinaldehyde, 2-hydroxy-adipaldehyde, 2-cyclopropyl-malondialdehyde, 3-methylglutaraldehyde, 2-phenyl-malondialdehyde, cyclohexane-1, 4-dicarboxaldehyde, 2-bromomalondialdehyde and 2-chloropropanedialdehyde.
5. The novel flame retardant print media of claim 1, wherein the ink receiving layer comprises a first ink receiving layer disposed over the flame retardant layer and a second ink receiving layer disposed over the first ink receiving layer.
6. The novel flame retardant print media of claim 5, wherein the basis weight of the ink-receiving layer is from 10gsm to 16gsm, the basis weight of the first ink-receiving layer is from 5gsm to 8gsm, and the basis weight of the second ink-receiving layer is from 5gsm to 8 gsm.
7. The novel flame retardant print medium of claim 5, wherein the ink-receiving layer has a thickness of 5-10um, the first ink-receiving layer has a thickness of 2.5-5um, and the second ink-receiving layer has a thickness of 2.5-5 um.
8. The novel flame retardant printing medium according to claim 1, wherein the ink receiving layer consists of 50-70 parts of hydrogel material, 10-40 parts of flame retardant and 0.1-1 part of functional additive;
the functional additive is selected from any one or more of fillers, fixing agents, release agents, optical agents, coloring agents and rheology modifiers.
9. The novel flame retardant printing medium as claimed in claim 1, wherein the thickness of the substrate layer is 120-150 μm, and the basis weight of the substrate layer is 100-150 gsm.
10. The novel flame-retardant printing medium according to claim 1, wherein the subbing layer is polyacrylic latex and water, wherein the weight ratio of the polyacrylic latex to the water is 1: 4;
the thickness of the bottom glue layer is 15-25um, and the basis weight of the bottom glue layer is 5-8 gsm.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4855507A (en) * 1988-03-28 1989-08-08 American Cyanamid Company 1,4-Disubstituted-2,3,5,6-tetrahydroxy-1,4-diphosphorinanes and their oxides or sulfides
CN104364086A (en) * 2012-07-18 2015-02-18 惠普发展公司,有限责任合伙企业 Fabric print media
CN108136807A (en) * 2015-11-06 2018-06-08 惠普发展公司,有限责任合伙企业 Printable recording medium
US20200338920A1 (en) * 2018-03-19 2020-10-29 Hewlett-Packard Development Company, L.P. Fabric printable medium
US20200407910A1 (en) * 2018-03-19 2020-12-31 Hewlett-Packard Development Company, L.P. Fabric printable medium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4855507A (en) * 1988-03-28 1989-08-08 American Cyanamid Company 1,4-Disubstituted-2,3,5,6-tetrahydroxy-1,4-diphosphorinanes and their oxides or sulfides
CN104364086A (en) * 2012-07-18 2015-02-18 惠普发展公司,有限责任合伙企业 Fabric print media
CN108136807A (en) * 2015-11-06 2018-06-08 惠普发展公司,有限责任合伙企业 Printable recording medium
US20200338920A1 (en) * 2018-03-19 2020-10-29 Hewlett-Packard Development Company, L.P. Fabric printable medium
US20200407910A1 (en) * 2018-03-19 2020-12-31 Hewlett-Packard Development Company, L.P. Fabric printable medium

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