CN115975497A - Printable antistatic emulsion with strong adhesion, preparation method, antistatic film and film preparation method - Google Patents
Printable antistatic emulsion with strong adhesion, preparation method, antistatic film and film preparation method Download PDFInfo
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- CN115975497A CN115975497A CN202310103193.2A CN202310103193A CN115975497A CN 115975497 A CN115975497 A CN 115975497A CN 202310103193 A CN202310103193 A CN 202310103193A CN 115975497 A CN115975497 A CN 115975497A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 30
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 30
- 229920000123 polythiophene Polymers 0.000 claims abstract description 29
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 229920006267 polyester film Polymers 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 229920003180 amino resin Polymers 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 230000001804 emulsifying effect Effects 0.000 claims description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000009998 heat setting Methods 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004640 Melamine resin Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 27
- 239000000853 adhesive Substances 0.000 abstract description 18
- 230000001070 adhesive effect Effects 0.000 abstract description 18
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000005507 spraying Methods 0.000 abstract description 3
- 238000007761 roller coating Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- -1 polyoxyethylene Polymers 0.000 description 15
- 239000002985 plastic film Substances 0.000 description 11
- 229920006255 plastic film Polymers 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- BSCCSDNZEIHXOK-UHFFFAOYSA-N phenyl carbamate Chemical compound NC(=O)OC1=CC=CC=C1 BSCCSDNZEIHXOK-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 5
- 229920003270 Cymel® Polymers 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000002216 antistatic agent Substances 0.000 description 5
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 description 5
- 150000004757 linear silanes Chemical class 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000013065 commercial product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- BANXPJUEBPWEOT-UHFFFAOYSA-N 2-methyl-Pentadecane Chemical compound CCCCCCCCCCCCCC(C)C BANXPJUEBPWEOT-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 229940043268 2,2,4,4,6,8,8-heptamethylnonane Drugs 0.000 description 1
- 229920003275 CYMEL® 325 Polymers 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- KUVMKLCGXIYSNH-UHFFFAOYSA-N isopentadecane Natural products CCCCCCCCCCCCC(C)C KUVMKLCGXIYSNH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- UBMUZYGBAGFCDF-UHFFFAOYSA-N trimethoxy(2-phenylethyl)silane Chemical compound CO[Si](OC)(OC)CCC1=CC=CC=C1 UBMUZYGBAGFCDF-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a printable antistatic emulsion with strong adhesive force, which comprises the following components in parts by weight: conductive polymer polythiophene and/or single-arm carbon nanotube aqueous solution: 10-50 parts; modified amino resin: 5-30 parts; carbamate modified nano silica hydrosol: 10-20 parts; surfactant (B): 1-5 parts; water (W) the method comprises the following steps: 20-55 parts. The antistatic emulsion can be coated on a plastic base material, particularly a polyester film (PET), by coating modes such as spraying, roller coating and the like, so that the antistatic capability of the base material is enhanced, the adhesive force of a resin carbon tape, UV ink and the like is enhanced, the printing is clear, and the probability of being wiped off is reduced.
Description
Technical Field
The invention relates to the technical field of antistatic emulsion, antistatic agent or antistatic composite material, in particular to printable antistatic emulsion with strong adhesive force, a preparation method thereof and a film preparation method.
Background
When products such as glass, various material plates, electronic products and the like are carried or used, the surfaces of the products are easily polluted or scratched by contact, so that the surfaces of the products can be covered by plastic films, and pollution or damage is avoided. The plastic film has a small dielectric constant, is a nonconductor, has high insulating property, and thus generates static electricity. And the electrostatic charge is accumulated on the surface of the plastic film, so that dust is easily adsorbed on the surface, even discharge is caused, and fire is caused.
Therefore, in order to avoid the accumulation of static electricity on the surface of the plastic film, the plastic film is subjected to antistatic treatment to increase the conductivity of the plastic film. It is conventional practice to apply antistatic agents to plastic films, but the current coating techniques have short retention times of antistatic properties, and in particular when the ambient humidity becomes low, the antistatic properties of the material deteriorate, i.e. the conductivity decreases or even fails.
In addition, with the rapid development of the label industry, the application range of the label is wider and wider, and the demand is larger and larger. However, the printable substrate on the market does not have an antistatic function, and during the rapid printing process, the printable substrate rapidly rotates, so that friction static electricity is extremely easy to generate, and the generation of the friction static electricity not only affects the printing effect, but also can bring potential safety hazards to the production due to the accumulation of a large amount of static electricity, such as the damage of equipment and even the generation of fire. Therefore, there is a need for a method of spraying an antistatic agent on the surface of a printable substrate to prevent the accumulation of a large amount of static electricity, and a need for an antistatic agent that adheres well to a printable substrate, such as uniform distribution, low surface resistivity, and strong adhesion. Meanwhile, common printing materials such as resin carbon tapes and UV (ultraviolet) ink used in the printing process can be well attached to the printable substrate, for example: the ink can resist wiping, keep the writing of the label clear and uniform for a long time, and ensure good printing effect.
Therefore, a printable antistatic emulsion with strong surface adhesion on plastic films and other materials and a preparation method thereof need to be developed.
Disclosure of Invention
In order to solve the above technical problems, a first object of the present invention is to provide a printable antistatic emulsion with strong adhesion, which can be coated on a plastic substrate, especially a polyester film (PET), by spraying, rolling, etc., in order to enhance the antistatic ability of the substrate, enhance the adhesion of a resin carbon tape, UV ink, etc., print clearly, and reduce the probability of being wiped off.
In order to achieve the purpose, the scheme adopted by the invention is as follows:
a printable antistatic emulsion with strong adhesion, comprising, by weight: conductive polymer polythiophene and/or single-arm carbon nanotube aqueous solution: 10-50 parts; modified amino resin: 5-30 parts; carbamate modified nano-silica hydrosol: 10-20 parts; surfactant (B): 1-5 parts; water: 20-55 parts.
As a preferable technical scheme, the carbamate modified nano-silica hydrosol is synthesized by the following steps:
the carbamate modified nano-silica hydrosol is prepared from the following components in percentage by weight: the carbamate and the nano silicon dioxide water-based sol are subjected to modification and ester exchange reaction, and low-boiling-point substances are removed under reduced pressure to obtain the polyurethane nano silicon dioxide water-based sol; wherein, the carbamate accounts for 10-50%, preferably 15-30% of the effective components of the nano silicon dioxide.
Further, based on the target carbamate modified nano-silica hydrosol, the modification and ester exchange reaction are carried out, the reaction temperature is controlled to be 18-100 ℃, and the reaction time is 1.5-48 hours;
in a preferred embodiment, the carbamate is a compound in which an amino group is directly bonded to a carbonyl group of a formate, and the compound of the formula RNHCOOR' may be used singly or in combination of two or more. Examples of carbamates include, but are not limited to: urethane dimethacrylate, N-allyl-O-isobutyl thiocarbamate, phenyl carbamate, N-vinyl carbamate.
As a preferable technical scheme, the nano-silica water sol is a commercial product, can be acidic or alkaline, and has a particle size range of 10-80nm, and preferably 20-50nm.
As a preferred technical solution, the conductive polymer polythiophene and/or the single-armed carbon nanotube aqueous solution is used as a conductive substance, wherein the conductive polymer polythiophene is a commercially available product, and is poly (3, 4-ethylenedioxythiophene) and derivatives thereof, and examples include but are not limited to: CLEVIOS by Heraeus TM ICP1010, ICP1020, ICP1050, etc., from P, ORGACON, inc. The main component of the single-arm carbon nanotube aqueous solution is a high-purity single-arm carbon nanotube, or a hydroxylated single-arm carbon nanotube, or a carboxylated single-arm carbon nanotube. The diameter of the single-arm carbon nanotube aqueous solution is 1-2nm, the length is 0.5-30um, and the specific surface area>450m 2 Per g, electrical conductivity>150s/cm. Is a commercial product. The conductive polymer polythiophene and the single-arm carbon nanotube aqueous solution can be used alone as a conductive substance or can be used in combination as a conductive substance.
In a preferred embodiment, the modified amino resin is a melamine resin modified by etherification, and may be used singly or in combination of two or more. Is a commercial product. Examples of modified amino resins include, but are not limited to: CYMEL 325, CYMEL 327, CYMEL 385, CYMEL1158, CYMEL1123, CYMEL XW3106, etc., from Cycote.
In a preferred embodiment, the surfactant is a quaternary ammonium salt cationic surfactant containing a long-chain alkyl group or a nonionic surfactant having a polyoxyethylene segment, and may be a single surfactant or two or more surfactants. The surfactant is used to emulsify the above materials into water. Examples of surfactants include, but are not limited to: octadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, polyoxyethylene (23) lauryl ether, polyoxyethylene tridecyl ether, nonylphenol polyoxyethylene ether, and the like.
The second purpose of the invention is to provide a preparation method of the antistatic emulsion.
As a preferable technical scheme, firstly, the carbamate modified nano-silica hydrosol is synthesized. The preparation method comprises the following steps:
adding dimethyl acrylic carbamate (the modification amount is 30% of the effective component of the nano-silica aqueous sol), dropwise adding acidic nano-silica aqueous sol (the particle size is 30-40 nm) under stirring, controlling the reaction temperature at 100 ℃ for 1.5h, and then carrying out reduced pressure distillation (100 ℃/-0.096 MPa) to remove low-boiling-point substances, thereby obtaining the semitransparent dimethyl acrylic carbamate modified nano-silica aqueous sol.
A printable antistatic emulsion with strong adhesion, comprising, by weight: 30 parts of a conductive polymer, polythiophene, ICP1010 of ORGACON; 15 parts of CYMEL1123;10 parts of the dimethyl acrylic carbamate modified nano silica hydrosol; 5 parts of octadecyl trimethyl ammonium bromide; and (3) emulsifying the materials by using 40 parts of water through homogenizing and emulsifying equipment, and filtering by using a 1-micron filter element to obtain the printable antistatic emulsion with strong adhesive force.
As another preferred technical scheme, firstly, the carbamate modified nano-silica hydrosol is synthesized. The preparation method comprises the following steps:
adding phenyl carbamate (the modification amount is 10 percent of the effective component of the nano-silica aqueous sol) into a four-neck flask with a stirring and refluxing condenser pipe, a thermometer and a dropping funnel, dropwise adding acidic nano-silica aqueous sol (the particle size is 10-20 nm) under the stirring state, controlling the reaction temperature to be 18 ℃, removing low-boiling-point substances by reduced pressure distillation (100 ℃ to 0.096 Mpa) after controlling the reaction time to be 48 hours, and obtaining the semitransparent phenyl carbamate modified nano-silica aqueous sol.
A printable antistatic emulsion with strong adhesion, comprising, by weight: 50 parts of single-arm carbon nanotube aqueous solution, the pipe diameter is 1-2nm, and the length is 5-30um;5 parts of CYMELXW3106;20 parts of the phenyl carbamate modified nano silica hydrosol; 5 parts of polyoxyethylene (23) lauryl ether; and (2) emulsifying the materials by using homogeneous emulsification equipment, and filtering by using a 1um filter element to obtain the printable antistatic emulsion with strong adhesive force.
As another preferred technical scheme, firstly, the carbamate modified nano-silica hydrosol is synthesized.
Adding N-vinyl carbamate (the modification amount is 15% of the effective component of the nano-silica aqueous sol), dropwise adding an alkaline nano-silica aqueous solvent (the particle size is 40-50 nm) under stirring, controlling the reaction temperature to be 35 ℃ and the reaction time to be 40h, and then carrying out reduced pressure distillation (100 ℃/-0.096 MPa) to remove low-boiling-point substances to obtain the semitransparent N-vinyl carbamate modified nano-silica aqueous sol.
A printable antistatic emulsion with strong adhesion, comprising, by weight: 20 parts of a conductive polymer, polythiophene (CLEVIOS from Heraeus) TM P) and 10 parts of single-arm carbon nanotube aqueous solution (the pipe diameter is 1-2nm, and the length is 5-30 um); 30 parts of CYMEL 385;19 parts of the N-vinyl carbamate modified nano silica hydrosol; 1 part of polyoxyethylene (23) lauryl ether; and (2) emulsifying the materials by using homogeneous emulsification equipment, and filtering by using a 1um filter element to obtain the printable antistatic emulsion with strong adhesive force.
As another preferred technical scheme, the method firstly synthesizes the urethane modified nano-silica hydrosol.
Adding dimethyl acrylic carbamate (the modification amount is 50 percent of the effective component of the nano-silica aqueous sol) into a four-neck flask with a stirring and refluxing condenser pipe, a thermometer and a dropping funnel, dropwise adding acidic nano-silica aqueous sol (the particle size is 70-80 nm) under the stirring state, controlling the reaction temperature to be 80 ℃, removing low-boiling-point substances by reduced pressure distillation (100 ℃ to 0.096 Mpa) after controlling the reaction time to be 8h, and obtaining the semitransparent dimethyl acrylic carbamate modified nano-silica aqueous sol.
A printable antistatic emulsion with strong adhesion, comprising, by weight: 10 parts of a conductive polymer, polythiophene, ICP1020 from ORGACON; 22 parts of CYMEL1158;10 parts of the urethane dimethacrylate-modified nano silica hydrosol; 3 parts of octadecyl trimethyl ammonium bromide; and 55 parts of water, emulsifying the materials by using homogenizing and emulsifying equipment, and filtering by using a 1um filter element to obtain the printable antistatic emulsion with strong adhesive force.
It is a third object of the present invention to provide a printable antistatic film having strong adhesion. Including the substrate layer with the antistatic layer of adhesion on at least one surface of substrate layer, the antistatic layer is mixed with water by the printable antistatic emulsion that the aforesaid has strong adhesive force to the coating forms at the preparation of substrate layer.
Further, the strongly adhering printable antistatic emulsion is mixed with water, for example, in a volume ratio of 1.
Further, the substrate layer is a polyester film layer.
The fourth purpose of the invention is to provide a preparation method for coating a printable antistatic film with strong adhesion on line. The steps are as follows:
1) Slicing, melting and extruding the polyester film;
2) Stretching by a biaxial stretching device, and longitudinally stretching;
3) Coating a strongly adhering printable antistatic emulsion according to any of claims 1 to 6 diluted with water, stretching in the transverse direction, heat-setting.
Further, the polyester chip is a polyethylene terephthalate chip.
Further, the preparation method comprises one or more of the following characteristics:
a) The longitudinal stretching ratio is 3.2-3.8;
b) The longitudinal stretching temperature is 100 ℃;
c) The transverse stretching ratio is 3.2-3.8;
d) The transverse stretching temperature is 105 ℃;
e) The temperature in the shaping area is 240-245 DEG C
F) Slicing the polyester film, and adjusting the viscosity to be 0.6-0.8 after melting.
Furthermore, in the preparation method, the thickness of the printable antistatic release layer with strong adhesion after heat setting is 0.05-0.3 μm.
The antistatic emulsion can also be coated on a non-plastic substrate, and the emulsion can also improve the adhesive capacity of the conductive polymer polythiophene and/or the single-arm carbon nanotube aqueous solution and the substrate, uniformly distribute the conductive polymer polythiophene and/or the single-arm carbon nanotube aqueous solution, enhance the adhesive capacity of a printing material, enhance the printing definition and reduce the wiping capacity of the printing material.
The noun interpretation:
the nano silicon dioxide water sol is a commercial product, and the effective percentage content of the nano silicon dioxide is 30-40%.
Compared with the prior art, the invention has the following advantages:
(1) The printable antistatic emulsion with strong adhesive force has the advantages that when the emulsion is formed into a film, the content of Volatile Organic Compounds (VOC) is low, and the production environment is friendly; after being applied to a film base material, the base material has good and stable surface resistance, excellent conductivity, good antistatic property and solvent wiping resistance, such as: is resistant to wiping by alcohol and is suitable for rapid printing by a plurality of printing modes such as bar code printing, UV ink printing and flexographic rapid printing.
(2) The conductive substance added into the printable antistatic emulsion with strong adhesive force is conductive polymer polythiophene and/or single-arm carbon nanotube water solution, both substances have conductive performance, and the antistatic emulsion can have good conductive performance and excellent antistatic effect by adding the conductive substance into the antistatic emulsion;
(3) The urethane modified nano-silica hydrosol can be subjected to polycondensation reaction with modified amino resin to obtain polyurethane, and the obtained polyurethane has good adhesive force to a film base material (PET), and also has good adhesive force to printing materials such as resin carbon ribbons, UV (ultraviolet) ink and the like, so that the probability of wiping off the printing materials is reduced, and the reagent wiping resistance of the printing materials is enhanced;
(4) The urethane modified nano-silica water sol can be fully fused with conductive polymer polythiophene and/or single-arm carbon nanotube aqueous solution through surfactant emulsification, and when the urethane modified nano-silica water sol is applied to film formation, nano-silica can be flatly spread on the surface of a base material, particularly a film base material (PET), so that the conductive polymer polythiophene and/or single-arm carbon nanotube aqueous solution is uniformly attached to the base material, the conductivity is stable, the adhesive force is enhanced, and the solvent wiping resistance is realized.
(5) When the carbamate modified nano-silica hydrosol is applied to film formation, the nano-silica can be flatly spread on the surface of a plastic film substrate (PET) to form a barrier, so that low oligomer of the plastic substrate can be effectively prevented from being separated out during high-temperature baking, the transparency of the plastic substrate in a high-temperature environment is not influenced, or the influence of the plastic substrate on other film-covered accessories is reduced.
(6) The antistatic emulsion is water-soluble, can be mixed with water to prepare a printable antistatic film with strong adhesive force, can be coated on line or off line relative to the current solvent-based antistatic film, is environment-friendly and applicable to various coating modes, and the flash-off phenomenon caused by volatilization of an organic solvent can not occur when the temperature rises in the preparation process.
(7) The invention adopts an online coating method to coat the antistatic emulsion to prepare the antistatic film, avoids the processes of repeated rolling, uncoiling and coating in the offline coating process and saves the production cost. Meanwhile, the antistatic agent is a water-soluble emulsion, so that the flash-burning phenomenon of a solvent type emulsion in a high-temperature coating process is avoided, and the production is safe. Meanwhile, the emulsion has strong adhesive force, stable antistatic performance and solvent wiping resistance, and can adapt to various printing modes for rapid printing, so that the antistatic film has high market application value.
Detailed Description
The present invention is further illustrated by the following specific examples, which are presently preferred embodiments of the invention, but are not intended to limit the scope of the invention, as claimed.
Example 1:
a printable antistatic emulsion with strong adhesion, comprising, by weight: 30 parts of a conductive polymer, polythiophene, ICP1010 from ORGACON; 15 parts of CYMEL1123;10 parts of urethane dimethacrylate modified nano silica hydrosol; 5 parts of octadecyl trimethyl ammonium bromide; 40 parts of water.
The preparation method of the urethane dimethacrylate modified nano-silica hydrosol comprises the following steps:
adding dimethyl acrylic carbamate (the modification amount is 30 percent of the effective component of the nano-silica aqueous sol) into a four-neck flask with a stirring and refluxing condenser pipe, a thermometer and a dropping funnel, dropwise adding acidic nano-silica aqueous sol (the particle size is 30-40 nm) under the stirring state, controlling the reaction temperature to be 100 ℃, removing low-boiling-point substances by reduced pressure distillation (100 ℃ to 0.096 Mpa) after controlling the reaction time to be 1.5h, and obtaining the semitransparent dimethyl acrylic carbamate modified nano-silica aqueous sol.
The preparation method of the printable antistatic emulsion with strong adhesion comprises the following steps:
1) According to the formula, 30 parts of conductive polymer polythiophene, ICP1010 of ORGACON company is weighed according to the parts by weight; 15 parts of CYMEL1123;10 parts of urethane dimethacrylate modified nano-silica hydrosol; 5 parts of octadecyl trimethyl ammonium bromide; 40 parts of water;
2) 30 parts of the conductive polymer polythiophene obtained in the step 1), ICP1010 of ORGACON company; 15 parts of CYMEL1123;10 parts of urethane dimethacrylate modified nano-silica hydrosol; 5 parts of octadecyl trimethyl ammonium bromide; putting 40 parts of water into homogenizing and emulsifying equipment, and homogenizing and emulsifying to obtain a primary emulsion;
3) Filtering the primary emulsion in the step 2) by using a 1um filter element to obtain the printable antistatic emulsion with strong adhesion.
Example 2:
a printable antistatic emulsion with strong adhesion, comprising, by weight: 50 parts of single-arm carbon nanotube aqueous solution, the pipe diameter is 1-2nm, and the length is 5-30um;5 parts of CYMELXW3106;20 parts of the phenyl carbamate modified nano silica hydrosol; 5 parts of polyoxyethylene (23) lauryl ether; 20 parts of water.
The preparation method of the phenyl carbamate modified nano-silica hydrosol comprises the following steps:
adding phenyl carbamate (the modification amount is 10 percent of the effective component of the nano-silica aqueous sol) into a four-neck flask with a stirring and refluxing condenser pipe, a thermometer and a dropping funnel, dropwise adding acidic nano-silica aqueous sol (the particle size is 10-20 nm) under the stirring state, controlling the reaction temperature to be 18 ℃, removing low-boiling-point substances by reduced pressure distillation (100 ℃ to 0.096 Mpa) after controlling the reaction time to be 48 hours, and obtaining the semitransparent phenyl carbamate modified nano-silica aqueous sol.
The preparation method of the printable antistatic emulsion with strong adhesion is the same as that of the example 1, except that substances are added in the corresponding steps, and the substances are added according to the formula in the example 2.
Example 3:
a printable antistatic emulsion with strong adhesion, comprising, by weight: 20 parts of a conductive polymer, polythiophene, CLEVOS from Heraeus TM P and 10 parts of single-arm carbon nano tube aqueous solution, wherein the tube diameter is 1-2nm, and the length is 5-30um;30 parts of CYMEL 385;19 parts of N-vinyl carbamate-modified nano silica hydrosol; 1 part of polyoxyethylene (23) lauryl ether; 20 parts of water.
The preparation method of the N-vinyl carbamate modified nano-silica hydrosol comprises the following steps:
adding N-vinyl carbamate (the modification amount is 15 percent of the effective component of the nano-silica aqueous sol) into a four-neck flask with a stirring and refluxing condenser pipe, a thermometer and a dropping funnel, dropwise adding an alkaline nano-silica aqueous solvent (the particle size is 40-50 nm) under the stirring state, controlling the reaction temperature to be 35 ℃, removing low-boiling-point substances by reduced pressure distillation (100 ℃ to 0.096 Mpa) after controlling the reaction time to be 40h, and obtaining the semitransparent N-vinyl carbamate modified nano-silica aqueous sol.
The preparation method of the printable antistatic emulsion with strong adhesion is the same as that of the example 1, except that substances are added in the corresponding steps, and the substances are added according to the formula in the example 3.
Example 4:
a printable antistatic emulsion with strong adhesion, comprising, by weight: 10 parts of a conductive polymer, polythiophene, ICP1020 from ORGACON; 22 parts of CYMEL1158;10 parts of urethane dimethacrylate-modified nano silica hydrosol; 3 parts of octadecyl trimethyl ammonium bromide; 55 parts of water.
The preparation method of the nano-silica water sol modified by the dimethyl acrylic carbamate comprises the following steps:
adding dimethyl acrylic carbamate (the modification amount is 50 percent of the effective component of the nano silicon dioxide aqueous sol) into a four-neck flask with a stirring and refluxing condenser pipe, a thermometer and a dropping funnel, dropwise adding acidic nano silicon dioxide aqueous sol (the particle size is 70-80 nm) under the stirring state, controlling the reaction temperature to be 80 ℃, removing low-boiling-point substances by reduced pressure distillation (100 ℃ to 0.096 Mpa) after controlling the reaction time to be 8h, and obtaining the semitransparent dimethyl acrylic carbamate modified nano silicon dioxide aqueous sol.
The preparation method of the printable antistatic emulsion with strong adhesion is the same as that of the example 1, except that substances are added in the corresponding steps, and the substances are added according to the formula in the example 4.
Comparative example 1:
comparative example 1 is simply ICP1010 of the electrically conducting polymer polythiophene ORGACON company.
Comparative example 2:
comparative example 2 is a formulation of patent ZL 201811640617.4, which is a coatable silicon antistatic emulsion with good stability, and the coatable silicon antistatic emulsion comprises the following components in parts by weight: 5-20 parts of epoxy-containing linear silane coupling agent, 0.05-1 part of phenyl hydroxyl reticular silicon resin, 5-50 parts of conductive polymer polythiophene, 0.5-20 parts of single-arm carbon nanotube aqueous solution, 1-5 parts of surfactant and 30-55 parts of water, and the structural formula of the phenyl hydroxyl reticular silicon resin and the structural formula of the epoxy-containing linear silane coupling agent are specifically limited. After the silicon-coatable anti-static emulsion with good stability is applied to a film substrate, the film substrate has good and stable anti-static performance and obtains a release function due to the addition of the epoxy-containing linear silane coupling agent, the phenyl hydroxyl reticular silicon resin, the conductive polymer polythiophene and the single-arm carbon nanotube aqueous solution, for example: the peel force, the 70 ℃ aging peel force, the residual adhesive force and the like are all superior to those of the comparative example.
The comparative example 2 specifically adopts a silicon-coatable antistatic emulsion with good stability, which comprises, by weight, 13.2 parts of an epoxy-containing linear silane coupling agent, 0.8 part of phenyl hydroxyl network silicone resin, 20 parts of a conductive polymer polythiophene, 10 parts of a single-arm carbon nanotube aqueous solution, 1 part of a surfactant and 55 parts of water. The kinds and amounts of the conductive materials (conductive polymer polythiophene and aqueous solution of single-walled carbon nanotubes) and the surfactant in the above formulation were the same as those in example 3.
The structural formula of the epoxy-containing linear silane coupling agent is as follows:
the structural formula of the phenyl hydroxyl reticular silicon resin is as follows:
wherein, R ' and R ' are same or different straight chain or branched chain aryl with 6-20 carbon atoms or aralkyl with 7-20 carbon atoms, and R ' is hydroxyl;
the preparation method of the phenyl hydroxyl network silicon resin comprises the steps of respectively adding 200g of distilled water and 1.2g of hydrochloric acid with the concentration of 1mol/L into a four-neck flask with a stirring and refluxing condenser pipe, a thermometer and a dropping funnel, stirring and mixing, then dropwise adding 339.51g of phenethyl (trimethoxy) silane and 272g of diphenyl diethoxy silane, then adding 100g of absolute ethyl alcohol, 1g of 37% hydrochloric acid and 380g of isohexadecane extractant, carrying out cohydrolysis-polycondensation, controlling the reaction temperature to be 90 ℃, standing and layering after controlling the reaction time to be 1h, removing a water phase, washing the organic phase to be neutral by using distilled water, filtering by using a filter membrane with the aperture of 0.5 mu m, then removing a neutral organic phase by reduced pressure distillation (110-130 ℃ to 0.096 Mpa), and obtaining the clear and transparent phenyl hydroxyl network structure silicon resin.
Preparation method and performance test of antistatic films of examples 1 to 4, comparative example 1 and comparative example 2:
(1) The preparation method of the antistatic film comprises the following steps:
1. base material: 25um plastic film base material (PET) film
2. Antistatic coating liquid: the antistatic emulsions of example 1, example 2, example 3, example 4, comparative example 1 and comparative example 2 described above were diluted with distilled water according to 1.
3. A Meyer bar: 5# standardized coating rod
4. And (3) a curing process: drying and curing at 120 deg.C for 3min
The printable antistatic films with strong adhesion in examples 1-4 were coated by the above-described off-line manner.
If the in-line coating is performed, a method of preparing a printable antistatic film having strong adhesion is as follows:
adjusting the intrinsic viscosity of the polyester chips to be 0.6-0.8, performing melt extrusion through an extruder, and then stretching through a biaxial stretching (BOPET) device, wherein the longitudinal stretching ratio is 3.2-3.8, and the longitudinal stretching temperature is 100 ℃; before transverse stretching, coating printable antistatic emulsion, wherein the coating weight is controlled to control the thickness of a dry coating to be 0.05-0.3um, the transverse stretching ratio is 3.2-3.8, and the transverse stretching temperature is 105 ℃; the temperature in the setting area is 240-245 ℃, and finally the printable antistatic polyester film is obtained.
The printable antistatic films with strong adhesion of examples 5 to 8 were coated by the in-line manner as described above.
(2) And (4) performance testing:
appearance: visual inspection, and testing for change in haze Δ H (ASTM D1003);
surface resistivity: the surface resistivity of the release surface was measured using a static tester SIMCO ST-4.
Solvent wiping resistance: the isopropanol wets the dust-free cloth, the pressure is 880kg/m < 2 >, and the surface of the sample is wiped with 10cycles. After wiping, after being placed at room temperature for 1min, the surface resistivity of the off-surface is tested by adopting a static tester SIMCO ST-4, and the data change before and after wiping is compared.
Printing appearance: and (4) visually observing whether the pattern is clear or not and enabling the color to be uniform.
Printing adhesion force: and (3) adhering the printed patterns by using a 3M 810 adhesive tape, slightly rubbing 5 fingers down, respectively carrying out quick tearing and slow tearing, and observing the definition and the color change of the printed patterns after tearing.
Alcohol wiping resistance of printing: testing with alcohol abrasion resistance instrument at pressure of 1kg/m 2 The run was 2.45cm, the speed was 60cycles/min, 100cycles were tested and the printed pattern was observed for clarity and color change.
And (4) performance testing:
thickness: DIN 53370
Tensile strength: DIN 53455
Elongation at break: DIN 53455
Thermal shrinkage rate: BMS TT 11
Haze: ASTM D1003
(3) And (3) testing results:
from the above test results, it can be seen that the surface resistivity and the surface resistivity after isopropyl alcohol wiping in examples 1 to 4 and comparative examples 1 and 2 illustrate the antistatic performance of the antistatic emulsion, and the lower the value, the better the antistatic (conductive) effect, wherein the surface resistivity and the surface resistivity after isopropyl alcohol wiping in examples 1 to 4 are both less than that in comparative example 1, which illustrates that the antistatic performance of the emulsion is better than that of polythiophene alone, and the conductive property (conductive polymer polythiophene and single-arm carbon nanotube aqueous solution) and the kind and amount of surfactant which are the same as those in example 3 are also added in comparative example 2, which also has more excellent antistatic performance but is not resistant to solvent wiping.
Further, from the appearance of bar code printing, UV ink printing and flexographic quick printing of the substrate, the antistatic emulsions of examples 1-4 were clear and uniform, and the antistatic emulsion of comparative example 1 was not uniform, and from the test of alcohol wiping resistance, the antistatic emulsions of examples 1-4 showed little or no peeling after alcohol wiping, while the antistatic emulsions of comparative example 1 showed 100% peeling after all three printing modes. Compared with comparative example 2, the adhesion of the three printing modes of the formula is weaker than that of examples 1-4, and the alcohol wiping resistance is also 100% of shedding resistance. The printable antistatic emulsion with strong adhesion has good adhesion to a base material, particularly a plastic film (PET) base material, enhances the adhesion to a printing material (a resin carbon ribbon, UV ink and the like), has good conductivity, and is an antistatic emulsion with excellent performance.
(4) Examples 5-8 formulations and preparation Process parameters
Example 5
Adjusting the intrinsic viscosity of the polyester chip to be 0.6, performing melt extrusion through an extruder, and then stretching through a biaxial stretching (BOPET) device, wherein the longitudinal stretching ratio is 3.5, and the longitudinal stretching temperature is 100 ℃; before transverse stretching, a printable antistatic emulsion is coated, the coating weight is controlled to control the thickness of a dry coating to be 0.05um, the transverse stretching ratio is 3.5, and the transverse stretching temperature is 105 ℃; the temperature in the setting zone was 243 ℃, and finally a printable antistatic polyester film was obtained. Examples 5-8 antistatic films were prepared according to the following table:
(5) The experimental test results are as follows:
examples 5-8 and comparative example 2, both showed better surface resistance performance, but the surface resistance after solvent wiping of comparative example 2 decreased by 4 grades, while examples 5-8 decreased by only about 1 grade, i.e., examples 5-8 had excellent solvent wiping resistance.
The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and equivalents thereof, which are intended to be included in the scope of the present invention.
Claims (12)
1. A printable antistatic emulsion with strong adhesion is characterized in that: the antistatic emulsion comprises the following components in parts by weight: conductive polymer polythiophene and/or single-arm carbon nanotube aqueous solution: 10-50 parts; modified amino resin: 5-30 parts; carbamate modified nano-silica hydrosol: 10-20 parts; surfactant (B): 1-5 parts; water: 20-55 parts.
2. Printable antistatic emulsion with strong adhesion according to claim 1, characterized in that: the carbamate modified nano-silica hydrosol is prepared from the following components in percentage by weight: the carbamate and the nano silicon dioxide water sol are subjected to modification and ester exchange reaction, and low-boiling-point substances are removed under reduced pressure to obtain the product; wherein, the carbamate accounts for 10 to 50 parts of the effective component of the nano silicon dioxide.
3. Printable antistatic emulsion with strong adhesion according to claim 2, characterized in that: the modification and ester exchange reaction is carried out at 18-100 deg.C for 1.5-48 hr.
4. Printable antistatic emulsion with strong adhesion according to claim 2, characterized in that: the carbamate is a compound with amino directly connected with carbonyl of the formate, and the general formula of the carbamate is one or more than one of RNHCOOR' compounds.
5. Printable antistatic emulsion with strong adhesion according to claim 1, characterized in that: including any one or more of the following i) -iii):
i) the electrically conductive polymer polythiophene is poly 3, 4-ethylenedioxythiophene and derivatives thereof;
ii) the single-arm carbon nanotube aqueous solution is one or more of single-arm carbon nanotubes, hydroxylated single-arm carbon nanotubes or carboxylated single-arm carbon nanotubes, and the single-arm carbon nanotube aqueous solution has the tube diameter of 1-2nm, the length of 0.5-30um, and the specific surface area>450m 2 Per g, electrical conductivity>150s/cm；
Iii) said nanosilica hydrosol, either acidic or basic, having a particle size in the range of 10-80nm.
6. Printable antistatic emulsion with strong adhesion according to claim 1, characterized in that: the modified amino resin is one or more of melamine resin modified by etherification.
7. The method for preparing a printable antistatic emulsion with strong adhesion according to any one of claims 1 to 4, characterized in that: the method comprises the following steps:
1) Weighing conductive polymer polythiophene and/or single-arm carbon nanotube aqueous solution, modified amino resin, carbamate modified nano-silica hydrosol, surfactant and water according to the formula in parts by weight;
2) Putting the conductive polymer polythiophene and/or single-arm carbon nanotube aqueous solution, the modified amino resin, the carbamate modified nano-silica water sol, the surfactant and the water in the step 1) into homogenizing and emulsifying equipment, and homogenizing and emulsifying to obtain a primary emulsion;
3) Filtering the primary emulsion in the step 2) by using a 1um filter element to obtain the printable antistatic emulsion with strong adhesion.
8. A printable antistatic film with strong adhesion characterized by: including the substrate layer and the antistatic layer of adhesion on at least one surface of substrate layer, its characterized in that: the antistatic layer is prepared by mixing the printable antistatic emulsion with strong adhesion of any one of claims 1 to 6 with water and coating the mixture on a substrate layer.
9. The printable antistatic film with strong adhesion according to claim 8, wherein: the substrate layer is a polyester film layer.
10. The printable antistatic film with strong adhesion according to claim 8, wherein: the printable antistatic emulsion with strong adhesion is mixed with water.
11. A preparation method for online coating a printable antistatic film with strong adhesion is characterized in that: the steps are as follows:
1) Slicing, melting and extruding the polyester film;
2) Stretching by a biaxial stretching device, and longitudinally stretching;
3) Coating a printable antistatic emulsion with strong adhesion according to any one of claims 1 to 6 diluted with water, stretching in transverse direction, heat-setting.
12. The method of claim 11, comprising one or more of the features a) -F):
a) The longitudinal stretching ratio is 3.2-3.8;
b) The longitudinal stretching temperature is 100 ℃;
c) The transverse stretching ratio is 3.2-3.8;
d) The transverse stretching temperature is 105 ℃;
e) The temperature in the shaping area is 240-245 DEG C
F) Slicing the polyester film, and adjusting the viscosity to be 0.6-0.8 after melting.
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