CN115975497B - Printable antistatic emulsion with strong adhesive force, preparation method, antistatic film and film preparation method - Google Patents
Printable antistatic emulsion with strong adhesive force, preparation method, antistatic film and film preparation method Download PDFInfo
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 32
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 32
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- 229920001940 conductive polymer Polymers 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
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- 239000000377 silicon dioxide Substances 0.000 claims description 42
- 239000000126 substance Substances 0.000 claims description 22
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 21
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- 239000002904 solvent Substances 0.000 description 9
- VKUKIBUYTWYNPL-UHFFFAOYSA-N carbamic acid 3-methylbut-2-enoic acid Chemical compound C(N)(O)=O.CC(=CC(=O)O)C VKUKIBUYTWYNPL-UHFFFAOYSA-N 0.000 description 8
- 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 8
- BSCCSDNZEIHXOK-UHFFFAOYSA-N phenyl carbamate Chemical compound NC(=O)OC1=CC=CC=C1 BSCCSDNZEIHXOK-UHFFFAOYSA-N 0.000 description 8
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- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 7
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- 239000010703 silicon Substances 0.000 description 6
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 5
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- BANXPJUEBPWEOT-UHFFFAOYSA-N 2-methyl-Pentadecane Chemical compound CCCCCCCCCCCCCC(C)C BANXPJUEBPWEOT-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
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- 229940043268 2,2,4,4,6,8,8-heptamethylnonane Drugs 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
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- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- 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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- PEOHLVWFSVQRLK-UHFFFAOYSA-N ethenylcarbamic acid Chemical compound OC(=O)NC=C PEOHLVWFSVQRLK-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
The invention discloses printable antistatic emulsion with strong adhesive force, which comprises the following components in parts by weight: aqueous solutions of conductive polymer polythiophene and/or single-arm carbon nanotubes: 10-50 parts of a lubricant; modified amino resin: 5-30 parts; urethane-modified nanosilica aqueous sol: 10-20 parts of a lubricant; and (2) a surfactant: 1-5 parts; water: 20-55 parts. The antistatic emulsion can be coated on plastic substrates, especially polyester films (PET) by spraying, roller coating and other coating modes, and aims to enhance the antistatic performance of the substrates, enhance the adhesive force of resin carbon strips, UV ink and the like, print clearly and reduce the wiping probability.
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
In the process of carrying or using products such as glass, plates made of various materials, electronic products and the like, the surfaces are easily polluted or scratched by contact, so that the surfaces are covered by plastic films, and pollution or injury is avoided. Since the plastic film has a small dielectric constant, belongs to a nonconductor, and has high insulating property, static electricity is generated. The static charges are 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, so that the conductivity of the plastic film is improved. The conventional operation is to coat an antistatic agent on a plastic film, but the current coating technology has a short retention time of antistatic properties, and particularly when the ambient humidity becomes low, the antistatic properties of the material are deteriorated, i.e., the conductivity is lowered or even fails.
In addition, with the rapid development of the label industry, the application range of labels is wider and wider, and the demand is larger and larger. However, the printable substrate currently on the market does not have an antistatic function, and in the rapid printing process, the printable substrate rapidly rotates, friction static electricity is extremely easy to generate, the generation of the friction static electricity not only can affect the printing effect, but also can bring potential safety hazards to production, such as equipment damage and even fire disaster, due to accumulation of a large amount of static electricity. Therefore, there is a need for a method of spraying an antistatic agent on the surface of a printable substrate to prevent accumulation of a large amount of static electricity, and for an antistatic agent to adhere well to a printable substrate, for example, uniformly distributed, with a low surface resistivity, and with a high adhesion. Meanwhile, common printing materials such as resin carbon tape, UV ink and the like used in the printing process can be well adhered to the printable substrate, for example: can be wiped resistant, can keep the writing of the label clear and uniform for a long time, and can ensure good printing effect.
Therefore, there is a need to develop a printable antistatic emulsion with strong adhesion on the surface of materials such as plastic films and a preparation method thereof.
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, roll coating, etc., in order to enhance the antistatic property 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 above purpose, the present invention adopts the following scheme:
a printable antistatic emulsion having strong adhesion, the antistatic emulsion comprising, in parts by weight: aqueous solutions of conductive polymer polythiophene and/or single-arm carbon nanotubes: 10-50 parts of a lubricant; modified amino resin: 5-30 parts; urethane-modified nanosilica aqueous sol: 10-20 parts of a lubricant; and (2) a surfactant: 1-5 parts; water: 20-55 parts.
As a preferred technical scheme, the carbamate modified nano silica aqueous sol is synthesized by the following steps:
the carbamate modified nano silicon dioxide aqueous sol is as follows: carrying out modification and transesterification on carbamate and nano silicon dioxide aqueous sol, and removing low-boiling-point substances under reduced pressure to obtain the modified nano silicon dioxide aqueous sol; wherein, the carbamate accounts for 10-50%, preferably 15-30% of the active ingredient of the nano silicon dioxide.
Further, the modification and transesterification reaction is carried out based on the target carbamate modified nano silicon dioxide aqueous sol, the reaction temperature is controlled to be 18-100 ℃, and the reaction time is controlled to be 1.5-48 hours;
as a preferable technical scheme, the carbamate is a compound in which amino groups are directly connected with carbonyl groups of the carbamate, and the general formula is RNHCOOR', and the compound can be single or mixed and used. Examples of carbamates include, but are not limited to: urethane dimethacrylate, N-allyl-O-isobutyl thiocarbamate, phenylcarbamate, N-vinylcarbamate.
As a preferable technical scheme, the nano silicon dioxide aqueous sol is a commercial product and can be acidic or alkaline, and the particle size range is 10-80nm, and the preferred particle size range is 20-50nm.
As a preferred technical solution, the conductive polymer polythiophene and/or the single-arm 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-vinyl dioxythiophene) and derivatives thereof, and examples include but are not limited to: CLEVIOS of Heraeus company TM ICP1010, ICP1020, ICP1050, etc. from P, ORGACON. 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 /g, conductivity>150s/cm. Is a commercial product. The above-mentioned aqueous solutions of the conductive polymer polythiophene and the single-arm carbon nanotube may be used alone as the conductive substance, or may be mixed and used as the conductive substance.
As a preferable technical scheme, the modified amino resin is melamine resin modified by etherification, and can be single or mixed by two or more of the modified amino resins. 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 cytet corporation.
As a preferable technical scheme, the surfactant refers to quaternary ammonium salt cationic surfactant containing long-chain alkyl or nonionic surfactant with polyoxyethylene chain segments, and the surfactant can be single surfactant or two or more surfactants. Surfactants are 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, polyoxyethylene nonylphenol ether, etc.
The second object of the invention is to provide a preparation method of the antistatic emulsion.
As a preferred technical solution, a urethane-modified nano silica aqueous sol is first synthesized. The preparation method comprises the following steps:
adding the dimethyl acrylic acid 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, reflux condenser, a thermometer and a dropping funnel, dropwise adding the acid nano silica aqueous sol (the particle size is 30-40 nm) in a stirring state, controlling the reaction temperature to be 100 ℃, controlling the reaction time to be 1.5h, and then removing low-boiling substances by vacuum distillation (100 ℃/-0.096 Mpa) to obtain the semitransparent dimethyl acrylic acid carbamate modified nano silica aqueous sol.
A printable antistatic emulsion having strong adhesion, the antistatic emulsion comprising, in parts by weight: 30 parts of a conductive polymer polythiophene, ICP1010 from ORGACON; 15 parts of CYMEL1123;10 parts of the above-mentioned urethane dimethacrylate modified nano silica aqueous sol; 5 parts of octadecyl trimethyl ammonium bromide; 40 parts of water, emulsifying the materials by using a homogenizing emulsifying device, and filtering by using a 1um filter element to obtain the printable antistatic emulsion with strong adhesive force.
As another preferred technical scheme, a urethane-modified nano silica aqueous sol is first synthesized. The preparation method comprises the following steps:
adding phenylcarbamate (the modification amount is 10% of the effective component of the nano silica aqueous sol) into a four-neck flask with a stirring, reflux condenser, a thermometer and a dropping funnel, dropwise adding acidic nano silica aqueous sol (the particle size is 10-20 nm) in a stirring state, controlling the reaction temperature to 18 ℃, controlling the reaction time to 48 hours, and then removing low-boiling substances by reduced pressure distillation (100 ℃/-0.096 Mpa) to obtain the semitransparent phenylcarbamate modified nano silica aqueous sol.
A printable antistatic emulsion having strong adhesion, the antistatic emulsion comprising, in parts by weight: 50 parts of single-arm carbon nanotube aqueous solution, wherein the pipe diameter is 1-2nm, and the length is 5-30um;5 parts of CYMELXW3106;20 parts of the phenylcarbamate modified nano silica aqueous sol; 5 parts of polyoxyethylene (23) lauryl ether; 20 parts of water, emulsifying the materials by using a homogenizing emulsifying device, and filtering by using a 1um filter element to obtain the printable antistatic emulsion with strong adhesive force.
As another preferred technical scheme, a urethane-modified nano silica aqueous sol is first synthesized.
Adding N-vinyl carbamate (the modified amount is 15 percent of the effective component of the nano silica aqueous sol) into a four-neck flask with a stirring, reflux condenser, a thermometer and a dropping funnel, dropwise adding an alkaline nano silica aqueous solvent (the particle size is 40-50 nm) in a stirring state, controlling the reaction temperature to be 35 ℃, controlling the reaction time to be 40 hours, and then removing low-boiling substances by vacuum distillation (100 ℃/-0.096 Mpa) to obtain the semitransparent N-vinyl carbamate modified nano silica aqueous sol.
A printable antistatic emulsion having strong adhesion, the antistatic emulsion comprising, in parts by weight: 20 parts of a conductive polymer polythiophene (CLEVIOS from Heraeus Co.) TM P) and 10 parts of a single-arm carbon nanotube aqueous solution (with the pipe diameter of 1-2nm and the length of 5-30 um); 30 parts of CYMEL 385;19 parts of the N-vinyl carbamate modified nano silica aqueous sol; 1 part of polyoxyethylene (23) lauryl ether; 20 parts of water, emulsifying the materials by using a homogenizing emulsifying device, and filtering by using a 1um filter element to obtain the printable antistatic emulsion with strong adhesive force.
As another preferred technical scheme, a urethane-modified nano silica aqueous sol is first synthesized.
Adding dimethyl acrylic acid carbamate (the modification amount is 50% of the effective component of the nano silica aqueous sol) into a four-neck flask with a stirring, reflux condenser, a thermometer and a dropping funnel, dropwise adding acid nano silica aqueous sol (the particle size is 70-80 nm) in a stirring state, controlling the reaction temperature to be 80 ℃, controlling the reaction time to be 8 hours, and then removing low-boiling substances by reduced pressure distillation (100 ℃/-0.096 Mpa) to obtain semitransparent dimethyl acrylic acid carbamate modified nano silica aqueous sol.
A printable antistatic emulsion having strong adhesion, the antistatic emulsion comprising, in parts by weight: 10 parts of a conductive polymer polythiophene, ICP1020 from ORGACON; 22 parts of CYMEL1158;10 parts of the above-mentioned urethane dimethacrylate modified nano silica aqueous sol; 3 parts of octadecyl trimethyl ammonium bromide; 55 parts of water, emulsifying the materials by using a homogenizing emulsifying device, and filtering by using a 1um filter element to obtain the printable antistatic emulsion with strong adhesive force.
A third object of the present invention is to provide a printable antistatic film with strong adhesion. The anti-static coating comprises a substrate layer and an anti-static layer adhered on at least one surface of the substrate layer, wherein the anti-static layer is prepared by mixing the printable anti-static emulsion with strong adhesive force with water and coating the mixture on the substrate layer.
Further, the high adhesion printable antistatic emulsion is mixed with water, for example, in a 1:3 volume ratio.
Further, the substrate layer is a polyester film layer.
A fourth object of the present invention is to provide a method for preparing an on-line coating printable antistatic film having strong adhesion. The method comprises the following steps:
1) Slicing, melting and extruding the polyester film;
2) Stretching by a biaxial stretching device, and longitudinally stretching;
3) The high adhesion printable antistatic emulsion of any one of claims 1-6 diluted with water for coating, transversely stretched, heat set.
Further, the polyester chips are polyethylene terephthalate chips.
Further, the preparation method comprises one or more of the characteristics of 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) The polyester film is sliced, and after melting, the viscosity is regulated to be 0.6-0.8.
Further, in the production 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 be coated on a non-plastic substrate, and can also improve the adhesion capability of the conductive polymer polythiophene and/or the single-arm carbon nanotube aqueous solution to the substrate, uniformly distribute the conductive polymer polythiophene and/or the single-arm carbon nanotube aqueous solution, enhance the adhesion capability of a printing material, enhance the printing definition and reduce the wiping capability of the printing material.
Noun interpretation:
the nano silicon dioxide aqueous sol is a commercial product, and the effective percentage 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 the emulsion has low content of Volatile Organic Compounds (VOC) when forming a film, and the production environment is friendly; after being applied to a film substrate, the substrate has good and stable surface resistance, excellent conductivity, good antistatic performance and solvent wiping resistance, for example: is resistant to alcohol wiping and is suitable for rapid printing in a variety of printing modes (e.g., bar code printing, UV ink printing, and flexographic rapid printing).
(2) The conductive substance is conductive polymer polythiophene and/or single-arm carbon nanotube aqueous solution, and the conductive substance and the single-arm carbon nanotube aqueous solution have conductive properties, so that the anti-static emulsion has good conductive properties and excellent anti-static effect after the conductive substance is added into the anti-static emulsion;
(3) The urethane modified nano silicon dioxide aqueous sol can be subjected to polycondensation reaction with modified amino resin to obtain polyurethane, and the obtained polyurethane has good adhesive force to a film substrate (PET), and also has good adhesive force to printing materials such as resin carbon strips, UV ink and the like, so that the wiping probability of the printing materials is reduced, and the reagent wiping resistance of the printing materials is enhanced;
(4) The urethane modified nano silicon dioxide aqueous sol can be fully fused with the conductive polymer polythiophene and/or the single-arm carbon nano tube aqueous solution through surfactant emulsification, and when the film is formed, the nano silicon dioxide can be flatly spread on the surface of a substrate, especially a film substrate (PET), so that the conductive polymer polythiophene and/or the single-arm carbon nano tube aqueous solution is uniformly attached to the substrate, the conductive performance is stable, and the adhesive force is enhanced, thereby being resistant to solvent wiping.
(5) When the carbamate modified nano silicon dioxide aqueous sol is applied to film formation, the nano silicon dioxide can be flatly spread on the surface of a plastic film substrate (PET) to form a layer of barrier, so that the precipitation of oligomers of the plastic substrate during high-temperature baking can be effectively prevented, the transparency of the plastic substrate in a high-temperature environment is not affected, 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 existing solvent type antistatic film, does not cause flash burning phenomenon caused by volatilization of an organic solvent when the temperature is increased in the preparation process, is environment-friendly, and is suitable for various coating modes.
(7) The invention adopts an online coating method to coat the antistatic emulsion to prepare the antistatic film, avoids the procedures of repeated winding, unwinding and coating in the offline coating process, and saves the production cost. Meanwhile, the antistatic agent is water-soluble emulsion, so that the flash-fire phenomenon of the solvent-based emulsion in the 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 be suitable for rapid printing in various printing modes, so that the antistatic film has higher market application value.
Detailed Description
The present invention will be further described by the following specific embodiments, which are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the following embodiments, and thus the scope of the present invention is not limited to the above.
Example 1:
a printable antistatic emulsion having strong adhesion, the antistatic emulsion comprising, in parts by weight: 30 parts of a conductive polymer polythiophene, ICP1010 from ORGACON; 15 parts of CYMEL1123;10 parts of a urethane dimethacrylate modified nano silica aqueous sol; 5 parts of octadecyl trimethyl ammonium bromide; 40 parts of water.
The preparation method of the urethane dimethacrylate modified nano silica aqueous sol comprises the following steps:
adding the dimethyl acrylic acid carbamate (the modification amount is 30% of the effective component of the nano silica aqueous sol) into a four-neck flask with a stirring, reflux condenser, a thermometer and a dropping funnel, dropwise adding the acid nano silica aqueous sol (the particle size is 30-40 nm) in a stirring state, controlling the reaction temperature to be 100 ℃, controlling the reaction time to be 1.5h, and then removing low-boiling substances by vacuum distillation (100 ℃/-0.096 Mpa) to obtain the semitransparent dimethyl acrylic acid carbamate modified nano silica aqueous sol.
The preparation method of the printable antistatic emulsion with strong adhesive force comprises the following steps:
1) According to the formula, weighing 30 parts of conductive polymer polythiophene, ICP1010 of ORGACON company according to parts by weight; 15 parts of CYMEL1123;10 parts of a urethane dimethacrylate modified nano silica aqueous sol; 5 parts of octadecyl trimethyl ammonium bromide; 40 parts of water;
2) 30 parts of the conductive polymer polythiophene of step 1) above, ICP1010 from ORGACON; 15 parts of CYMEL1123;10 parts of a urethane dimethacrylate modified nano silica aqueous sol; 5 parts of octadecyl trimethyl ammonium bromide; 40 parts of water is put into homogenizing and emulsifying equipment to be homogenized and emulsified, so as to obtain primary emulsion;
3) And (3) filtering the primary emulsion obtained in the step (2) by using a 1um filter element to obtain the printable antistatic emulsion with strong adhesive force.
Example 2:
a printable antistatic emulsion having strong adhesion, the antistatic emulsion comprising, in parts by weight: 50 parts of single-arm carbon nanotube aqueous solution, wherein the pipe diameter is 1-2nm, and the length is 5-30um;5 parts of CYMELXW3106;20 parts of the phenylcarbamate modified nano silica aqueous sol; 5 parts of polyoxyethylene (23) lauryl ether; 20 parts of water.
The preparation method of the nano silicon dioxide aqueous sol modified by the phenyl carbamate comprises the following steps:
adding phenylcarbamate (the modification amount is 10% of the effective component of the nano silica aqueous sol) into a four-neck flask with a stirring, reflux condenser, a thermometer and a dropping funnel, dropwise adding acidic nano silica aqueous sol (the particle size is 10-20 nm) in a stirring state, controlling the reaction temperature to 18 ℃, controlling the reaction time to 48 hours, and then removing low-boiling substances by reduced pressure distillation (100 ℃/-0.096 Mpa) to obtain the semitransparent phenylcarbamate modified nano silica aqueous sol.
The preparation method of the printable antistatic emulsion with strong adhesive force is the same as that of the example 1, except that substances are added in the corresponding steps, and the preparation method is added according to the formula of the example 2.
Example 3:
a printable antistatic emulsion having strong adhesion, the antistatic emulsion comprising, in parts by weight: 20 parts of a conductive polymer polythiophene, CLEVIOS from Heraeus TM P and 10 parts of single-arm carbon nano tube aqueous solution, wherein the pipe diameter is 1-2nm, and the length is 5-30um;30 parts of CYMEL 385;19 parts of N-vinyl carbamate modified nano silica aqueous sol; 1 part of polyoxyethylene (23) lauryl ether; 20 parts of water.
The preparation method of the N-vinyl carbamate modified nano silicon dioxide aqueous sol comprises the following steps:
adding N-vinyl carbamate (the modification amount is 15% of the effective component of the nano silica aqueous sol) into a four-neck flask with a stirring, reflux condenser, a thermometer and a dropping funnel, dropwise adding an alkaline nano silica aqueous solvent (the particle size is 40-50 nm) in a stirring state, controlling the reaction temperature to be 35 ℃, controlling the reaction time to be 40h, and then removing low-boiling substances by vacuum distillation (100 ℃/-0.096 Mpa) to obtain the semitransparent N-vinyl carbamate modified nano silica aqueous sol.
The preparation method of the printable antistatic emulsion with strong adhesive force is the same as that of the example 1, except that substances are added in the corresponding steps, and the preparation method is added according to the formula of the example 3.
Example 4:
a printable antistatic emulsion having strong adhesion, the antistatic emulsion comprising, in parts by weight: 10 parts of a conductive polymer polythiophene, ICP1020 from ORGACON; 22 parts of CYMEL1158;10 parts of a urethane dimethacrylate modified nano silica aqueous sol; 3 parts of octadecyl trimethyl ammonium bromide; 55 parts of water.
The preparation method of the nano silica aqueous sol modified by the dimethyl acrylic carbamate comprises the following steps:
adding dimethyl acrylic acid carbamate (the modification amount is 50% of the effective component of the nano silica aqueous sol) into a four-neck flask with a stirring, reflux condenser, a thermometer and a dropping funnel, dropwise adding acid nano silica aqueous sol (the particle size is 70-80 nm) in a stirring state, controlling the reaction temperature to be 80 ℃, controlling the reaction time to be 8 hours, and then removing low-boiling substances by reduced pressure distillation (100 ℃/-0.096 Mpa) to obtain semitransparent dimethyl acrylic acid carbamate modified nano silica aqueous sol.
The preparation method of the printable antistatic emulsion with strong adhesive force is the same as that of the example 1, except that substances are added in the corresponding steps, and the preparation method is added according to the formula of the example 4.
Comparative example 1:
comparative example 1 is only ICP1010 from polythiophene ORGACON, a conductive polymer.
Comparative example 2:
comparative example 2 is a formulation of patent ZL 201811640617.4, which is a silicon-coatable antistatic emulsion with good stability, and the composition of the silicon-coatable antistatic emulsion is as follows, in parts by weight: 5-20 parts of linear silane coupling agent containing epoxy groups, 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 nano tube 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 linear silane coupling agent containing epoxy groups are specifically limited. The silicon-coatable antistatic emulsion with good stability is added with the linear silane coupling agent containing epoxy groups, the phenyl hydroxyl reticular silicon resin, the conductive polymer polythiophene and the single-arm carbon nano tube aqueous solution, so that the film substrate has good stable antistatic performance and has a release function after being applied to the film substrate, for example: the peel force, the aged peel force at 70 ℃ and the residual adhesive force are all superior to those of the comparative example.
The comparative example 2 specifically adopts a silicon-coatable antistatic emulsion with good stability, and comprises, by weight, 13.2 parts of epoxy-containing linear silane coupling agent, 0.8 part of phenyl hydroxyl reticular silicon resin, 20 parts of conductive polymer polythiophene, 10 parts of single-arm carbon nanotube aqueous solution, 1 part of surfactant and 55 parts of water. The types and amounts of the conductive substance (conductive polymer polythiophene and single arm carbon nanotube aqueous solution) and the surfactant in the above formulation were the same as those used in example 3.
The structural formula of the epoxy group-containing linear silane coupling agent is as follows:
the structural formula of the phenyl hydroxyl reticular silicon resin is as follows:
wherein R, R ', R ' are identical or different straight-chain or branched aryl groups with 6 to 20 carbon atoms or aralkyl groups with 7 to 20 carbon atoms, and R ' is hydroxyl;
200g of distilled water and 1.2g of hydrochloric acid with the concentration of 1mol/L are respectively added into a four-neck flask with a stirring, reflux condenser, a thermometer and a dropping funnel, after stirring and mixing, 339.51g of phenethyl (trimethoxy) silane and 272g of diphenyldiethoxysilane are added dropwise, then 100g of absolute ethyl alcohol, 10g of 37% hydrochloric acid and 380g of isohexadecane extractant are added for cohydrolysis-polycondensation, the reaction temperature is 90 ℃, standing and layering are carried out after the reaction time is controlled to be 1h, the water phase is removed, the organic phase is washed to be neutral by distilled water, the neutral organic phase is filtered by a filter membrane with the aperture of 0.5 mu m, and low-boiling-point substances are removed by reduced pressure distillation (110-130 ℃ per-0.096 Mpa), so that the clear and transparent phenyl hydroxyl reticular silicon resin is obtained.
Preparation methods and performance tests 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. a base material: 25um plastic film substrate (PET) film
2. Antistatic coating liquid: the antistatic emulsions of the above examples 1, 2, 3,4, comparative example 1 and 2 were diluted with distilled water at 1:3, respectively.
3. Meyer rod: 5# standardized coating rod
4. The curing process comprises the following steps: drying and solidifying at 120deg.C for 3min
The printable antistatic films of examples 1-4 with strong adhesion were applied by the off-line mode described above.
If on-line coating is performed, a printable antistatic film with strong adhesion is made as follows:
adjusting the intrinsic viscosity of the polyester chip to be 0.6-0.8, carrying out melt extrusion by an extruder, and then stretching by a biaxially oriented polyethylene terephthalate (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 quantity is controlled 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 shaping area is 240-245 ℃, and finally the printable antistatic polyester film is obtained.
The printable antistatic films of examples 5-8, which have strong adhesion, are coated by the in-line method described above.
(2) Performance test:
appearance: visual inspection, and testing for haze value change Δh (ASTM D1003);
surface resistivity: the surface resistivity of the release surface was measured using an electrostatic tester SIMCO ST-4.
Solvent rub resistance: the isopropyl alcohol wets the dust-free cloth, the pressure is 880kg/m2, and the sample surface is wiped, 10cycles. After wiping, the surface resistivity of the release surface was measured by using an electrostatic tester SIMCO ST-4 after standing at room temperature for 1min, and the data change before and after wiping was compared.
Printing appearance: visual inspection to determine whether the pattern is clear and the color is uniform.
Printing adhesive force: and (3) using the 810 adhesive tape of 3M to attach the printed pattern, respectively carrying out quick tearing and slow tearing under the condition of lightly rubbing 5 with fingers, and observing the definition and color change of the printed pattern after tearing.
Printing alcohol rub resistance: alcohol abrasion resistance tester is used for testing, and the pressure intensity is 1kg/m 2 The travel was 2.45cm, the speed was 60cycles/min, 100cycles were tested, and the sharpness and color change of the printed pattern were observed.
Performance test:
thickness: DIN 53370
Tensile strength: DIN 53455
Elongation at break: DIN 53455
Heat shrinkage rate: BMS TT 11
Haze: ASTM D1003
(3) Test results:
from the above test results, it can be seen that the surface resistivity after wiping with isopropyl alcohol in examples 1 to 4 and comparative examples 1 and 2 shows the antistatic property of the antistatic emulsion, and the lower the number, the better the antistatic (conductive) effect, wherein the surface resistivity of examples 1 to 4 and the surface resistivity after wiping with isopropyl alcohol are both smaller than those of comparative example 1, which shows that the antistatic property of the emulsion is better than that of polythiophene alone, and the same kind and amount of conductive material (conductive polymer polythiophene and aqueous solution of single arm carbon nanotube) and surfactant as those in example 3 are also added in comparative example 2, which also has more excellent conductive property but is not resistant to solvent wiping.
The examples 1 to 4 were clear and uniform in appearance from the bar code printing, UV ink printing and flexo rapid printing of the substrate, the comparative example 1 showed non-uniformity, the anti-static emulsions of the examples 1 to 4 showed little or no shedding after alcohol wiping after three printing modes, and the three printing modes of comparative example 1 showed 100% shedding. In comparison with comparative example 2, the three printing modes of the formulation all have weaker adhesion than examples 1-4 and the alcohol rub resistance is 100% release. The printable antistatic emulsion with strong adhesive force has good adhesive force to a substrate, especially a plastic film (PET) substrate, and simultaneously enhances the adhesive force to printing materials (resin carbon tape, UV ink and the like), and meanwhile, the emulsion also has good conductivity, thus being the antistatic emulsion with excellent performance.
(4) Examples 5-8 formulation and preparation Process parameters
Example 5
Adjusting the intrinsic viscosity of the polyester chip to be 0.6, carrying out melt extrusion through an extruder, and then stretching through a biaxially oriented polyethylene terephthalate (BOPET) device, wherein the longitudinal stretching ratio is 3.5, and the longitudinal stretching temperature is 100 ℃; before transverse stretching, coating printable antistatic emulsion, wherein the coating quantity is controlled to be 0.05um, the transverse stretching ratio is 3.5, and the transverse stretching temperature is 105 ℃; the temperature in the shaping area is 243 ℃, and finally the printable antistatic polyester film is obtained. The preparation process of the antistatic films of examples 5 to 8 is shown in the following table:
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(5) The experimental test results are as follows:
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examples 5-8 and comparative example 2 each exhibited better surface resistance properties, but the surface resistance after solvent wiping of comparative example 2 was reduced by 4 grades, whereas examples 5-8 were reduced by only about 1 grade, i.e., examples 5-8 had excellent solvent wiping resistance.
The foregoing is illustrative of the present invention and is not to be construed as limiting thereof, but rather as various changes, modifications, substitutions, combinations, and simplifications which may be made therein without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A printable antistatic emulsion having strong adhesion, characterized by: the antistatic emulsion comprises the following components in parts by weight: aqueous solutions of conductive polymer polythiophene and/or single-arm carbon nanotubes: 10-50 parts of a lubricant; modified amino resin: 5-30 parts; urethane-modified nanosilica aqueous sol: 10-20 parts of a lubricant; and (2) a surfactant: 1-5 parts; water: 20-55 parts;
the carbamate modified nano silicon dioxide aqueous sol is as follows: carrying out modification and transesterification on carbamate and nano silicon dioxide aqueous sol, and removing low-boiling-point substances under reduced pressure to obtain the modified nano silicon dioxide aqueous sol; wherein, the carbamate accounts for 10% -50% of the effective component of the nano silicon dioxide aqueous sol;
the modification and transesterification are carried out, the reaction temperature is controlled to be 18-100 ℃, and the reaction time is controlled to be 1.5-48 hours; the reduced pressure is used for removing low-boiling substances, and the reduced pressure distillation temperature is 100 ℃ and the pressure is-0.096 Mpa.
2. The printable antistatic emulsion having strong adhesion according to claim 1, characterized in that: comprising any one or more of the following features i) to iii):
the conductive polymer polythiophene is poly 3, 4-vinyl dioxythiophene and derivatives thereof;
ii) the main component of the single-arm carbon nanotube aqueous solution is one or more of single-arm carbon nanotubes, hydroxylated single-arm carbon nanotubes and carboxylated single-arm carbon nanotubes, the pipe diameter of the single-arm carbon nanotube aqueous solution is 1-2nm, the length is 0.5-30 mu m, and the specific surface area>450m 2 /g, conductivity>150s/cm；
Iii) the nano-silica aqueous sol is acidic or alkaline and has a particle size ranging from 10 nm to 80nm.
3. The printable antistatic emulsion having strong adhesion according to claim 1, characterized in that: the modified amino resin is one or more of melamine resins modified by etherification.
4. A process for the preparation of a printable antistatic emulsion having strong adhesion according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
1) Weighing conductive polymer polythiophene and/or single-arm carbon nano tube aqueous solution, modified amino resin, carbamate modified nano silicon dioxide aqueous sol, surfactant and water according to the formula in parts by weight;
2) Placing the conductive polymer polythiophene and/or the single-arm carbon nano tube aqueous solution, the modified amino resin, the carbamate modified nano silicon dioxide aqueous sol, the surfactant and the water in the step 1) into homogenizing and emulsifying equipment for homogenizing and emulsifying to obtain primary emulsion;
3) And (3) filtering the primary emulsion obtained in the step (2) by using a 1 mu m filter element to obtain the printable antistatic emulsion with strong adhesive force.
5. A printable antistatic film having strong adhesion, characterized by: comprising a substrate layer and an antistatic layer adhered to at least one surface of the substrate layer, characterized in that: the antistatic layer is prepared by mixing the printable antistatic emulsion with strong adhesive force according to any one of claims 1 to 3 with water and coating the mixture on a substrate layer.
6. The printable antistatic film having strong adhesion according to claim 5, wherein: the substrate layer is a polyester film layer.
7. A method for preparing a printable antistatic film with strong adhesive force by on-line coating, which is characterized in that: the method comprises the following steps:
1) Slicing, melting and extruding the polyester film;
2) Stretching by a biaxial stretching device, and longitudinally stretching;
3) A printable antistatic emulsion with strong adhesion according to any one of claims 1-3 diluted with water for coating, stretched transversely and heat set.
8. The method of claim 7, 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 ℃;
f) The polyester film is sliced, and after melting, the viscosity is regulated to be 0.6-0.8.
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