CN113388142A - Polyurethane protective film and preparation method thereof - Google Patents
Polyurethane protective film and preparation method thereof Download PDFInfo
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- CN113388142A CN113388142A CN202110880176.0A CN202110880176A CN113388142A CN 113388142 A CN113388142 A CN 113388142A CN 202110880176 A CN202110880176 A CN 202110880176A CN 113388142 A CN113388142 A CN 113388142A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The invention relates to a polyurethane protective film and a preparation method thereof, wherein the polyurethane protective film comprises a single-side antistatic PET substrate layer, an antistatic coating coated on the other side of the single-side antistatic PET substrate layer and a PET antistatic ionization type film layer, and the antistatic coating comprises the following components in parts by weight: 40-70 parts of composite polyurethane resin; 0.4-4.0 parts of curing agent; 0.2-2.8 parts of a leveling agent; 100-140 parts of a solvent, wherein the composite polyurethane resin comprises polyurethane resin and a modified antistatic agent; the antistatic agent comprises trihydroxyethyl methyl quaternary ammonium methyl sulfate, or one or any combination of the trihydroxyethyl methyl quaternary ammonium methyl sulfate, polyethylene glycol stearate and polyethylene glycol laurate; the ratio of the polyethylene glycol laurate to the trihydroxyethyl methyl quaternary ammonium methyl sulfate to the polyethylene glycol stearate is 0-0.4: 1: 0-0.6. The polyurethane protective film disclosed by the invention has lower tearing voltage generated when the protective film of the touch screen is torn off, and the modified antistatic agent is not easy to precipitate under the conditions of high temperature and high humidity.
Description
Technical Field
The invention relates to the technical field of films, in particular to a polyurethane protective film and a preparation method thereof.
Background
In recent years, with the advent of various electronic products such as smart phones and tablet computers, a screen protection film is generally adhered to the surface of a screen of the electronic product in order to prevent the liquid crystal screen of the electronic product from being scratched or worn and affecting the use effect. Among various types of protective films, a Polyurethane (PU) protective film is a functional protective film formed by coating a transparent polyester film as a base material with polyurethane glue on one surface and then attaching a release film thereto. The PU protective film has the advantages of smooth surface, good exhaust performance, good adsorption performance and the like, and is mainly used for high-temperature manufacture protection of liquid crystal panels and shipment protection of ITO and glass panels. A touch module is arranged behind TP glass of the display screen, and the touch sensor is broken down due to overlarge film tearing voltage to cause damage, so that each large screen manufacturer puts forward a certain requirement on the film tearing voltage, which is generally less than 500V. The tearing voltage of most PU protective films in the market at present can not meet the requirement. In addition, an antistatic agent is added to the protective film in order to reduce the peeling voltage of the PU protective film, but if the antistatic agent is added in an excessive amount, the antistatic agent is precipitated and contaminates the electronic screen.
Chinese patent CN202010836975.3 discloses an antistatic PU protective film, which has good corrosion resistance, antistatic, abrasion-proof, scratch-proof and antifouling effects, high tensile strength, suitable adhesive force and peel strength, good water resistance and low temperature resistance. However, when the protective film is removed, the PU protective film generates a large film removal voltage, which may break down or damage functional components such as electronic components in the TP. Meanwhile, the antistatic agent added under the high-temperature and high-humidity conditions has the possibility of precipitation, and can cause pollution to an electronic screen.
Disclosure of Invention
The invention provides a PU protective film with low tearing voltage, which can maintain the excellent adsorption effect and exhaust performance, and has better antistatic performance and difficult precipitation performance under high temperature and high humidity, in order to solve the problem of higher tearing voltage of the existing optical PU protective film and the problem of screen pollution caused by easy precipitation of an antistatic agent added into the PU protective film under the high temperature and high humidity environment.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a polyurethane protective film comprises a single-side antistatic PET substrate layer, an antistatic coating coated on the other side of the single-side antistatic PET substrate layer, and a PET antistatic ionization type film layer; the antistatic coating comprises the following components in parts by weight:
the composite polyurethane resin comprises polyurethane resin and a modified antistatic agent; the modified antistatic agent is an antistatic agent pretreated by a silane coupling agent; the antistatic agent comprises trihydroxyethyl methyl quaternary ammonium methyl sulfate, or one or any combination of the trihydroxyethyl methyl quaternary ammonium methyl sulfate, polyethylene glycol stearate and polyethylene glycol laurate; the ratio of the polyethylene glycol laurate to the trihydroxyethyl methyl quaternary ammonium methyl sulfate to the polyethylene glycol stearate is 0-0.4: 1: 0-0.6.
Further, the modified antistatic agent is present in an amount of 3 to 6 parts by weight per 100 parts by weight of the composite polyurethane resin.
Further, the silane coupling agent comprises vinyltrimethoxysilane, or one or any combination of vinyltrimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane and vinyl tri (2-methoxyethoxy) silane; the ratio of the gamma-methacryloxypropylmethyldiethoxysilane, the vinyltrimethoxysilane and the vinyltris (2-methoxyethoxy) silane is 0-0.3: 1: 0-0.5.
The modified antistatic agent is obtained by hydrolyzing alkoxy on the silane coupling agent and then condensing with hydroxyl in the antistatic agent to form a chemical covalent bond, so that the compatibility of the antistatic agent and polyurethane resin is improved, the binding force of the antistatic agent and the resin is improved, and the added antistatic agent is not easy to precipitate under the conditions of high temperature and high humidity.
Further, antistatic ionosphere type rete of PET sets gradually PET base film layer, antistatic coating and organosilicon oil reservoir from bottom to top, antistatic coating set up in organosilicon coating lower part.
Further, the polyurethane resin is polymerized from isocyanate and a hydroxyl compound.
Further, the curing agent is a melamine curing agent selected from one or a combination of isobutylated melamine formaldehyde resin and methylated melamine resin. The isobutyl melamine formaldehyde resin and the methylated melamine resin have good chemical stability, and can be placed at room temperature for up to six months; the two curing agents have good intermiscibility with the composite polyurethane resin and can be uniformly dispersed in the composite polyurethane resin; and the composite polyurethane resin has good reactivity and can be quickly cured at room temperature.
Further, the leveling agent is one or a combination of an acrylate leveling agent and an organic silicon leveling agent. The acrylic ester leveling agent and the organic silicon leveling agent can promote the flowing and leveling of the composite polyurethane resin after film forming, the interlayer adhesion force of the formed film is not influenced, and the defoaming effect is realized, so that the surface of the obtained polyurethane protective film is flat and smooth; the two flatting agents and the composite polyurethane resin have ideally controlled intermiscibility, can be uniformly distributed on the surface of a coating film, form a new interface layer on the surface of the coating film, and play a good leveling role.
Further, the solvent comprises a mixed solvent composed of an ester solvent and cyclohexane, the ester solvent comprises one or a combination of ethyl acetate and butyl acetate, and the weight part ratio of the ester solvent to the cyclohexane is 3: 1-1: 3.
The invention also provides a preparation method of the polyurethane protective film, which comprises the following steps:
(1) mixing petroleum ether and dichloromethane according to the ratio of 3: 2-2: 3, adding 20-40 parts by weight of antistatic agent into 50-100 parts by weight of mixed solvent, reacting with 0.4-0.8 part by weight of silane coupling agent for 1.5-3 hours at the temperature of 30-50 ℃, and drying in vacuum to obtain the modified antistatic agent.
(2) Adding polyurethane resin, adding dichloromethane and triethylamine as solvents, stirring for 15 minutes at room temperature to uniformly distribute the polyurethane resin in the solvent, adding a modified antistatic agent, polymerizing for 2-4 hours at 70-90 ℃, and naturally cooling to room temperature to obtain the composite polyurethane resin.
(3) Uniformly mixing the polyurethane resin and the solvent according to the weight part, adding the curing agent and the flatting agent according to the weight part, uniformly mixing to obtain a coating liquid, coating the coating liquid on an optical-grade antistatic polyester film, drying, coating the antistatic release film, and finally curing to obtain the polyurethane protective film with low film tearing voltage performance.
Compared with the prior art, the invention has the following beneficial effects:
1. the antistatic agent has good antistatic performance, and is subjected to hydrolysis by alkoxy groups on the silane coupling agent and then condensed with hydroxyl groups in the antistatic agent to form chemical covalent bonds, so that the modified antistatic agent is obtained, and the compatibility of the antistatic agent and polyurethane resin is improved, so that the binding force of the antistatic agent and the resin is improved, and the added antistatic agent is not easy to precipitate under the conditions of high temperature and high humidity.
2. According to the polyurethane protective film, the amino functional group is connected to the polyurethane resin and can react with the ester functional group connected to the antistatic agent to generate an amide functional group and form a chemical covalent bond, so that the stability of the polyurethane protective film is greatly improved. The polyurethane protective film disclosed by the invention adopts the structure of the antistatic PET substrate layer, the antistatic coating coated on the surface of the polyester film and the PET antistatic ionization type film layer, and is beneficial to static electricity release, so that the tearing voltage generated when the protective film of the touch screen is torn is lower.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The weight part of the modified antistatic agent in the composite polyurethane resin is 3-6 parts, and when the weight part proportion of the antistatic agent is less than 3 parts, the antistatic property is poor, and the tear film voltage is high; when the weight part of the antistatic agent is more than 6 parts, the antistatic agent is antistatic and is easy to separate out under a high-temperature and high-humidity environment, so that screen pollution is caused.
The polyester film described in each example is optical grade polyester film.
The acrylate leveling agent comprises BYK380N and Dre 835, and the organic silicon leveling agent comprises BYK346 and BYK 306.
The modified antistatic agent is prepared by mixing petroleum ether and dichloromethane in a ratio of 3: 2-2: 3, adding 20-40 parts by weight of the antistatic agent into 50-100 parts by weight of a mixed solvent, reacting with 0.4-0.8 part by weight of a silane coupling agent at 30-50 ℃ for 1.5-3 hours, and drying in vacuum.
The proportion of the polyethylene glycol laurate, the trihydroxyethyl methyl quaternary ammonium methyl sulfate and the polyethylene glycol stearate is 0-0.4: 1: 0-0.6, and when the dosage of the polyethylene glycol laurate exceeds 0.4 and the dosage of the polyethylene glycol stearate exceeds 0.6, antistatic precipitation is easily caused in a high-temperature and high-humidity environment.
The composite polyurethane resin can be obtained by the following ways: 100g of polyurethane resin, 3-6g of modified antistatic agent, 80-105g of dichloromethane and 2.5-6.0g of triethylamine are used. Polymerizing for 2-4 hours at 70-90 ℃, and naturally cooling to room temperature to obtain the composite polyurethane resin. Under the conditions, the amino functional group connected with the polyurethane resin can react with the ester functional group connected with the modified antistatic agent to generate an amide functional group and form a chemical covalent bond, thereby obtaining the composite polyurethane resin.
Firstly adding polyurethane resin, then adding dichloromethane and triethylamine as solvents, and stirring for 15 minutes at room temperature to uniformly distribute the polyurethane resin in the solvent. Then adding a modified antistatic agent, and polymerizing for 2-4 hours at 70-90 ℃. When the reaction temperature is lower than 70 ℃, the reaction cannot occur or the reaction rate is very slow; when the reaction temperature is higher than 90 ℃, the phenomenon of implosion is easily caused when the reaction rate is too fast. The polymerization time is 2 hours to 4 hours, and when the polymerization time is less than 2 hours, the reaction is not completely carried out; when the polymerization time is more than 4 hours, many side reactions are liable to occur. And finally, naturally cooling to room temperature to obtain the composite polyurethane resin.
Example 1
Weighing 40g of petroleum ether and 60g of dichloromethane, stirring at a high speed, uniformly mixing, adding 5g of polyethylene glycol laurate, 15g of trihydroxyethyl methyl quaternary ammonium methyl sulfate, 5g of polyethylene glycol stearate, 0.1g of gamma-methacryloxypropyl methyldiethoxysilane, 0.5g of vinyl trimethoxy silane and 0.1g of vinyl tris (2-methoxyethoxy) silane, reacting at the temperature of 30 ℃ for 3 hours, and finally drying in vacuum to obtain the modified antistatic agent.
Stirring 100g of polyurethane resin, 80g of dichloromethane and 2.5g of triethylamine for 15 minutes at room temperature, adding 3g of modified antistatic agent, polymerizing for 4 hours at 70 ℃, and naturally cooling to room temperature to obtain the composite polyurethane resin. Under such conditions, the amino functional group attached to the polyurethane resin may react with the ester functional group attached to the modified antistatic agent to generate an amide functional group, forming a chemical covalent bond, thereby obtaining a composite polyurethane resin.
Weighing 45g of the composite polyurethane resin, 30g of ethyl acetate, 30g of butyl acetate and 40g of cyclohexane, uniformly mixing, adding 0.4g of isobutylated melamine-formaldehyde resin, 0.2g of methylated melamine resin, 0.3g of BYK380N, 0.5g of Delhi 835 and 0.2g of BYK346, uniformly mixing to obtain a coating liquid, coating the coating liquid on an optical-grade antistatic polyester film, drying, coating an antistatic release film, and curing to obtain the polyurethane protective film with low tear film voltage performance.
Example 2
Weighing 50g of petroleum ether and 50g of dichloromethane, stirring at a high speed, uniformly mixing, adding 6g of polyethylene glycol laurate, 18g of trihydroxyethyl methyl quaternary ammonium methyl sulfate, 8g of polyethylene glycol stearate, 0.1g of gamma-methacryloxypropyl methyldiethoxysilane, 0.5g of vinyl trimethoxy silane and 0.2g of vinyl tris (2-methoxyethoxy) silane, reacting at 35 ℃ for 2.5 hours, and finally drying in vacuum to obtain the modified antistatic agent.
Stirring 110g of polyurethane resin, 85g of dichloromethane and 2.8g of triethylamine for 15 minutes at room temperature, adding 4g of modified antistatic agent, polymerizing for 3.6 hours at 75 ℃, and naturally cooling to room temperature to obtain the composite polyurethane resin. Under such conditions, the amino functional group attached to the polyurethane resin may react with the ester functional group attached to the modified antistatic agent to generate an amide functional group, forming a chemical covalent bond, thereby obtaining a composite polyurethane resin.
Weighing 50g of the composite polyurethane resin, 40g of ethyl acetate, 55g of butyl acetate and 10g of cyclohexane, uniformly mixing, adding 0.45g of isobutylated melamine-formaldehyde resin, 0.15g of methylated melamine resin, 0.35g of BYK380N, 0.6g of Delhi 835 and 0.15g of BYK346, uniformly mixing to obtain a coating liquid, coating the coating liquid on an optical-grade antistatic polyester film, drying, coating an antistatic release film, and curing to obtain the polyurethane protective film with low tear film voltage performance.
Example 3
Weighing 55g of petroleum ether and 45g of dichloromethane, stirring at a high speed, uniformly mixing, adding 3g of polyethylene glycol laurate, 16g of trihydroxyethyl methyl quaternary ammonium methyl sulfate, 9g of polyethylene glycol stearate, 0.05g of gamma-methacryloxypropyl methyldiethoxysilane, 0.5g of vinyl trimethoxy silane and 0.25g of vinyl tris (2-methoxyethoxy) silane, reacting at 35 ℃ for 2.5 hours, and finally drying in vacuum to obtain the modified antistatic agent.
Stirring 120g of polyurethane resin, 90g of dichloromethane and 3.5g of triethylamine for 15 minutes at room temperature, adding 5g of modified antistatic agent, polymerizing for 3 hours at 80 ℃, and naturally cooling to room temperature to obtain the composite polyurethane resin. Under such conditions, the amino functional group attached to the polyurethane resin may react with the ester functional group attached to the modified antistatic agent to generate an amide functional group, forming a chemical covalent bond, thereby obtaining a composite polyurethane resin.
Weighing 55g of the composite polyurethane resin, 55g of ethyl acetate and 50g of butyl acetate, uniformly mixing, adding 0.35g of isobutylated melamine-formaldehyde resin, 0.45g of methylated melamine resin, 0.4g of BYK380N, 0.55g of Delhi 835 and 0.1g of BYK346, uniformly mixing to obtain a coating liquid, coating the coating liquid on an optical-grade antistatic polyester film, drying, coating an antistatic release film, and finally curing to obtain the polyurethane protective film with low tear film voltage performance.
Example 4
The results of the performance tests are shown in Table 1.
60g of petroleum ether and 40g of dichloromethane are weighed, stirred at a high speed and mixed uniformly, then 2.5g of polyethylene glycol laurate, 15g of trihydroxyethyl methyl quaternary ammonium methyl sulfate, 6g of polyethylene glycol stearate, 0.15g of gamma-methacryloxypropyl methyldiethoxysilane, 0.35g of vinyl trimethoxy silane and 0.30g of vinyl tris (2-methoxyethoxy) silane are added, the reaction is carried out for 2 hours at the temperature of 40 ℃, and finally the modified antistatic agent is obtained after vacuum drying.
Stirring 130g of polyurethane resin, 95g of dichloromethane and 6.5g of triethylamine for 15 minutes at room temperature, adding 6g of modified antistatic agent, polymerizing for 2.6 hours at 85 ℃, and naturally cooling to room temperature to obtain the composite polyurethane resin. Under such conditions, the amino functional group attached to the polyurethane resin may react with the ester functional group attached to the modified antistatic agent to generate an amide functional group, forming a chemical covalent bond, thereby obtaining a composite polyurethane resin.
Weighing 60g of the composite polyurethane resin, 60g of ethyl acetate and 40g of cyclohexane, uniformly mixing, adding 0.6g of isobutylated melamine-formaldehyde resin, 0.2g of methylated melamine resin, 0.25g of BYK380N, 0.15g of Delhi 835 and 0.4g of BYK346, uniformly mixing to obtain a coating liquid, coating the coating liquid on an optical-grade antistatic polyester film, drying, coating an antistatic release film, and finally curing to obtain the polyurethane protective film with low-tear film voltage performance.
Example 5
Weighing 65g of petroleum ether and 35g of dichloromethane, stirring at a high speed, uniformly mixing, adding 2g of polyethylene glycol laurate, 20g of trihydroxyethyl methyl quaternary ammonium methyl sulfate, 8g of polyethylene glycol stearate, 0.05g of gamma-methacryloxypropyl methyldiethoxysilane, 0.55g of vinyl trimethoxy silane and 0.2g of vinyl tris (2-methoxyethoxy) silane, reacting at 40 ℃ for 2 hours, and finally drying in vacuum to obtain the modified antistatic agent.
Stirring 140g of polyurethane resin, 100g of dichloromethane and 8g of triethylamine for 15 minutes at room temperature, adding 6.5g of modified antistatic agent, polymerizing for 2.6 hours at 85 ℃, and naturally cooling to room temperature to obtain the composite polyurethane resin. Under such conditions, the amino functional group attached to the polyurethane resin may react with the ester functional group attached to the modified antistatic agent to generate an amide functional group, forming a chemical covalent bond, thereby obtaining a composite polyurethane resin.
Weighing 65g of the composite polyurethane resin, 55g of butyl acetate and 45g of cyclohexane, uniformly mixing, adding 0.45g of isobutylated melamine-formaldehyde resin, 0.35g of methylated melamine resin, 0.4g of BYK380N, 0.25g of Delhi 835 and 0.15g of BYK346, uniformly mixing to obtain a coating liquid, coating the coating liquid on an optical-grade antistatic polyester film, drying, coating an antistatic release film, and finally curing to obtain the low-tear-film voltage protection film.
Comparative example
Weighing 50g of polyurethane resin, 40g of ethyl acetate, 30g of butyl acetate and 30g of cyclohexane, uniformly mixing, adding 0.3g of polyethylene glycol laurate, 1.2g of trihydroxyethyl methyl quaternary ammonium methyl sulfate, 0.6g of polyethylene glycol stearate, 0.6g of isobutylated melamine formaldehyde resin, 0.8g of methylated melamine resin, 0.9g of BYK380N and 0.8g of Delhi 835, uniformly mixing to obtain a coating liquid, coating the coating liquid on an optical-grade antistatic polyester film, drying, coating an antistatic release film, and finally curing to obtain the low-tear-film voltage protective film.
The polyurethane protective films and the low-tear-film-voltage protective films obtained in the above examples and comparative examples were subjected to performance tests, and the specific test methods were as follows:
(1) resistance test of antistatic coatings
The polyurethane protective film was cut into a size of 12 × 12mm, and the surface resistance of the antistatic layer was measured on a high resistance meter (model: SME-8310).
(2) Tear film voltage test
And (3) tearing off the release film of the polyurethane protective film, namely, the voltage between the release films at the moment of tearing off the release film, and the tearing dynamic film tearing voltage of the protective film, wherein the measured voltage value is the maximum electrostatic voltage during stripping, and the material stripping speed is more than 20 cm/s.
(3) High temperature high humidity Performance test
Cutting the polyurethane protective film into 12cm by 12cm, attaching the adhesive surface to a glass panel, then placing the glass panel into a programmable constant temperature and humidity test chamber (model: WHTH-150L-40-880) with the temperature of 60 ℃ and the relative humidity of 90% RH for 72 hours, taking out the glass panel, cooling the glass panel to room temperature after the completion of the test, tearing off the low-tear-film voltage protective film, and performing visual evaluation on the dirt degree of the screen after the protective film is torn off.
Cutting the polyurethane protective film into 12cm by 12cm, then placing the polyurethane protective film into an electric heating constant-temperature air-blowing drying oven (model: DHG-9140A) with the temperature of 80 ℃ for 500 hours, and then testing the surface resistance of the high-temperature-resistant coating.
The test results are shown in table 1:
TABLE 1 Performance data Table
Note: the result of the attaching surface is excellent, which means that the polyurethane protective film is attached to the surface of the screen, after the screen is cooled to room temperature after being examined for 72 hours under the conditions that the temperature is 60 ℃ and the relative humidity is 90% RH, the surface of the screen after the protective film is torn off is flat and smooth, and has no white fog and no adhesive residue.
As can be seen from Table 1, the adhesion surfaces of examples 1 to 5 were all excellent, while the adhesion surface of the comparative example had significant white fog and adhesive residue, indicating that the resulting modified antistatic agent increased the compatibility of the antistatic agent with polyurethane resin, thereby improving the bonding force between the antistatic agent and the resin and making the added antistatic agent less likely to precipitate under high temperature and high humidity conditions. The voltage between the release films and the voltage for tearing the dynamic tearing film of the polyurethane protective film at the instant of tearing the release films in the embodiments 1 to 5 are both far lower than those of the comparative examples, which shows that the polyurethane protective film of the present invention adopts the structure of the antistatic PET substrate layer, the antistatic coating coated on the surface of the polyester film and the antistatic PET ionogenic film layer, which is beneficial to the release of static electricity, so that the tearing voltage generated when the protective film of the touch screen is torn is lower. The initial surface resistance of the examples 1 to 5 is similar to that of the comparative example, but after high temperature treatment, the surface resistance of the examples 1 to 5 is obviously lower than that of the comparative example, which shows that the amino functional group connected to the polyurethane resin can react with the ester functional group connected to the antistatic agent to generate an amide functional group to form a chemical covalent bond, so that the stability of the polyurethane resin is greatly improved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A polyurethane protective film comprises a single-side antistatic PET substrate layer, an antistatic coating coated on the other side of the single-side antistatic PET substrate layer and a PET antistatic ionization type film layer; the antistatic coating is characterized by comprising the following components in parts by weight:
the composite polyurethane resin comprises polyurethane resin and a modified antistatic agent; the modified antistatic agent is an antistatic agent pretreated by a silane coupling agent; the antistatic agent comprises trihydroxyethyl methyl quaternary ammonium methyl sulfate, or one or any combination of the trihydroxyethyl methyl quaternary ammonium methyl sulfate, polyethylene glycol stearate and polyethylene glycol laurate; the ratio of the polyethylene glycol laurate to the trihydroxyethyl methyl quaternary ammonium methyl sulfate to the polyethylene glycol stearate is 0-0.4: 1: 0-0.6.
2. The polyurethane protective film according to claim 1, wherein the modified antistatic agent is included in an amount of 3 to 6 parts by weight based on 100 parts by weight of the composite polyurethane resin.
3. The polyurethane protective film according to claim 1, wherein the silane coupling agent comprises vinyltrimethoxysilane, or one or any combination of vinyltrimethoxysilane and gamma-methacryloxypropylmethyldiethoxysilane or vinyltris (2-methoxyethoxy) silane; the ratio of the gamma-methacryloxypropylmethyldiethoxysilane, the vinyltrimethoxysilane and the vinyltris (2-methoxyethoxy) silane is 0-0.3: 1: 0-0.5.
4. The polyurethane protective film according to claim 1, wherein the PET antistatic type film layer is provided with a PET base film layer, an antistatic coating and a silicone oil layer from bottom to top in sequence, and the antistatic coating is provided on the lower portion of the silicone coating.
5. The protective polyurethane film according to claim 1, wherein the polyurethane resin is obtained by polymerizing an isocyanate and a hydroxyl compound.
6. The protective polyurethane film according to claim 1, wherein the curing agent is a melamine-based curing agent selected from isobutylated melamine-formaldehyde resin, methylated melamine resin, or a combination thereof.
7. The polyurethane protective film according to claim 1, wherein the leveling agent is one of an acrylate leveling agent, an organosilicon leveling agent, or a combination thereof.
8. The polyurethane protective film according to claim 1, wherein the solvent comprises a mixed solvent composed of an ester solvent and cyclohexane, the ester solvent comprises one or a combination of ethyl acetate and butyl acetate, and the weight part ratio of the ester solvent to the cyclohexane is 3: 1-1: 3.
9. A method for producing a polyurethane protective film according to any one of claims 1 to 8, characterized by comprising the steps of:
(1) mixing petroleum ether and dichloromethane in a ratio of 3: 2-2: 3 to obtain a mixed solvent, adding 20-40 parts by weight of an antistatic agent into 50-100 parts by weight of the mixed solvent, reacting with 0.4-0.8 part by weight of a silane coupling agent at 30-50 ℃ for 1.5-3 hours, and drying in vacuum to obtain the modified antistatic agent.
(2) Adding polyurethane resin, adding dichloromethane and triethylamine as solvents, stirring for 15 minutes at room temperature to uniformly distribute the polyurethane resin in the solvent, adding a modified antistatic agent, polymerizing for 2-4 hours at 70-90 ℃, and naturally cooling to room temperature to obtain the composite polyurethane resin.
(3) Uniformly mixing the composite polyurethane resin and the solvent in parts by weight, adding the curing agent and the flatting agent in parts by weight, uniformly mixing to obtain a coating liquid, coating the coating liquid on an optical-grade antistatic polyester film, drying, coating an antistatic release film, and curing to obtain the polyurethane protective film with low film tearing voltage performance.
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| CN115785884A (en) * | 2023-01-29 | 2023-03-14 | 太仓斯迪克新材料科技有限公司 | Adhesive for electrostatic protection film and electrostatic protection film with ultralow film tearing voltage |
| CN115926664A (en) * | 2022-12-26 | 2023-04-07 | 苏州泰仑电子材料有限公司 | Low-tear-film-voltage polyurethane protective film for touch screen and preparation method thereof |
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