High-hardness and high-wear-resistance antistatic film and preparation method thereof

Abstract

The invention discloses a high-hardness and high-wear-resistance antistatic film and a preparation method thereof.The antistatic film comprises a base material, a hardened layer, an antistatic layer and an anti-fingerprint layer which are sequentially arranged in a stacked mode, the hardened layer is obtained by coating the base material layer with hardened coating liquid and then curing the hardened coating liquid, and the anti-fingerprint layer is obtained by coating the hardened coating liquid on the anti-fingerprint layer. The hardening coating liquid is prepared from the following components in parts by weight: 50 to 70 parts of printable acrylic resin, 5 to 20 parts of polyfunctional acrylic monomer, 1 to 5 parts of first photoinitiator and 30 to 50 parts of first solvent. The hard coating is adopted for bottoming to achieve high hardness, the screened stable anti-static layer which does not affect transmittance is utilized in the middle to achieve the anti-static effect, the anti-fingerprint layer on the uppermost layer regulates the thickness, on the premise that the anti-static effect is not affected, the hydrophobic and wear-resistant performance of the membrane material is achieved, and the anti-static performance of the membrane material is improved. Therefore, the problems that a conventional antistatic film is not resistant to scraping, unstable in surface resistivity and short in service life can be solved.

Description

Technical Field

[0001] The invention relates to the field of antistatic film materials, and in particular to an antistatic film with high hardness and high wear resistance and a preparation method thereof. Background Art

[0002] With the widespread use of smart displays such as mobile phones and tablets, people have found that display screens are prone to static electricity during use, which may absorb dust and fine particles, affecting the clarity and appearance of the screen. When antistatic film is applied to the optical display screen, it can not only quickly dissipate the electrons accumulated on the screen surface, but also reduce the energy on the screen surface and reduce dust adsorption. At the same time, the antistatic film will not only not affect the use of the screen, such as touch sensitivity and high transmittance required by optical display, but also increase the physical properties of hardness, wear resistance and anti-fingerprint. This application scenario can effectively protect the smart display module and extend its service life.

[0003] The antistatic performance of the antistatic film obtained by the prior art may gradually decline over time, as the use environment changes, and as a result of external forces such as friction, scratching, and bending during transportation and use. The antistatic film has a short service life and unstable surface resistivity. At the same time, the antistatic film may have a certain effect on the transparency of the film due to the addition of conductive materials such as metal powder, conductive carbon black, metal oxides, or other functional components, making it less clear than ordinary films. This may not be ideal for use in optical display screens with high requirements for transparency and transmittance.

[0004] Therefore, it is necessary to improve the existing technology to provide a more reliable solution. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a high-hardness and high-wear-resistant antistatic film and a preparation method thereof in view of the deficiencies in the above-mentioned prior art. The present invention uses a hardened coating as a base to achieve high hardness performance, uses a screened stable antistatic layer that does not affect transmittance in the middle to achieve an antistatic effect, and adjusts the thickness of the top anti-fingerprint layer to achieve the hydrophobic and wear-resistant performance of the film material without affecting the antistatic effect, thereby solving the problems of conventional antistatic films being not scratch-resistant, having unstable surface resistivity, and having a short service life, and is suitable for the field of optical display elements.

[0006] To achieve the above object, the technical solution adopted by the present invention is: In the first aspect of the present invention, a high-hardness and high-wear-resistant antistatic film is provided, comprising a substrate, a hardening layer, an antistatic layer and an anti-fingerprint layer stacked in sequence:

[0007] The hardened layer is obtained by coating a hardening coating liquid on the substrate layer and then curing the coating liquid. The hardening coating liquid comprises, by weight: 50-70 parts of a printable acrylic resin, 5-20 parts of a multifunctional acrylic monomer, 1-5 parts of a first photoinitiator, and 30-50 parts of a first solvent.

[0008] Preferably, the printable acrylic resin is selected from one or more of polyurethane acrylic resin, polyester acrylic resin, epoxy acrylic resin, and pure acrylic resin;

[0009] The multifunctional acrylic monomer is selected from one or more of dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, pentaerythritol triacrylate, trimethylolpropane ethoxy triacrylate, 1,6-hexanediol diacrylate, propoxylated glycerol triacrylate, propylene propyl triacrylate, propoxylated glycerol triacrylate, and tripropylene glycol diacrylate.

[0010] Preferably, the first photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, hydroxydimethyl acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide;

[0011] The first solvent is selected from one or more of methyl ethyl ketone, isopropanol, ethyl acetate, toluene, butanone, methyl isobutyl ketone, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

[0012] Preferably, the antistatic layer is obtained by coating an antistatic coating liquid on the substrate layer and then curing it, and the antistatic coating liquid comprises, by weight: 30-60 parts of polyurethane acrylic resin, 5-10 parts of active monomer, 5-10 parts of antistatic agent, 1-5 parts of second photoinitiator, and 30-60 parts of second solvent.

[0013] Preferably, the polyurethane acrylic resin is selected from one or more of trifunctional aromatic polyurethane acrylic resin, trifunctional aliphatic polyurethane acrylic resin, tetrafunctional aromatic polyurethane acrylic resin, tetrafunctional aliphatic polyurethane acrylic resin, and hexafunctional aliphatic polyurethane acrylic resin;

[0014] The active monomer is an acrylic monomer with 3-6 functionalities, selected from one or more of pentaerythritol tetraacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, and trimethylolpropane ethoxy triacrylate.

[0015] Preferably, the antistatic agent is an organic surfactant selected from one or more of sodium alkyl sulfonate, organic phosphate, organic phosphate, allyl imine, and long carbon chain quaternary ammonium salt;

[0016] The second photoinitiator is a ketone initiator selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzyl dimethyl ketal, hydroxydimethyl acetophenone, and hydroxycyclohexyl phenyl ketone;

[0017] The second solvent is an alcohol or ether solvent, selected from one or more of propylene glycol methyl ether, isopropanol, ethanol, and ethylene glycol methyl ether.

[0018] Preferably, the anti-fingerprint layer is obtained by coating an anti-fingerprint coating liquid on the substrate layer and then curing it, and the anti-fingerprint coating liquid comprises, by weight: 30-50 parts of a prepolymer, 5-20 parts of an active diluent, 1-5 parts of a fluorine-containing auxiliary agent, 1-5 parts of a third photoinitiator, and 40-70 parts of a third solvent.

[0019] Preferably, the prepolymer is selected from one or more of fluorosilicone modified polyester acrylic resin, fluorosilicone modified polyurethane acrylic resin, fluorosilicone modified epoxy acrylic resin, fluorosilicone modified acrylic resin, nanoparticle hybrid resin, and silicone resin.

[0020] Preferably, the reactive diluent is one or more of low-functional acrylic ester monomers such as isobornyl acrylate, N,N-dimethylacrylamide, 4-acryloylmorpholine, 1,6-hexanediol diacrylate, multifunctional acrylic monomers, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate;

[0021] The third photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 4-dimethylamino-ethyl benzoate, hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylformyl-diphenylphosphine oxide, and methyl benzoylformate;

[0022] The third solvent is selected from one or more of methyl ethyl ketone, propylene glycol methyl ether, methyl isobutyl ketone, isopropanol, ethyl acetate, toluene, butanone, and methyl isobutyl ketone.

[0023] The second aspect of the present invention provides a method for preparing the high-hardness and high-wear-resistant antistatic film as described above, comprising the following steps:

[0024] S1. Mix the printable acrylic resin, multifunctional acrylic monomer, first photoinitiator and first solvent evenly to obtain a hardening coating solution, apply the hardening coating solution on the substrate, heat and dry, 300-500mJ / cm 2Light curing to obtain a hardened layer with a thickness of 5-7 μm;

[0025] S2, polyurethane acrylic resin, active monomer, antistatic agent, second photoinitiator, second solvent are mixed evenly to obtain antistatic coating liquid, the antistatic coating liquid is coated on the hardened layer, and after heating and drying, 400-600mJ / cm 2 Photocuring to obtain an antistatic layer with a thickness of 1-3 μm;

[0026] S3, prepolymer, active diluent, fluorine-containing auxiliary agent, third photoinitiator, third solvent are mixed evenly to obtain anti-fingerprint coating liquid, anti-fingerprint coating liquid is applied on the antistatic layer, and after heating and drying, 500-800mJ / cm 2 Photocuring is performed to obtain an anti-fingerprint layer with a thickness of 300-600 nm; and finally the antistatic film with high hardness and high wear resistance is obtained.

[0027] The beneficial effects of the present invention are:

[0028] The present invention provides an antistatic film with high hardness and high wear resistance and a preparation method thereof. The antistatic film of the present invention comprises a substrate, a hardening layer, an antistatic layer and an anti-fingerprint layer which are stacked in sequence, and has high hardness and high wear resistance. A hardening coating is used as a base to achieve high hardness performance, and a screened stable antistatic layer that does not affect transmittance is used in the middle to achieve antistatic effect. The thickness of the top anti-fingerprint layer is adjusted to achieve the hydrophobic and wear-resistant performance of the film material without affecting the antistatic effect, thereby solving the problems of conventional antistatic films being not scratch-resistant, having unstable surface resistivity and having a short service life. In some preferred embodiments, the finished antistatic film provided by the present invention can achieve a transmittance of >90%, a haze of <1%, a high hardness of 750g3H, a wear resistance of 1000g1000 times of steel wool, and a surface resistivity stable at 10 8-9 Ω / m 2 It has good performance and can be widely used in the field of optical display. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a schematic structural diagram of the high-hardness and high-wear-resistant antistatic film of the present invention.

[0030] Description of reference numerals:

[0031] 1—substrate; 2—hardening layer; 3—antistatic layer; 4—anti-fingerprint layer. DETAILED DESCRIPTION

[0032] The present invention is further described in detail below in conjunction with embodiments so that those skilled in the art can implement the invention with reference to the description.

[0033] It should be understood that the terms such as “having”, “including” and “comprising” used herein do not exclude the existence or addition of one or more other elements or combinations thereof.

[0034] The test methods used in the following examples are conventional methods unless otherwise specified. The materials and reagents used in the following examples are all commercially available unless otherwise specified. In the following examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if the manufacturer is not specified, are all conventional products that can be purchased commercially.

[0035] The present invention provides an antistatic film with high hardness and high wear resistance, referring to Figure 1 , from bottom to top, including a substrate 1, a hardening layer 2, an antistatic layer 3 and an anti-fingerprint layer 4 stacked in sequence:

[0036] The hardened layer is obtained by coating a hardening coating liquid on the substrate layer and then curing the coating liquid. The hardening coating liquid comprises, by weight: 50-70 parts of a printable acrylic resin, 5-20 parts of a multifunctional acrylic monomer, 1-5 parts of a first photoinitiator, and 30-50 parts of a first solvent.

[0037] In a preferred embodiment, the printable acrylic resin is selected from one or more of polyurethane acrylic resin, polyester acrylic resin, epoxy acrylic resin, and pure acrylic resin.

[0038] In a preferred embodiment, the multifunctional acrylic monomer is selected from one or more of dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, pentaerythritol triacrylate, trimethylolpropane ethoxy triacrylate, 1,6-hexanediol diacrylate, propoxylated glycerol triacrylate, propylene glycol triacrylate, propoxylated glycerol triacrylate, and tripropylene glycol diacrylate.

[0039] In a preferred embodiment, the first photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, hydroxydimethyl acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0040] In a preferred embodiment, the first solvent is selected from one or more of methyl ethyl ketone, isopropanol, ethyl acetate, toluene, butanone, methyl isobutyl ketone, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

[0041] In a preferred embodiment, the antistatic layer is obtained by coating an antistatic coating liquid on the substrate layer and then curing the coating liquid. The antistatic coating liquid comprises, by weight: 30-60 parts of a polyurethane acrylic resin, 5-10 parts of an active monomer, 5-10 parts of an antistatic agent, 1-5 parts of a second photoinitiator, and 30-60 parts of a second solvent.

[0042] In a preferred embodiment, the polyurethane acrylic resin is selected from one or more of a trifunctional aromatic polyurethane acrylic resin, a trifunctional aliphatic polyurethane acrylic resin, a tetrafunctional aromatic polyurethane acrylic resin, a tetrafunctional aliphatic polyurethane acrylic resin, and a hexafunctional aliphatic polyurethane acrylic resin.

[0043] In a preferred embodiment, the active monomer is an acrylic monomer with 3-6 functionalities, selected from one or more of pentaerythritol tetraacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, and trimethylolpropane ethoxy triacrylate.

[0044] In a preferred embodiment, the antistatic agent is an organic surfactant selected from one or more of sodium alkyl sulfonate, organic phosphate ester, organic phosphate, allyl imine, and long carbon chain quaternary ammonium salt.

[0045] In a preferred embodiment, the second photoinitiator is a ketone initiator selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzyl dimethyl ketal, hydroxydimethyl acetophenone, and hydroxycyclohexyl phenyl ketone.

[0046] In a preferred embodiment, the second solvent is an alcohol or ether solvent, selected from one or more of propylene glycol methyl ether, isopropanol, ethanol, and ethylene glycol methyl ether.

[0047] In a preferred embodiment, the anti-fingerprint layer is obtained by coating an anti-fingerprint coating liquid on the substrate layer and then curing the coating liquid. The anti-fingerprint coating liquid comprises, by weight: 30-50 parts of a prepolymer, 5-20 parts of an active diluent, 1-5 parts of a fluorine-containing auxiliary agent, 1-5 parts of a third photoinitiator, and 40-70 parts of a third solvent.

[0048] In a preferred embodiment, the prepolymer is selected from one or more of fluorosilicone modified polyester acrylic resin, fluorosilicone modified polyurethane acrylic resin, fluorosilicone modified epoxy acrylic resin, fluorosilicone modified acrylic resin, nanoparticle hybrid resin, and silicone resin.

[0049] In a preferred embodiment, the fluorine-containing auxiliary agent is a fluorine-containing antifouling additive, such as Shin-Etsu KY-1200 series, Arakawa 1207, and the like.

[0050] In a preferred embodiment, the active diluent is one or more of low-functional acrylic ester monomers such as isobornyl acrylate, N,N-dimethylacrylamide, 4-acryloylmorpholine, 1,6-hexanediol diacrylate, multifunctional acrylic monomers, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate.

[0051] In a preferred embodiment, the third photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 4-dimethylamino-ethyl benzoate, hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylformyl-diphenylphosphine oxide, and methyl benzoylformate.

[0052] In a preferred embodiment, the third solvent is selected from one or more of methyl ethyl ketone, propylene glycol methyl ether, methyl isobutyl ketone, isopropanol, ethyl acetate, toluene, butanone, and methyl isobutyl ketone.

[0053] The present invention also provides a method for preparing the above high-hardness and high-wear-resistant antistatic film, comprising the following steps:

[0054] S1. Mix the printable acrylic resin, multifunctional acrylic monomer, first photoinitiator and first solvent evenly to obtain a hardening coating solution, apply the hardening coating solution on the substrate, heat and dry, 300-500mJ / cm 2 Photocuring is used to obtain a hardened layer with a thickness of 5-7 μm, high hardness and repeatable printing. The curing energy and coating thickness of the hardened layer need to be strictly controlled.

[0055] S2, polyurethane acrylic resin, active monomer, antistatic agent, second photoinitiator, second solvent are mixed evenly to obtain antistatic coating liquid, the antistatic coating liquid is coated on the hardened layer, and after heating and drying, 400-600mJ / cm 2 Photocuring to obtain an antistatic layer with a thickness of 1-3μm; since this type of antistatic agent is a transparent liquid and contains a lipophilic segment with a longer carbon chain, it can increase the binding and cross-linking degree between the active monomer and the polyurethane acrylic resin, and can solve the problem of the antistatic agent affecting the transmittance, thereby obtaining an antistatic coating with stable surface resistivity and optical transmittance; the curing energy and coating thickness of the antistatic layer need to be strictly controlled.

[0056] S3, prepolymer, active diluent, fluorine-containing auxiliary agent, third photoinitiator, third solvent are mixed evenly to obtain anti-fingerprint coating liquid, anti-fingerprint coating liquid is applied on the antistatic layer, and after heating and drying, 500-800mJ / cm 2Photocuring is performed to obtain an anti-fingerprint layer with a thickness of 300-600nm, which has wear resistance and does not affect antistatic properties; wherein the curing energy and coating thickness of the anti-fingerprint layer need to be strictly controlled; and finally an antistatic film with high hardness and high wear resistance is obtained.

[0057] The laminated structure of the substrate, hardened layer, antistatic layer and anti-fingerprint layer designed by the present invention can achieve optical transmittance, high hardness and wear resistance and stable surface resistivity. Among them, the selection of multifunctional acrylic monomers and the strict control of the addition amount and the thickness of the hardened layer can achieve high hardness support and high adhesion and weather resistance of the coating on the substrate. If the thickness of the hardened layer is too thin, the hardness will be too low; if the thickness of the hardened layer is too thick, it will lead to incomplete curing, adhesion problems and easy cracking of the coating. The antistatic agent containing a lipophilic chain segment with a longer carbon chain is selected in the antistatic layer, which increases the binding and crosslinking degree between the active monomer and the polyurethane acrylic resin, and can solve the problem of the antistatic agent affecting the transmittance, thereby achieving stable surface resistivity and optical transmittance. The design and matching of prepolymers, fluorine-containing additives and active diluents in the anti-fingerprint layer can achieve high wear resistance. At the same time, the strict control of the thickness of the anti-fingerprint layer can achieve the performance of high wear resistance and stable surface resistivity of the finished antistatic film. If the anti-fingerprint layer is too thin, the fluorine mobility on the surface of the anti-fingerprint layer will be reduced and the wear resistance will be weakened; if the anti-fingerprint layer is too thick, the static charge will not be able to leak quickly and the antistatic property will be reduced.

[0058] The above is the overall concept of the present invention, and detailed embodiments and comparative examples are provided below on the basis of the overall concept of the present invention to further illustrate the present invention.

[0059] Example 1

[0060] An antistatic film with high hardness and wear resistance comprises a substrate, a hardening layer, an antistatic layer, and an anti-fingerprint layer which are stacked in sequence from bottom to top, and a preparation method thereof comprises the following steps:

[0061] S1. Preparation of hardened layer:

[0062] Weigh 60 parts by weight of a printable acrylic resin (Changxing Chemical DR-U384), 10 parts by weight of a multifunctional acrylic monomer (dipentaerythritol hexaacrylate), 3 parts by weight of a first photoinitiator (hydroxydimethylacetophenone), and 30 parts by weight of a first solvent (a mixture of propylene glycol methyl ether and ethyl acetate in a mass ratio of 1:1), mix and stir for 1 hour at a speed of 800 rpm to prepare a hardened coating solution.

[0063] The hardening coating liquid was coated on a 125 μm PET substrate using a 30# wire rod, baked in an oven at 80°C for 2 min, and cured in a UV curing machine with a UV energy of 400 mJ / cm 2, under nitrogen protection, a hardened layer with a dry thickness of 6.2μm was obtained after curing.

[0064] S2. Preparation of antistatic layer:

[0065] Weigh 50 parts by weight of a polyurethane acrylic resin (Sartomer CN968), 10 parts by weight of an active monomer (pentaerythritol triacrylate), 10 parts by weight of an antistatic agent (3M FC4400), 5 parts by weight of a second photoinitiator (1-hydroxycyclohexyl phenyl ketone), and 40 parts by weight of a second solvent (a mixture of propylene glycol methyl ether and isopropanol in a mass ratio of 1:1), mix and stir for 1 hour at a speed of 600 rpm to prepare an antistatic layer coating solution.

[0066] The antistatic coating liquid was coated on the hardened coating using a 15# wire rod, baked in an oven at 80°C for 2 minutes, and cured in a UV curing machine with a UV energy of 500mJ / cm 2 , under nitrogen protection, an antistatic layer with a dry thickness of 2.1 μm was obtained after curing.

[0067] S3, preparing anti-fingerprint layer:

[0068] Weigh 30 parts by weight of prepolymer (DSM NeoRad U-60), 15 parts by weight of active diluent (trimethylolpropane triacrylate), 2 parts by weight of fluorine-containing additive (Arakawa 1207), 4 parts by weight of the third photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone), and 70 parts by weight of the third solvent (a mixture of methyl isobutyl ketone: isopropanol in a mass ratio of 1:2), mix and stir for 1 hour at a speed of 700 rpm to prepare an anti-fingerprint coating liquid.

[0069] The anti-fingerprint coating liquid was coated on the antistatic coating using a 10# wire rod, baked in an oven at 80°C for 2 minutes, and cured in a UV curing machine with a UV energy of 800mJ / cm 2 , under nitrogen protection, an anti-fingerprint layer with a dry thickness of 500nm is obtained after curing, and finally an antistatic film with high hardness and high wear resistance is obtained.

[0070] Example 2

[0071] An antistatic film with high hardness and wear resistance comprises a substrate, a hardening layer, an antistatic layer, and an anti-fingerprint layer which are stacked in sequence from bottom to top, and a preparation method thereof comprises the following steps:

[0072] S1. Preparation of hardened layer:

[0073] Weigh 70 parts by weight of a printable acrylic resin (Changxing Chemical DR-U384), 5 parts by weight of a multifunctional acrylic monomer (trimethylolpropane ethoxy triacrylate), 5 parts by weight of a first photoinitiator (1-hydroxycyclohexyl phenyl ketone), and 50 parts by weight of a first solvent (a mixture of propylene glycol methyl ether and ethyl acetate in a mass ratio of 1:1), mix and stir for 1 hour at a speed of 800 rpm to prepare a hardening layer coating solution.

[0074] The coating liquid was coated on a 125 μm PET substrate using a 30# wire rod, baked in an oven at 80°C for 2 min, and cured in a UV curing machine with a UV energy of 500 mJ / cm 2 , under nitrogen protection, a hardened layer with a dry thickness of 7μm was obtained after curing.

[0075] S2. Preparation of antistatic layer:

[0076] Weigh 60 parts by weight of a polyurethane acrylic resin (Sartomer CN959), 8 parts by weight of an active monomer (trimethylolpropane triacrylate), 7 parts by weight of an antistatic agent (3M FC4400), 4 parts by weight of a second photoinitiator (hydroxycyclohexyl phenyl ketone), and 30 parts by weight of a second solvent (a mixture of propylene glycol methyl ether and ethanol in a mass ratio of 1:1), mix and stir for 1 hour at a speed of 600 rpm to prepare an antistatic layer coating solution.

[0077] The coating liquid was coated on the hardened coating using a 15# wire rod, baked in an oven at 80°C for 2 minutes, and cured in a UV curing machine with a UV energy of 600mJ / cm 2 , under nitrogen protection, an antistatic layer with a dry thickness of 3μm was obtained after curing.

[0078] S3, preparing anti-fingerprint layer:

[0079] Weigh 45 parts by weight of prepolymer (DSM NeoRad U-60), 20 parts by weight of active diluent (pentaerythritol tetraacrylate), 5 parts by weight of fluorine-containing additive (Shin-Etsu KY-1206), 1 part by weight of the third photoinitiator (2,4,6-trimethylformyl-diphenylphosphine oxide), and 40 parts by weight of the third solvent (propylene glycol methyl ether: ethyl acetate = 1:1), mix and stir for 1 hour at a speed of 700 rpm to prepare an anti-fingerprint coating liquid.

[0080] The coating liquid was coated on the antistatic coating using a 10# wire rod, baked in an oven at 80°C for 2 minutes, and cured in a UV curing machine with a UV energy of 700mJ / cm 2 , under nitrogen protection, after curing, an anti-fingerprint layer with a dry thickness of 600nm was obtained, and finally an antistatic film with high hardness and high wear resistance was obtained.

[0081] Example 3

[0082] An antistatic film with high hardness and wear resistance comprises a substrate, a hardening layer, an antistatic layer, and an anti-fingerprint layer which are stacked in sequence from bottom to top, and a preparation method thereof comprises the following steps:

[0083] S1. Preparation of hardened layer:

[0084] Weigh 50 parts by weight of a printable acrylic resin (Changxing Chemical DR-U384), 20 parts by weight of a multifunctional acrylic monomer (a mixture of trimethylolpropane ethoxy triacrylate: pentaerythritol triacrylate in a mass ratio of 1:1), 1 part by weight of a first photoinitiator (hydroxydimethylacetophenone), and 35 parts by weight of a first solvent (a mixture of propylene glycol methyl ether: butanone in a mass ratio of 1:2), mix and stir for 1 hour at a speed of 800 rpm to prepare a hardening layer coating solution.

[0085] The coating liquid was coated on a 125 μm PET substrate using a 30# wire rod, baked in an oven at 80°C for 2 min, and cured in a UV curing machine with a UV energy of 300 mJ / cm 2 , under nitrogen protection, a hardened layer with a dry thickness of 5μm was obtained after curing.

[0086] S2. Preparation of antistatic layer:

[0087] Weigh 30 parts by weight of a polyurethane acrylic resin (Sartomer CN980), 5 parts by weight of an active monomer (a mixture of pentaerythritol triacrylate: trimethylolpropane triacrylate in a mass ratio of 1:2), 5 parts by weight of an antistatic agent (3MFC4400), 1 part by weight of a second photoinitiator (1-hydroxycyclohexyl phenyl ketone), and 60 parts by weight of a second solvent (a mixture of ethylene glycol methyl ether: isopropanol in a mass ratio of 1:3), mix and stir for 1 hour at a speed of 600 rpm to prepare an antistatic layer coating solution.

[0088] The coating liquid was coated on the hardened coating using a 15# wire rod, baked in an oven at 80°C for 2 minutes, and cured in a UV curing machine with a UV energy of 400mJ / cm 2 , under nitrogen protection, an antistatic layer with a dry thickness of 1 μm was obtained after curing.

[0089] S3, preparing anti-fingerprint layer:

[0090] Weigh 50 parts by weight of prepolymer (DSM NeoRad U-60), 5 parts by weight of active diluent (pentaerythritol tetraacrylate), 1 part by weight of fluorine-containing additive (Shin-Etsu KY-1206), 5 parts by weight of the third photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone), and 65 parts by weight of the third solvent (a mixture of propylene glycol methyl ether: toluene in a mass ratio of 1:1), mix and stir for 1 hour at a speed of 700 rpm to prepare an anti-fingerprint coating liquid.

[0091] The coating liquid was coated on the antistatic coating using a 10# wire rod, baked in an oven at 80°C for 2 minutes, and cured in a UV curing machine with a UV energy of 500mJ / cm 2 , under nitrogen protection, an anti-fingerprint layer with a dry thickness of 300nm is obtained after curing, and finally an antistatic film with high hardness and high wear resistance is obtained.

[0092] Example 4

[0093] An antistatic film with high hardness and wear resistance comprises a substrate, a hardening layer, an antistatic layer, and an anti-fingerprint layer which are stacked in sequence from bottom to top, and a preparation method thereof comprises the following steps:

[0094] S1. Preparation of hardened layer:

[0095] Weigh 45 parts by weight of a printable acrylic resin (Changxing Chemical DR-U384), 12 parts by weight of a multifunctional acrylic monomer (trimethylolpropane ethoxy triacrylate), 3 parts by weight of a first photoinitiator (a mixture of hydroxydimethylacetophenone: 1-hydroxycyclohexyl phenyl ketone in a mass ratio of 1:1), and 40 parts by weight of a first solvent (a mixture of propylene glycol methyl ether: butanone: ethyl acetate in a mass ratio of 1:1:1), mix and stir for 1 hour at a speed of 800 rpm to prepare a hardening layer coating solution.

[0096] The coating liquid was coated on a 100 μm PET substrate using a 30# wire rod, baked in an oven at 80°C for 2 min, and cured in a UV curing machine with a UV energy of 450 mJ / cm 2 , under nitrogen protection, a hardened layer with a dry thickness of 5.8μm was obtained after curing.

[0097] S2. Preparation of antistatic layer:

[0098] Weigh 45 parts by weight of a polyurethane acrylic resin (Sartomer CN980), 8 parts by weight of an active monomer (a mixture of pentaerythritol triacrylate and trimethylolpropane triacrylate in a mass ratio of 1:1), 7 parts by weight of an antistatic agent (3MFC4400), 3 parts by weight of a second photoinitiator (a mixture of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-1-propanone in a mass ratio of 1:1), and 55 parts by weight of a second solvent (a mixture of ethylene glycol methyl ether and isopropanol in a mass ratio of 2:1), mix and stir for 1 hour at a speed of 600 rpm to prepare an antistatic layer coating solution.

[0099] The coating liquid was coated on the hardened coating using a 15# wire rod, baked in an oven at 80°C for 2 minutes, and cured in a UV curing machine with a UV energy of 450mJ / cm 2 , under nitrogen protection, an antistatic layer with a dry thickness of 1.8 μm was obtained after curing.

[0100] S3, preparing anti-fingerprint layer:

[0101] Weigh 45 parts by weight of prepolymer (DSM NeoRad U-60), 6 parts by weight of active diluent (pentaerythritol tetraacrylate), 4 parts by weight of fluorine-containing additive (Shin-Etsu KY-1206), 4 parts by weight of the third photoinitiator (a mixture of hydroxydimethylacetophenone:1-hydroxycyclohexyl phenyl ketone in a mass ratio of 1:1), and 65 parts by weight of the third solvent (a mixture of propylene glycol methyl ether:toluene in a mass ratio of 1:1), mix and stir for 1 hour at a speed of 700 rpm to prepare an anti-fingerprint coating liquid.

[0102] The coating liquid was coated on the antistatic coating using a 10# wire rod, baked in an oven at 80°C for 2 minutes, and cured in a UV curing machine with a UV energy of 450mJ / cm 2 , under nitrogen protection, an anti-fingerprint layer with a dry thickness of 350nm was obtained after curing, and finally an antistatic film with high hardness and high wear resistance was obtained.

[0103] Example 5

[0104] An antistatic film with high hardness and wear resistance comprises a substrate, a hardening layer, an antistatic layer, and an anti-fingerprint layer which are stacked in sequence from bottom to top, and a preparation method thereof comprises the following steps:

[0105] S1. Preparation of hardened layer:

[0106] Weigh 55 parts by weight of a printable acrylic resin (Changxing Chemical DR-U384), 12 parts by weight of a multifunctional acrylic monomer (a mixture of trimethylolpropane ethoxy triacrylate: pentaerythritol triacrylate: trimethylolpropane triacrylate in a mass ratio of 1:1:1), 3 parts by weight of a first photoinitiator (a mixture of hydroxydimethylacetophenone: 1-hydroxycyclohexyl phenyl ketone in a mass ratio of 1:1), and 35 parts by weight of a first solvent (propylene glycol methyl ether), mix and stir for 1 hour at a speed of 800 rpm to prepare a hardening layer coating solution.

[0107] The coating liquid was coated on a 100 μm PET substrate using a 30# wire rod, baked in an oven at 80°C for 2 min, and cured in a UV curing machine with a UV energy of 350 mJ / cm 2 , under nitrogen protection, a hardened layer with a dry thickness of 6.7μm was obtained after curing.

[0108] S2. Preparation of antistatic layer:

[0109] Weigh 55 parts by weight of a polyurethane acrylic resin (Sartomer CN980), 10 parts by weight of an active monomer (a mixture of pentaerythritol triacrylate and trimethylolpropane triacrylate in a mass ratio of 2:1), 8 parts by weight of an antistatic agent (3MFC4400), 5 parts by weight of a second photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone), and 45 parts by weight of a second solvent (a mixture of ethylene glycol methyl ether and isopropanol in a mass ratio of 1:1), mix and stir for 1 hour at a speed of 600 rpm to prepare an antistatic layer coating solution.

[0110] The coating liquid was coated on the hardened coating using a 15# wire rod, baked in an oven at 80°C for 2 minutes, and cured in a UV curing machine with a UV energy of 550mJ / cm 2 , under nitrogen protection, an antistatic layer with a dry thickness of 2.4 μm was obtained after curing.

[0111] S3, preparing anti-fingerprint layer:

[0112] Weigh 35 parts by weight of prepolymer (DSM NeoRad U-60), 8 parts by weight of active diluent (pentaerythritol tetraacrylate), 3 parts by weight of fluorine-containing additive (Shin-Etsu KY-1206), 3 parts by weight of the third photoinitiator (a mixture of hydroxydimethylacetophenone:1-hydroxycyclohexyl phenyl ketone in a mass ratio of 2:1), and 60 parts by weight of the third solvent (a mixture of propylene glycol methyl ether:toluene in a mass ratio of 1:2), mix and stir for 1 hour at a speed of 700 rpm to prepare an anti-fingerprint coating liquid.

[0113] The coating liquid was coated on the antistatic coating using a 10# wire rod, baked in an oven at 80°C for 2 minutes, and cured in a UV curing machine with a UV energy of 400mJ / cm 2 , under nitrogen protection, after curing, an anti-fingerprint layer with a dry thickness of 450nm was obtained, and finally an antistatic film with high hardness and high wear resistance was obtained.

[0114] Comparative Example 1

[0115] Different from Example 1, the antistatic film of this embodiment includes a substrate, a hardening layer, and an anti-fingerprint layer stacked in sequence from bottom to top, and an antistatic agent is added to the hardening layer. The preparation method thereof includes the following steps:

[0116] S1. Preparation of hardened layer:

[0117] Weigh 60 parts by weight of a printable acrylic resin (Changxing Chemical DR-U384), 10 parts by weight of a multifunctional acrylic monomer (dipentaerythritol hexaacrylate), 10 parts by weight of an antistatic agent (3M FC4400), 3 parts by weight of a first photoinitiator (hydroxydimethylacetophenone), and 30 parts by weight of a first solvent (a mixture of propylene glycol methyl ether and ethyl acetate in a mass ratio of 1:1), mix and stir for 1 hour at a speed of 800 rpm to prepare a hardening layer coating solution.

[0118] The coating liquid was coated on a 125 μm PET substrate using a 30# wire rod, baked in an oven at 80°C for 2 min, and cured in a UV curing machine with a UV energy of 400 mJ / cm 2 , under nitrogen protection, after curing, an antistatic hardened layer with a dry thickness of 6.2μm was obtained.

[0119] S2. Preparation of anti-fingerprint layer:

[0120] Weigh 30 parts by weight of prepolymer (DSM NeoRad U-60), 15 parts by weight of active diluent (trimethylolpropane triacrylate), 2 parts by weight of fluorine-containing additive (Arakawa 1207), 4 parts by weight of the third photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone), and 70 parts by weight of the third solvent (a mixture of methyl isobutyl ketone: isopropanol in a mass ratio of 1:2), mix and stir for 1 hour at a speed of 700 rpm to prepare an anti-fingerprint coating liquid.

[0121] The coating liquid was coated on the hardened layer with antistatic agent using a 10# wire rod, baked in an oven at 80°C for 2 minutes, and cured in a UV curing machine with a UV energy of 800mJ / cm 2 , in nitrogen protection, after curing, an anti-fingerprint layer with a dry thickness of 500nm was obtained, and finally an antistatic film with high hardness and high wear resistance was obtained. Among them, the antistatic agent added to the hardened layer caused the hardness to be significantly reduced.

[0122] Comparative Example 2

[0123] Different from Example 1, the thickness of the hardened layer is adjusted to 3.5 μm. Since the thickness of the hardened layer is relatively thin, the hardness of the finished film is relatively low.

[0124] Comparative Example 3

[0125] Different from Example 1, the thickness of the anti-fingerprint layer is adjusted to 2 μm. Since the thickness of the anti-fingerprint layer is too thick, the antistatic performance of the finished film is unstable.

[0126] Comparative Example 4

[0127] Different from Example 1, the thickness of the anti-fingerprint layer is adjusted to 100 nm. Since the thickness of the anti-fingerprint layer is relatively thin, the anti-scratch and wear resistance of the finished film is poor.

[0128] Comparative Example 5

[0129] Different from Example 1, the antistatic agent in the antistatic layer is carbon black, metal oxides, etc. Since carbon black and metal oxides have dark colors, poor dispersibility, and poor compatibility with resins, the transmittance of the finished film is low.

[0130] The antistatic films prepared in the examples and comparative examples were subjected to the following performance tests:

[0131] (1) Transmittance and haze: The transmittance and haze of the optical film were measured using a Nippon Denshoku NDH 2000N haze meter using a transmitted light method in accordance with JIS K-7105.

[0132] (2) Pencil hardness: According to JISK-5600 standard, use Elcometer 3086 pencil hardness tester to measure the pencil hardness of optical film. Test method: Use Mitsubishi pencil with hardness of H to 3H to draw 5 lines with a length of 5 cm under a load of 500g, then observe whether the optical film coating is scratched under fluorescent light and judge according to the following standards.

[0133]

Judgment criteria

[0134] 0 to 2 scratches, judged OK

[0135] 3 to 5 scratches, judged as NG

[0136] (3) Steel wool abrasion resistance: According to ASTM F2496 standard, Shanghai Chengwei Instrument Technology Steel Wool Abrasion Resistance Tester was used with a load of 1000g and Japanese Bonstar #0000 steel wool. The test head area was 2*2cm. The surface of the optical film was rubbed back and forth at a speed of 40 cycles / min and a stroke of about 40mm to confirm the scratch condition of the coating surface.

[0137] (4) Surface resistivity: Surface resistivity tester RT-100 is used for testing, voltage 100V, ambient temperature 25℃, humidity RH 60%, surface resistivity display value range is 10 6 -10 12 Ω / m 2 .

[0138] (5) Water contact angle (WCA): A CA10000 water contact angle tester manufactured by Dongguan Kandi Electronic Equipment Co., Ltd. was used with a 2.0 μL droplet. The optical film was placed face up on the test bench and fixed with tape. The water contact angle was calculated using the measurement method using the test software.

[0139] (6) Grid: According to ASTM D-3359, use a 1*1 cm grid cutter to draw grids on the surface of the optical film. Attach 3M600 tape to the drawn grid and flatten it with a rubber roller. Quickly tear off the tape and use a magnifying glass to observe the grid peeling status.

[0140]

Judgment criteria

[0141] 5B: The cut edges are completely smooth, and there is no peeling on the lattice edges.

[0142] 4B: There is small flakes at the intersection of the cuts, and the damage in the cross-cut area is ≤5%.

[0143] 3B: The edges and / or intersections of the cuts are peeled off, with an area of ​​5-15%.

[0144] 2B: There is partial or complete peeling along the edge of the cut, and / or part of the grid is completely peeled off. The peeled area is 15-35%.

[0145] 1B: Large pieces of the cut edge peel off / or some squares peel off partially or completely, with an area of ​​35-65%.

[0146] 0B: Large pieces of the cut edge peel off / or some squares peel off partially or completely, with an area of ​​>65%.

[0147] The test results are shown in Table 1 below:

[0148] Table 1 Summary of test data of embodiments and comparative examples

[0149]

[0150]

[0151] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to specific details.

Claims

1. A high-hardness and high-wear-resistant antistatic film, characterized in that: It includes a substrate, a hardening layer, an antistatic layer and an anti-fingerprint layer which are stacked in sequence: The hardened layer is obtained by coating a hardening coating liquid on the substrate layer and then curing the coating liquid. The hardening coating liquid comprises, by weight: 50-70 parts of a printable acrylic resin, 5-20 parts of a multifunctional acrylic monomer, 1-5 parts of a first photoinitiator, and 30-50 parts of a first solvent.

2. The high-hardness and high-wear-resistant antistatic film according to claim 1, characterized in that: The printable acrylic resin is selected from one or more of polyurethane acrylic resin, polyester acrylic resin, epoxy acrylic resin and pure acrylic resin; The multifunctional acrylic monomer is selected from one or more of dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, pentaerythritol triacrylate, trimethylolpropane ethoxy triacrylate, 1,6-hexanediol diacrylate, propoxylated glycerol triacrylate, propylene propyl triacrylate, propoxylated glycerol triacrylate, and tripropylene glycol diacrylate.

3. The high-hardness and high-wear-resistant antistatic film according to claim 1, characterized in that: The first photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, hydroxydimethyl acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; The first solvent is selected from one or more of methyl ethyl ketone, isopropanol, ethyl acetate, toluene, butanone, methyl isobutyl ketone, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

4. The high-hardness and high-wear-resistant antistatic film according to claim 1, characterized in that: The antistatic layer is obtained by coating an antistatic coating liquid on the substrate layer and then curing the coating liquid. The antistatic coating liquid comprises, by weight: 30-60 parts of polyurethane acrylic resin, 5-10 parts of active monomer, 5-10 parts of antistatic agent, 1-5 parts of second photoinitiator, and 30-60 parts of second solvent.

5. The high-hardness and high-wear-resistant antistatic film according to claim 4, characterized in that: The polyurethane acrylic resin is selected from one or more of trifunctional aromatic polyurethane acrylic resin, trifunctional aliphatic polyurethane acrylic resin, tetrafunctional aromatic polyurethane acrylic resin, tetrafunctional aliphatic polyurethane acrylic resin, and hexafunctional aliphatic polyurethane acrylic resin; The active monomer is an acrylic monomer with 3-6 functionalities, selected from one or more of pentaerythritol tetraacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, and trimethylolpropane ethoxy triacrylate.

6. The high-hardness and high-wear-resistant antistatic film according to claim 4, characterized in that: The antistatic agent is an organic surfactant selected from one or more of sodium alkyl sulfonate, organic phosphate, organic phosphate, allyl imine, and long carbon chain quaternary ammonium salt; The second photoinitiator is a ketone initiator selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzyl dimethyl ketal, hydroxydimethyl acetophenone, and hydroxycyclohexyl phenyl ketone; The second solvent is an alcohol or ether solvent, selected from one or more of propylene glycol methyl ether, isopropanol, ethanol, and ethylene glycol methyl ether.

7. The high-hardness and high-wear-resistant antistatic film according to claim 1, characterized in that: The anti-fingerprint layer is obtained by coating an anti-fingerprint coating liquid on the substrate layer and then curing the coating liquid. The anti-fingerprint coating liquid comprises, by weight: 30-50 parts of prepolymer, 5-20 parts of active diluent, 1-5 parts of fluorine-containing auxiliary agent, 1-5 parts of a third photoinitiator, and 40-70 parts of a third solvent.

8. The high-hardness and high-wear-resistant antistatic film according to claim 7, characterized in that: The prepolymer is selected from one or more of fluorosilicone modified polyester acrylic resin, fluorosilicone modified polyurethane acrylic resin, fluorosilicone modified epoxy acrylic resin, fluorosilicone modified acrylic resin, nanoparticle hybrid resin, and silicone resin.

9. The high-hardness and high-wear-resistant antistatic film according to claim 7, characterized in that: The active diluent is one or more of low-functional acrylic ester monomers such as isobornyl acrylate, N,N-dimethylacrylamide, 4-acryloylmorpholine, 1,6-hexanediol diacrylate, multifunctional acrylic monomers, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate; The third photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 4-dimethylamino-ethyl benzoate, hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylformyl-diphenylphosphine oxide, and methyl benzoylformate; The third solvent is selected from one or more of methyl ethyl ketone, propylene glycol methyl ether, methyl isobutyl ketone, isopropanol, ethyl acetate, toluene, butanone, and methyl isobutyl ketone.

10. A method for preparing a high-hardness and high-wear-resistant antistatic film according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1. Mix the printable acrylic resin, multifunctional acrylic monomer, first photoinitiator and first solvent evenly to obtain a hardening coating solution, apply the hardening coating solution on the substrate, heat and dry, 300-500mJ / cm 2 Light curing to obtain a hardened layer with a thickness of 5-7 μm; S2, polyurethane acrylic resin, active monomer, antistatic agent, second photoinitiator, second solvent are mixed evenly to obtain antistatic coating liquid, the antistatic coating liquid is coated on the hardened layer, and after heating and drying, 400-600mJ / cm 2 Photocuring to obtain an antistatic layer with a thickness of 1-3 μm; S3, prepolymer, active diluent, fluorine-containing auxiliary agent, third photoinitiator, third solvent are mixed evenly to obtain anti-fingerprint coating liquid, anti-fingerprint coating liquid is applied on the antistatic layer, and after heating and drying, 500-800mJ / cm 2 Photocuring is performed to obtain an anti-fingerprint layer with a thickness of 300-600 nm; and finally the antistatic film with high hardness and high wear resistance is obtained.

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