A photocurable hard coating liquid composition, a hard coating film and a method for producing the same

Abstract

A photocurable coating liquid composition and a hard coating film, the photocurable coating liquid composition comprising the following components: a hexafunctional polyurethane acrylate oligomer, a mercapto silane compound, a trifunctional acrylate, a UV absorber, a leveling agent, and a photoinitiator. The hard coating layer prepared from the photocurable coating liquid composition can simultaneously have good flexibility, good adhesion, high hardness, and the like, and also has low R-angle thermoforming properties.

Description

Technical Field

[0001] This application belongs to the field of photocurable coating technology, specifically relating to a photocurable hard coating composition with high hardness, good flexibility and substrate adhesion, a hardened film and its preparation method. Background Technology

[0002] In-mold decoration (IMD) is a popular surface decoration technology, primarily used for the surface decoration of panels in various small household appliances, such as POS machine panels, robot vacuum cleaner control panels, rice cooker control panels, refrigerator control panels, charging pile panels, and car dashboards. IMD involves placing a decorated film carrier in an injection mold at a specific temperature, achieving integrated molding during the molten plastic injection process. This ensures the decorative film carrier adheres firmly to the surface of the plastic component with a predetermined shape. Products made using IMD technology offer a better sense of solidity and scratch resistance compared to the traditional technique of first injection molding and then printing the design onto the product surface. They also avoid defects such as ink fading and peeling.

[0003] CN202110450637.0 discloses a photocurable composition and a hard coating film; the photocurable composition comprises the following components: a high-functionality polyurethane acrylate oligomer, a multifunctional thiol compound, a hyperbranched unsaturated resin, a low-functionality fluorinated acrylate oligomer, and inorganic nanoparticles.

[0004] To adapt to the IMD molding process, IMD films are required to possess not only high hardness and scratch resistance, but also the ability to withstand the thermoforming of 3D curved surfaces with small radius angles without coating cracking. While PET film is a commonly used substrate for IMD decorative films due to its excellent optical transparency and thermoforming tensile properties, its drawbacks include low surface hardness and poor abrasion resistance. Applying a hardening coating to the surface of PET film can significantly improve its surface hardness and abrasion / scratch resistance; however, currently used hardening coatings are brittle and cannot withstand the tensile deformation during the IMD thermoforming process, leading to cracking. Therefore, achieving a hardened IMD film that combines high hardness and excellent thermoforming properties is a key technological challenge for the industry.

[0005] Furthermore, for some IMD curable film products used in automotive applications, outdoor applications, or those requiring high standards for aging and yellowing prevention, it is often necessary to add UV-absorbing additives, such as benzophenones, benzotriazoles, or triazines, to the hard coating. Regarding UV-curable hard coatings, the inventors of this application have found that the addition of these UV-absorbing additives interferes with the UV curing reaction of the curing formulation, resulting in poor adhesion between the coating and the substrate. Therefore, how to balance and resolve this contradiction has become a research hotspot in the field of IMD technology. Summary of the Invention

[0006] To address the problems of poor adhesion to the substrate and easy cracking in 3D thermoforming of existing in-mold decorative UV-resistant hard coatings, this application provides a photocurable hard coating liquid composition, a hard coating film, and a preparation method thereof for in-mold decoration. The photocurable UV-resistant hard coating film has good adhesion to the substrate and can adapt to 3D thermoforming with small radius angles.

[0007] To solve the above-mentioned technical problems, this application adopts the following technical solution.

[0008] This application provides a photocurable hard coating composition comprising the following components: 20-40 parts by weight of a high-functionality polyurethane-propionic acid oligomer, wherein the high-functionality polyurethane-propionic acid oligomer has a functionality of six or more; 5-10 parts by weight of a mercaptosilane compound; 5-15 parts by weight of an acrylate monomer; 0.5-1.0 parts by weight of a leveling agent; 1-5 parts by weight of a UV absorber; 1.0-3.5 parts by weight of a photoinitiator; and 35-55 parts by weight of a solvent.

[0009] Furthermore, the total weight parts of the high-functionality polyurethane propionate oligomer, mercaptosilane compound, acrylate monomer, leveling agent, ultraviolet absorber, photoinitiator, and solvent are 100 parts by weight.

[0010] Furthermore, the high-functionality polyurethane acrylate oligomer is selected from one of hexafunctional polyurethane acrylate oligomers, heptfunctional polyurethane acrylate oligomers, and octafunctional polyurethane acrylate oligomers, with hexafunctional polyurethane acrylate oligomers being preferred.

[0011] Furthermore, the high-functionality polyurethane propionate oligomer is present in amounts of 25-35 parts by weight, or 28, 30, or 32 parts by weight.

[0012] Furthermore, the mercaptosilane compound is a mercaptosilane oligomer.

[0013] Furthermore, the mercaptosilane compound is selected from mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, or oligomers thereof, preferably mercaptopropyltrimethoxysilane oligomers.

[0014] Furthermore, the mercaptosilane compound is present in parts by weight of 6, 7, 8, and 9.

[0015] Furthermore, the mercaptosilane compound can participate in the UV-initiated free radical curing crosslinking reaction through the mercapto group, which has the following advantages: it can reduce the decrease in hardness and wear resistance of the coating surface due to the oxygen inhibition effect; by controlling the gradual increase of the degree of polymerization, the shrinkage stress during the coating curing process is small; and the introduction of thioether bonds with low rotation barriers into the hardened coating system gives the hardened coating good toughness.

[0016] Furthermore, the inventors discovered that while simply using multi-thiol compounds (such as pentaerythritol tetrakis(3-mercaptopropionic acid)) partially solves the adhesion problem with PET substrates, introducing siloxane bonds into the thiol compounds can significantly increase the adhesion between the coating and the substrate through the reaction of active hydrogen groups on the substrate surface.

[0017] The polythiol silane oligomers of this application can be prepared using commercially available products or by self-preparation. For example, in a 1000ml three-necked flask, under the protection of high-purity nitrogen, 350g of mercaptopropyltrimethoxysilane and 85g of anhydrous methanol are added sequentially. Then, a mixture of 18g of deionized water and 70g of anhydrous methanol is slowly added dropwise to the above system through a dropping funnel. After completion, the system is heated and refluxed at 85°C for 3 hours to distill off the methanol, thereby obtaining the polythiol propyltrimethoxysilane oligomers.

[0018] Furthermore, the acrylate monomer is selected from one of trimethylolpropane triacrylate, 3-propoxypropanetriol triacrylate, pentaerythritol triacrylate, and trimethylolpropane trimethacrylate, preferably pentaerythritol triacrylate.

[0019] Furthermore, the acrylate monomers are present in parts by weight of 6, 8, 10, and 11.

[0020] Furthermore, the leveling agent is selected from one or at least two of fluorinated leveling agents, organosiloxane leveling agents, or organosilicone modified leveling agents, preferably organosiloxane leveling agents, such as one or at least two of BYK 333, BYK 337, and BYK 310.

[0021] Furthermore, the leveling agent has a weight ratio of 0.6, 0.7, 0.8, or 0.9.

[0022] Furthermore, the UV absorber is selected from one or a combination of two of benzophenones, benzotriazoles, or triazines. Considering higher UV absorption efficiency and a wider absorption wavelength range, benzotriazole UV absorbers are preferred. The addition ratio is preferably 2-5 parts by weight. Too little addition will not have an effective anti-UV aging effect, while excessive addition of UV absorbers will interfere with the UV curing reaction of the hard coating liquid, thereby causing a decrease in adhesion or even precipitation leading to fogging of the film surface.

[0023] Furthermore, the ultraviolet absorber is present in parts by weight of 2, 3, and 4.

[0024] Furthermore, the photoinitiator is selected from one or a combination of at least two of photoinitiator 184, photoinitiator TPO, photoinitiator 1173, or photoinitiator 127, preferably photoinitiator 184, with an addition ratio preferably of 2.0-3.5 parts by weight, and the ratio of the added photoinitiator to the added UV absorber needs to be greater than or equal to 0.5, or 0.6, 0.8, or 1.0. When the amount of photoinitiator added is small and the ratio is less than 0.5, the photocuring reaction is incomplete, and the UV absorber is prone to precipitation, causing haze on the film surface. On the other hand, excessive addition of photoinitiator will lead to deterioration of coating performance, resulting in yellowing and brittleness.

[0025] Furthermore, the photoinitiator has a weight ratio of 1.5, 2.0, 2.5, or 3.0.

[0026] Furthermore, the solvent is selected from one or a combination of at least two of methyl isobutyl ketone (MIBK), butanone (MEK), propylene glycol monomethyl ether (PMC), isopropanol (IPA), and ethyl acetate (EA), preferably a blend of two or three solvents, such as a blend of IPA, MEK, and PMC in a certain proportion. The blending of high and low boiling point solvents allows for relatively uniform evaporation of the solvent in the wet film after coating, ensuring a smooth and glossy surface.

[0027] Furthermore, the solvent has a weight ratio of 40, 45, 50, or 53.

[0028] Meanwhile, this application provides a hard coating film, including a substrate and a hardening layer, wherein the hardening layer is formed by curing the aforementioned photocurable hard coating composition.

[0029] Meanwhile, this application provides a method for preparing a hard coating film, comprising the following steps: first, preparing a photocurable hard coating liquid composition; applying the photocurable hard coating liquid composition onto a substrate, then performing a solvent removal treatment on the coating, and then photocuring to form the coating.

[0030] Furthermore, the solvent removal process is carried out at 50-100°C, or at 60°C, 70°C, or 80-90°C.

[0031] Furthermore, the thickness of the hard coating is 1.0-15μm, or 3.0, 5.0, 7.0, 10.0, or 12.0μm.

[0032] Furthermore, the coating method is selected from any one of bar coating, comma blade coating, roller coating, slot coating, and microgravure coating, with microgravure coating being preferred.

[0033] Furthermore, the substrate is a transparent substrate, which is one of PET, PC, TAC, and PEN, preferably PET film, and the substrate thickness is 75-250μm, or 100, 120, 150, 180, 200, or 220μm.

[0034] The technical solution provided in this application has the following advantages over the prior art: by introducing mercaptosilane oligomers into the hard coating film and adding a reasonable amount of photoinitiator, the UV-resistant IMD hardened film can have high hardness and anti-aging yellowing, while also having good adhesion to the substrate and excellent coating flexibility, which can meet the requirements of 3D thermoforming with smaller R-angles without the coating cracking. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the structure of the hard coating film for in-mold decoration described in this application.

[0036] Figure 2 This is a photograph of a product formed by in-mold injection molding of polycarbonate with the hard coating film described in this application (the outermost layer is the hard coating film of this application). Detailed implementation method:

[0037] The preferred embodiments of this application are described in detail below to make the advantages and features of this application more easily understood by those skilled in the art, thereby providing a clearer and more definite definition of the scope of protection of this application. The performance of the hard coating film provided by this application is tested according to the following method:

[0038] (1) Haze and total light transmittance: The haze was measured using a Japanese Densho NDH 2000N haze meter by the transmitted light method.

[0039] (2) Pencil Hardness: The hardness of the pencils in the product was measured using an Elcometer 3086 pencil hardness tester. The measurement method was to use a Mitsubishi pencil with a hardness of H to 9H, draw 5 lines under a 500g load, and then observe whether there were any scratches on the hard coating. The hardness grade was determined according to the standard, that is, 0-1 scratches were judged as "OK" and qualified, and 2-5 scratches were judged as "NG" and unqualified.

[0040] (3) Coating thickness: The thickness of the transparent hardened coating was tested using the ETA-SST coating thickness test system based on the principle of light diffraction.

[0041] (4) 380nm transmittance: The transmittance was measured using an NDH SD700 colorimeter by means of the transmittance method.

[0042] (5) Coating adhesion test: Use a cross-cutting tool to gently cut out 100 grids on the coating, and then use 3M 600 to press and flatten it onto the cut part of the cross-cutting. After 5 minutes, tear off the tape and observe the coating fall-off situation in the cross-cutting with a magnifying glass. The coating retention percentage is used for evaluation. If the coating falls off completely, it is judged as 0% and if the coating is completely retained, it is judged as 100%.

[0043] (6) Elongation of coating cracking: Using Haida Instruments' electronic universal tensile testing machine, five 10mm × 150mm tensile samples were cut along the MD direction. At a tensile rate of 100mm / min, the elongation corresponding to the appearance of microcracks in the surface coating was observed. The higher the elongation, the less likely the hardened coating is to crack.

[0044] (7) Determination of bending flexibility: Cut a strip 10cm long × 2cm wide, with the hardened coating facing outwards, and wrap it sequentially around steel rods with diameters of 3cm, 2.5cm, 2cm, 1.5cm, and 1cm. After unfolding, observe the fine cracks on the coating surface. The steel rod above which the fine cracks appear is the bending radius (R-angle) corresponding to the sample. The bending radius (R-angle) is used to characterize the flexibility of the hardened coating; the smaller the bending radius (R-angle), the better the flexibility of the hardened coating.

[0045] Example 1

[0046] The formulation of the UV-curable hard coating composition is as follows: 32 parts by weight of hexafunctional polyurethane propionate oligomer, 5 parts by weight of mercaptopropyltrimethoxysilane oligomer, 8 parts by weight of pentaerythritol triacrylate monomer, 0.2 parts by weight of BYK-333 leveling agent, 4 parts by weight of EVERSORB 109 UV absorber from Yongguang Chemical, 2.5 parts by weight of photoinitiator 184, 29 parts by weight of methyl ethyl ketone (MEK), and 19.3 parts by weight of propylene glycol methyl ether (PMC).

[0047] The uniformly mixed photocurable hard coating composition was coated onto one side of a 125μm thick optical-grade PET film (Toray Industries, Korea, XG7PL2). After drying in an oven at 80-90℃ for 3 minutes, it was then subjected to a curing process at 400mJ / cm². 2 The ultraviolet light energy is used to photocur the dried coating to obtain a hard coating film. The relevant physical property data are shown in Table 1.

[0048] Example 2

[0049] The formulation of the UV-curable hard coating composition is as follows: 32 parts by weight of hexafunctional polyurethane propionate oligomer, 7.5 parts by weight of mercaptopropyltrimethoxysilane oligomer, 8 parts by weight of pentaerythritol triacrylate monomer, 0.2 parts by weight of BYK-333 leveling agent, 4 parts by weight of EVERSORB 109 UV absorber from Yongguang Chemical, 2.5 parts by weight of photoinitiator 184, 28 parts by weight of methyl ethyl ketone (MEK), and 18.2 parts by weight of propylene glycol methyl ether (PMC).

[0050] The uniformly mixed photocurable hard coating composition was coated onto one side of a 125μm thick optical-grade PET film (Toray Industries, Korea, XG7PL2). After drying in an oven at 80-90℃ for 3 minutes, it was then subjected to a curing process at 400mJ / cm². 2 The ultraviolet light energy is used to photocur the dried coating to obtain a hard coating film. The relevant physical property data are shown in Table 1.

[0051] Example 3

[0052] The formulation of the UV-curable hard coating composition is as follows: 32 parts by weight of hexafunctional polyurethane propionate oligomer, 10 parts by weight of mercaptopropyltrimethoxysilane oligomer, 8 parts by weight of pentaerythritol triacrylate monomer, 0.2 parts by weight of BYK-333 leveling agent, 4 parts by weight of EVERSORB 109 UV absorber from Yongguang Chemical, 2.5 parts by weight of photoinitiator 184, 26 parts by weight of methyl ethyl ketone (MEK), and 17.3 parts by weight of propylene glycol methyl ether (PMC).

[0053] The uniformly mixed photocurable hard coating composition was coated onto one side of a 125μm thick optical-grade PET film (Toray Industries, Korea, XG7PL2). After drying in an oven at 80-90℃ for 3 minutes, it was then subjected to a curing process at 400mJ / cm². 2 The ultraviolet light energy is used to photocur the dried coating to obtain a hard coating film. The relevant physical property data are shown in Table 1.

[0054] Example 4

[0055] The formulation of the UV-curable hard coating composition is as follows: 32 parts by weight of hexafunctional polyurethane propionate oligomer, 5 parts by weight of mercaptopropyltrimethoxysilane oligomer, 8 parts by weight of pentaerythritol triacrylate monomer, 0.2 parts by weight of BYK-333 leveling agent, 4 parts by weight of EVERSORB 109 UV absorber from Yongguang Chemical, 2.0 parts by weight of photoinitiator 184, 29 parts by weight of methyl ethyl ketone (MEK), and 19.8 parts by weight of propylene glycol methyl ether (PMC).

[0056] The uniformly mixed photocurable hard coating composition was coated onto one side of a 125μm thick optical-grade PET film (Toray Industries, Korea, XG7PL2). After drying in an oven at 80-90℃ for 3 minutes, it was then subjected to a curing process at 400mJ / cm².2 The ultraviolet light energy is used to photocur the dried coating to obtain a hard coating film. The relevant physical property data are shown in Table 1.

[0057] Example 5

[0058] The formulation of the UV-curable hard coating composition is as follows: 32 parts by weight of hexafunctional polyurethane propionate oligomer, 5 parts by weight of mercaptopropyltrimethoxysilane oligomer, 8 parts by weight of pentaerythritol triacrylate monomer, 0.2 parts by weight of BYK-333 leveling agent, 5 parts by weight of EVERSORB 109 UV absorber from Yongguang Chemical, 3.5 parts by weight of photoinitiator 184, 35 parts by weight of methyl ethyl ketone (MEK), and 24.3 parts by weight of propylene glycol methyl ether (PMC).

[0059] The uniformly mixed photocurable hard coating composition was coated onto one side of a 125μm thick optical-grade PET film (Toray Industries, Korea, XG7PL2). After drying in an oven at 80-90℃ for 3 minutes, it was then subjected to a curing process at 400mJ / cm². 2 The ultraviolet light energy is used to photocur the dried coating to obtain a hard coating film. The relevant physical property data are shown in Table 1.

[0060] Example 6

[0061] The formulation of the UV-curable hard coating composition is as follows: 28 parts by weight of hexafunctional polyurethane propionate oligomer, 5 parts by weight of mercaptopropyltrimethoxysilane oligomer, 7 parts by weight of pentaerythritol triacrylate monomer, 0.2 parts by weight of BYK-333 leveling agent, 4 parts by weight of EVESROB 109 UV absorber, 2.5 parts by weight of photoinitiator 184, 32 parts by weight of methyl ethyl ketone (MEK), and 21.3 parts by weight of propylene glycol methyl ether (PMC).

[0062] The uniformly mixed photocurable hard coating composition was coated onto one side of a 125μm thick optical-grade PET film (Toray Industries, Korea, XG7PL2). After drying in an oven at 80-90℃ for 3 minutes, it was then subjected to a curing process at 400mJ / cm². 2 The ultraviolet light energy is used to photocur the dried coating to obtain a hard coating film. The relevant physical property data are shown in Table 1.

[0063] Example 7

[0064] The formulation of the UV-curable hard coating composition is as follows: 30 parts by weight of hexafunctional polyurethane propionate oligomer, 5 parts by weight of mercaptopropyltrimethoxysilane oligomer, 7.5 parts by weight of pentaerythritol triacrylate monomer, 0.2 parts by weight of BYK-333 leveling agent, 4 parts by weight of EVERSORB 109 UV absorber from Yongguang Chemical, 2.5 parts by weight of photoinitiator 184, 31 parts by weight of methyl ethyl ketone (MEK), and 19.8 parts by weight of propylene glycol methyl ether (PMC).

[0065] The uniformly mixed photocurable hard coating composition was coated onto one side of a 125μm thick optical-grade PET film (Toray Industries, Korea, XG7PL2). After drying in an oven at 80-90℃ for 3 minutes, it was then subjected to a curing process at 400mJ / cm². 2 The ultraviolet light energy is used to photocur the dried coating to obtain a hard coating film. The relevant physical property data are shown in Table 1.

[0066] Comparative Example 1

[0067] The formulation of the light-curing hard coating liquid composition is as follows: 32 parts by weight of hexa-energy polyurethane propionate oligomer, 8 parts by weight of pentaerythritol triacrylate monomer, 0.2 parts by weight of BYK-333 leveling agent, 1.8 parts by weight of photoinitiator 184, 35 parts by weight of methyl ethyl ketone (MEK) and 23 parts by weight of propylene glycol methyl ether (PMC).

[0068] The uniformly mixed photocurable hard coating composition was coated onto one side of a 125μm thick optical-grade PET film (Toray Industries, Korea, XG7PL2). After drying in an oven at 80-90℃ for 3 minutes, it was then subjected to a curing process at 400mJ / cm². 2 The ultraviolet light energy is used to photocur the dried coating to obtain a hard coating film. The relevant physical property data are shown in Table 2.

[0069] The difference between Comparative Example 1 and this application is that it does not contain UV absorbers and mercaptosilane oligomers.

[0070] Comparative Example 2

[0071] The formulation of the UV-curable hard coating composition is as follows: 32 parts by weight of hexafunctional polyurethane propionate oligomer, 8 parts by weight of pentaerythritol triacrylate monomer, 0.2 parts by weight of BYK-333 leveling agent, 4 parts by weight of EVERSORB 109 UV absorber from Yongguang Chemical, 2.5 parts by weight of photoinitiator 184, 32 parts by weight of methyl ethyl ketone (MEK), and 21.3 parts by weight of propylene glycol methyl ether (PMC).

[0072] The uniformly mixed photocurable hard coating composition was coated onto one side of a 125μm thick optical-grade PET film (Toray Industries, Korea, XG7PL2). After drying in an oven at 80-90℃ for 3 minutes, it was then subjected to a curing process at 400mJ / cm². 2 The ultraviolet light energy is used to photocur the dried coating to obtain a hard coating film. The relevant physical property data are shown in Table 2.

[0073] The difference between Comparative Example 2 and this application is that no mercaptosilane oligomer is added.

[0074] Comparative Example 3

[0075] The formulation of the UV-curable hard coating composition is as follows: 32 parts by weight of hexafunctional polyurethane propionate oligomer, 5 parts by weight of mercaptopropyltrimethoxysilane oligomer, 8 parts by weight of pentaerythritol triacrylate monomer, 0.2 parts by weight of BYK-333 leveling agent, 4 parts by weight of EVERSORB 109 UV absorber from Yongguang Chemical, 1.5 parts by weight of photoinitiator 184, 30 parts by weight of methyl ethyl ketone (MEK), and 19.3 parts by weight of propylene glycol methyl ether (PMC).

[0076] The uniformly mixed photocurable hard coating composition was coated onto one side of a 125μm thick optical-grade PET film (Toray Industries, Korea, XG7PL2). After drying in an oven at 80-90℃ for 3 minutes, it was then subjected to a curing process at 400mJ / cm². 2 The ultraviolet light energy is used to photocur the dried coating to obtain a hard coating film. The relevant physical property data are shown in Table 2.

[0077] The difference between Comparative Example 3 and this application is that the amount of photoinitiator is reduced so that the ratio of it to the ultraviolet absorber is less than 0.5.

[0078] Comparative Example 4

[0079] The formulation of the UV-curable hard coating composition is as follows: 32 parts by weight of hexafunctional polyurethane propionate oligomer, 5 parts by weight of mercaptopropyltrimethoxysilane oligomer, 8 parts by weight of pentaerythritol triacrylate monomer, 0.2 parts by weight of BYK-333 leveling agent, 5.5 parts by weight of EVESROB 109 UV absorber, 2.5 parts by weight of photoinitiator 184, 28 parts by weight of methyl ethyl ketone (MEK), and 18.8 parts by weight of propylene glycol methyl ether (PMC).

[0080] The uniformly mixed photocurable hard coating composition was coated onto one side of a 125μm thick optical-grade PET film (Toray Industries, Korea, XG7PL2). After drying in an oven at 80-90℃ for 3 minutes, it was then subjected to a curing process at 400mJ / cm². 2 The ultraviolet light energy is used to photocur the dried coating to obtain a hard coating film. The relevant physical property data are shown in Table 2.

[0081] The difference between Comparative Example 4 and this application is that the amount of ultraviolet absorber is increased, so that the ratio of the amount of photoinitiator to the amount of photoinitiator is less than 0.5.

[0082] Table 1. Appearance and properties of the hard coatings in the technical solutions described in Examples 1-5

[0083]

[0084] Table 2 shows the appearance and properties of the hard coatings in the technical solutions described in Comparative Examples 1-4.

[0085]

[0086]

[0087] As can be seen from Tables 1 and 2, the addition of mercaptosilane oligomers can improve the adhesion and flexibility (R value less than or equal to 1.5) of the UV-resistant hard coating film to the substrate, and can withstand in-mold injection thermoforming under extremely small R angle conditions without cracking.

[0088] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0089] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A photocurable hard coat liquid composition, characterized by comprising: The photocuring hard coating liquid composition comprises the following components: 20-40 parts by weight of a high-functionality polyurethane propionate oligomer having a functionality of six or more, 5-10 parts by weight of a mercapto silane compound, 5-12 parts by weight of an acrylate monomer, 0.5-1.0 parts by weight of a leveling agent, 1-5 parts by weight of a UV absorber, 1.0-3.5 parts by weight of a photoinitiator, and 35-55 parts by weight of a solvent; The photoinitiator is selected from one or a combination of photoinitiator 184, photoinitiator TPO, photoinitiator 1173, or photoinitiator 127; the ratio of the added amount of the photoinitiator to the UV absorber is not less than 0.

5.

2. The photocuring hard coat liquid composition according to claim 1, wherein The high-functionality polyurethane acrylate oligomer is selected from one or a combination of a hexafunctional polyurethane acrylate oligomer, a heptafunctional polyurethane acrylate oligomer, and an octafunctional polyurethane acrylate oligomer.

3. The photocuring hard coat liquid composition according to claim 1 or 2, characterized by, The mercapto silane compound is selected from mercapto propyl trimethoxysilane, mercapto propyl triethoxysilane, or an oligomer thereof.

4. The photocuring hard coat liquid composition according to claim 1 or 2, characterized by, The acrylate monomer is selected from one or a combination of trimethylolpropane triacrylate, 3-propoxy glycerol triacrylate, pentaerythritol triacrylate, and trimethylolpropane trimethacrylate.

5. The photocuring hard coat liquid composition according to claim 1 or 2, characterized by, The UV absorber is selected from one or a combination of benzophenone, benzotriazole, or triazine.

6. The photocuring hard coat liquid composition according to claim 1 or 2, characterized by, The solvent is one or a combination of methyl isobutyl ketone, butanone, propylene glycol monomethyl ether, and ethyl acetate; the leveling agent is one or a combination of a fluorine-based leveling agent, an organosiloxane leveling agent, or an organosilicone-modified leveling agent.

7. A high-hardness, high-flexibility hard coating film, characterized in that, It comprises a substrate and a hardened layer formed by curing the photocuring hard coating liquid composition according to any one of claims 1-6.

8. The hard coat film according to claim 7, characterized by The substrate is one of PET, PC, TAC, or PEN.

9. A method for producing the hard coat film according to claim 7, characterized by, It comprises the following steps: first, configuring a photocuring hard coating liquid composition; applying the photocuring hard coating liquid composition on the substrate; then, performing a desolventizing drying process on the coating; and then, forming by photocuring.

10. The method for producing a hard coat film according to claim 9, wherein The substrate is one of PET, PC, TAC, or PEN. It comprises a substrate and a hardened layer formed by curing the photocuring hard coating liquid composition according to any one of claims 1-6. The substrate is one of PET, PC, TAC, or PEN. It comprises the following steps: first, configuring a photocuring hard coating liquid composition; applying the photocuring hard coating liquid composition on the substrate; then, performing a desolventizing drying process on the coating; and then, forming by photocuring. The substrate is one of PET, PC, TAC, or PEN.

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