Photocurable resin composition, hard coat film, and molded article using the same

Abstract

The present invention provides a photocurable resin composition suitable for molding applications, which has high elongation at break, good moldability, and good alcohol resistance, as well as a hard coat film coated therewith, and a molded product using the same. [Solution] A photocurable resin composition comprising a urethane acrylate obtained by reacting a diisocyanate, which is made by reacting (poly)ethylene glycol with isophorone diisocyanate, with pentaerythritol triacrylate, a leveling agent, and a photopolymerization initiator, wherein the leveling agent includes a silicone-based leveling agent and a fluorine-based leveling agent.

Description

Technical Field

[0001] The present invention relates to a photocurable resin composition excellent in moldability, a hard coat film having a cured layer of the resin, and further a molded article using the same. Background Art

[0002] Acrylic photocurable resins are used in many fields to impart special properties to the surfaces of plastic films and plastic molded articles. For example, hard coat films obtained by applying an acrylic photocurable resin onto a PET (polyethylene terephthalate) film to impart high hardness are widely used in large quantities as touch panel films and molding films.

[0003] Among these, particularly for molding applications, insert molding films are well known, in which three-dimensional molding is performed in a state softened by heating after printing a pattern on the film surface. However, when the hard coat resin layer applied to the film is hardened, microcracks are prone to occur on curved surfaces during processing into a three-dimensional shape, which imposes restrictions on the processable shape. For this reason, the applicant has previously invented a hard coat agent containing a triazine ring-containing (meth)acrylate prepolymer and organic fine particles having an average primary particle diameter of 80 to 500 nm as a hard coat resin for insert molding that achieves both surface hardness and moldability (Patent Document 1). This hard coat agent had a film thickness of 1 to 10 µm and was excellent in that it could achieve both sufficient flexibility and surface physical properties.

[0004] While selecting hard coat agents suitable for these molding applications has somewhat alleviated processing constraints, as the applications of insert molded products expand, various properties beyond the conventionally required moldability are now being demanded. For example, in automotive interior applications, disinfection with alcohol is frequently performed to reduce the risk of infection from viruses such as COVID-19. For instance, thoroughly soaking a cotton cloth in ethyl alcohol-based disinfectant and rubbing it against the hard coat surface could cause significant damage to the hard coat film. Therefore, there was a need for a moldable hard coat film that offered sufficient moldability while also being highly resistant to alcohol. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 4848200 [Overview of the project] [Problems that the invention aims to solve]

[0006] The object of the present invention is to provide a photocurable resin composition suitable for molding applications, which has high elongation at break, good moldability, and good alcohol resistance, as well as a hard coat film coated therewith, and a molded product using the same. [Means for solving the problem]

[0007] To solve the above problems, the invention of claim 1 provides a photocurable resin composition comprising a urethane acrylate (A) obtained by reacting a diisocyanate, which is obtained by reacting (poly)ethylene glycol with isophorone diisocyanate, with pentaerythritol triacrylate, a leveling agent (B), and a photopolymerization initiator (C), wherein (B) comprises a silicone-based leveling agent (b1) and a fluorine-based leveling agent (b2).

[0008] The invention of claim 2 provides the photocurable resin composition according to claim 1, characterized in that (b1) is a polyether-modified polydimethylsiloxane.

[0009] The invention of claim 3 provides the photocurable resin composition according to claim 1, further comprising a stabilizer (D).

[0010] The invention of claim 4 provides a hard coat film characterized by having a cured layer of a photocurable resin composition according to any one of claims 1 to 3 on a plastic substrate.

[0011] The invention of claim 5 provides a method for manufacturing an insert molded product, in which a hard coat film for molding described in claim 4 is shaped using a mold, and then molten resin is injected from the side opposite to the photocurable resin curing layer to form a resin molded product.

[0012] The invention of claim 6 provides an insert molded article or an out-molded article using the hard coat film described in claim 4. [Effects of the Invention]

[0013] The photocurable resin composition of the present invention and the hard coat film coated therewith (hereinafter referred to as HC film) have high elongation at break and good moldability, as well as good alcohol resistance, making them useful as HC agents for molded HC films used in molded products such as those used in the interior of automobiles. [Best Mode for Carrying Out the Invention]

[0014] The photocurable resin composition of the present invention comprises a urethane acrylate (A) having a structure obtained by reacting a diisocyanate, which is produced by reacting (poly)ethylene glycol with isophorone diisocyanate (hereinafter referred to as IPDI), with pentaerythritol triacrylate (hereinafter referred to as PETA), a leveling agent (B), and a photopolymerization initiator (C). In this specification, (meth)acrylate includes both acrylate and methacrylate. Furthermore, (poly)ethylene glycol includes both polyethylene glycol and ethylene glycol.

[0015] The alicyclic diisocyanate IPDI used in the synthesis described in (A) exhibits no yellowing, excellent weather resistance, and high rigidity, thereby increasing the hardness of the cured product. By using ethylene glycol with a very short carbon chain instead of polyethylene glycol, it is possible to increase the concentration of urethane bonds within the molecule, thereby forming a rigid, linear main skeleton with superior chemical resistance.

[0016] There are no particular restrictions on the synthesis method of (A), and known methods can be used. The reaction may be carried out without a solvent, but since stirring may become difficult as the molecular weight of (A) increases, ketones such as MEK, aromatic inert solvents such as xylene, etc. may be used. Furthermore, it is preferable to use a catalyst for the reaction between the hydroxyl groups of (poly)ethylene glycol and PETA and the isocyanate groups. Examples of catalysts in this case include tin-based catalysts such as dibutyltin dilaurate and metal alkoxide-based catalysts such as cobalt naphthenate. The reaction temperature can be set as appropriate, but 40 to 120°C is preferred, and 60 to 100°C is more preferred.

[0017] The weight-average molecular weight (hereinafter referred to as Mw) of (A) is preferably 1,000 to 30,000, more preferably 2,000 to 15,000, and particularly preferably 3,000 to 10,000. A value of 1,000 or more ensures sufficient moldability, and a value of 30,000 or less ensures sufficient abrasion resistance and scratch resistance. The Mw of (A) can be adjusted by the molar ratio of (poly)ethylene glycol to IPDI to be reacted, and as the molar ratio of IPDI to (poly)ethylene glycol approaches, Mw tends to increase. The Mw was measured and calculated as the molecular weight on a standard polystyrene basis using gel permeation chromatography with a column packed with a styrenedivinylbenzene substrate and a tetrahydrofuran eluent.

[0018] The amount of (A) described above is preferably 65 to 96% by weight, more preferably 70 to 94% by weight, and particularly preferably 75 to 92% by weight, based on the total amount of solids (however, if filler components are included, the same applies to (B) to (D) below). Sufficient moldability can be ensured by setting it to 65% by weight or more, and sufficient curability and scratch resistance can be ensured by setting it to 96% by weight or less.

[0019] The leveling agent (B) used in the present invention is formulated to improve leveling performance during coating, ensure a good appearance, enhance the water-resistant properties of the cured film, and improve the alcohol resistance of the cured film. It contains a silicone-based leveling agent (b1) and a fluorine-based leveling agent (b2) as essential components. By using (b1) and (b2) in combination, the alcohol resistance of the cured film can be greatly improved.

[0020] The aforementioned (b1) contributes to improved scratch resistance as well as alcohol resistance, and examples include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyester-modified siloxanes, and polyether-modified siloxanes, which can be used alone or in combination of two or more. Among these, it is preferable to include polyether-modified dimethylsiloxane.

[0021] The blending amount of (b1) is preferably 0.3 to 3% by weight, more preferably 0.5 to 1.5% by weight, based on the total amount of solid content. By setting the blending amount within this range, sufficient abrasion resistance and alcohol resistance can be secured. Commercially available products thereof include BYK-UV3570 (trade name, manufactured by BYK Chemie, an acryloyl group-containing polyester-modified polydimethylsiloxane compound), BYK-342 (trade name, manufactured by BYK Chemie, an acryloyl group-containing polyester-modified polydimethylsiloxane compound), and the like.

[0022] The component (b2) contributes to improving antifouling properties as well as alcohol resistance. It includes fluorine-based silicones in addition to fluorine-based ones, and can be used alone or in combination of two or more types. It is preferable that (b2) has a reactive functional group capable of polymerizing with a binder resin to form a cured coating film, because this prevents loss from the cured film over time due to bleeding or the like, and allows the weather resistance effect to be maintained over a long period of time.

[0023] The blending amount of (b2) is preferably 0.3 to 3% by weight, more preferably 0.5 to 1.5% by weight, based on the total amount of solid content. By setting the blending amount within this range, sufficiently stable coating appearance and alcohol resistance can be secured. Commercially available products thereof include KY-1203 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., a reactive fluorine-based silicone compound), Optool DAC-100 (trade name, manufactured by Daikin Industries, Ltd., a reactive fluorine compound), and the like.

[0024] The blending amount of the total (B) including (b1) and (b2) is preferably 0.8 to 5% by weight, more preferably 1.0 to 3% by weight, and particularly preferably 1.2 to 2.0% by weight, based on the total amount of solid content. When the blending amount is 0.8% by weight or more, sufficient alcohol resistance can be secured, and when it is 5% by weight or less, sufficient curability can be obtained and deterioration in appearance caused by excessive blending can be suppressed. The blending ratio of (b1) to (b2) is preferably 3:7 to 7:3, more preferably 4:6 to 6:4.

[0025] The photopolymerization initiator (C) used in this invention generates radicals upon irradiation with ultraviolet light or electron beams, and these radicals trigger the polymerization reaction. General-purpose photopolymerization initiators such as benzyl ketal, acetophenone, and phosphine oxide can be used. By arbitrarily selecting the light absorption wavelength of the polymerization initiator, curability can be imparted over a wide wavelength range from the ultraviolet region to the visible light region. Specifically, examples include 2,2-dimethoxy-1,2-diphenylethane-1-one as a benzyl ketal, 1-hydroxycyclohexyl-phenyl-ketone and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one as α-hydroxyacetophenones, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one as an α-aminoacetophenone, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide as acylphosphine oxides, which can be used individually or in combination of two or more.

[0026] Among these, it is preferable to include an α-hydroxyacetophenone-based compound that is less prone to yellowing, and commercially available examples include Omnirad 127D, 184, and 2959 (trade name: manufactured by IGM Resins). The amount of compounding with respect to 100 parts by weight of the radical polymerizable component of (C) above is preferably 2 to 15 parts by weight, and more preferably 5 to 10 parts by weight.

[0027] The photocurable resin composition of the present invention preferably further contains a light stabilizer (D). The inclusion of (D) can reduce the deterioration of the cured film due to exposure to ultraviolet light and radiant heat. Examples include a radical scavenger (d1) that efficiently traps alkyl radicals and peroxy radicals generated from polymers that have been photodegraded by ultraviolet light, and an ultraviolet absorber (d2) that suppresses polymer decomposition by converting the energy of absorbed ultraviolet light into thermal energy or the like.

[0028] The aforementioned (d1) can be, for example, a hindered amine (hereinafter referred to as HALS), a hindered phenol, or an aromatic amine, and can be used alone or in combination of two or more. Among these, the HALS is preferred because it has high radical scavenging efficiency even at low concentrations. The amount of (d1) is preferably 1 to 10% by weight, more preferably 2 to 8% by weight, and particularly preferably 3 to 6% by weight, based on the total amount of solids. By setting it within this range, sufficient photostability can be ensured. A commercially available HALS product is Tinuvin 249 (product name: manufactured by BASF Japan).

[0029] (d2) is a radical chain initiation inhibitor having an absorption band in the high-energy, harmful ultraviolet region, and when used in combination with (d1), it is possible to further improve and stabilize weather resistance. Examples include benzotriazole, triazine, and benzophenone types, which can be used alone or in combination of two or more. Among these, hydroxyphenyltriazine types that can strongly absorb the long wavelength portion of ultraviolet light are preferred. The amount of (d2) added is preferably 0.3 to 5% by weight, more preferably 0.5 to 3.0% by weight, and particularly preferably 0.6 to 1.5% by weight, based on the total amount of solids. By setting it within this range, sufficient ultraviolet absorption characteristics can be ensured. Examples of commercially available products include Tinuvin 460 and 477 (product name: manufactured by BASF Japan).

[0030] The amount of (D) containing (d1) and (d2) is preferably 1.0 to 12% by weight, more preferably 1.5 to 10% by weight, and particularly preferably 3.0 to 8.0% by weight, relative to the total amount of solids. An amount of 1.0% by weight or more can be expected to improve weather resistance, while an amount of 12% by weight or less avoids excessive blending and ensures sufficient adhesion to the substrate.

[0031] The photocurable resin composition of the present invention (hereinafter referred to as "this composition") may contain, as necessary, reactive diluents, various fillers, adhesion promoters, bluing agents, pigments, defoaming agents, thickeners, anti-precipitation agents, antistatic agents, anti-fogging agents, antibacterial agents, waxes, matting agents, hydrophilic agents, water-repellent agents, organic fine particles, etc., to the extent that it does not impair performance.

[0032] As the reactive diluent, it is preferable to use a polyfunctional (meth)acrylate due to its low viscosity and excellent compatibility with (A). For example, bifunctional diluents include (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and dicyclopentanyl diacrylate; trifunctional diluents include trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; tetrafunctional ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and diglycerin tetra(meth)acrylate; pentaerythritol penta(meth)acrylate; and hexafunctional dipentaerythritol hexa(meth)acrylate, etc. These can be used individually or in combination of two or more.

[0033] The amount of the reactive diluent is preferably 30 parts by weight or less, and more preferably 15 parts by weight or less, per 100 parts by weight of (A). By using 30 parts by weight or less, it is possible to improve reactivity while ensuring sufficient moldability. Furthermore, the blending ratio to the total solid content is preferably 20% by weight or less, and more preferably 15% by weight or less.

[0034] Examples of the aforementioned fillers include nanoalumina particles as an inorganic filler. By incorporating nanoalumina particles, the hardness of the hardened layer can be increased, improving wear resistance. It is also expected to improve resistance to scratches caused by car washes and the like.

[0035] The primary mean particle diameter of the nanoalumina particles is preferably 10 to 200 nm, and more preferably 50 to 150 nm. A particle diameter of 10 nm or more improves resistance to car wash scratches, while a particle diameter of 200 nm or less ensures good optical properties in the film. In particular, a particle diameter of 50 nm to 150 nm significantly improves resistance to car wash scratches. The average particle diameter is defined as the median diameter (d=50) measured by dynamic light scattering (DLS).

[0036] The amount of nanoalumina particles blended is preferably ~20.0% by weight or less, and more preferably 1.0 to 10.0% by weight, relative to the total solid content of the resin composition. An amount of 0.1% by weight or more is expected to improve resistance to car wash scratches, while an amount of 20.0% by weight or less ensures sufficient moldability.

[0037] When applying this composition to a plastic substrate, it may be diluted with a solvent to improve coating properties. Examples of solvents include alcohol-based solvents such as ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and diacetone alcohol; ketone-based solvents such as acetone, methyl ethyl ketone (hereinafter referred to as MEK), methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as ethyl acetate and butyl acetate; ether-based solvents such as propylene glycol monomethyl ether (hereinafter referred to as PGM), diethyl ether, and diisopropyl ether; and hydrocarbon-based solvents such as cyclohexane and methylcyclohexane. These can be used individually or in combination of two or more. When diluting, the solid content is exemplified as 10-70%, but there is no particular requirement, and it can be appropriately set to achieve a viscosity that is easy to coat.

[0038] Examples of plastic substrates to which this composition is applied include polyester film, triacetylcellulose film, polycarbonate film, polysulfone film, nylon film, cycloolefin film, acrylic (hereinafter referred to as PMMA) film, polyimide film, ABS film, polypropylene film, PVC film, PVA film, and the like.

[0039] Among these, it is preferable to use a composite substrate consisting of a polycarbonate (hereinafter referred to as PC) substrate, which has excellent impact resistance and high heat resistance, and an acrylic substrate, which has high transparency and hardness. Polypropylene film is also preferred because it can be molded at low temperatures and has excellent flexibility at room temperature. Here, a composite substrate of a PC substrate and an acrylic substrate (hereinafter referred to as "this composite substrate") means a resin laminate having an acrylic resin layer on at least one side of a PC resin layer. The method for laminating the PC resin and the acrylic resin is preferably co-extrusion molding.

[0040] The aforementioned plastic substrate can be subjected to surface treatments such as primer treatment, sandblasting, solvent treatment to create surface irregularities, or corona discharge treatment, chromic acid treatment, or ozone / ultraviolet irradiation treatment to improve adhesion with the composition.

[0041] The method of applying this composition is not particularly limited and can be achieved by known coating methods such as spray coating, roll coating, die coating, air knife coating, blade coating, spin coating, reverse coating, gravure coating, and wire bar coating, or by printing methods such as gravure printing, screen printing, offset printing, and inkjet printing. The coated film thickness can be exemplified as 1 μm to 10 μm when dry, but is not limited thereto.

[0042] The ultraviolet light source used to cure this composition can be a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, an LED lamp, or an electrodeless ultraviolet lamp. The irradiation atmosphere can be air or an inert gas such as nitrogen or argon. Furthermore, heating the coating film with a back roll or an IR heater during ultraviolet irradiation can further improve curing performance. The irradiation conditions are set to an irradiation intensity of 500 mW / cm². 2 ~3000mW / cm 2 Exposure dose: 50-400 mJ / cm² 2 Examples are given, but this is not an exhaustive list.

[0043] The HC film (hereinafter referred to as "this HC film") obtained by coating a plastic substrate with this composition and curing it preferably has a break elongation of 100% or more, more preferably 150% or more, and particularly preferably 200% or more, in a 130°C atmosphere. By achieving a break elongation of 100% or more, sufficient moldability can be expected.

[0044] This HC film may be provided with a decorative layer as needed. Methods of decoration include, for example, printing or metal vapor deposition, or a combination of both. Furthermore, an adhesive layer or primer layer may be provided to improve adhesion with the injection-molded resin.

[0045] A protective film may be laminated onto the HC film to protect the surface coated with this composition. Using a protective film can prevent scratches during insert molding and out-mold molding processes, which is expected to improve yield.

[0046] One method of using this HC film in insert molding is to position the film so that the side coated with this composition faces the inner wall of the mold (so that the side opposite the hardened layer of this composition is in contact with the molding resin), pre-form the HC film to conform to the mold shape as needed, then close the mold and inject molten molding resin into the cavity, and solidify the resin to form a resin molded product.

[0047] Methods for performing the above-mentioned pre-forming include preheating the HC film above its softening point, placing it in a mold, and using vacuum suction through suction holes in the mold, or using a separate molding mold from the injection molding mold and employing known molding methods such as vacuum forming, pressure forming, or press forming. It is also possible to perform the molding and integral molding of the injection resin simultaneously by injection pressure from the molding resin without performing these pre-forming steps.

[0048] As the resin used for injection molding, any known resin capable of injection molding can be used. Examples include polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, acrylic resin, urethane resin, polyester resin, polycarbonate resin, polyphenylene ether resin, polyacetal resin, and polysulfone resin, which can be used individually or in combination of two or more. In cases of large sizes, such as automobile bodies, or in cases of small sizes but thin walls, defects such as warping can be avoided by making the shrinkage rate after molding similar to that of HC film.

[0049] Furthermore, by coloring the injection molding resin itself, it becomes possible to eliminate the decorative layer of the HC film or to fuse the color of the decorative layer with that of the injection-molded resin, thereby creating a deeper appearance. Moreover, in cases where the exterior is colored with paint, such as when replacing an automobile body with insert molding, coloring the resin used for injection molding makes it possible to omit the exterior painting with paint. In this case, it is possible to eliminate appearance defects such as orange peel and pitting that often occur with exterior painting.

[0050] Furthermore, this HC film can also be used in out-mold molding. For example, it can be used in TOM (Three-Dimensional Overlay Method) molding. TOM molding is a film molding method in which a three-dimensional surface decoration is applied to a pre-molded substrate in an airtight box using vacuum and pressure molding. By using this HC film, it is possible to handle large three-dimensional products regardless of the material of the substrate.

[0051] The present invention will be described in detail below with reference to examples and comparative examples, but these are merely examples and the invention is not limited to them. Unless otherwise stated, measurements were taken under conditions of 25°C and 65% relative humidity. The amounts of ingredients are expressed in parts by weight on a solid content basis.

[0052] Preparation of Ureac 1 In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 200 parts by weight of ethylene glycol, 808 parts by weight of IPDI (37.5% NCO group), catalyst, and MEK were charged to a solid content of 50%. The mixture was stirred and reacted at 80°C for 6 hours, and the reaction was terminated when the isocyanate group peak reached the desired amount by infrared absorption analysis. Next, 371 parts by weight of PETA (hydroxyl value 120 mg KOH / g) was added, and the mixture was stirred and reacted at 70°C for 6 hours. After confirming the disappearance of the isocyanate group by infrared absorption analysis, the solid content was adjusted to 50% with MEK to obtain hexafunctional urea 1 at Mw 7,800.

[0053] Preparation of Ureac 2 Instead of the ethylene glycol used in the preparation of Ureac 1, polyethylene glycol PEG200 (product name: manufactured by Toho Chemical Industry Co., Ltd.) was used and reacted according to the above method. The solid content was adjusted to 50% using MEK to obtain Ureac 2, a hexafunctional compound with a Mw of 8,000. The proportions of each raw material were adjusted as appropriate to achieve this Mw.

[0054] Examples, Comparative Examples As (A) above, the ureaac 1-2 prepared above; as (b1) BYK-342 (manufactured by BYK Chemie, polyether-modified polydimethylsiloxane compound) and BYK-UV3500 (product name: manufactured by BYK Chemie, acryloyl group-containing polyether-modified polydimethylsiloxane compound); as (b2) KY-1203 (product name: manufactured by Shin-Etsu Chemical Co., Ltd., reactive fluorine-based silicone compound) and DAC-100 (product name: manufactured by Daikin Corporation, reactive fluorine compound); (C) Omnirad2959 and 127D (product name: IGM (D) Resins Co., Ltd. Tinuvin 249 (trade name: BASF Japan Co., Ltd.) as (d1) and Tinuvin 477 (trade name: BASF Japan Co., Ltd.) as (d2), and DPHA (dipentaerythritol hexaacrylate) as a reactive diluent, were stirred until uniformly dissolved and dispersed in the formulations shown in Tables 1 and 2. Further dilution and stirring were performed by adding PGM so that the solid content was 30%, to obtain the photocurable resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3.

[0055] Table 1 JPEG2026142590000001.jpg128167

[0056] Table 2 JPEG2026142590000002.jpg149167

[0057] The evaluation method was as follows:

[0058] Preparation of HC film 1 The photocurable resin compositions prepared in the examples and comparative examples were applied to the PMMA side of a Yupilon film (product name: DF02UL, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 254 μm, PMMA / PC laminated film) to a dry film thickness of 6 μm. After drying in a constant temperature bath at 80°C for 1 minute, the resin was heated with a high-pressure mercury lamp at an output of 1300 mW / cm². 2 The film for evaluation was prepared by irradiating it with ultraviolet light so that the cumulative light intensity was 200 mJ.

[0059] Abrasion resistance: Using the FR-IBS friction tester manufactured by Suga Test Machine Co., Ltd., the resin composition coated surface of the hard coat film was subjected to a load of 9N using a friction element (16 mm in diameter) fitted with a test white cotton cloth (Kanakin No. 3), and moved back and forth 100 mm at a speed of 1 back and forth per second. The presence or absence of scratches after 100 back and forth was checked, with ○ indicating no scratches and × indicating scratches.

[0060] Alcohol resistance: Test the HC surface with a cotton cloth thoroughly soaked in ethyl alcohol at approximately 0.1 kgf / cm². 2 The object was rubbed back and forth 10 times under a load, and changes in appearance were visually checked. No change was marked with ○, and any cloudiness or other noticeable changes were marked with ×.

[0061] Adhesion: In accordance with the cross-cut method of JIS K 5600-5-6, a 10x10 grid was created on the coated surface at 1mm intervals. Cellophane tape CT-24 (product name: Nichiban Co., Ltd.) was applied, and the peeling condition was checked by pulling it upwards. ○ was used if there was no peeling, and × if there was peeling. No peeling: 100 / 100, Peeling present: 0 / 100~99 / 100

[0062] Moldability: HC film was cut to 25mm x 110mm and subjected to a tensile test using a Minebea TechnoGraph TGI-1KN with a chuck distance of 50mm, ambient temperature of 130°C, and tensile speed of 300mm / min. Cracks were visually inspected for evaluation, with elongation less than 100% marked as ×, 100% to 200% marked as ○, and over 200% marked as ◎. Calculation formula: The calculation is based on how many millimeters it has grown, with 50mm as the base. Length elongated (mm) / 50mm × 100 = Elongation rate %

[0063] Example Evaluation Results Table 3 JPEG2026142590000003.jpg61135

[0064] Comparison Example Evaluation Results Table 4 JPEG2026142590000004.jpg68135

[0065] The examples demonstrated excellent performance in all aspects, including abrasion resistance, alcohol resistance, adhesion, and moldability.

[0066] On the other hand, Comparative Example 1, which did not contain (b1), had poor abrasion resistance and alcohol resistance, and Comparative Example 3, which did not contain (b2), had poor alcohol resistance. Furthermore, Comparative Example 3, which did not contain (A), had poor moldability, and all of these were unsuitable for the present invention.

Claims

1. A photocurable resin composition comprising a urethane acrylate (A) obtained by reacting a diisocyanate, which is a diisocyanate obtained by reacting (poly)ethylene glycol with isophorone diisocyanate, with pentaerythritol triacrylate, a leveling agent (B), and a photopolymerization initiator (C), wherein (B) comprises a silicone-based leveling agent (b1) and a fluorine-based leveling agent (b2).

2. The photocurable resin composition according to claim 1, characterized in that (b1) is a polyether-modified polydimethylsiloxane.

3. The photocurable resin composition according to claim 1, further characterized by containing a stabilizer (D).

4. A hard coat film characterized by having a cured layer of the photocurable resin composition according to any one of claims 1 to 3 on a plastic substrate.

5. A method for manufacturing an insert molded product, wherein the moldable hard coat film described in claim 4 is shaped using a mold, and then molten resin is injected from the side opposite to the photocurable resin curing layer to form a resin molded product.

6. An insert molded article or an out-molded article using the hard coat film described in claim 4.

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