Photocurable resin composition, hard coat film for molding, molded article using the same, and method for manufacturing insert molded article

Abstract

To provide a photocurable resin composition which has abrasion resistance and chemical resistance, has high elongation at break and good moldability, has excellent weather resistance enough to withstand outdoor use, and is suitable for molding application, a hard coat film for molding coated with the same and a molded article, and a method for manufacturing an insert-molded article.SOLUTION: A photocurable resin composition contains urethane acrylate obtained by further reacting pentaerythritol triacrylate with diisocyanate obtained by reacting ethylene glycol with isophorone diisocyanate, silicone-containing acryl(meth)acrylate, a photostabilizer, and a photopolymerization initiator, where a weight average molecular weight of the urethane acrylate is 2,000-12,000, and a blending amount of the silicone-containing acryl(meth)acrylate is 0.5-30 pts.wt. with respect to 100 pts.wt. of the urethane acrylate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photocurable resin composition having excellent moldability, a molding hard coat film having a cured resin layer thereof, and a method for producing a molded article and an insert molded article using the same. [Background technology]

[0002] Acrylic photocurable resins are used in many fields to impart special properties to the surfaces of plastic films and plastic moldings. For example, hard-coated films, which are applied to PET (polyethylene terephthalate) films to impart high hardness, are used in large quantities as films for touch panels and molding films.

[0003] Among these, molding films are well known for their molding applications, in which a pattern is printed on the film surface and then heated to soften it for three-dimensional molding. However, if the hard coat resin layer applied to the film is hardened, microcracks are more likely to occur on the curved surface when the film is processed into a three-dimensional shape, limiting the shape that can be processed. For this reason, the applicant previously invented a hard coat agent containing a triazine ring-containing (meth)acrylate prepolymer and organic fine particles with an average primary particle size of 80 to 500 nm as a hard coat resin for insert molding that combines surface hardness and moldability (Patent Document 1). This hard coat agent was excellent, achieving both sufficient flexibility and surface properties at a film thickness of 1 to 10 μm.

[0004] By selecting hard coating agents suitable for these molding applications, processing constraints have been alleviated to some extent, but as the applications of insert molding products expand, various other properties are now required in addition to the moldability and abrasion resistance that have been traditionally required. For example, in applications where products are used outdoors all the time, such as the exterior of automobiles or the exterior of equipment stored outdoors, sufficient weather resistance and durability to withstand ultraviolet rays and temperature changes are now required. Therefore, there was room for improvement in order to provide sufficient weather resistance to withstand outdoor use in addition to the traditional required properties of sufficient moldability, abrasion resistance, chemical resistance, etc. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 4848200 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a photocurable resin composition suitable for molding applications that has abrasion resistance and chemical resistance, high breaking elongation and good moldability, as well as excellent weather resistance that enables it to withstand outdoor use; a molding hard coat film coated with the same; and a method for producing a molded article and an insert molded article using the same. [Means for solving the problem]

[0007] In order to solve the above problems, the invention of claim 1 provides a composition comprising: a urethane acrylate (A) obtained by further reacting pentaerythritol triacrylate with a diisocyanate obtained by reacting ethylene glycol with isophorone diisocyanate; a silicone-containing acrylic (meth)acrylate (B); a light stabilizer (C); and a photopolymerization initiator (D), wherein the weight average molecular weight of (A) is 2,000 to 12,000; the blending amount of (A) is 55 to 95% by weight based on the total solid content of the entire composition, The amount of (B) 0.4 to 21% by weight of the total solid content of the entire composition The present invention provides a photocurable resin composition characterized by:

[0008] A second aspect of the present invention provides the photocurable resin composition according to the first aspect, wherein (B) is an acrylic (meth)acrylate having a silicone side chain on an acrylic main chain.

[0009] The invention of claim 3 provides a hard coat film for molding, characterized by having a cured layer of the photocurable resin composition according to claim 1 or 2 on a plastic substrate.

[0010] The invention of claim 4 is A method for producing an insert-molded product, comprising: forming the hard-coated film for molding according to claim 3 using a mold; and then injecting a molten resin from the side opposite to the photocurable resin cured layer to form a resin molded product. to provide.

[0011] The invention of claim 5 is as follows: An insert-molded product or an out-molded product using the hard coat film for molding according to claim 3. to provide. [Effects of the Invention]

[0016] The photocurable resin composition of the present invention and the hard-coated film (hereinafter referred to as HC film) coated with the same have abrasion resistance and chemical resistance, high breaking elongation, good formability, and excellent weather resistance, and are therefore useful as materials for insert-molded products and out-molded products to be used outdoors. BEST MODE FOR CARRYING OUT THE INVENTION

[0017] The photocurable resin composition of the present invention comprises a urethane acrylate (A) obtained by further reacting PETA with a diisocyanate obtained by reacting ethylene glycol with IPDI, a silicone-containing acrylic (meth)acrylate (B), a light stabilizer (C), and a photopolymerization initiator (D). In this specification, the term "(meth)acrylate" encompasses both acrylate and methacrylate.

[0018] The alicyclic diisocyanate IPDI used in the synthesis of (A) does not yellow and has excellent weather resistance, while at the same time being highly rigid, allowing for increased hardness of the cured product. By reacting it with ethylene glycol, which has a very short carbon chain, it is possible to increase the concentration of urethane bonds within the molecule, forming a highly rigid, linear main skeleton with excellent chemical resistance. Using polyethylene glycol instead of ethylene glycol tends to decrease the concentration of urethane bonds, resulting in reduced chemical resistance.

[0019] The synthesis method for (A) is not particularly limited, and known methods can be used. The reaction can be carried out without a solvent. However, as the molecular weight of (A) increases, stirring can become difficult. Therefore, ketones such as butanone, or aromatic inert solvents such as xylene can be used. Furthermore, it is preferable to use a catalyst for the reaction between the hydroxyl groups of ethylene glycol and PETA and the isocyanate groups. Examples of such a catalyst 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 is preferably 40 to 120°C, and more preferably 60 to 100°C.

[0020] The weight-average molecular weight (hereinafter referred to as Mw) of (A) is 2,000 to 12,000, preferably 2,500 to 11,000, and more preferably 3,000 to 10,000. If it is less than 2,000, the elongation at break will be low, making it difficult to ensure sufficient moldability. If it exceeds 12,000, the abrasion resistance will be reduced and it will be difficult to adjust the viscosity to a workable level. The Mw of (A) can be adjusted by the molar ratio of ethylene glycol and IPDI to be reacted; as the molar ratio of IPDI to ethylene glycol approaches, the Mw tends to increase. The Mw was measured and calculated by gel permeation chromatography using a column with a styrene-divinylbenzene-based packing material and a tetrahydrofuran eluent, in terms of the molecular weight converted to standard polystyrene.

[0021] The blending amount of (A) is preferably 55 to 95% by weight, more preferably 60 to 90% by weight, and particularly preferably 65 to 88% by weight, based on the total solid content. By making it 55% by weight or more, sufficient breaking strength and chemical resistance can be ensured, and by making it 95% by weight or less, sufficient weather resistance can be ensured.

[0022] The silicone-containing acrylic (meth)acrylate (B) used in the present invention is added for the purposes of improving the slipperiness of the cured surface, improving abrasion resistance, and forming a coating film with excellent durability, and examples thereof include acrylic (meth)acrylates having silicone side chains on an acrylic main chain. By having a reactive (meth)acryloyl group in the molecule, it bonds firmly with (A), suppressing the occurrence of bleed-out over time and imparting good slipperiness and abrasion resistance to the cured surface for a long period of time.

[0023] The blending amount of (B) is 0.5 to 30 parts by weight, preferably 0.8 to 28 parts by weight, more preferably 3 to 20 parts by weight, and particularly preferably 5 to 15 parts by weight, per 100 parts by weight of (A). If it is less than 0.5 parts by weight, it becomes difficult to ensure sufficient abrasion resistance, and if it exceeds 30 parts by weight, haze tends to increase and the appearance tends to deteriorate. The blending amount is preferably 0.4 to 21% by weight, more preferably 0.6 to 20% by weight, based on the total solid content. Examples of commercially available products of (B) include GL-02R (trade name: manufactured by Kyoeisha Chemical Co., Ltd.).

[0024] The light stabilizer (C) used in the present invention is blended for the purpose of preventing deterioration of the cured film due to exposure to ultraviolet light when used outdoors or due to radiant heat. Examples include radical scavengers (c1) that efficiently trap alkyl radicals and peroxy radicals generated from polymers photodegraded by ultraviolet light, and ultraviolet absorbers (c2) that convert the energy of absorbed ultraviolet light into heat energy, thereby suppressing polymer decomposition.

[0025] The radical scavengers (c1) used in the present invention include, for example, hindered amines (hereinafter referred to as HALS), hindered phenols, aromatic amines, etc., which can be used alone or in combination of two or more. Among these, HALS is preferred because it has a high radical scavenging efficiency even at low concentrations.

[0026] The blending amount of (c1) 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 solid content. By adjusting the blending amount to within this range, sufficient light stability can be ensured. Commercially available HALS-based products include Tinuvin 123 and Tinuvin 249 (trade names: manufactured by BASF Japan Ltd.).

[0027] The ultraviolet absorber (c2) used in the present invention is a radical chain initiation inhibitor having an absorption band in the region of harmful, high-energy ultraviolet light, and when used in combination with the aforementioned (c1), it is possible to further improve and stabilize weather resistance. Examples include benzotriazole-based, triazine-based, and benzophenone-based absorbers, which can be used alone or in combination of two or more. Among these, hydroxyphenyltriazine-based absorbers, which can strongly absorb the long-wavelength portion of ultraviolet light, are preferred.

[0028] The blending amount of (c2) is preferably 0.5 to 5 wt. % of the total solid content, more preferably 0.8 to 3.0 wt. %, and particularly preferably 1.0 to 2.0 wt. By using this range, sufficient UV absorption characteristics can be ensured. Commercially available products include Tinuvin 460 and 477 (trade names: manufactured by BASF Japan Ltd.). The blending amount of (C), the sum of (c1) and (c2), is preferably 1.0 to 12 wt. % of the total solid content, more preferably 1.5 to 10 wt. %, and particularly preferably 4.0 to 8.0 wt. By using a blending amount of 1.0 wt. % or more, improved weather resistance can be expected, and by using a blending amount of 12 wt. % or less, excessive blending is avoided, ensuring sufficient adhesion to the substrate.

[0029] The photopolymerization initiator (D) used in the present invention generates radicals upon irradiation with ultraviolet light or an electron beam, and these radicals trigger the polymerization reaction, and general-purpose photopolymerization initiators such as benzyl ketals, acetophenones, and phosphine oxides can be used. By arbitrarily selecting the light absorption wavelength of the polymerization initiator, it is possible to impart curability over a wide wavelength range from the ultraviolet region to the visible light region. Specifically, benzyl ketals include 2,2-dimethoxy-1,2-diphenylethan-1-one, α-hydroxyacetophenones include 1-hydroxy-cyclohexyl-phenyl-ketone and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, α-aminoacetophenones include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and acylphosphine oxides include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and these can be used alone or in combination of two or more.

[0030] Among these, it is preferable to use an α-hydroxyacetophenone-based resin that is less prone to yellowing, and commercially available products include Omnirad 127D, 184, and 2959 (trade names: manufactured by IGM Resins), etc. The amount of (D) added per 100 parts by weight of the radically polymerizable component is preferably 2 to 12 parts by weight, more preferably 3 to 10 parts by weight.

[0031] To the photocurable resin composition of the present invention (hereinafter referred to as the present composition), crosslinking agents, adhesion promoters, antioxidants, bluing agents, pigments, leveling agents, antifoaming agents, thickeners, anti-suspending agents, antistatic agents, antifogging agents, antibacterial agents, waxes, matting agents, hydrophilic agents, water-repellent agents, inorganic fillers, organic fine particles, and the like may be added as needed, provided that the performance is not impaired.

[0032] As the crosslinking agent, it is preferable to use a multifunctional (meth)acrylate because of its low viscosity and excellent compatibility with (A) and (B). Examples of bifunctional crosslinkers include (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and dicyclopentanyl diacrylate; trifunctional crosslinkers include trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; tetrafunctional crosslinkers include ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and diglycerin tetra(meth)acrylate; pentafunctional crosslinkers include dipentaerythritol penta(meth)acrylate; and hexafunctional crosslinkers include dipentaerythritol hexa(meth)acrylate. These crosslinkers can be used alone or in combination of two or more. Among these, dipentaerythritol hexaacrylate (hereinafter referred to as DPHA) is preferred because of its good reactivity and resistance to deterioration in moldability.

[0033] The amount of the crosslinking agent is preferably 30 parts by weight or less, more preferably 25 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. The blending ratio relative to the total solid content is preferably 20% by weight or less, more preferably 10% by weight or less.

[0034] When applying the composition to a plastic substrate, it may be diluted with a solvent to improve coating properties. Examples of suitable 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 (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 (PGM), diethyl ether, and diisopropyl ether; and hydrocarbon-based solvents such as cyclohexane and methylcyclohexane. These solvents may be used alone or in combination. The solids content of the diluted composition is typically 10 to 70%, but there are no specific limitations and the viscosity can be adjusted appropriately to achieve a coating viscosity that is easy to apply.

[0035] Examples of plastic substrates onto which the composition can be applied include polyester film, triacetyl cellulose film, polycarbonate (hereinafter referred to as PC) film, polysulfone film, nylon film, cycloolefin film, acrylic (hereinafter referred to as PMMA) film, polyimide film, ABS film, polyolefin film, PVC film, and PVA film. Among these, biaxially oriented polyester film is preferred from the viewpoints of weather resistance, processability, dimensional stability, etc. Furthermore, PMMA film and PC film are preferred for automotive interior decoration, and laminated films thereof are also acceptable. The film thickness should be approximately 25 μm to 500 μm.

[0036] In order to improve adhesion to the composition, the plastic substrate may be subjected to a surface treatment such as a primer treatment, a sandblasting method, a solvent treatment, or the like to create a rough surface, or a surface oxidation treatment such as a corona discharge treatment, a chromic acid treatment, or an ozone / ultraviolet irradiation treatment.

[0037] The method for applying the composition is not particularly limited, and the composition can be formed by known coating methods such as spray coating, roll coating, die coating, air knife coating, blade coating, spin coating, reverse coating, gravure coating, wire bar coating, etc., or printing methods such as gravure printing, screen printing, offset printing, inkjet printing, etc. The thickness of the coated film when dried can be, for example, 1 μm to 10 μm, but is not limited to this.

[0038] The light source of ultraviolet radiation used to cure this composition includes low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, LED lamps, and electrodeless ultraviolet lamps. The irradiation atmosphere may be air or an inert gas such as nitrogen or argon. Furthermore, the curing property can be further improved by heating the coating film during ultraviolet irradiation using a back roll or an IR heater. The irradiation conditions are an irradiation intensity of 500 mW / cm. 2 ~3000mW / cm 2 , exposure dose 50-400mJ / cm 2 are exemplified, but are not limited to these.

[0039] The HC film (hereinafter referred to as the present HC film) obtained by coating the present composition on a plastic substrate and curing it preferably has a breaking elongation of 50% or more, more preferably 100% or more, and particularly preferably 200% or more in an atmosphere of 130°C. By making the breaking elongation 80% or more, sufficient formability can be expected.

[0040] The HC film can be provided with a decorative layer if necessary. Examples of decorative methods include printing and metal deposition, and both methods may be used. Furthermore, an adhesive layer or a primer layer may be provided to improve adhesion with the injection molding resin.

[0041] A protective film may be attached to the HC film to protect the surface to which the composition is applied. Using a protective film can prevent scratches during insert molding and out-molding processes, which is expected to improve yield.

[0042] The present HC film can be used in insert molding, for example, by placing the surface coated with the present composition facing the inner wall of the mold (so that the surface opposite the cured layer of the present composition is in contact with the molding resin), and preforming the present HC film to conform to the shape of the mold as needed. Next, the mold is closed and the molten molding resin is injected into the cavity, allowing the resin to solidify, thereby forming a resin molded product.

[0043] The preforming method may be a method in which the HC film is preheated to above its softening point and placed in a mold, followed by vacuum suction through suction holes in the mold, or a known molding method such as vacuum forming, compressed air forming, or press molding using a molding mold separate from the injection molding mold. It is also possible to simultaneously perform molding and integral molding of the injected resin by the injection pressure of the molding resin without performing these preforming methods.

[0044] The resin to be injection-molded can be any known resin that can be injection-molded. 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. These resins can be used alone or in combination of two or more. In the case of large sizes such as automobile bodies, or small sizes but thin thicknesses, problems such as warping can be avoided by making the shrinkage rate after molding similar to that of HC film.

[0045] Furthermore, by coloring the injection molding resin itself, it is possible to eliminate the decorative layer of the HC film, or to blend the color of the decorative layer with the color of the injection molding resin, resulting in a more sophisticated appearance. Furthermore, when replacing products that typically use paint for their exteriors, such as automobile bodies, with insert molding, coloring the injection-molded resin makes it possible to omit the exterior painting process. This also eliminates the appearance defects that often occur with exterior painting, such as orange peel and pitting.

[0046] Furthermore, this HC film can also be used for out-molding. For example, it can be used for TOM (Three-Dimensional Overlay Method) molding. TOM molding is a film molding method in which a pre-formed substrate is molded in an airtight box and three-dimensional surface decoration is performed using vacuum and pressure molding. By using this HC film, it is possible to handle large three-dimensional products regardless of the substrate material.

[0047] The present invention will be described in detail below with reference to examples and comparative examples, but these are intended to be specific examples and are not intended to limit the scope of the present invention. Unless otherwise specified, measurements were carried out at a room temperature of 25°C and a relative humidity of 65%. The blend amounts are expressed in parts by weight as solid content.

[0048] Preparation of ureac 1 A four-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 200 parts by weight of ethylene glycol, 825 parts by weight of IPDI (NCO group 37.5%), a catalyst, and MEK (50% solids). The mixture was stirred and reacted at 80°C for 6 hours. The reaction was terminated when the isocyanate group peak reached a predetermined level by infrared absorption analysis. Next, 438 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 groups by infrared absorption analysis, the solids were adjusted to 50% with MEK to obtain 1, a hexafunctional urea with a molecular weight of 6,200.

[0049] Preparation of ureac 2 A four-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 200 parts by weight of ethylene glycol, 930 parts by weight of IPDI (NCO group 37.5%), a catalyst, and MEK (50% solids). The mixture was stirred and reacted at 80°C for 6 hours. The reaction was terminated when the isocyanate group peak reached a predetermined level by infrared absorption analysis. Next, 886 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 groups by infrared absorption analysis, the solids were adjusted to 50% with MEK to obtain 2, a hexafunctional urea with a molecular weight of 3,200.

[0050] Preparation of ureac 3 A four-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 200 parts by weight of ethylene glycol, 895 parts by weight of IPDI (NCO group 37.5%), a catalyst, and MEK (50% solids). The mixture was stirred and reacted at 80°C for 6 hours. The reaction was terminated when the isocyanate group peak reached a predetermined level by infrared absorption analysis. Next, 743 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 groups by infrared absorption analysis, the solids were adjusted to 50% with MEK to obtain 3,800 Mw, a hexafunctional urea.

[0051] Preparation of ureac 4 A four-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 200 parts by weight of ethylene glycol, 808 parts by weight of IPDI (NCO group 37.5%), a catalyst, and MEK (50% solids). The mixture was stirred and reacted at 80°C for 6 hours. The reaction was terminated when the isocyanate group peak reached a predetermined level 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 groups by infrared absorption analysis, the solids were adjusted to 50% with MEK to yield 4, a hexafunctional urea with a molecular weight of 7,800.

[0052] Preparation of ureac 5 A four-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 200 parts by weight of ethylene glycol, 790 parts by weight of IPDI (NCO group 37.5%), a catalyst, and MEK (50% solids). The mixture was stirred and reacted at 80°C for 6 hours. The reaction was terminated when the isocyanate group peak reached a predetermined level by infrared absorption analysis. Next, 295 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 groups by infrared absorption analysis, the solids were adjusted to 50% with MEK to yield 6-functional urea 5 with a molecular weight of 9,800.

[0053] According to the above-mentioned production method, Ureacs A and B, which have the same skeleton as Ureacs 1 to 5 but different Mw, and Ureac C, which uses polyethylene glycol instead of ethylene glycol, were obtained. Ureac A: PETA-IPDI-(ethylene glycol-IPDI)n-PETA backbone, 6 functional groups, solid content 50%, Mw 1,800 Ureac B: PETA-IPDI-(ethylene glycol-IPDI)n-PETA backbone, 6 functional groups, solid content 50%, Mw 13,000 Urea C: PETA-IPDI-polyethylene glycol-IPDI-PETA backbone, 6 functional groups, solids content 50%, Mw 6,000

[0054] Examples 1 to 11 The above-prepared Ureacs 1 to 5 were used as (A), GL-02R (trade name: Kyoeisha Chemical Co., Ltd., an acrylic acrylate having a silicone side chain on an acrylic main chain, 20% solids diluted with butyl acetate) as (B), Tinuvin 249 (trade name: BASF Japan Ltd.) as (c1), Tinuvin 477 (trade name: BASF Japan Ltd.) as (c2), Omnirad 2959 and 127D (trade name: IGM Resins) as (D), and DPHA as a crosslinker were stirred until uniformly dissolved and dispersed in the formulation shown in Table 1, and PGM was further added to the mixture so that the solids content was 30%, followed by dilution and stirring to obtain the photocurable resin compositions of Examples 1 to 11.

[0055] Comparative Examples 1 to 6 In addition to the materials used in the examples, the above-mentioned ureacs A to C were used as oligomers in the formulations shown in Table 2, which were stirred until uniformly dissolved and dispersed. PGM was then added to the mixture so that the solid content was 30%, and the mixture was diluted and stirred to obtain photocurable resin compositions for Comparative Examples 1 to 6.

[0056] Table 1 JPEG0007783756000001.jpg75135

[0057] Table 2 JPEG0007783756000002.jpg119135

[0058] The evaluation method was as follows.

[0059] Preparation of HC films The photocurable resin compositions prepared in the examples and comparative examples were applied to Iupilon film (product name: DF02UL, manufactured by Mitsubishi Gas Chemical Company, Inc., thickness 254 μm, PMMA / PC laminate film) so that the photocurable resin was applied to the PMMA side so that the dry film thickness was 3 μm. The film was then dried in a thermostatic chamber at 80°C for 1 minute, and then irradiated with ultraviolet light from a high-pressure mercury lamp at an output of 1300 mW / cm2 and an accumulated light amount of 200 mJ to prepare a film for evaluation.

[0060] Preparation of injection molded parts Using the HC film obtained by curing the photocurable resin composition of Example 1, insert molding was actually carried out using black ABS as the injection molding resin.

[0061] Curability: Using an HC film, the tackiness of the coating surface was confirmed by touching with the finger, with no tack being rated as ◯ and tackiness being rated as ×.

[0062] Adhesion: In accordance with the cross-cut method of JIS K 5600-5-6, a 10 x 10 grid was created on the coated surface at 1 mm intervals, and cellophane tape CT-24 (product name: manufactured by Nichiban Co., Ltd.) was attached and pulled upward to check for peeling, with no peeling marked as ◯ and peeling marked as ×. No peeling: 100 / 100, Peeling: 0 / 100~99 / 100

[0063] Haze: Measured in accordance with JIS K7361-1 using Haze-GARD2 manufactured by Toyo Seiki Seisakusho, with 1.0% or less being rated as ◯ and more than 1.0% being rated as x.

[0064] Abrasion resistance: Using a friction tester FR-IBS manufactured by Suga Test Instruments, the resin composition coated surface of the hard coat film was rubbed with a friction element (diameter 16 mm) equipped with a test white cotton cloth (Kanakin No. 3) under a load of 9 N, and moved back and forth 100 mm at a speed of 1 reciprocation per second. After 1000 reciprocations, the presence or absence of scratches was checked, with a circle representing no scratches and an x ​​representing scratches.

[0065] Chemical resistance: Hand cream Neutrogena SPF45 (trade name: Johnson & Johnson) was applied to the cured film and left at 80°C for 6 hours, then returned to room temperature and wiped off, after which the surface was observed. ○ indicates no trace of application, × indicates trace of application.

[0066] Weather resistance: Using HC film, the appearance was visually inspected after irradiating with 500 kJ in accordance with SAE standard J2527. No change in appearance was evaluated as ◯, and any change in appearance (whitening, cracking, yellowing) was evaluated as ×.

[0067] Breaking elongation: The HC film was cut into a piece 25 mm wide x 50 mm long, and a tensile test was carried out using a TechnoGraph TGI-1KN manufactured by Minebia at an ambient temperature of 130°C and a pulling rate of 300 mm / min. Cracks were checked visually, and an elongation rate of 80% or more was marked as ○, and an elongation rate of 200% or more was marked as ⊚. Calculation formula: Calculate how many mm it has stretched based on 50 mm. Stretched length (mm) / 50mm x 100 = stretch rate %

[0068] Appearance: Using a BYK WaveScan 3 Dual paint surface quality measuring device, the film surface of the injection molded product and the painted surface of the painted steel plate were measured, and LW (long wave) and SW (short wave) data were measured and compared.

[0069] Example evaluation results Table 3 JPEG0007783756000003.jpg60135

[0070] Comparative Example Evaluation Results Table 4 JPEG0007783756000004.jpg99135

[0071] Table 5 JPEG0007783756000005.jpg47135

[0072] The examples were satisfactory in all aspects, including curability, adhesion, haze, abrasion resistance, chemical resistance, weather resistance, and elongation at break. Furthermore, the appearance of insert-molded articles made by injection molding using the colored resins was free of any appearance defects, such as orange peel.

[0073] On the other hand, Comparative Example 1, in which the amount of (B) was less than the lower limit, had low abrasion resistance, and Comparative Example 2, in which the amount was above the upper limit, had high haze. Furthermore, Comparative Example 3, in which the Mw of (A) was below the lower limit, had low elongation at break, Comparative Example 4, in which the Mw was above the upper limit, had poor abrasion resistance, Comparative Example 7, in which a polyethylene glycol-based oligomer was used, had poor chemical resistance, and Comparative Example 6, in which no (C) was added, had poor weather resistance, and none of these were suitable for the present invention.

Claims

1. 1. A photocurable resin composition comprising: a urethane acrylate (A) obtained by further reacting pentaerythritol triacrylate with a diisocyanate obtained by reacting ethylene glycol with isophorone diisocyanate; a silicone-containing acrylic (meth)acrylate (B); a light stabilizer (C); and a photopolymerization initiator (D); wherein the weight-average molecular weight of (A) is 2,000 to 12,000; the blending amount of (A) is 55 to 95 wt % based on the total solid content of the entire composition; and the blending amount of (B) is 0.4 to 21 wt % based on the total solid content of the entire composition.

2. 2. The photocurable resin composition according to claim 1, wherein the component (B) is an acrylic (meth)acrylate having a silicone side chain on an acrylic main chain.

3. 3. A molding hard coat film comprising a plastic substrate and a cured layer of the photocurable resin composition according to claim 1 or 2 on the plastic substrate.

4. A method for manufacturing an insert molded product, characterized in that the molding hard coat film described in claim 3 is shaped using a mold, and then molten resin is injected from the side opposite the photocurable resin cured layer to form a resin molded product.

5. An insert-molded or out-molded product using the hard coat film for molding according to claim 3.

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