JP2023119087A - Photocurable resin composition, hard coat film for molding, and molded article using the same, and method for manufacturing insert-molded article - Google Patents

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 The present invention relates to a photocurable resin composition excellent in moldability, a hard coat film for molding having a cured resin layer thereof, and a method for producing molded articles and insert molded articles using the same.

Acrylic photo-curing resins are used in many fields to impart special performance to the surface of plastic films and plastic moldings. The resulting hard coat film is used in large quantities as a film for touch panels and a film for molding.

Among these, particularly for molding, molding films are well known in which a pattern is printed on the surface of the film and then three-dimensional molding is performed in a state in which the film is softened by heating. If the material is hardened, microcracks are likely to occur on the curved surface when it is processed into a three-dimensional shape, and there are restrictions on the shape to be processed. Therefore, in the past, the applicant has proposed a hard coating 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 coating resin for insert molding that achieves both surface hardness and moldability. (Patent Document 1). This hard coating agent had a film thickness of 1 to 10 μm and was excellent in that both sufficient flexibility and surface physical properties were compatible.

By selecting a hard coating agent suitable for such molding applications, restrictions on processing have been eased to some extent. , various characteristics are required. For applications that are always used outdoors, such as the exterior of automobiles and the exterior of equipment stored outdoors, there is a new demand for sufficient weather resistance and durability to withstand ultraviolet rays and temperature differences. Ta. Therefore, in addition to the conventionally required properties such as sufficient moldability, abrasion resistance, and chemical resistance, there is room for improvement in order to provide sufficient weather resistance to withstand outdoor use.

Patent No. 4848200

The object of the present invention is to provide a light suitable for molding applications that has wear resistance and chemical resistance, high breaking elongation and good moldability, and has excellent weather resistance that can withstand outdoor use. An object of the present invention is to provide a curable resin composition, a molding hard coat film coated with the same, a molded article using the same, and a method for producing an insert molded article.

In order to solve the above problems, the invention of claim 1 provides a urethane acrylate (A ), 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, and the amount of (B) is 0.5 to 30 parts by weight per 100 parts by weight of (A).

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

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

The invention of claim 4 is characterized in that the plastic base material is a base material selected from the group consisting of a polycarbonate base material, an acrylic base material, a polyester base material, or a composite base material thereof. A molding hard coat fill is provided.

The invention of claim 5 provides the hard coat film for molding according to any one of claims 3 and 4, characterized in that the hard coat film for molding is for insert molding or outmold molding.

The invention according to claim 6 is characterized in that after shaping the hard coat film for molding using a mold, a resin molded product is formed by injecting a molten resin from the side opposite to the photocurable resin cured layer. A method for manufacturing an insert-molded product according to claim 3 or 4 is provided.

The invention of claim 7 provides the method of manufacturing an insert-molded product according to claim 6, wherein the molten resin is colored.

The invention according to claim 8 provides the method for manufacturing an insert-molded product according to claim 6 or 7, wherein the insert-molded product is used for vehicle exteriors.

The invention according to claim 9 provides an insert-molded article or an out-molded article using the molding hard coat film according to any one of claims 3 to 5.

The photocurable resin composition of the present invention and the hard coat film (hereinafter referred to as HC film) coated with the same have abrasion resistance and chemical resistance, high breaking elongation and good moldability. Because of its weather resistance, it is useful as a material for insert-molded products and out-molded products for outdoor use.

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

IPDI, which is an alicyclic diisocyanate used in the synthesis of (A), is free from yellowing, has excellent weather resistance stability, and has high rigidity, so that the hardness of the cured product can be increased. By reacting with ethylene glycol, which has a very short carbon chain, it is possible to increase the concentration of urethane bonds in the molecule, forming a highly rigid straight-chain main skeleton with excellent chemical resistance. When polyethylene glycol is used in place of ethylene glycol, the concentration of urethane bonds tends to decrease and chemical resistance tends to decrease.

The method for synthesizing (A) is not particularly limited, 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, a ketone such as butanone or an aromatic inert solvent such as xylene may be used. Moreover, it is preferable to use a catalyst for the reaction between the hydroxyl group of ethylene glycol and PETA and the isocyanate group. Examples thereof include tin-based agents such as dibutyltin dilaurate and metal alkoxide-based agents such as cobalt naphthenate. Although the reaction temperature can be set appropriately, it is preferably 40 to 120°C, more preferably 60 to 100°C.

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

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

The silicone-containing acrylic (meth)acrylate (B) used in the present invention is added for the purpose of improving the slipperiness of the surface of the cured product, improving the abrasion resistance, and forming a coating film with excellent durability. , for example, an acrylic (meth)acrylate having a silicone side chain on the acrylic main chain. Having a reactive (meth)acryloyl group in the molecule firmly binds to (A), suppresses the occurrence of bleed-out over time, and provides good lubricity and wear resistance on the surface of the cured product over a long period of time. You can give it character.

The 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 5 to 15 parts by weight with respect to 100 parts by weight of (A). Part is particularly preferred. If it is less than 0.5 parts by weight, it will be difficult to ensure sufficient abrasion resistance, and if it exceeds 30 parts by weight, the haze will increase and the appearance will tend to deteriorate. It is preferably 0.4 to 21% by weight, more preferably 0.6 to 20% by weight, based on the total solid content. Commercially available products of (B) include GL-02R (trade name: manufactured by Kyoeisha Chemical Co., Ltd.).

The light stabilizer (C) used in the present invention is blended for the purpose of preventing deterioration of the cured film due to ultraviolet exposure and radiant heat when used outdoors. For example, a radical scavenger (c1) that efficiently traps alkyl radicals and peroxy radicals generated from polymers photodegraded by ultraviolet rays, or by converting the energy of absorbed ultraviolet rays into heat energy, suppresses the decomposition of polymers. An ultraviolet absorber (c2) and the like can be mentioned.

Examples of the radical scavenger (c1) used in the present invention include hindered amine-based (hereinafter referred to as HALS-based), hindered phenol-based, and aromatic amine-based agents, which may be used alone or in combination of two or more. be able to. Among these, the HALS system, which has a high radical scavenging efficiency even at a low concentration, is preferred.

The content of (c1) is preferably 1 to 10% by weight, more preferably 2 to 8% by weight, particularly preferably 3 to 6% by weight, based on the total solid content. Sufficient photostability can be ensured by setting it as this range. Examples of commercially available HALS products include Tinuvin123 and Tinuvin249 (trade name: manufactured by BASF Japan).

The ultraviolet absorber (c2) used in the present invention is a radical chain initiation inhibitor having an absorption band in the high-energy, harmful ultraviolet region. It is possible to For example, benzotriazole-based, triazine-based, benzophenone-based, etc. can be mentioned, and can be used alone or in combination of two or more. Among these, the hydroxyphenyltriazine system is preferable because it can strongly absorb the long wavelength region of ultraviolet rays.

The content of (c2) is preferably 0.5 to 5% by weight, more preferably 0.8 to 3.0% by weight, particularly preferably 1.0 to 2.0% by weight, based on the total solid content. By setting it as this range, sufficient ultraviolet absorption characteristics can be ensured. Commercially available products include Tinuvin 460 and 477 (trade name: manufactured by BASF Japan). The amount of (C), which is the sum of (c1) and (c2), is preferably 1.0 to 12% by weight, more preferably 1.5 to 10% by weight, more preferably 4.0 to 4.0% by weight, based on the total solid content. 8.0% by weight is particularly preferred. When the content is 1.0% by weight or more, an improvement in weather resistance can be expected, and when the content is 12% by weight or less, excessive compounding can be avoided and sufficient adhesion to the substrate can be ensured.

The photopolymerization initiator (D) used in the present invention generates radicals when irradiated with ultraviolet rays, electron beams, or the like, and the radicals trigger a polymerization reaction. general-purpose photopolymerization initiators such as Curability can be imparted over a wide wavelength range from the ultraviolet region to the visible light region by arbitrarily selecting the light absorption wavelength of the polymerization initiator. Specifically, 2,2-dimethoxy-1,2-diphenylethan-1-one is a benzyl ketal system, and 1-hydroxy-cyclohexyl-phenyl-ketone and 1-[4-(2- hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one is 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 as α-aminoacetophenone -on includes acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, either singly or in combination of two or more can be used in combination.

Among these, it is preferable to contain an α-hydroxyacetophenone type resin that is resistant to yellowing. The content of (D) 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.

The photocurable resin composition of the present invention (hereinafter referred to as the present composition) may optionally contain a cross-linking agent, an adhesion promoter, an antioxidant, a bluing agent, a pigment, a leveling agent, as long as the performance is not impaired. Defoamers, thickeners, anti-settling agents, anti-static agents, anti-fogging agents, antibacterial agents, waxes, matting agents, hydrophilic agents, water repellent agents, inorganic fillers, organic fine particles and the like may be added.

As the cross-linking agent, it is preferable to use a polyfunctional (meth)acrylate from the viewpoint of low viscosity and excellent compatibility with (A) and (B). For example, bifunctional (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, dicyclopentanyl diacrylate, and trifunctional trimethylolpropane tri(meth)acrylate, pentaerythritol tri( meth)acrylates include tetrafunctional ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and diglycerin tetra(meth)acrylate, and pentafunctional dipentaerythritol penta(meth)acrylate, 6 Functionality includes dipentaerythritol hexa(meth)acrylate and the like, which can be used alone or in combination of two or more. Among these, dipentaerythritol hexaacrylate (hereinafter referred to as DPHA) is preferable because it has good reactivity and does not easily deteriorate moldability.

The content of the cross-linking 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 making it 30 parts by weight or less, it is possible to improve the reactivity while ensuring sufficient moldability. Also, the blending ratio of the total solid content is preferably 20% by weight or less, more preferably 10% by weight or less.

When the composition is applied to a plastic substrate, it may be diluted with a solvent to improve coating properties. For example, alcohol solvents such as ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and diacetone alcohol, ketone solvents such as acetone, methyl ethyl ketone (hereinafter referred to as MEK), methyl isobutyl ketone, and cyclohexanone, ethyl acetate , ester solvents such as butyl acetate, ether solvents such as propylene glycol monomethyl ether (hereinafter referred to as PGM), diethyl ether and diisopropyl ether, and hydrocarbon solvents such as cyclohexane and methylcyclohexane. can be used in combination. The solid content in the case of dilution is exemplified as 10 to 70%, but there is no particular specification, and it can be appropriately set so that the viscosity is easy to apply.

Plastic substrates to which the present composition is applied include polyester films, triacetylcellulose films, polycarbonate (hereinafter referred to as PC) films, polysulfone films, nylon films, cycloolefin films, acrylic (hereinafter referred to as PMMA) films, and polyimide films. , ABS film, polyolefin film, PVC film, PVA film and the like. Among them, a biaxially stretched polyester film is preferably used from the viewpoint of weather resistance, workability, dimensional stability, and the like. Furthermore, PMMA films and PC films are preferably used for automotive interior decoration, and laminated films thereof may also be used. The thickness of the film may be approximately 25 μm to 500 μm.

For the purpose of improving adhesion to the present composition, the plastic substrate may be subjected to a roughening treatment such as primer treatment, sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, ozone/ultraviolet irradiation treatment. Surface treatment such as surface oxidation treatment can be applied.

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

Light sources for ultraviolet irradiation used for curing the present composition include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, LED lamps, electrodeless ultraviolet lamps, and the like. The atmosphere for irradiation may be air or an inert gas such as nitrogen or argon. Curability can be further increased by heating the coating film with a back roll or an IR heater during ultraviolet irradiation. Examples of irradiation conditions include an irradiation intensity of 500 mW/cm ² to 3000 mW/cm ² and an exposure amount of 50 to 400 mJ/cm ² , but are not limited to these.

The HC film obtained by applying the present composition to a plastic substrate and curing (hereinafter referred to as the present HC film) preferably has a breaking elongation of 50% or more, and preferably 100% or more, in an atmosphere of 130°C. is more preferred, and 200% or more is particularly preferred. Sufficient moldability can be expected by setting the breaking elongation to 80% or more.

The present HC film can be provided with a decorative layer if necessary. Examples of the decorating method include printing and metal vapor deposition, and both of these methods may be used for decorating. Further, an adhesive layer or a primer layer may be provided in order to improve adhesion with the injection molding resin.

A protective film may be attached to the HC film to protect the surface coated with the composition. By using a protective film, it is possible to prevent damage during insert molding and out molding processes, and an improvement in yield can be expected.

As a method of using the present HC film in insert molding, for example, the surface coated with the present composition is arranged so as to face the inner wall surface of the mold (so that the opposite surface of the cured layer of the present composition is in contact with the molding resin), If necessary, the HC film is made to conform to the shape of the mold for preforming, and then the mold is closed to inject molding resin in a molten state into the cavity to solidify the resin to form a resin molded product. be able to.

As a method for carrying out the preforming, the present HC film is preheated to a softening point or higher, placed in a mold, and subjected to vacuum suction through a suction hole provided in the mold. A known molding method such as vacuum molding, air pressure molding, or press molding can be used using a molding die. It is also possible to simultaneously perform molding and integral molding with the injection resin by injection pressure of the molding resin without performing these pre-molding.

As the resin for injection molding, it is possible to use a known resin that can be injection molded. Examples include polyethylene resins, polypropylene resins, polystyrene resins, ABS resins, AS resins, acrylic resins, urethane resins, polyester resins, polycarbonate resins, polyphenylene ether resins, polyacetal resins, polysulfone resins, and the like. They can be used singly or in combination of two or more. In the case of a large size such as an automobile body, or in the case of a small size but thin thickness, problems such as warping can be avoided by approximating the shrinkage rate after molding to that of HC film. .

In addition, by coloring the injection molding resin itself, it is possible to eliminate the decoration layer of the HC film, or to combine the color of the decoration layer and the injection molding resin to create a deeper appearance. . Furthermore, when insert molding is used for a product whose exterior is to be colored with paint, such as an automobile body, it is possible to omit exterior coating with paint by coloring the resin to be injection molded. In this case, it is possible to eliminate appearance defects such as citrus peel and pits that often occur in exterior painting.

Further, the present HC films can also be used for out-molding. For example, it may be used for TOM (Three-Dimensional Overlay Method) molding. TOM molding is a film molding method that performs three-dimensional surface decoration on a base material pre-formed in an airtight box by vacuum/pneumatic molding. , three-dimensional large-scale products can also be handled.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but these are specific examples and are not intended to limit the invention in particular. Unless otherwise specified, the measurement was performed at a room temperature of 25° C. and a relative humidity of 65%. Moreover, the blending amount is converted to solid content and shown in parts by weight.

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 and 825 parts by weight of IPDI (37.5% NCO groups) and catalyst were added. and MEK were charged so as to give a solid content of 50%, stirred and reacted at 80° C. for 6 hours, and the reaction was terminated when the isocyanate group peak reached a predetermined amount in infrared absorption analysis. Next, 438 parts by weight of PETA (hydroxyl value 120 mgKOH/g) was added, and after stirring and reacting at 70 ° C. for 6 hours, it was confirmed by infrared absorption analysis that the isocyanate group had disappeared. % to obtain ureac 1 having a Mw of 6,200 and a hexafunctionality.

Preparation of Ureac 2 In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 200 parts by weight of ethylene glycol and 930 parts by weight of IPDI (37.5% NCO groups) and catalyst were added. and MEK were charged so as to give a solid content of 50%, stirred and reacted at 80° C. for 6 hours, and the reaction was terminated when the isocyanate group peak reached a predetermined amount in infrared absorption analysis. Next, 886 parts by weight of PETA (hydroxyl value 120 mg KOH / g) was added, and after stirring and reacting at 70 ° C. for 6 hours, it was confirmed by infrared absorption analysis that the isocyanate group had disappeared, and the solid content was reduced to 50 by MEK. % to obtain a hexafunctional ureac 2 with Mw of 3,200.

Preparation of Ureac 3 In a four-necked flask equipped with stirrer, reflux condenser, addition funnel and thermometer, 200 parts by weight of ethylene glycol and 895 parts by weight of IPDI (37.5% NCO groups) and catalyst were added. and MEK were charged so as to give a solid content of 50%, stirred and reacted at 80° C. for 6 hours, and the reaction was terminated when the isocyanate group peak reached a predetermined amount in infrared absorption analysis. Next, 743 parts by weight of PETA (hydroxyl value 120 mgKOH/g) was added, and after stirring and reacting at 70 ° C. for 6 hours, it was confirmed by infrared absorption analysis that the isocyanate group had disappeared, and the solid content was reduced to 50 by MEK. % to obtain a hexafunctional ureac 3 with Mw of 3,800.

Preparation of Ureac 4 In a four-necked flask equipped with stirrer, reflux condenser, dropping funnel and thermometer, 200 parts by weight of ethylene glycol and 808 parts by weight of IPDI (37.5% NCO groups) and catalyst were added. and MEK were charged so as to give a solid content of 50%, stirred and reacted at 80° C. for 6 hours, and the reaction was terminated when the isocyanate group peak reached a predetermined amount in infrared absorption analysis. Next, 371 parts by weight of PETA (hydroxyl value 120 mgKOH/g) was added, and after stirring and reacting at 70° C. for 6 hours, it was confirmed by infrared absorption analysis that the isocyanate group had disappeared. % to obtain a hexafunctional ureac 4 with Mw of 7,800.

Preparation of Ureac 5 Into a four-neck flask equipped with stirrer, reflux condenser, dropping funnel and thermometer, 200 parts by weight of ethylene glycol and 790 parts by weight of IPDI (37.5% NCO groups) and catalyst were added. and MEK were charged so as to give a solid content of 50%, stirred and reacted at 80° C. for 6 hours, and the reaction was terminated when the isocyanate group peak reached a predetermined amount in infrared absorption analysis. Next, 295 parts by weight of PETA (hydroxyl value 120 mgKOH/g) was added, and after stirring and reacting at 70 ° C. for 6 hours, it was confirmed by infrared absorption analysis that the isocyanate group had disappeared, and the solid content was reduced to 50 by MEK. %, ureac 5 having a Mw of 9,800 and a hexafunctionality was obtained.

Ureaac A and B having the same skeleton as Ureaac 1 to 5 but different Mw, and Ureaac C using polyethylene glycol instead of ethylene glycol were obtained according to the above-mentioned production method.
Ureac A: PETA-IPDI-(ethylene glycol-IPDI) n-PETA skeleton,
Hexafunctional, solid content 50%, Mw 1,800
Ureac B: PETA-IPDI-(ethylene glycol-IPDI) n-PETA skeleton,
Hexafunctional, solid content 50%, Mw 13,000
Ureac C: PETA-IPDI-polyethylene glycol-IPDI-PETA skeleton, hexafunctional, solid content 50%, Mw 6,000

Examples 1-11
Ureac 1 to 5 prepared above as (A), and GL-02R (trade name: manufactured by Kyoeisha Chemical Co., Ltd., acrylic acrylate having a silicone side chain in the acrylic main chain, solid content 20% diluted with butyl acetate) as (B) product), Tinuvin 249 (trade name: manufactured by BASF Japan) as (c1), Tinuvin 477 (trade name: manufactured by BASF Japan) as (c2), Omnirad 2959 and 127D (trade name: IGM Resins) as (D) ), DPHA as a cross-linking agent is stirred until it is uniformly dissolved and dispersed according to the formulation shown in Table 1, and then PGM is added and stirred for dilution so that the solid content becomes 30%. A photocurable resin composition was obtained.

Comparative Examples 1-6
In addition to the materials used in the examples, the above Ureac A to C as oligomers are stirred until they are uniformly dissolved and dispersed according to the formulation shown in Table 2, and then PGM is added so that the solid content is 30%, and diluted and stirred. Then, photocurable resin compositions of Comparative Examples 1 to 6 were obtained.

Table 1

Table 2

The evaluation method was as follows.

The photocurable resin compositions prepared in the HC film preparation examples and comparative examples were coated on the PMMA surface side using an Iupilon film (trade name: DF02UL, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 254 μm, PMMA/PC laminated film). A photocurable resin is applied so that the dry film thickness is 3 μm, dried in a constant temperature bath at 80° C. for 1 minute, then irradiated with ultraviolet rays from a high-pressure mercury lamp at an output of 1300 mW/cm2 and an integrated light intensity of 200 mJ, and evaluated. A film for use was prepared.

PREPARATION OF INJECTION MOLDED PRODUCT Using the HC film obtained by curing the photocurable resin composition of Example 1, insert molding was actually performed using black ABS as the resin for injection molding.

Curability: Using an HC film, the tackiness of the surface of the coating film was also checked by finger touch.

Adhesion: Based on the cross-cut method of JIS K 5600-5-6, create 10 × 10 squares at intervals of 1 mm on the coated surface, paste cellophane tape CT-24 (product name: manufactured by Nichiban Co., Ltd.), The state of peeling was checked by pulling it upward, and the absence of peeling was indicated by ◯, and the presence of peeling was indicated by x.
No peeling: 100/100, with peeling: 0/100 to 99/100

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

Abrasion resistance: Using a friction tester FR-IBS manufactured by Suga Test Instruments Co., Ltd., the resin composition coated surface of the hard coat film is subjected to a load of 9 N with a friction element (diameter 16 mm) attached with a white cotton cloth for testing (Kanakin No. 3). It was reciprocated 100 mm at a speed of 1 reciprocation/1 second under a high pressure, and after 1000 reciprocations, the presence or absence of scratches was confirmed.

Chemical resistance: Hand cream Neutrogena SPF45 (trade name: manufactured by Johnson & Johnson) was applied to the cured film, allowed to stand at 80°C for 6 hours, then returned to room temperature, wiped off, and then the surface was observed. The absence of traces of application was indicated by ◯, and the presence of traces was indicated by ×.

Weather resistance: HC film was used, and according to SAE standard J2527, the appearance was visually confirmed when irradiated at 500 kJ.

Breaking elongation: Cut the HC film into 25 mm wide x 50 mm long, and use TechnoGraph TGI-1KN manufactured by Minebia to perform a tensile test at an ambient temperature of 130 ° C. and a tensile speed of 300 mm / min. 80% or more was evaluated as ◯, and 200% or more as ⊚.
Calculation formula: Calculated by how many mm it has grown based on 50 mm.
Elongated length (mm) / 50 mm x 100 = elongation %

Appearance: Using BYK's WAVE SCAN 3 DUAL coating surface property measuring machine, measure the film surface of the injection molded product and the coated surface of the coated steel plate, measure and compare the LW (long wave) and SW (short wave) data. did.

Example evaluation results Table 3

Comparative example evaluation results Table 4

Table 5

The examples had no problems in all aspects of curability, adhesion, haze, wear resistance, chemical resistance, weather resistance and elongation at break. In addition, the appearance of the insert-molded product injection-molded using the colored resin did not have appearance defects such as citrus peel.

On the other hand, Comparative Example 1 in which the blending amount of (B) was less than the lower limit had low abrasion resistance, and Comparative Example 2 in which the blending amount of (B) exceeded the upper limit had high haze. In addition, Comparative Example 3 in which Mw of (A) is below the lower limit has low breaking elongation, Comparative Example 4 in which Mw is above the upper limit has poor wear resistance, and Comparative Example 7 using an oligomer having a polyethylene glycol skeleton exhibits chemical resistance. Furthermore, Comparative Example 6, which did not contain (C), had poor weather resistance, and neither of them was suitable for the present invention.

Claims (9)

Urethane acrylate (A) obtained by further reacting pentaerythritol triacrylate with diisocyanate obtained by reacting ethylene glycol and isophorone diisocyanate, silicone-containing acrylic (meth)acrylate (B), light stabilizer (C), and photopolymerization and an initiator (D), wherein the weight average molecular weight of (A) is 2,000 to 12,000, and the blending amount of (B) is 0.5 to 100 parts by weight of (A). 30 parts by weight of a photocurable resin composition. 2. The photocurable resin composition according to claim 1, wherein the (B) is an acrylic (meth)acrylate having a silicone side chain on the acrylic main chain. A molding hard coat film comprising a cured layer of the photocurable resin composition according to claim 1 on a plastic substrate. 4. The molding hard coat film according to claim 3, wherein the plastic substrate is a substrate selected from the group consisting of a polycarbonate substrate, an acrylic substrate, a polyester substrate, and a composite substrate thereof. 5. The hard coat film for molding according to claim 3, wherein the hard coat film for molding is for insert molding or outmold molding. 5. A molded resin product is formed by injecting a molten resin from the side opposite to the photocurable resin cured layer after shaping the hard coat film for molding using a mold. A method for producing an insert-molded product according to any one of the above. 7. The method of manufacturing an insert-molded product according to claim 6, wherein said molten resin is colored. 8. The method for producing an insert-molded product according to claim 6, wherein the insert-molded product is used for vehicle exteriors. An insert-molded article or an out-molded article using the molding hard coat film according to any one of claims 3 to 5.