JP2024009744A - Hard coat film for molding and molding using the same, and manufacturing method of insert molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film which has abrasion resistance and chemical resistance, has high elongation at break and good moldability even in a large size, has such excellent weather resistance as to be durable to outdoor use, and is suitable for molding application, a molding using the same, and a manufacturing method of an insert molding.

SOLUTION: A hard coat film has a curable layer of a photocurable resin composition on a composite base material of a polycarbonate base material and an acrylic base material, in which the photocurable resin composition contains urethane acrylate having such a structure that pentaerythritol triacrylate is further reacted with diisocyanate obtained by reaction of ethylene glycol with isophorone diisocyanate, a photostabilizer, and a photopolymerization initiator, a weight average molecular weight of the urethane acrylate is 2,000-12,000, and ΔE before and after irradiation with UVB (0.55 W/m2), 60°C and for 1,000 hours of the composite base material is 1.0 or less.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a hard coat film for molding having excellent moldability and weather resistance, and further to a method for producing molded products and insert molded products using the same.

In recent years, resin moldings have been increasingly used for the purpose of reducing the weight of interior and exterior parts of automobiles, exterior parts of information terminals, and parts for home appliances, and various methods are being used to decorate their surfaces. It is used. Among these methods, the method of decorating the outermost surface of the molded body using a film increases the degree of freedom in design compared to the use of paints such as spray painting, and also allows for the creation of three-dimensional irregularities. It is widely used because it is easy to decorate a shaped surface and has excellent productivity.

A well-known method for molding these films is insert molding, in which a pattern is printed on the surface of the film, the film is softened by heating and then three-dimensionally molded, and then the film is set in a mold and injection molded. In particular, for interior parts such as automobile instrument panels and consoles, hydraulic transfer, which has traditionally been mainstream, tends to be avoided due to drainage problems and VOC (volatile organic compounds) problems, and it is increasingly being used as an alternative method. be. Furthermore, in recent years, the use of resin for exterior applications such as front grills and roofs has become increasingly popular due to the growing demand for lighter parts due to the shift to EVs, and as coatings on resin parts have begun to be avoided for environmental reasons, films are being used. The introduction of molding is progressing.

Molded films used in insert molding are sometimes provided with a hard coat layer for the purpose of improving surface hardness and scratch resistance, but if the hard coat resin layer is hardened, microscopic particles may appear on curved surfaces when processed into three-dimensional shapes. There was a problem that cracks appeared and it became difficult to mold. Therefore, in the past, the applicant has invented a hard coat agent for insert molding that contains a triazine ring-containing (meth)acrylate prepolymer and organic fine particles with an average primary particle size of 80 to 500 nm (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 properties could be achieved.

However, in automotive exterior applications, in addition to the traditional requirements of moldability, abrasion resistance, chemical resistance, etc., stable moldability in large sizes and sufficient properties to withstand ultraviolet rays and temperature differences are required. Weather resistance and durability are required, and there has been no moldable film with a hard coat layer that can meet these requirements. Therefore, there has been a need for a hard coat film for molding that has sufficient moldability, chemical resistance, weather resistance, and durability and can be used for automotive exterior applications.

Patent No. 4848200

The object of the present invention is to provide molding applications that have wear resistance and chemical resistance, high elongation at break, good moldability even in large sizes, and excellent weather resistance that can withstand outdoor use. An object of the present invention is to provide a suitable hard coat film, a molded article using the same, and a method for manufacturing an insert molded article.

In order to solve the above problems, the invention according to claim 1 provides a hard coat film characterized by having a cured layer of a photocurable resin composition on a composite base material of a polycarbonate base material and an acrylic base material. The photocurable resin composition includes a urethane acrylate (A) having a structure in which pentaerythritol triacrylate is further reacted with a diisocyanate obtained by reacting ethylene glycol and isophorone diisocyanate, and a light stabilizer (B). It contains a photopolymerization initiator (C) and a fluorine-based silicone compound having a reactive functional group, the weight average molecular weight of the above (A) is 3,500 to 12,000, and the UVB ( Provided is a hard coat film for molding, which has a ΔE of 1.0 or less before and after irradiation at 0.55 W/m ² ) at 60° C. for 1000 hours, and is used for automobile exteriors. (Hereinafter, m2 shall mean m ^2. )

The invention according to claim 2 is characterized in that (B) includes a radical scavenger (b1) and an ultraviolet absorber (b2), and the blending amount of (b1) is 1 to 10% by weight based on the total solid content, ( There is provided a hard coat film for molding according to claim 1, characterized in that the blending amount of b2) is 0.3 to 5% by weight.

The invention according to claim 3 is characterized in that the amount of the fluorine-based silicone compound having a reactive functional group is 0.1 to 3% by weight based on the total solid content. Provides hard coat films for molding.

The invention according to claim 4 provides the hard coat film for molding according to any one of claims 1 to 3, characterized in that the hard coat film for molding is used for insert molding or out molding.

The invention according to claim 5 is a method of forming the hard coat film for molding according to any one of claims 1 to 3 using a mold, and then injecting molten resin from the side opposite to the photocurable resin cured layer. Provided is a method for manufacturing an insert molded product, which comprises forming a molded product.

A sixth aspect of the invention provides the method for manufacturing an insert molded product according to the fifth aspect, wherein the molten resin is colored.

The invention of claim 7 provides an insert molded product or an out-mold molded product using the hard coat film for molding according to any one of claims 1 to 3.

The hard coat film (hereinafter referred to as HC film) of the present invention has abrasion resistance and chemical resistance, high elongation at break, good moldability, and excellent weather resistance, so it can be used outdoors. For example, it is useful as a material for insert-molded products and out-molded products such as those used for automobile exteriors.

The composition of the HC resin composition used in the present invention is a urethane acrylate having a structure in which pentaerythritol triacrylate (hereinafter referred to as PETA) is further reacted with a diisocyanate obtained by reacting ethylene glycol and isophorone diisocyanate (hereinafter referred to as IPDI). (A), a light stabilizer (B), and a photopolymerization initiator (C). In this specification, (meth)acrylate includes both acrylate and methacrylate.

The alicyclic diisocyanate IPDI used in the synthesis of (A) has no yellowing and excellent weather resistance stability, and at the same time has high rigidity and can increase the hardness of the cured product. By reacting 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 main skeleton with a highly rigid linear chain structure that has excellent chemical resistance. When polyethylene glycol is used instead of ethylene glycol, the concentration of urethane bonds tends to decrease, resulting in a decrease in chemical resistance.

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

The weight average molecular weight (hereinafter referred to as Mw) of the above (A) is 2,000 to 12,000, preferably 2,500 to 11,000, more preferably 3,000 to 10,000, and 3,500 to 9 ,800 are particularly preferred. If it is less than 2,000, the elongation at break becomes low, making it difficult to ensure sufficient formability, and if it exceeds 12,000, the abrasion resistance decreases, and it becomes difficult to adjust the viscosity to a value that provides good workability. The Mw of (A) can be adjusted by changing the molar ratio of ethylene glycol and IPDI to be reacted, and as the molar ratio of IPDI to ethylene glycol approaches, the Mw tends to increase. Note that 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 blending amount of (A) is preferably 55 to 95% by weight, more preferably 65 to 92% by weight, and particularly preferably 70 to 90% by weight based on the total solid content. By setting the content to 55% by weight or more, sufficient breaking strength and chemical resistance can be ensured, and by setting the content to 95% by weight or less, sufficient weather resistance can be ensured.

The light stabilizer (B) used in the present invention is blended for the purpose of preventing deterioration of the cured film due to exposure to ultraviolet rays and radiant heat when used outdoors. For example, radical scavengers (b1) that efficiently trap alkyl radicals and peroxyl radicals generated from polymers photodegraded by ultraviolet rays, and suppress the decomposition of polymers by converting the energy of absorbed ultraviolet rays into thermal energy, etc. Examples include ultraviolet absorbers (b2). It is preferable to use (b1) and (b2) together.

Examples of the radical scavenger (b1) used in the present invention include hindered amine type (hereinafter referred to as HALS type), hindered phenol type, aromatic amine type, etc., and they may be used alone or in combination of two or more types. be able to. Among these, HALS systems are preferred because they have high radical scavenging efficiency even at low concentrations.

The blending amount of (b1) 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 setting it as this range, sufficient photostability can be ensured. Examples of commercially available HALS products include Tinuvin 123 and Tinuvin 249 (trade name: manufactured by BASF Japan).

The ultraviolet absorber (b2) used in the present invention is a radical chain initiation inhibitor that has an absorption band in the harmful ultraviolet region with high energy, and when used in combination with the above (b1), it further improves and stabilizes weather resistance. It becomes possible to do so. Examples include benzotriazole type, triazine type, benzophenone type, etc., which can be used alone or in combination of two or more types. Among these, hydroxyphenyltriazine-based materials are preferred because they can strongly absorb long-wavelength ultraviolet rays.

The blending amount of (b2) 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 solid content. By setting it as this range, sufficient ultraviolet absorption characteristics can be ensured. Further, the blending amount of (B), which is the sum of (b1) and (b2), is preferably 1.0 to 12% by weight, more preferably 1.5 to 10% by weight, and more preferably 4.0 to 12% by weight based on the total solid content. Particularly preferred is 8.0% by weight. When the content is 1.0% by weight or more, weather resistance can be expected to improve, and when the content is 12% by weight or less, it is not excessively blended and sufficient adhesion to the base material can be ensured. Commercially available products of (b2) include Tinuvin 460 and 477 (trade name: manufactured by BASF Japan).

The photopolymerization initiator (C) used in the present invention generates radicals when irradiated with ultraviolet rays or electron beams, and these radicals trigger the polymerization reaction, and include benzyl ketal, acetophenone, and phosphine oxide types. General-purpose photopolymerization initiators 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, 2,2-dimethoxy-1,2-diphenylethan-1-one is a benzyl ketal type, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy is an α-hydroxyacetophenone type. -2-Methyl-1-propan-1-one and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1 -one is α-aminoacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and acylphosphine oxide is 2.4.6-trimethylbenzoyl-diphenyl. -phosphine oxide and bis(2.4.6-trimethylbenzoyl)-phenylphosphine oxide, which can be used alone or in combination of two or more.

Among these, it is preferable to include α-hydroxyacetophenone, which is resistant to yellowing, and commercially available products include Omnirad 127D, 184, and 2959 (trade name: manufactured by IGM Resins). The content of the radically polymerizable component (C) is preferably 2 to 12 parts by weight, more preferably 3 to 10 parts by weight.

The HC resin composition used in the present invention (hereinafter referred to as the present composition) may contain crosslinking agents, leveling agents, adhesion promoters, antioxidants, bluing agents, pigments, erasers, etc. as necessary to the extent that performance is not impaired. Foaming agents, thickeners, anti-settling agents, antistatic agents, antifogging agents, antibacterial agents, waxes, matting agents, hydrophilic agents, water repellents, inorganic fillers, organic fine particles, etc. may be added.

As the crosslinking agent, polyfunctional (meth)acrylate is preferably used because it has low viscosity and excellent compatibility with (A). For example, difunctional compounds include (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and dicyclopentanyl diacrylate; trifunctional compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri( meth)acrylate is tetrafunctional, such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, diglycerine tetra(meth)acrylate, and pentafunctional, dipentaerythritol penta(meth)acrylate, 6 Examples of functional substances include dipentaerythritol hexa(meth)acrylate, which can be used alone or in combination of two or more types. Among these, dipentaerythritol hexaacrylate (hereinafter referred to as DPHA) is preferred because it has good reactivity and does not easily deteriorate moldability.

The amount of the crosslinking agent blended is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, per 100 parts by weight of (A). By setting the amount to 30 parts by weight or less, reactivity can be improved 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.

The leveling agent spreads itself into a thin film on the surface of the coating film, thereby making the surface tension uniform, and repairing defects before the coating film is formed. effective. Examples include silicone-based, fluorine-based, fluorine-based silicone, acrylic, etc., but they do not polymerize with the binder resin because they do not come off from the cured film due to bleeding over time and maintain their effects over a long period of time. It is preferable to have a reactive functional group that can form a cured coating film, and fluorine-based silicone compounds are particularly preferable.

The blending amount of the leveling agent is preferably 0.1 to 3% by weight, more preferably 0.3 to 1% by weight based on the total solid content. By setting it as this range, sufficient leveling property can be ensured at the time of coating. Commercially available products include X-71-1203M (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., acryloyl group-containing fluorine silicone compound).

The substrate to which the present composition is applied is a composite substrate of a polycarbonate (hereinafter referred to as PC) substrate that has excellent impact resistance and high heat resistance, and an acrylic substrate that has high transparency and hardness. Here, the composite base material of a PC base material and an acrylic base material (hereinafter referred to as the present composite base material) means a resin laminate having an acrylic resin layer on at least one side of a PC resin layer. The method of laminating the PC resin and the acrylic resin is preferably a coextrusion molding method.

The ΔE of the present composite base material before and after irradiation with UVB (0.55 W/m2) at 60° C. for 1000 hours is 1.0 or less, preferably 0.8 or less, and more preferably 0.5 or less. If it exceeds 1.0, the damage to the decorative layer caused by the transmitted ultraviolet rays will increase, and especially if the decorative layer uses red or blue colors with poor UV resistance, discoloration over time is likely to increase. .

When applying the present composition to the present composite substrate, it may be diluted with a solvent in order 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, and ethyl acetate. , ester solvents such as butyl acetate, ether solvents such as propylene glycol monomethyl ether (hereinafter referred to as PGM), diethyl ether, diisopropyl ether, hydrocarbon solvents such as cyclohexane, methylcyclohexane, etc., and these solvents may be used singly or in combination. Can be used in combination. The solid content when diluting is exemplified as 10 to 70%, but there is no particular specification and it can be set as appropriate so as to provide a viscosity that is easy to coat.

The method for applying the present composition is not particularly limited, and there are 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 gravure printing, It can be formed by printing methods such as screen printing, offset printing, and inkjet printing. The thickness of the coated film is, for example, 1 μm to 10 μm when dry, but is not limited thereto.

Light sources for ultraviolet irradiation used when 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, etc. The atmosphere for irradiation may be air or an inert gas such as nitrogen or argon. Moreover, by heating the back roll or heating the coating film with an IR heater or the like during ultraviolet irradiation, the curability can be further improved. Irradiation conditions include, but are not limited to, an irradiation intensity of 500 mW/cm ² to 3000 mW/cm ² and an exposure amount of 50 to 400 mJ/cm ² .

The HC film obtained by applying the present composition to the present composite base material and curing it (hereinafter referred to as the present HC film) preferably has a breaking elongation of 50% or more in an atmosphere of 130°C, and preferably 100% or more. More preferably, 200% or more is particularly preferable. By setting the elongation at break to 50% or more, sufficient moldability can be expected.

This HC film can be provided with a decorative layer if necessary. Examples of the decorating method include printing, metal vapor deposition, and the like, and both of these methods may be used for decoration. Furthermore, an adhesive layer or a primer layer may be provided to further improve adhesion to 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 scratches during insert molding and out-mold molding processes, and it is expected to improve yields.

A method of using the present HC film in insert molding is, for example, by arranging the surface coated with the present composition so as to face the inner wall surface of the mold (so that the surface opposite to the cured layer of the present composition is in contact with the molding resin), If necessary, the HC film is preformed to follow the shape of the mold, then the mold is closed and the molten molding resin is injected into the cavity, and the resin is solidified to form a resin molded product. be able to.

The above preforming can be performed by preheating the HC film above its softening point, placing it in a mold, and vacuuming it through suction holes provided in the mold, or by using a separate mold for injection molding. A known molding method such as vacuum molding, pressure molding, press molding, etc. can be used using a mold for molding. It is also possible to perform molding and integral molding with the injection resin at the same time by using the injection pressure of the molding resin without performing these preliminary moldings.

As the resin to be injection molded, any known resin that can be injection molded 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, polysulfone resin, etc. They can be used alone or in combination of two or more. When the size is large, such as the body of a car, or when the wall thickness is thin even if the size is small, problems such as warping can be avoided by making the shrinkage rate after molding approximate that of HC film. .

In addition, by coloring the injection molding resin itself, it is possible to eliminate the decorative layer of the HC film, or to create a deeper appearance by merging the colors of the decorative layer and the injection molding resin. . Furthermore, when replacing a product whose exterior is colored with paint, such as the body of an automobile, by insert molding, it is possible to omit external painting with paint by coloring the injection molded resin. In this case, it is possible to eliminate appearance defects such as orange skin and pits that often occur during external painting.

Furthermore, the present HC film can also be used for out-molding. For example, it may be used in TOM (Three-Dimensional Overlay Method) molding. TOM molding is a film molding method that applies three-dimensional surface decoration to a base material that has been preformed in an airtight box using vacuum/pressure molding. , it is also possible to handle large three-dimensional products.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but these are intended to be specific examples and are not particularly limited to these. Unless otherwise specified, the measurements were performed at a room temperature of 25° C. and a relative humidity of 65%. In addition, the blending amount is expressed in parts by weight in terms of solid content.

Preparation of Ureac 1 In a four-necked flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, 200 parts by weight of ethylene glycol, 825 parts by weight of IPDI (37.5% NCO groups), and catalyst. and MEK were charged so that the solid content was 50%, stirred and reacted at 80° C. for 6 hours, and the reaction was terminated when the peak of isocyanate groups 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 groups had disappeared, and the solid content was reduced to 50% by MEK. % to obtain hexafunctional ureac 1 with Mw of 6,200.

Preparation of Ureac 2 In a four-necked flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, 200 parts by weight of ethylene glycol, 930 parts by weight of IPDI (NCO group 37.5%), and catalyst. and MEK were charged so that the solid content was 50%, stirred and reacted at 80° C. for 6 hours, and the reaction was terminated when the peak of isocyanate groups reached a predetermined amount in infrared absorption analysis. Next, 886 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 groups had disappeared, and the solid content was reduced to 50% by MEK. % to obtain hexafunctional ureac 2 with an Mw of 3,200.

Preparation of Ureac 3 In a four-necked flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, 200 parts by weight of ethylene glycol, 895 parts by weight of IPDI (37.5% NCO groups), and catalyst. and MEK were charged so that the solid content was 50%, stirred and reacted at 80° C. for 6 hours, and the reaction was terminated when the peak of isocyanate groups 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 groups had disappeared, and the solid content was reduced to 50% by MEK. % to obtain hexafunctional ureac 3 with an Mw of 3,800.

Preparation of Ureac 4 In a four-necked flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, 200 parts by weight of ethylene glycol, 808 parts by weight of IPDI (37.5% NCO group), and catalyst. and MEK were charged so that the solid content was 50%, stirred and reacted at 80° C. for 6 hours, and the reaction was terminated when the peak of isocyanate groups 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, and the solid content was reduced to 50% by MEK. % to obtain hexafunctional ureac 4 with an Mw of 7,800.

Preparation of Ureac 5 In a four-neck flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, 200 parts by weight of ethylene glycol, 790 parts by weight of IPDI (37.5% NCO groups), and catalyst. and MEK were charged so that the solid content was 50%, stirred and reacted at 80° C. for 6 hours, and the reaction was terminated when the peak of isocyanate groups 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 groups had disappeared, and the solid content was reduced to 50% by MEK. % to obtain hexafunctional ureac 5 with an Mw of 9,800.

According to the above production method, Ureac A and B having the same skeleton as Ureac 1 to 5 but different in Mw, and Ureac C using polyethylene glycol instead of ethylene glycol were obtained.
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

The HC resin composition was evaluated as follows.

Practical formulation examples 1 to 9
Ureac 1 to 5 prepared above as (A), Tinuvin 249 (product name: manufactured by BASF Japan) as (b1), Tinuvin 477 (product name: manufactured by BASF Japan) as (b2), (C) Omnirad 2959 and 127D (trade name: manufactured by IGM Resins) were used, DPHA was used as a crosslinking agent, and X-71-1203M (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., a fluorine-based silicone compound containing an acryloyl group) was used as a leveling agent. The mixture described in Example 1 was stirred until uniformly dissolved and dispersed, and then PGM was added and diluted to a solid content of 30% and stirred to obtain HC resin compositions of Practical Formulation Examples 1 to 9.

Comparative formulation examples 1 to 3
In addition to the materials used in the above practical formulation examples, the above-mentioned ureac A to C as oligomers were stirred until uniformly dissolved and dispersed in the formulation shown in Table 2, and then PGM was added so that the solid content was 30%. The mixture was diluted and stirred to obtain HC resin compositions of Comparative Formulation Examples 1 to 3.

Table 1

The evaluation method for the HC resin composition was as follows.

HC film preparation for resin composition evaluation The HC resin compositions prepared in the practical formulation examples and comparative formulation examples were prepared using Iupilon film (trade name: DF02PUL, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 125 μm, PMMA/PC laminated film). , Apply a photocurable resin to the PMMA side to a dry film thickness of 3 μm, dry in a constant temperature bath at 80°C for 1 minute, and then use a high-pressure mercury lamp to obtain an output of 1300 mW/cm2 and an integrated light amount of 200 mJ. An HC film for evaluation was prepared by irradiating ultraviolet light in a nitrogen atmosphere.

Curability: Using an HC film, the tackiness of the surface of the coating film was also confirmed by touching with a finger, and no tack was evaluated as ○, and tack was evaluated as ×.

Adhesion: Based on the cross-cut method of JIS K 5600-5-6, create 10 x 10 squares at 1 mm intervals on the coated surface, apply cellophane tape CT-24 (product name: Nichiban Co., Ltd.), The state of peeling was checked by pulling upward, and no peeling was marked as ○, and peeling was marked as x.
No peeling: 100/100, peeling: 0/100 to 99/100

Abrasion resistance: Using a friction tester FR-IBS manufactured by Suga Test Instruments, the resin composition coated surface of the hard coat film was 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 made to reciprocate 100 mm at a speed of 1 reciprocation/1 second, and the presence or absence of scratches was checked after 20 reciprocations.

Chemical resistance: A hand cream, Neutrogena SPF45 (trade name: Johnson & Johnson) was applied to the cured film, left at 80°C for 4 hours, then returned to room temperature, wiped off, and the surface was observed. No traces of coating were rated as ○, and those with marks were rated as ×.

Breaking elongation: The HC film was cut into 25 mm width x 50 mm length, and a tensile test was performed using TechnoGraph TGI-1KN manufactured by Minebia at an ambient temperature of 130°C and a tensile speed of 300 mm/min, and cracks were visually confirmed. rated 50% or more as ○, and 200% or more as ◎.
Calculation formula: Calculated based on how many mm it has expanded based on 50 mm.
Stretched length (mm)/50mm x 100 = elongation rate %

Formulation example evaluation results Table 2

The HC resin composition of the practical formulation example had no problems and was good in all aspects of curability, adhesion, abrasion resistance, chemical resistance, weather resistance, and elongation at break.

On the other hand, Comparative Blend Example 1 with Mw below the lower limit has low elongation at break, Comparative Blend Example 2 with Mw above the upper limit has poor wear resistance, and Comparative Blend Example 3 using ureac with a polyethylene skeleton has poor chemical resistance. Both were inferior and unsuitable for the present invention.

Next, the molding film was evaluated as follows.

Examples and Comparative Examples Using the resin compositions of Practical Formulation Examples 1, 4, and 7, a photocurable resin was applied onto the substrate listed in Table 3 to a dry film thickness of 3 μm, and the resin was heated in a constant temperature bath. After drying at 80°C for 1 minute, ultraviolet rays were irradiated with a high-pressure mercury lamp at an output of 1300 mW/cm2 and an integrated light amount of 200 mJ to prepare molding films of Examples 1 to 3 and Comparative Examples 1 to 8. (

Table 3

(*1: Wavelock Advanced Technology Co., Ltd.

The evaluation method for the formed film was as follows.

ΔE of base material alone: Using a color difference measuring instrument SD-6000 manufactured by Nippon Denshoku Kogyo Co., Ltd., in accordance with JIS Z 8722, UVB (0.55 W/m2 ) The color appearance before and after irradiation at 60° C. for 1000 hours was measured, and the difference ΔE was measured.

Weather resistance: Under the same conditions as above, the ΔE of the molded film coated with the HC resin was measured, and a case of less than 1.0 was given as ○, and a case of more than 1.0 was given as ×.

Formability: After heating the formed film to a substrate temperature of 180°C, vacuum forming is performed using a vacuum forming machine using a cylindrical mold with a diameter of 30 mm x 4 mm. Incomplete cases were marked as ×.

Cloth trace test: When a 50 mm x 50 mm gauze is brought into contact with the resin composition coated surface of the molded film, a load of 500 kg/4 cm ² is applied, and no trace remains when the cloth is removed after being left at 80°C for 60 minutes. It was marked as ○, and the case where a mark remained was marked as ×.

Abrasion property: Using a friction tester FR-IBS manufactured by Suga Test Instruments, the resin composition coated surface of the molded film was subjected to a load of 1 kg/cm2 with a friction element (diameter 16 mm) attached with white cotton cloth for testing (Kanakin No. 3). It was made to reciprocate 100 mm at a speed of 1 reciprocation/1 second, and the presence or absence of scratches was checked after 20 reciprocations.

Pencil hardness: Based on JISK5600-5-4 (1999 edition), measured with a 500g load using a pencil scratch coating hardness tester (type P) manufactured by Toyo Seiki Seisakusho, H or higher is ○, F or lower was marked as ×.

Table 4

The examples had no problems and were good in all aspects of weather resistance, moldability, cloth trace test, abrasion resistance, and pencil hardness.

On the other hand, Comparative Examples 1 to 3 using a PMMA/PC base material with a ΔE of more than 1.0 had poor weather resistance, and Comparative Example 4 using a PC base material had poor weather resistance and pencil hardness. Furthermore, Comparative Example 5, which was made of an acrylic resin material, was inferior in cloth mark test and pencil hardness, and Comparative Example 6, which was made of a PET base material, was inferior in weather resistance and moldability. Furthermore, Comparative Examples 7 and 8, which were not coated with HC resin, had poor abrasion resistance and pencil hardness, and in particular, Comparative Example 8, which was a PC base material, had poor weather resistance, and both were unsuitable for the present invention.

Next, injection molding was evaluated as follows.

Preparation of injection molded product Using the HC film of Example 1, insert molding was actually performed using black ABS as the injection molding resin.

Appearance: Measure the film surface of the injection molded product and the painted surface of the painted steel plate using BYK's painted surface quality measuring machine WaveScan 3 Dual, measure and compare LW (long wave) and SW (short wave) data. did.

Table 5

The appearance of the insert molded product injection molded using the colored resin did not have the appearance defect of orange peel unlike the painted steel plate.

In order to solve the above problems, the invention according to claim 1 provides a hard coat film characterized by having a cured layer of a photocurable resin composition on a base material, the hard coat film having a cured layer of a photocurable resin composition on a base material. is a urethane acrylate (A) having a structure obtained by further reacting pentaerythritol triacrylate with a diisocyanate obtained by reacting ethylene glycol and isophorone diisocyanate, a light stabilizer (B), and a photopolymerization initiator (C), a fluorine-based silicone compound having a reactive functional group, the elongation at break of the hard coat film is 100% or more at an ambient temperature of 130° C. and a tensile speed of 300 mm/min, and a UVB (0.55 W/m ² ), 60°C, 1000 hours irradiation before and after ΔE is 1.0 or less, to provide a hard coat film for molding. (Hereinafter, m2 shall mean m ^2. )

The invention according to claim 2 provides the hard coat film for molding according to claim 1, wherein the (B) includes a radical scavenger (b1) and an ultraviolet absorber (b2).

The invention according to claim 3 provides the hard coat film for molding according to either claim 1 or 2, which is used for the exterior of automobiles .

A fourth aspect of the invention provides the hard coat film for molding according to any one of claims 1 and 2 , characterized in that the hard coat film for molding is used for insert molding or out molding.

The invention according to claim 5 is a method of forming the hard coat film for molding according to claim 4 using a mold, and then injecting molten resin from the side opposite to the photocurable resin cured layer to form a resin molded product. A method for manufacturing an insert molded product is provided.

The invention according to claim 7 provides an insert molded product or an out-mold molded product using the hard coat film for molding according to claim 4 .

Claims (7)

A hard coat film comprising a cured layer of a photocurable resin composition on a composite substrate of a polycarbonate base material and an acrylic base material, the photocurable resin composition comprising ethylene glycol and isophorone diisocyanate. A urethane acrylate (A) having a structure obtained by further reacting pentaerythritol triacrylate with diisocyanate, a light stabilizer (B), a photoinitiator (C), and fluorine having a reactive functional group. containing a silicone compound, the weight average molecular weight of (A) is 3,500 to 12,000, and the composite base material is irradiated with UVB (0.55 W/m ² ), 60° C., for 1000 hours. A hard coat film for molding, characterized in that it has a ΔE of 1.0 or less and is used for the exterior of automobiles. The above (B) contains a radical scavenger (b1) and an ultraviolet absorber (b2), the amount of (b1) is 1 to 10% by weight based on the total solid content, and the amount of (b2) is 0. The hard coat film for molding according to claim 1, characterized in that the amount is 3 to 5% by weight. 3. The hard coat film for molding according to claim 1, wherein the amount of the fluorine-based silicone compound having a reactive functional group is 0.1 to 3% by weight based on the total solid content. The hard coat film for molding according to any one of claims 1 to 3, wherein the hard coat film for molding is used for insert molding or out-mold molding. After shaping the hard coat film for molding according to any one of claims 1 to 3 using a mold, a resin molded product is formed by injecting molten resin from the side opposite to the photocurable resin cured layer. A manufacturing method for featured insert molded products. 6. The method for manufacturing an insert molded product according to claim 5, wherein the molten resin is colored. An insert-molded article or an out-molded article using the hard coat film for molding according to any one of claims 1 to 3.