WO2024014053A1 - Hard coat resin composition for automotive exterior molding film, hard coat film for molding, method for producing insert molded product, insert molded product, and out-mold molded product - Google Patents

Abstract

This hard coat resin composition for an automotive exterior molding film comprises: a urethane acrylate (A) having a structure in which a pentaerythritol triacrylate is further reacted with a diisocyanate obtained by reacting an ethylene glycol and an isophorone diisocyanate; a light stabilizer (B); a photopolymerization initiator (C); and a fluorine-based silicone compound having a reactive functional group. The weight-average molecular weight of (A) is 3,500 to 12,000.

Description

Hard coat resin composition for automotive exterior molding film, hard coat film for molding, method for producing insert molded products, insert molded products, and out-mold molded products Cross-reference of related applications

This international application claims priority based on Japanese Patent Application No. 2022-110973 filed with the Japan Patent Office on July 11, 2022, and is based on Japanese Patent Application No. 2022-110973. The entire contents are incorporated by reference into this international application.

The present disclosure relates to a hard coat resin composition for a molding film for automobile exteriors, a hard coat film for molding, a method for producing an insert molded product, an insert molded product, and an out-mold molded product.

In recent years, resin molded bodies have been increasingly used for the interior and exterior parts of automobiles, exterior parts of information terminals, parts for home appliances, etc. for the purpose of reducing weight. Various methods are used to decorate or decorate the surface of a resin molded body. Among the methods of decorating or decorating the surface of a resin molded object, the method of decorating the outermost surface of the resin molded object using a film has a higher degree of freedom in design than methods that use paint such as spray painting. It has been widely adopted because it can increase the surface area, it is easy to decorate surfaces with three-dimensional unevenness, and it has excellent productivity.

Insert molding is a well-known molding method using film. In insert molding, after printing a pattern on the film surface, three-dimensional molding is performed while the film is softened by heating, and then the film is set in a mold and injection molding is performed. In particular, for interior parts such as automobile instrument panels and consoles, the conventionally mainstream hydraulic transfer tends to be avoided due to problems with drainage and VOC (volatile organic compounds), so inserts are being used as an alternative method. Molding has been introduced. Furthermore, recently, molding methods using films have been increasingly introduced for exterior applications such as front grilles and roofs. The reason for this is that the use of resin parts has increased due to the demand for lighter parts for EVs, and the use of paint on resin parts has begun to be avoided for environmental reasons.

A hard coat resin layer is sometimes provided on the molded film used in insert molding for the purpose of improving surface hardness and scratch resistance. The molded film provided with the hard coat resin layer is a hard coat film for molding. In a hard coat film for molding, if the hard coat resin layer is hardened, there is a problem in that microcracks occur in the hard coat resin layer on curved surfaces when processing it into a three-dimensional shape, making it difficult to mold.

The applicant has disclosed, as a hard coat resin for insert molding, 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 (Patent Document 1) reference). This hard coating agent can have both sufficient flexibility and surface properties when the film thickness is 1 to 10 μm.

In the case of automotive exterior applications, it is desirable that the hard coat film for molding has properties appropriate to the application. Characteristics suitable for automotive exterior use include, for example, one or more of the following: stable moldability in large sizes, chemical resistance, sufficient weather resistance to withstand ultraviolet rays and temperature differences, and durability. It will be done.

Patent No. 4848200

In one aspect of the present disclosure, there is provided a hard coat resin composition for a film for molding an automotive exterior, a hard coat film for molding, a method for manufacturing an insert molded product, an insert molded product, and an insert molded product having characteristics suitable for automotive exterior applications. Preferably, a molded article is provided.

One aspect of the present disclosure provides 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, a light stabilizer (B), and a photopolymerization initiator. A hard coat resin composition for a molding film for automobile exteriors, which comprises an agent (C) and a fluorine-based silicone compound having a reactive functional group, and wherein the weight average molecular weight of the above (A) is 3,500 to 12,000. It is a thing.

A hard coat resin composition for a molding film for automobile exteriors, which is one aspect of the present disclosure, has characteristics suitable for automobile exterior uses.

Another aspect of the present disclosure is to shape a hard coat film for molding having a base material and a cured layer on the base material using a mold, and inject molten resin from the side opposite to the cured layer. This is a method for manufacturing an insert molded product, in which a resin molded product is formed.

The cured layer contains urethane acrylate (A) having a structure in which pentaerythritol triacrylate is further reacted with a diisocyanate obtained by reacting ethylene glycol and isophorone diisocyanate, a light stabilizer (B), and a photopolymerization initiator (C). ) and a fluorine-based silicone compound having a reactive functional group, and the resin composition of (A) has a weight average molecular weight of 3,500 to 12,000.

According to the method for manufacturing an insert molded product, which is another aspect of the present disclosure, it is possible to manufacture an insert molded product with characteristics suitable for automotive exterior applications.

An exemplary embodiment of the present disclosure will be described.

1. Hard coat resin composition for molding film for automobile exterior The hard coat resin composition for molding film for automobile exterior (hereinafter referred to as HC resin composition) of the present disclosure contains ethylene glycol and isophorone diisocyanate (hereinafter referred to as IPDI). A urethane acrylate (A) having a structure in which pentaerythritol triacrylate (hereinafter referred to as PETA) was further reacted with the reacted diisocyanate, a light stabilizer (B), a photopolymerization initiator (C), and a reactive A fluorine-based silicone compound having a functional group.

Note that (meth)acrylate in this specification means both acrylate and methacrylate. The HC resin composition is used to form a hard coat layer of a moldable film. Molding films are used for molding exterior parts of automobiles.

IPDI used in the synthesis of (A) is an alicyclic diisocyanate. IPDI has little yellowing, excellent weather resistance stability, high rigidity, and can increase the hardness of the cured product of the HC resin composition. By reacting IPDI 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 structure with excellent chemical resistance. When polyethylene glycol is used instead of ethylene glycol, the concentration of urethane bonds tends to be low, leading to a decrease in chemical resistance.

The method for synthesizing (A) is not particularly limited, and any known synthesis method can be used. The reaction when synthesizing (A) may be carried out without a solvent, but as the molecular weight of (A) increases, stirring may become difficult. The reaction may be carried out using a group inert solvent or the like.

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 the 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, more preferably 60 to 100°C.

The weight average molecular weight (hereinafter referred to as Mw) of (A) is 3,500 to 12,000, preferably 3,500 to 11,000, more preferably 3,500 to 10,000, and 3,500 to 12,000. 9,800 is particularly preferred.

If the Mw of (A) is less than 3,500, the elongation at break of the HC resin composition will be low, making it difficult to ensure sufficient moldability. When the Mw of (A) exceeds 12,000, the abrasion resistance of the HC resin composition decreases, and it becomes difficult to adjust the viscosity of the HC resin composition to a viscosity that provides good workability. The Mw of (A) can be adjusted by adjusting the molar ratio of ethylene glycol and IPDI to be reacted.

When the molar ratio of IPDI to ethylene glycol approaches 1:1, the Mw of (A) tends to increase. The Mw of (A) was calculated by measuring the molecular weight in terms of standard polystyrene by gel permeation chromatography. To measure the Mw of (A), a column using a styrene divinylbenzene-based packing material and a tetrahydrofuran eluent were used.

The blending amount of (A) is preferably 55 to 95% by weight, more preferably 65 to 92% by weight, particularly preferably 70 to 90% by weight, based on the total solid content of the HC resin composition. By setting the blending amount of (A) to 55% by weight or more, sufficient breaking strength and chemical resistance of the HC resin composition can be ensured. By setting the blending amount of (A) to 95% by weight or less, sufficient weather resistance of the HC resin composition can be ensured.

The light stabilizer (B) used in the present disclosure is blended to suppress deterioration of the cured film of the HC resin composition due to exposure to ultraviolet rays or radiant heat when used outdoors. For example, examples of the light stabilizer (B) include (b1) and (b2). (b1) is a radical scavenger that efficiently traps alkyl radicals and peroxy radicals generated from polymers photodegraded by ultraviolet rays. (b2) is an ultraviolet absorber that suppresses polymer decomposition by converting absorbed ultraviolet energy into thermal energy or the like. It is preferable to use (b1) and (b2) together.

Examples of the radical scavenger (b1) used in the present disclosure include hindered amine type (hereinafter referred to as HALS type), hindered phenol type, aromatic amine type, and the like. (b1) can be used alone or in combination of two or more types. 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 of the HC resin composition. By setting the blending amount of (b1) within this range, sufficient photostability of the HC resin composition can be ensured. Examples of HALS-based commercial products include Tinuvin 123 and Tinuvin 249 (trade name: manufactured by BASF Japan).

The ultraviolet absorber (b2) used in the present disclosure is a radical chain initiation inhibitor that has an absorption band in the harmful ultraviolet region with high energy. By using (b2) and (b1) in combination, it becomes possible to further improve the weather resistance of the HC resin composition and to make the weather resistance more stable. Examples of (b2) include benzotriazole, triazine, and benzophenone. (b2) 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 more preferably 0.6 to 1.5% by weight based on the total solid content of the HC resin composition. is particularly preferred. By setting the blending amount of (b2) within this range, sufficient ultraviolet absorption characteristics of the HC resin composition 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 based on the total solid content of the HC resin composition. , 4.0 to 8.0% by weight is particularly preferred. By setting the blending amount of (B), which is the sum of (b1) and (b2), to 1.0% by weight or more, it can be expected that the weather resistance of the HC resin composition will be improved. By setting the blending amount of (B), which is the sum of (b1) and (b2), to 12% by weight or less, (B) will not be excessively blended and will maintain sufficient adhesion between the HC resin composition and the base material. Can be secured. Commercially available products of (b2) include Tinuvin 460 and 477 (trade name: manufactured by BASF Japan).

The photopolymerization initiator (C) used in the present disclosure generates radicals when irradiated with ultraviolet rays, electron beams, etc. The generated radicals trigger a polymerization reaction. As (C), for example, general-purpose photopolymerization initiators such as benzyl ketal, acetophenone, and phosphine oxide can be used.

By arbitrarily selecting the light absorption wavelength of the polymerization initiator, curability can be imparted over a wide wavelength range from the ultraviolet region to the visible light region. Specifically, as a benzyl ketal type, there is 2,2-dimethoxy-1,2-diphenylethan-1-one. As α-hydroxyacetophenone type, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one and 2-hydroxy-1-{4-[4- (2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one. As an α-aminoacetophenone type, there is 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. Examples of acylphosphine oxides include 2.4.6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2.4.6-trimethylbenzoyl)-phenylphosphine oxide. (C) 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. Examples of commercially available α-hydroxyacetophenone products include Omnirad 127D, 184, and 2959 (trade name: IGM manufactured by Resins). The amount of (C) to be blended 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 HC resin composition of the present disclosure may contain a crosslinking agent, a leveling agent, an adhesion promoter, an antioxidant, a bluing agent, a pigment, an antifoaming agent, a thickener, and an anti-settling agent as necessary within a range that does not impair performance. agent, antistatic agent, antifogging agent, antibacterial agent, wax, matting agent, hydrophilic agent, water repellent, inorganic filler, organic fine particles, etc. may be added.

As the crosslinking agent, it is preferable to use polyfunctional (meth)acrylate because it has low viscosity and excellent compatibility with (A). For example, bifunctional (meth)acrylates include (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and dicyclopentanyl diacrylate.

Examples of trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate.

Examples of tetrafunctional (meth)acrylates include ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and diglycerintetra(meth)acrylate.

Examples of pentafunctional (meth)acrylates include dipentaerythritol penta(meth)acrylate.

Examples of hexafunctional (meth)acrylates include dipentaerythritol hexa(meth)acrylate and the like. Polyfunctional (meth)acrylates can be used alone or in combination of two or more types. Among these, dipentaerythritol hexaacrylate (hereinafter referred to as DPHA) is preferable because it has good reactivity and does not easily deteriorate moldability.

The blending amount of the crosslinking agent is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, based on 100 parts by weight of (A). By controlling the amount of the crosslinking agent to be 30 parts by weight or less, it is possible to improve the reactivity while ensuring sufficient moldability of the HC resin composition. Further, the blending ratio of the crosslinking agent to the total solid content of the HC resin composition is preferably 20% by weight or less, more preferably 10% by weight or less.

The leveling agent has the effect of repairing defects in the coating film before forming the coating film of the HC resin composition. The reasons for repairing defects in the paint film are as follows. Non-uniform surface tension may occur on the surface of the coating film of the HC resin composition. The leveling agent spreads over the coating surface in a thin film to even out the surface tension. As a result, defects in the paint film can be repaired.

Examples of the leveling agent include silicone-based, fluorine-based, fluorine-based silicone, acrylic-based, and the like. Preferably, the leveling agent has a reactive functional group that can polymerize with the binder resin to form a cured coating. In this case, the leveling agent is less likely to be removed from the cured film due to bleeding or the like over time, and the effect can be maintained over a long period of time. As the leveling agent having a reactive functional group capable of polymerizing with the binder resin to form a cured coating film, a fluorine-based silicone compound is 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 of the HC resin composition. By setting the amount of the leveling agent within this range, sufficient leveling properties can be ensured during application of the HC resin composition. Examples of commercially available leveling agents include X-71-1203M (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., acryloyl group-containing fluorine-based silicone compound).

2. Hard Coat Film for Molding As the base material to which the HC resin composition is applied, a composite base material of a polycarbonate (hereinafter referred to as PC) base material and an acrylic base material (hereinafter referred to as PC/acrylic composite base material) is preferable. PC has excellent impact resistance and high heat resistance. Acrylic base materials have high transparency and high hardness.

Here, the PC/acrylic composite base material is, for example, a resin laminate having an acrylic resin layer on at least one side of a PC resin layer. The method for laminating the PC resin and the acrylic resin is preferably a coextrusion molding method.

The ΔE before and after irradiating the PC/acrylic composite substrate with UVB having an intensity of 0.55 W/m ² at 60°C for 100 hours is preferably 1.0 or less, and 0.8 or less. It is more preferable that it is, and it is especially preferable that it is 0.5 or less. When ΔE exceeds 1.0, the damage to the decorative layer caused by the transmitted ultraviolet rays increases. In particular, when red or blue, which has poor UV resistance, is used in the decorative layer, discoloration over time tends to increase.

When applying the HC resin composition to a substrate, the HC resin composition may be diluted with a solvent in order to improve coating properties. Examples of solvents include alcoholic solvents such as ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and diacetone alcohol, and ketones such as acetone, methyl ethyl ketone (hereinafter referred to as MEK), methyl isobutyl ketone, and cyclohexanone. Examples include ester solvents such as ethyl acetate and 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. .

As the solvent, the above-mentioned solvents can be used alone or in combination of two or more. When diluting with a solvent, the solid content of the HC resin composition after dilution is, for example, 10 to 70%, but there is no particular specification, and it can be set as appropriate so as to have a viscosity that is easy to apply.

There are no particular restrictions on the method of applying the HC resin composition. As a method for applying the HC resin composition, a known coating method or a known printing method can be used. Known coating methods include, for example, spray coating, roll coating, die coating, air knife coating, blade coating, spin coating, reverse coating, gravure coating, wire bar, and the like. Examples of known printing methods include gravure printing, screen printing, offset printing, and inkjet printing. The thickness of the applied film is, for example, 1 μm to 10 μm when dry, but is not limited thereto.

As a light source for ultraviolet irradiation used when curing the coating film of the HC resin composition, 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. There is. The atmosphere in which ultraviolet rays are irradiated may be air or an inert gas such as nitrogen or argon. Moreover, the curability of the coating film can be further improved by heating the coating film using a back roll, an IR heater, or the like during the ultraviolet irradiation. Examples of ultraviolet 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 thereto.

The hard coat film for molding (hereinafter referred to as HC film) obtained by coating and curing the HC resin composition on a base material preferably has a breaking elongation of 50% or more in an atmosphere of 130°C, and preferably 100% or more. It is more preferable that it be at least 200%, particularly preferably 200% or more. By setting the elongation at break to 50% or more, sufficient moldability can be expected.

A decorative layer can be provided on the HC film if necessary. Examples of methods for providing the decorative layer include printing, metal vapor deposition, and the like. Further, decoration may be performed using both printing and metal vapor deposition. Further, in order to further improve the adhesion between the injection molded resin and the HC film, an adhesive layer or a primer layer may be provided on the HC film.

A protective film may be attached to the HC film to protect the surface coated with the HC resin composition. By using a protective film, it is possible to suppress scratches during insert molding and out-mold molding processes, and it is expected that yields will improve.

HC film has abrasion resistance and chemical resistance, high elongation at break, good moldability, and excellent weather resistance. Therefore, HC film is suitable as a material for insert-molded products and out-mold products used outdoors. Examples of insert molded products and out molded products used outdoors include insert molded products and out molded products for automobile exterior applications.

3. Insert molded product and out-mold molded product Examples of methods for using HC film in insert molding include the following methods. First, an HC film is placed in a mold. At this time, it is arranged so that the surface coated with the HC resin composition faces the inner wall surface of the mold (that is, the surface opposite to the cured layer of the HC resin composition is in contact with the molding resin). If necessary, the HC film is preformed to follow the shape of the mold. Next, the mold is closed, molten molding resin is injected into the cavity, and the resin is solidified to form an insert molded product.

Methods for performing the above-mentioned preforming include a method in which the HC film is preheated to a temperature above its softening point, placed in a mold, and vacuum suctioned through suction holes provided in the mold; Examples include a method using a mold and a known forming method such as vacuum forming, pressure forming, press forming, etc. 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, it is possible to use a known resin that can be injection molded. Examples of resins to be injection molded 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. Examples include resin. As the resin for injection molding, it can be used alone or in combination of two or more types. 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 approximating the shrinkage rate of the injection molded resin after molding to the shrinkage rate of the HC film. can be suppressed.

Furthermore, by coloring the injection molding resin described above, the decorative layer of the HC film can be eliminated. Furthermore, the injection molding resin described above can be colored to fuse the color of the decorative layer and the color of the injection molding resin. In this case, it becomes possible to give the insert molded product a deeper appearance.

Insert molded products can be used instead of products whose exterior is colored with paint. Examples of products whose exteriors are colored with paint include automobile bodies. By coloring the injection molding resin, it is possible to omit external painting with paint in insert molded products. Appearance defects such as citrus skin and pits often occur during exterior painting. If external painting is omitted, appearance defects are less likely to occur in the insert molded product.

HC film can also be used for out-mold forming. For example, the HC film may be used for TOM (Three-Dimensional Overlay Method) molding. TOM molding is a film molding method in which three-dimensional surface decoration is performed on a preformed base material by vacuum/pressure molding in an airtight box. By using HC film for out-mold molding, large three-dimensional products can be manufactured regardless of the material of the base material.

4. Examples Hereinafter, the present disclosure will be described in detail with reference to Examples and Comparative Examples, but the Examples are for illustrating specific examples and are not particularly limited to the Examples. In addition, unless there is a description of the measurement conditions, the measurement was performed under the conditions of 25° C. and 65% relative humidity. Moreover, the blending amount means parts by weight in terms of solid content.

(4-1) Preparation of Ureac (i) Preparation of Ureac 1 In a four-neck flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 200 parts by weight of ethylene glycol and IPDI (NCO group: 37.5 %), 825 parts by weight of the catalyst, and MEK to give a solid content of 50%, stirred and reacted at 80°C for 6 hours, and when the peak of isocyanate groups reached a predetermined amount in infrared absorption analysis, the reaction was completed. was terminated.

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. Next, the solid content was adjusted to 50% using MEK. Through the above steps, a hexafunctional ureac 1 having an Mw of 6,200 was obtained. Ureac means urethane acrylate.

(ii) Preparation of Ureac 2 In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, add 200 parts by weight of ethylene glycol, 930 parts by weight of IPDI (NCO group 37.5%), and the catalyst. MEK was 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. Next, the solid content was adjusted to 50% using MEK. Through the above steps, a hexafunctional ureac 2 having an Mw of 3,200 was obtained.

(iii) Preparation of Ureac 3 In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 200 parts by weight of ethylene glycol, 895 parts by weight of IPDI (NCO group 37.5%), and a catalyst were added. MEK was charged to give a solid content of 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. Next, the solid content was adjusted to 50% using MEK. Through the above steps, a hexafunctional ureac 3 having an Mw of 3,800 was obtained.

(iv) Preparation of Ureac 4 In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 200 parts by weight of ethylene glycol, 808 parts by weight of IPDI (NCO group 37.5%), and the catalyst were added. MEK was charged to give a solid content of 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 groups had disappeared. Next, the solid content was adjusted to 50% using MEK. Through the above steps, a hexafunctional ureac 4 having an Mw of 7,800 was obtained.

(v) Preparation of Ureac 5 In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, add 200 parts by weight of ethylene glycol, 790 parts by weight of IPDI (NCO group 37.5%), and the catalyst. MEK was charged to give a solid content of 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. Next, the solid content was adjusted to 50% using MEK. Through the above steps, a hexafunctional ureac 5 having an Mw of 9,800 was obtained.

(vi) Preparation of Ureacs A to C Ureacs A and B were obtained by a method similar to that of Ureacs 1 to 5, but having the same skeleton and different Mw as Ureacs 1 to 5. In addition, Ureac C was obtained using polyethylene glycol instead of ethylene glycol by a manufacturing method similar to that of Ureacs 1 to 5. The contents of Ureac A to C were as follows.

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.

(4-2) Production of HC resin composition The components listed in Table 1 are mixed in the amounts listed in Table 1, stirred until uniformly dissolved and dispersed, and further adjusted to a solid content of 30%. PGM was added to the mixture, and the mixture was diluted and stirred to produce HC resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3.

In addition, the components listed in Table 2 are mixed in the amounts listed in Table 2, stirred until uniformly dissolved and dispersed, and then diluted and stirred by adding PGM so that the solid content is 30%. HC resin compositions of Comparative Examples 4 and 5 were produced.

In Tables 1 and 2, (A) is Ureac 1 to 5. (b1) is Tinuvin249 (trade name: manufactured by BASF Japan). (b2) is Tinuvin477 (trade name: manufactured by BASF Japan). (C) is Omnirad 2959 and 127D (trade name: manufactured by IGM Resins). The crosslinking agent is DPHA.

The additives are X-71-1203M (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., acryloyl group-containing fluorine-based silicone compound) and BYK-UV3500 (trade name: manufactured by BYK Company, polydimethylsiloxane copolymer compound). X-71-1203M is a leveling agent.

(4-3) Evaluation method of HC resin composition The HC resin composition of each Example and each Comparative Example was evaluated by the following method.

(i) Preparation of HC film for evaluation As a base material, Iupilon film DF02PUL (trade name: manufactured by Mitsubishi Gas Chemical Co., Ltd.) was prepared. The substrate was a PMMA/PC laminate film. The thickness of the base material was 125 μm.

The HC resin composition was applied to the PMMA layer side of the base material to form a layer of the HC resin composition. The dry film thickness of the layer of the HC resin composition was 3 μm. Next, the layer of HC resin composition was dried in a constant temperature bath at a temperature of 80° C. for 1 minute. Next, using a high-pressure mercury lamp, the HC resin composition layer was irradiated with ultraviolet rays in a nitrogen atmosphere to obtain an HC film for evaluation. The output of the high pressure mercury lamp was 1300 mW/cm ² . The cumulative amount of ultraviolet light was 200 mJ.

(ii) Evaluation of curability Among the HC films for evaluation, the surface coated with the HC resin composition (hereinafter referred to as the coated surface) was touched with a finger to determine the presence or absence of tack. The curability of the HC resin composition layer was evaluated based on the following criteria. ○ means that the evaluation result is better than ×.

○: No tack.

×: There is a tack.

(iii) Evaluation of adhesion Evaluation of adhesion was performed in accordance with the cross-cut method of JIS K 5600-5-6. A grid-like cut was formed on the coated surface of the evaluation HC film using a cutting tool. The grid had 10 x 10 squares. The spacing between the cuts was 1 mm.

Next, cellophane tape CT-24 (trade name: manufactured by Nichiban Co., Ltd.) was applied to the part where the incision was made, and the cellophane tape was pulled upward. The peeling status of the HC resin composition layer was confirmed. The adhesion of the HC resin composition layer was evaluated according to the following criteria.

○: Among the 100 squares, there is no square in which the layer of the HC resin composition has peeled off.

×: Among 100 squares, there is one or more squares in which the layer of the HC resin composition has peeled off.

(iv) Evaluation of wear resistance For evaluation of wear resistance, a friction tester FR-IBS manufactured by Suga Test Instruments was used. A white cotton cloth for testing (Kanakin No. 3) was attached to a friction element with a diameter of 16 mm. This friction element was brought into contact with the coated surface of the HC film for evaluation under a load of 9N. The friction element was made to reciprocate 20 times at a speed of 1 reciprocation/1 second. The distance of one round trip was 100 mm. After 20 reciprocations, the coated surface of the HC film for evaluation was observed, and the wear resistance of the HC resin composition layer was evaluated based on the following criteria.

○: No scratches.

×: There are scratches.

(v) Evaluation of chemical resistance A hand cream was applied to the coated surface of the HC film for evaluation, and the film was left at 80° C. for 4 hours. The hand cream was Neutrogena SPF45 (trade name: Johnson & Johnson). Next, the temperature of the HC film for evaluation was returned to room temperature, and the hand cream was wiped off. The surface on which the hand cream was wiped off was observed, and the chemical resistance of the HC resin composition layer was evaluated based on the following criteria.

○: There is no trace of hand cream application.

×: There are traces of hand cream application.

(vi) Evaluation of breaking elongation The HC film for evaluation was cut into a rectangular shape measuring 25 mm in width and 110 mm in length to prepare a test piece. A tensile test was performed on the test piece using Minebia's TechnoGraph TGI-1KN at an ambient temperature of 130° C. and a tensile speed of 300 mm/min. In the tensile test, the distance between chucks was 50 mm. During the tensile test, the presence or absence of cracks in the test piece was visually confirmed. The elongation at break X (%) was calculated using the following formula (1).

Formula (1) X=(A/50)×100
In formula (1), A is the amount of elongation (mm) of the test piece when the test piece breaks. Since the distance between the chucks is 50 mm, A is the amount of elongation of the test piece per 50 mm.

The elongation at break of the HC film for evaluation was evaluated according to the following criteria. ◎ means an even better evaluation result than ○.

◎: Elongation at break is 200% or more.

○: The elongation at break is 50% or more and less than 200%.

×: Elongation at break is less than 50%.

(4-4) Evaluation results of HC resin compositions Tables 3 and 4 show the evaluation results of HC resin compositions.

The HC resin compositions of each example had good evaluation results in all of curability, adhesion, abrasion resistance, chemical resistance, and elongation at break.

Comparative Example 1 containing Ureac A with a small Mw had a low elongation at break. Comparative Example 2 containing Ureac B having a large Mw had poor wear resistance. Comparative 3 containing ureac with a polyethylene skeleton had poor chemical resistance. Comparative Example 4, which did not contain X-71-1203M, had poor wear resistance. Comparative Example 5, which includes BYK-UV3500 in place of X-71-1203M, has poor weather resistance when a molding film is produced using it. This will be shown in the evaluation of the HC film described below.

(4-5) Production of HC films HC films S1 to S13 were produced using the HC resin compositions and base materials shown in Table 5 or Table 6.

"WAT" in Table 5 means Wavelock Advanced Technology, Inc. "HC resin" in Tables 5 and 6 means an HC resin composition. "Composition" in Tables 5 and 6 means the composition of the base material. "Manufacturer" in Tables 5 and 6 means the manufacturer of the base material. "PMMA/PC" in Tables 5 and 6 means a PC/acrylic composite base material.

The manufacturing method of HC films S1 to S13 was as follows. The HC resin composition was applied to one side of the base material to form a layer of the HC resin composition. When the composition of the base material was a PC/acrylic composite base material, the HC resin composition was applied on the PMMA layer side to form a layer of the HC resin composition. However, in S10 to S11, the HC resin composition was not applied to the base material.

The dry film thickness of the layer of the HC resin composition was 3 μm. Next, the layer of HC resin composition was dried in a constant temperature bath at a temperature of 80° C. for 1 minute. Next, the HC resin composition layer was irradiated with ultraviolet rays in a nitrogen atmosphere using a high-pressure mercury lamp to obtain an HC film. The output of the high pressure mercury lamp was 1300 mW/cm ² . The cumulative amount of ultraviolet light was 200 mJ.

(4-6) Evaluation method of HC films HC films S1 to S13 were evaluated by the following method.

(i) ΔE of base material alone
The ΔE of the base material alone to which the HC resin composition was not applied was measured. The method for measuring ΔE was based on JIS Z 8722. For the measurement of ΔE, a color difference measuring instrument SD-6000 manufactured by Nippon Denshoku Kogyo Co., Ltd. was used. The specific method for measuring ΔE was as follows.

Before irradiating the base material alone with UVB, the color appearance of the base material alone was measured. Next, the base material alone was irradiated with UVB at 60° C. for 1000 hours. The UVB intensity was 0.55 W/ ^m2 . Next, the color appearance of the base material alone was measured again. The difference between the color appearance of the base material alone before UVB irradiation and the color appearance of the base material alone after UVB irradiation was defined as ΔE of the base material alone.

(ii) Weather resistance The ΔE of the HC film was measured in the same manner as the method for measuring ΔE of the base material alone. The weather resistance of the HC film was evaluated according to the following criteria.

○: ΔE of the HC film is less than 1.0.

×: ΔE of the HC film exceeds 1.0.

(iii) Formability The HC film was heated until the temperature of the base material reached 180°C. Next, the HC film was vacuum formed using a cylindrical mold with a diameter of 30 mm and a height of 4 mm in a vacuum forming machine. The moldability of the HC film was evaluated based on the following criteria.

○: Complete shaping was possible.

×: Whitening and cracks occurred. Or, the excipient was incomplete.

(iv) Fabric trace test A 50 mm x 50 mm gauze was brought into contact with the coated surface of the HC film under a load of 500 kg/4 cm ² . The gauze was left under a load at 80° C. for 60 minutes. Next, the gauze was removed from the coated surface, and the coated surface was observed. The results of the cloth trace test were evaluated according to the following criteria.

○: No cloth marks remain on the coated surface.

×: Cloth marks remain on the coated surface.

(v) Abrasion property A friction tester FR-IBS manufactured by Suga Test Instruments was used to evaluate the abrasion property. A white cotton cloth for testing (Kanakin No. 3) was attached to a friction element with a diameter of 16 mm. This friction element was brought into contact with the coated surface of the HC film under a load of 1 Kg/cm ² . The friction element was made to reciprocate 20 times at a speed of 1 reciprocation/1 second. The distance of one round trip was 100 mm. After 20 reciprocations, the coated surface of the HC film was observed, and the abrasion resistance of the HC film was evaluated based on the following criteria.

○: No scratches.

×: There are scratches.

(vi) Pencil hardness The HC film was applied under the condition of 500g load using a pencil scratch coating hardness tester (type P) manufactured by Toyo Seiki Seisakusho in accordance with JIS K5600-5-4 (1999 edition). The pencil hardness of the surface was measured. The measurement results of pencil hardness were evaluated based on the following criteria.

○: Pencil hardness is H or higher.

×: Pencil hardness is F or less.

(4-7) Evaluation results of HC film The evaluation results of HC film are shown in Tables 7 and 8.

S1 to S3 had good evaluation results in all of weather resistance, moldability, cloth trace test, abrasion resistance, and pencil hardness.

On the other hand, samples S4 to S6 using PMMA/PC substrates with a ΔE of more than 1.0 had poorer weather resistance evaluation results than samples S1 to S3. Furthermore, S7 using a PC base material had inferior evaluation results of weather resistance and pencil hardness compared to S1 to S3.

Additionally, S8, which uses an acrylic resin base material, had poorer cloth trace test and pencil hardness evaluation results than S1 to S3. Furthermore, S9 using a PET base material had inferior evaluation results of weather resistance and moldability compared to S1 to S3.

Furthermore, S10 to S11 to which the HC resin composition was not applied had poor evaluation results for wear resistance and pencil hardness. Further, S11 was also inferior in weather resistance evaluation results. In addition, S12, in which the HC resin composition was Comparative Example 4, had poor abrasion resistance evaluation results. Moreover, S13 whose HC resin composition was Comparative Example 5 had poor weather resistance evaluation results.

(4-8) Evaluation of injection molding Insert molding was performed using HC film S1 to produce an insert molded product. The injection molding resin was black ABS. LW (long wave) and SW (short wave) on the film surface of the insert molded product were measured using a painted surface property measuring machine WaveScan 3 Dual manufactured by BYK. In addition, measurements were conducted in the same manner on the painted surface of a painted steel plate for comparison. The measurement results are shown in Table 9. In addition, the appearance of the film surface of the insert molded product and the painted surface of the painted steel plate was observed and evaluated. The evaluation results are shown in Table 9.

The film surface of the insert-molded product had no defect in appearance due to the citron skin. On the other hand, the painted surface of the painted steel plate had an appearance defect of citrus skin.

5. Other Embodiments Although the embodiments of the present disclosure have been described above, the present disclosure is not limited to the above-described embodiments and can be implemented with various modifications.

(5-1) The function of one component in each of the above embodiments may be shared among multiple components, or the function of multiple components may be performed by one component. Further, a part of the configuration of each of the above embodiments may be omitted. Further, at least a part of the configuration of each of the above embodiments may be added to, replaced with, etc. in the configuration of other embodiments.

(5-2) In addition to the above-mentioned HC resin composition, the present disclosure can also be realized in various forms, such as products containing the HC resin composition as a component and methods for producing the HC resin composition.

Claims (9)

1. 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, a light stabilizer (B), a photopolymerization initiator (C), and reactivity. a fluorine-based silicone compound having a functional group, and wherein the weight average molecular weight of (A) is 3,500 to 12,000.
2. The hard coat resin composition for a molding film for automobile exterior according to claim 1,
   (B) includes a radical scavenger (b1) and an ultraviolet absorber (b2),
   A film for forming an automobile exterior, wherein the blending amount of (b1) is 1 to 10% by weight based on the total solid content, and the blending amount of (b2) is 0.3 to 5% by weight based on the total solid content. Hard coat resin composition.
3. The hard coat resin composition for a molding film for automobile exterior according to claim 1,
   A hard coat resin composition for a molding film for automobile exteriors, 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.
4. base material and
   A cured layer of the hard coat resin composition for a molding film for automobile exteriors according to any one of claims 1 to 3, which is on the base material;
   Hard coat film for molding.
5. The hard coat film for molding according to claim 4,
   The base material is a composite base material of a polycarbonate base material and an acrylic base material,
   A hard coat film for molding, wherein the composite substrate has a ΔE of 1.0 or less before and after being irradiated with UVB having an intensity of 0.55 W/m ² at 60° C. for 100 hours.
6. A molding hard coat film having a base material and a cured layer on the base material is shaped using a mold,
   A method for manufacturing an insert molded product, the method comprising: injecting molten resin from the side opposite to the cured layer to form a resin molded product,
   The cured layer contains urethane acrylate (A) having a structure in which pentaerythritol triacrylate is further reacted with a diisocyanate obtained by reacting ethylene glycol and isophorone diisocyanate, a light stabilizer (B), and a photopolymerization initiator (C). ) and a fluorine-based silicone compound having a reactive functional group, and a method for producing an insert molded article, which is a cured product of the resin composition of (A) having a weight average molecular weight of 3,500 to 12,000. .
7. A method for manufacturing an insert molded product according to claim 6, comprising:
   A method for manufacturing an insert molded product, in which the molten resin is colored.
8. An insert molded product using the hard coat film for molding according to claim 4.
9. An out-mold molded product using the hard coat film for molding according to claim 4.