Curable resin composition, and film and molded article using the same

Abstract

To provide a curable resin composition that makes it possible to produce a functional film that can maintain excellent transparency even in an atmosphere of high moisture.SOLUTION: A curable resin composition has (1) an ethylenically unsaturated monomer that does not include a hydroxy group, a carboxyl group or a phosphate group, (2) a metal compound, (3) a photopolymerization initiator, and (4) a silane coupling agent having a functional group that reacts with the ethylenically unsaturated monomer.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel curable resin composition, and a film and a molded article using the same. [Background technology]

[0002] Surface coating technology is applied to the interior or exterior of industrial products such as automobiles and home appliances in order to improve their abrasion resistance (scratch resistance), design, etc. Conventionally, a method has been adopted in which a surface coating layer is formed separately on a molded product that has already been molded by injection molding or the like. In this case, methods for forming the surface coating layer include painting methods and hydraulic transfer methods in which a water-soluble film that has been previously printed is spread on the water surface to transfer the printed layer to the product.

[0003] In contrast to this, in recent years, insert molding and the like have been widely used in which a film is used as a hard coat material and is molded integrally with a separately prepared resin composition. More specifically, for example, in insert molding, as shown in FIG. 1, a laminated film 10 in which a functional layer 12 (cured film (hard coat layer)) is laminated on a substrate film 11 is placed between a male die 21a and a female die 21b of a mold (FIG. 1(a)), and then a molten resin 13a is poured into the mold to perform injection molding (FIG. 1(b)). After the resin is cured, unnecessary parts of the substrate film 11 are cut (trimmed), and a molded product 30 (product) consisting of the resin layer 13 / substrate film 11 / functional layer 12 is taken out of the mold (FIG. 1(c)). As the functional layer (cured film) used in such insert molding, resins such as polycarbonate (PC), polyethylene terephthalate (PET), and polymethyl methacrylate (PMMA) are commonly used because they are relatively excellent in transparency, gloss, scratch resistance, and the like.

[0004] Various resin compositions have been proposed as curable compositions suitable for such molding. For example, an active energy ray-curable resin composition is known that contains an ethylenically unsaturated monomer (A) having at least one functional group selected from a primary hydroxyl group, a secondary hydroxyl group, a carboxyl group, and a phosphoric acid group, a metal compound (B), another ethylenically unsaturated monomer (C), and a photopolymerization initiator (D) (Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2017-101206 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the conventional curable resin composition needs to be further improved in terms of transparency. More specifically, the film formed from the conventional curable resin composition is prone to whitening, cracks, etc. in a moisture-rich atmosphere, so there is a problem that the transparency of the film decreases over time. Therefore, in a molded article (product) having a functional layer made of such a curable resin composition, the appearance may deteriorate and in some cases, the quality may deteriorate.

[0007] Therefore, a main object of the present invention is to provide a curable resin composition capable of producing a functional film capable of maintaining good transparency even in a moisture-rich atmosphere. [Means for solving the problem]

[0008] As a result of extensive research conducted in light of the problems in the prior art, the present inventors discovered that the above object can be achieved by employing a composition having a specific composition, and thus completed the present invention.

[0009] That is, the present invention relates to the following curable resin composition, and a film and a molded article using the same. 1. A curable resin composition comprising: (1) An ethylenically unsaturated monomer having no hydroxyl group, no carboxyl group, and no phosphoric acid group, (2) metal compounds, (3) a photoinitiator, and (4) A silane coupling agent having a functional group that reacts with the ethylenically unsaturated monomer. A curable resin composition comprising: 2. The curable resin composition according to item 1, wherein the functional group is at least one of an acryloyl group and a methacryloyl group. 3. The curable resin composition according to item 1 or 2, comprising 30 to 200 parts by weight of the silane coupling agent per 100 parts by weight of the ethylenically unsaturated monomer. 4. The curable resin composition according to any one of items 1 to 3, wherein the metal compound is an aluminum chelate compound. 5. The curable resin composition according to any one of items 1 to 4, further comprising an organic solvent and having a liquid state. 6. A film obtained by curing a coating film containing the curable resin composition according to any one of items 1 to 5. 7. The film according to item 6, which is used to protect the surface of an article. 8. A molded article obtained by molding the film according to item 6 or a laminate containing the film. Effect of the Invention

[0010] According to the present invention, it is possible to provide a curable resin composition capable of producing a functional film capable of maintaining good transparency even in a moisture-rich atmosphere.

[0011] That is, in the present invention, a specific ethylenically unsaturated monomer is used, and a metal compound and a silane coupling agent that reacts with the monomer are used in combination, so that the film obtained by curing the curable resin composition containing it can effectively suppress the whitening phenomenon even when it is immersed in hot water or placed in a high humidity atmosphere.Therefore, the film of the present invention can maintain good transparency for a relatively long period of time. [Brief description of the drawings]

[0012] [Figure 1] An example of a process for producing a laminate (molded body) by insert molding is shown below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] 1. Curable resin composition The curable resin composition of the present invention (the composition of the present invention) is (1) An ethylenically unsaturated monomer having no hydroxyl group, no carboxyl group, and no phosphoric acid group, (2) metal compounds, (3) a photoinitiator, and (4) A silane coupling agent having a functional group that reacts with the ethylenically unsaturated monomer. Each component contained in the composition of the present invention will be described below.

[0014] (1) Ethylenically unsaturated monomers that do not have a hydroxyl group, a carboxyl group, or a phosphate group The ethylenically unsaturated monomer having no hydroxyl group, carboxyl group, or phosphoric acid group (monomer of the present invention) is an ethylenically unsaturated monomer having no hydroxyl group, carboxyl group, or phosphoric acid group as a functional group. Therefore, any ethylenically unsaturated monomer that does not have such a functional group can be used as the monomer of the present invention. In other words, the monomer of the present invention may have a functional group other than a hydroxyl group, a carboxyl group, or a phosphoric acid group within a range that does not impair the effects of the present invention.

[0015] The composition of the present invention may contain a small amount of an ethylenically unsaturated monomer having a hydroxyl group, a carboxyl group, or a phosphoric acid group (also referred to as "other ethylenically unsaturated monomer" in this specification) within a range that does not impair the effects of the present invention. In particular, the amount of such an ethylenically unsaturated monomer may be in the range of about 0 to 25% by weight based on 100% by weight of the composition of the present invention (solid content), and from the viewpoint of the effects of the present invention, it is particularly preferable that the amount is 0 to 20% by weight, more preferably 0 to 10% by weight, and most preferably 0 to 5% by weight.

[0016] As the monomer of the present invention, the following ethylenically unsaturated monomers (particularly monofunctional ethylenically unsaturated monomers) can be used alone or in combination of two or more.

[0017] In the present invention, unless otherwise specified, acryloyl group or methacryloyl group will be collectively referred to as "(meth)acryloyl group". Also, acryloyloxy group or methacryloyloxy group will be collectively referred to as "(meth)acryloyloxy group". Furthermore, acrylate or methacrylate will be collectively referred to as "(meth)acrylate", and acrylic acid or methacrylic acid will be collectively referred to as "(meth)acrylic acid".

[0018] Examples of linear or branched alkyl group-containing (meth)acrylic acid ester monomers include linear or branched alkyl group-containing (meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, isodecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, and isostearyl (meth)acrylate.

[0019] Examples of aromatic ring-containing monomers include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethoxylated o-phenyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate. To et al. Examples include:

[0020] Examples of alicyclic structure-containing monomers include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl methacrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl)methyl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, 1-adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.

[0021] Examples of ether chain-containing monomers include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-isopropoxyethyl methacrylate, 3-methoxybutyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-butoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, octoxypolyethylene glycol-polypropylene glycol-mono(meth)acrylate, lauroxypolyethylene glycol mono(meth)acrylate, and stearoxypolyethylene glycol mono(meth)acrylate.

[0022] Examples of nitrogen-containing monomers include t-butylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate, pentamethylpiperidinyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, acryloylmorpholine, quaternized dimethylaminoethyl methacrylate, dimethylacrylamide, and isopropylacrylamide.

[0023] Among these, at least one (meth)acrylic acid ester monomer can be preferably used, and thus, for example, isobornyl (meth)acrylate can be preferably used.

[0024] The content ratio of the monomer of the present invention in the composition of the present invention is not particularly limited, but is usually in the range of about 10 to 60% by weight based on 100% by weight of the composition of the present invention (solid content), and from the viewpoint of the effects of the present invention, it is particularly preferably 20 to 50% by weight.

[0025] (2) Metal compounds The metal compound is not limited as long as it can be bonded to at least a silane coupling agent, but particularly preferred are organometallic compounds such as organoaluminum compounds, organotitanium compounds, organozirconium compounds, organotin compounds, and organozinc compounds. These can be used alone or in combination of two or more.

[0026] Among the organometallic compounds, metal chelate compounds are preferred. In particular, chelate compounds of aluminum, titanium or zirconium are preferred. These metal chelate compounds themselves can be known, and commercially available compounds such as so-called chelate compounds can also be used.

[0027] Examples of aluminum chelate compounds include aluminum trisacetylacetonate, aluminum trisethylacetoacetate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum monoacetylacetonate bis(ethylacetoacetate), aluminum tris(acetylacetonate), aluminum ethylacetoacetate diisopropylate, and aluminum tris(ethylacetoacetate).

[0028] Examples of titanium chelate compounds include titanium acetylacetonate, titanium ethylacetoacetate, titanium octylene glycolate, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium triethanolamine, and titanium aminoethylaminoethanolate.

[0029] Examples of the zirconium chelate compound include zirconium tetraacetylacetonate, zirconium monoacetylacetonate, and zirconium tetraacetylacetonate.

[0030] The content of the metal compound can be appropriately set depending on the type of metal compound used, etc., but it is usually sufficient to set it in the range of about 10 to 60% by weight based on 100% by weight of the composition of the present invention (solid content). From the standpoint of water resistance, etc., it is particularly preferable to set it in the range of 20 to 50% by weight.

[0031] (3) Photopolymerization initiator The photopolymerization initiator is not particularly limited, and examples thereof include dimethyl-2,2'-azobis(2-methylpropionate), 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylbenzophene, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, benzyl dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the methyl ether include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, methylbenzoyl formate, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, etc. These can be used alone or in combination of two or more.

[0032] The content of the photopolymerization initiator can be appropriately set depending on the type of the photopolymerization initiator used, but it is usually sufficient to set it in the range of about 1 to 30% by weight based on 100% by weight of the composition of the present invention (solid content), and from the viewpoint of curability, it is particularly preferably set to 3 to 15% by weight.

[0033] (4) A silane coupling agent having a functional group that reacts with the ethylenically unsaturated monomer. The silane coupling agent is not limited as long as it has a functional group that reacts with the ethylenically unsaturated monomer coexisting in the composition of the present invention, and in particular, the functional group can be at least one of an acryloyl group and a methacryloyl group, which can more reliably bond to the ethylenically unsaturated monomer.

[0034] Examples of silane coupling agents having such functional groups include, but are not limited to, at least one of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and methacryloxyoctyltrimethoxysilane.

[0035] The content of the silane coupling agent can be appropriately set depending on the type of the silane coupling agent used, but it is usually in the range of about 10 to 60% by weight, and particularly preferably 15 to 50% by weight, based on 100% by weight of the composition of the present invention (solid content). This allows for more excellent effects, particularly in terms of water resistance and chemical resistance, to be obtained.

[0036] The ratio of the silane coupling agent to the monomer of the present invention is not limited, but is usually about 30 to 200 parts by weight, and particularly preferably 40 to 140 parts by weight, per 100 parts by weight of the monomer of the present invention, from the viewpoint of water resistance and chemical resistance.

[0037] (5) Organic solvents In the composition of the present invention, an organic solvent can be used as necessary. This allows the composition of the present invention to be in a liquid state, and can be used, for example, as a coating liquid. As the organic solvent, various organic solvents can be used, such as ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, and methoxypropyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, propylene glycol monomethyl ether acetate, and diethylene glycol dimethyl ether; and aromatic solvents such as toluene and xylene. In particular, in the present invention, it is preferable to use a ketone solvent from the viewpoint of adhesion and the like.

[0038] When an organic solvent is used, the amount of the organic solvent used is not limited, and may be appropriately set depending on the type of ethylenically unsaturated monomer used, the desired viscosity, etc., within the range of, for example, a solid content of 10 to 90% by weight.

[0039] (6) Other ingredients (optional ingredients) Furthermore, in the composition of the present invention, additives contained in known hard coats can be appropriately blended as optional components within the range that does not hinder the effect of the present invention.For example, crosslinking agent, inorganic fine particles (oxide fine particles such as silica, alumina, titania, zirconia, etc.), antifouling agent (slip agent), surface conditioner, ultraviolet absorber, light stabilizer, dispersant (surfactant), wetting agent, thickener, antioxidant, polymerization inhibitor, polymerization adjuster, colorant, etc. can be mentioned.

[0040] 2. Method for producing curable resin composition The composition of the present invention can be prepared by mixing the above-mentioned components to a uniform state. The order of mixing the components is not limited. The temperature during mixing is not limited, and the mixing can be carried out, for example, at room temperature and pressure. The mixing can be carried out using a known or commercially available device such as a mixer or kneader.

[0041] 3. Use of the curable resin composition The composition of the present invention can be used in the same manner as known or commercially available curable resin compositions. For example, a cured film can be obtained by using the liquid composition of the present invention as a coating liquid, applying it to an object to be coated, and then curing it. The method for forming the cured film will be described later in "4. Film".

[0042] 4. Film The present invention encompasses a film (the film of the present invention) obtained by curing a coating film containing a curable resin composition. This film may be a film cured by any of heat curing, active energy ray curing, and the like. Among them, it is preferable that the composition of the present invention has active energy ray curing properties. This allows for rapid curing, excellent productivity, and allows the equipment for curing to be made smaller, and also omits the need for drying by heating.

[0043] The thickness of the film of the present invention is not particularly limited, but can generally be appropriately set within the range of about 3 to 15 μm.

[0044] Furthermore, the film of the present invention is usually transparent, and the haze value of the film itself (when there is no base film) is preferably within the range of about 0.1 to 0.6%.

[0045] The film of the present invention has a property that the transparency is not easily deteriorated even in a moisture-rich atmosphere, and therefore, even in the boiling water immersion test or the moist heat rise resistance test described later, the haze value after the test can be maintained in the range of about 0.1 to 4.0%.

[0046] The film of the present invention can be suitably produced, for example, by a method including a step of forming a coating film of the liquid composition of the present invention (first step) and a step of curing the coating film by irradiating the coating film with active energy rays (second step). A cured film of such a coating film can be obtained as the film of the present invention.

[0047] 1st step In the first step, a coating film of the liquid composition of the present invention is formed. For example, the coating film can be suitably formed by applying the liquid composition of the present invention onto a substrate film.

[0048] The liquid composition of the present invention can be prepared as a coating liquid having a desired viscosity by adding a suitable organic solvent to the composition of the present invention as described above. That is, a coating liquid can be used in which the composition of the present invention is dissolved or dispersed in an organic solvent so that the solid content is within the range of 10 to 90% by weight.

[0049] As the substrate film, a single layer or laminate of various resin films can be used, for example, polyester-based (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyolefin-based (polyethylene, polypropylene, etc.), cellulose-based (cellophane, diacetyl cellulose, triacetyl cellulose, etc.), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polyether ether ketone, polyetherimide film, polyimide, fluororesin, polyamide, acrylic resin (polymethyl methacrylate, etc.), etc. can be mentioned.

[0050] In the present invention, in order to further increase the adhesion between the coating film formed by the coating liquid and the base film, for example, an acrylic resin layer can be interposed between the coating film and the base film. That is, a laminate film in which an acrylic resin layer is laminated in advance on a film serving as a core material can be suitably used as the base film.

[0051] Furthermore, in the present invention, in order to further increase the adhesion between the coating film of the coating liquid and the substrate film, various surface treatments can be applied to the substrate film surface (coated surface) as necessary. For example, known methods such as sandblasting, solvent treatment, and corona discharge treatment can be adopted.

[0052] The method for applying the coating liquid is not particularly limited, and any known method such as spray coating, spin coating, doctor blade coating, roller coating, bar coating, etc. can be appropriately used.

[0053] The amount of coating may be, for example, an amount that will result in a desired thickness of the cured film, and can usually be appropriately set so that the thickness of the resulting cured film is within the range of about 1 to 50 μm (preferably within the range of 3 to 15 μm).

[0054] The coating film formed by coating can be dried as necessary. When drying, either natural drying or forced drying (heat drying) can be used. When drying by heating, the temperature should be within a range that does not adversely affect the base film, and for example, heating can be performed at about 70 to 120°C.

[0055] 2nd process In the second step, the coating film is cured by irradiating the coating film with active energy rays. The second step may be performed at any stage. For example, the second step may be performed at any stage, such as a) before laminating the coating film with other layers, b) after laminating the coating film with other layers, c) before integrating the coating film with other molded products, or b) after integrating the coating film with other molded products.

[0056] The active energy rays used to cure the coating film are not particularly limited as long as they induce a polymerization reaction in the coating film to cure it, and examples of such rays include electron beams (EB), ultraviolet rays (UV), and infrared rays (IR).

[0057] In the present invention, ultraviolet light can be preferably used because it can be cured relatively easily. When irradiating ultraviolet light, the light source is not limited, and examples thereof include a high-pressure mercury lamp, an iron-doped metal halide lamp, a gallium lamp, a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, an ultraviolet laser, and an LED. Therefore, curing can be performed using a publicly known or commercially available device equipped with these.

[0058] When irradiating with ultraviolet light, the wavelength is, for example, in the range of about 100 to 400 nm, and the dose is 100 to 5000 mJ / cm 2 However, the irradiation method is not limited to this.

[0059] When the cured film is formed on the substrate film in the second step, the cured film may be peeled off from the substrate film and collected as necessary, or the laminate consisting of the substrate film and the cured film may be used as is for the production of a molded product. As described later in 5, a laminate containing the cured film and another layer may also be formed. Furthermore, when in-mold molding is employed as a post-step, a molten resin is poured into the cured film side of the laminate containing the cured film and substrate film to press the cured film and the resin together, and then only the substrate film is peeled off to obtain a molded product in which the cured film is transferred to the surface of the resin molded product.

[0060] 5. Molded products including films The present invention also includes a molded article obtained by molding the film (cured film) of the present invention or a laminate containing the film. In particular, the film of the present invention can be suitably used as a protective layer (hard coat layer) of a molded article (article). Examples of such molded articles include molded articles obtained by molding the film of the present invention or a laminate containing the film alone, as well as molded articles obtained by integrally molding the film of the present invention or the laminate with other materials.

[0061] The laminate may include a laminate containing one or more layers of the film of the present invention and one or more other layers. In particular, it is preferred that the film of the present invention is disposed as the outermost layer (exposed surface) on at least one surface of the laminate.

[0062] As the other layers, at least one of various functional layers (for example, a substrate layer, an antistatic layer, a moisture-blocking layer, an adhesive layer, an anchor coat layer, a primer layer, a printed layer, an antireflection layer, etc.) can be laminated. These layers can be made of resins applied to the substrate film, as well as metals (metal particles, metal foils, metal vapor deposition films, etc.), inorganic materials, etc. Composite materials of these can also be used.

[0063] When the film of the present invention or a laminate containing the film is molded alone, the molding method is not limited, and molded products can be produced according to known molding methods.

[0064] Examples of molded articles obtained by integrally molding the film of the present invention or a laminate containing the film with other materials include, but are not limited to, molded articles obtained by integrating the film of the present invention or a laminate containing the film with a resin-containing molded article.

[0065] The resin contained in the resin-containing molded product may be at least one of various thermoplastic resins or thermosetting resins, which may be appropriately selected depending on the application of the molded product. For example, examples of thermoplastic resins include general-purpose plastics such as polyvinyl chloride, polystyrene, polymethyl methacrylate (PMMA), polyethylene, polypropylene, and acrylonitrile-butadiene-styrene (ABS), as well as engineering plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonate, polyamide, polyimide, polyacetal, and fluororesin. Examples of thermosetting resins include polyurethane, phenolic resin, epoxy resin, melamine resin, and silicone resin.

[0066] In addition to these resins, the resin-containing molded product may contain various additives as necessary. The additives may be the same as those listed above under "(6) Other Components (Optional Components)".

[0067] Furthermore, the shape, size, etc. of the resin-containing molded article are not particularly limited, and can be set to a size, shape, etc. according to the desired molded article (product).

[0068] The method for producing the molded product is not particularly limited as long as it can integrate the film of the present invention with the resin-containing molded product, but a method that can integrate at least the resin-containing molded product at the same time as molding can be preferably adopted. Here, "integration" refers to bonding (preferably directly) the coating film of the composition of the present invention or its cured film (the film of the present invention) or a laminate containing the cured film to the resin-containing molded product to fix them. Therefore, for example, known molding methods such as insert molding, in-mold molding, and lamination method (TOM (Three dimension Overlay Method) method) can be preferably adopted.

[0069] For example, when the film of the present invention and the resin-containing molded product are integrated by insert molding as a representative example, it can be carried out according to the method shown in Fig. 1. That is, a method including a first step (Fig. 1(a)) of arranging a laminated film 10, in which a cured film 12 (hard coat layer) is laminated on a substrate film 11, between a male die 21a and a female die 21b of a mold, a second step (Fig. 1(b)) of pouring a molten resin (resin composition) 13a into the mold to perform injection molding, and a third step (Fig. 1(c)) of obtaining a molded product 30 (product) consisting of a resin layer (resin-containing molded product) 13 / substrate film 11 / cured film 12 after the resin (resin composition) is cured can be suitably adopted.

[0070] In this case, similarly to known insert molding, in addition to the above steps, additional steps may be included, such as a step of heating and softening the laminated film or cured film prior to the first step, a step of preforming the laminated film prior to the second step, and a step of cutting off (trimming) unnecessary portions.

[0071] In the above method, a cured film (film of the present invention) is used, but this can be replaced with a coating film of the composition of the present invention (before curing). In this case, for example, the coating film may be cured by irradiating it with ultraviolet light or the like before or after the molded product is removed from the mold, to form a cured film.

[0072] The molded article of the present invention can be used as various products including the interior or exterior of automobiles, home appliances, etc. More specifically, examples of the molded article include exterior materials (door handles, bumpers, front grilles, side moldings, wheel caps, mirror housings, front under covers, etc.) and interior materials (meter panels, shift knobs, switches, center consoles, door ornaments, etc.) for various vehicles such as automobiles, trains, and aircraft. Examples of home appliances include refrigerators, washing machines, vacuum cleaners, personal computers, tablets, printers, multifunction machines, mobile phones, audio products, etc. EXAMPLES

[0073] The features of the present invention will be described in more detail below with reference to examples and comparative examples, although the scope of the present invention is not limited to the examples.

[0074] Example 1 A liquid curable resin composition (liquid composition) was prepared by uniformly mixing the components shown in Table 1. The content of each component in Table 1 is expressed as "% by weight." Next, a film was produced using the obtained liquid composition. A polycarbonate film with the outermost layer covered with an acrylic resin was used as a substrate, and the liquid composition was applied onto the substrate. The coating was performed by a bar coating method, and the thickness of the cured film (film) after curing was adjusted to 10 μm. Thereafter, the substrate to which the liquid composition was applied was placed in an oven at 80° C., dried for 3 minutes, and then irradiated with ultraviolet rays as active energy rays to cure the curable resin composition, thereby obtaining a cured film. In this way, a laminate in which a cured film was formed on a polycarbonate film was obtained.

[0075] Examples 2 to 3 and Comparative Examples 1 to 5 A liquid composition was prepared in the same manner as in Example 1 except that the components shown in Table 1 were used, and a laminate was then produced.

[0076] [Table 1]

[0077] The components shown in Table 1 are represented as follows: IBXA: Isobornyl acrylate (monomer of the present invention) · MAHP: 2-Acryloyloxyethylhexahydrophthalate (another ethylenically unsaturated monomer) AL-D: Aluminum monoacetylacetonate bis(ethylacetoacetate) IC-184: 1-Hydroxycyclohexyl phenyl ketone ·APTMS: 3-acryloxypropyltrimethoxysilane ·MOTMS: Methacryloxyoctyltrimethoxysilane ·TMMS: Trimethoxymethylsilane MEK: Methyl ethyl ketone

[0078] Test Example 1 The laminates produced in the examples and comparative examples were evaluated for the following physical properties. The results are also shown in Table 1. In order to clarify the change in transparency before and after the boiling water test and before and after the moist heat resistance test, the values ​​for "appearance after immersion in boiling water" and "appearance after moist heat resistance test" listed in the experimental results indicate the value (ΔHaze value) obtained by subtracting the initial haze value from the measured haze value.

[0079] (1) Appearance evaluation The haze value (unit: %) of the laminate was measured using a haze meter conforming to "JIS K 7136."

[0080] (2) Adhesion evaluation According to "JIS K 5600-5-6", the presence or absence of peeling of the cured film of the laminate was visually evaluated as follows: In the fractional notation in the table, the denominator represents the number of squares (100) obtained by cutting the cured film into a grid pattern, and the numerator represents the number of squares of the cured film remaining after peeling with tape.

[0081] (3) Chemical resistance evaluation Chemical resistance: 0.5g of sunscreen (Neutrogena Ultra Sheer Dry Touch Sunscreen SPF45) applied to 25cm 2 The sunscreen was applied evenly to the area and allowed to stand at 80°C for 4 hours, after which the sunscreen was washed off with a large amount of water and the cured film was visually inspected for the presence or absence of whitening. ○: No abnormalities ×: Abnormal (whitening of the cured film)

[0082] (4) Evaluation of appearance after immersion in boiling water for 30 minutes The laminate was immersed in boiling water for 30 minutes, and then the appearance of the dried cured film was measured using a haze meter conforming to JIS K 7136. The initial haze value was subtracted from the measured haze value to evaluate the change in transparency. The difference in haze value (unit: %) is shown in Table 1.

[0083] (5) Evaluation of appearance after immersion in boiling water for 45 minutes The laminate was immersed in boiling water for 45 minutes, and then the appearance of the dried cured film was measured using a haze meter conforming to JIS K 7136. The initial haze value was subtracted from the measured haze value to evaluate the change in transparency. The difference in haze value (unit: %) is shown in Table 1.

[0084] (6) Evaluation of coating appearance after moist heat resistance test After leaving the film at rest for 120 hours at a temperature of 90°C and a relative humidity of 90%, the appearance of the cured film was measured using a haze meter conforming to JIS K 7136, and the change in transparency was evaluated by subtracting the initial haze value from the measured haze value. The difference in haze value (unit: %) is shown in Table 1. [Industrial Applicability]

[0085] The composition of the present invention has excellent transparency, particularly since it can maintain good transparency even in a humid atmosphere, and therefore can be used as a protective layer for molded articles that require scratch resistance, such as the interior and exterior of automobiles and electrical appliances.

Claims

1. A curable resin composition comprising: (1) isobornyl (meth)acrylate, an ethylenically unsaturated monomer having no hydroxyl group, no carboxyl group, and no phosphoric acid group: 30.3 to 60% by weight, (2) chelate compounds of aluminum, titanium, or zirconium as organometallic compounds: 22.9 to 60% by weight, (3) a photopolymerization initiator: 3 to 30% by weight, and (4) A silane coupling agent having a functional group capable of reacting with the ethylenically unsaturated monomer: 19.2 to 60% by weight A curable resin composition comprising:

2. The curable resin composition according to claim 1 , wherein the functional group is at least one of an acryloyl group and a methacryloyl group.

3. The curable resin composition according to claim 1 or 2, comprising 30 to 200 parts by weight of the silane coupling agent per 100 parts by weight of the ethylenically unsaturated monomer.

4. The curable resin composition according to any one of claims 1 to 3, wherein the metal compound is an aluminum chelate compound.

5. The curable resin composition according to any one of claims 1 to 4, further comprising an organic solvent and having a liquid state.

6. A film obtained by curing a coating film containing the curable resin composition according to any one of claims 1 to 5.

7. The film according to claim 6, which is used to protect the surface of an article.

8. A molded article obtained by molding the film according to claim 6 or a laminate containing the film.

Images