Functional film for coating resin molded articles, method for manufacturing the same, resin molded article, and method for manufacturing the same

Abstract

To provide a functional film for coating a resin molding which is excellent in moldability when coating a resin molding, prevents sticking to a mold in molding, roughness of a surface, whitening and peeling, and can impart good abrasion resistance to the resin molding, a method for manufacturing the same, a resin molding, and a method for manufacturing the same.SOLUTION: A functional film for coating a resin molding contains a thermoplastic resin film, and a hard coat layer and a low refractive index layer layered in this order on at least one surface of the thermoplastic resin film, wherein the hard coat layer is formed of a curable resin composition which is at least partially cured, the curable resin composition contains at least a thermosetting resin component, the thermosetting resin component is cured and at least partially has a crosslinking structure, the low refractive index layer is formed of an uncured active energy ray-curable resin composition, and the refractive index of the low refractive index layer when the active energy ray-curable resin composition is cured is lower than the refractive index of the hard coat layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a functional film for coating resin molded articles that can impart functionality such as anti-reflective properties to the resin molded article, a method for manufacturing the same, a resin molded article, and a method for manufacturing the same. [Background technology]

[0002] It has been common practice to form functional layers such as hard coat layers, anti-reflective layers, and anti-glare layers on the surface of electronic devices such as televisions, personal computers, and smartphones using coating or other methods to improve visibility and abrasion resistance. Similarly, it has become common to form such functional layers on the surface of information display parts in automotive instrument panels and navigation systems. In recent years, designs have been proposed that integrate the instrument panel, navigation system, various control panels, display units, and other components of an automobile with the interior of the vehicle. In such designs, the information display parts, such as the instrument panel and navigation system, are incorporated into the molded body that makes up the interior of the automobile. However, the surface of the information display part is not necessarily planar, but may have a three-dimensional shape. However, when a surface has a three-dimensional shape, it is not easy to impart functionality such as visibility and wear resistance using conventional coating methods without compromising such a design. One method for decorating, protecting, or adding functionality to the surface of molded parts such as automotive interior components, which have a three-dimensional shape, is the so-called film insert injection molding method, in which a molding film, on which functional layers such as decorative layers and protective layers are pre-formed on a film-like substrate, is laminated onto the surface of the molded part during injection molding.

[0003] In recent years, it has been proposed to use laminated films with a hard coat layer and an antireflection layer formed on the surface of a molded article in order to impart the above-mentioned functionality. For example, Patent Document 1 describes an antireflection body in which a hard coat layer and a low refractive index layer are sequentially laminated on a triacetylcellulose film, and an impregnated portion is provided on the surface of the hard coat layer in which the components of the low refractive index layer are impregnated. Patent Document 2 describes a laminated film for molding having a hard coat layer with a crack elongation of 5% or more and a low refractive index layer with a refractive index of 1.47 or less in that order on a base film such as a polyethylene terephthalate film. Patent Document 3 describes a laminated film having a hard coat layer and a low refractive index layer on an acrylic resin film. On the other hand, as a composite film for multilayering thermoplastic resin sheets, Patent Document 4 describes a composite film in which one side of a semi-cured resin layer that can be cured by energy rays is supported on a heat-sealable resin film, and the other side is covered with a release resin film. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2003-240906 [Patent Document 2] Japanese Patent Publication No. 2014-041244 [Patent Document 3] International Public Gazette No. 2019-181752 [Patent Document 4] Japanese Patent Publication No. 2006-150949 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, conventional laminated films described in Patent Documents 1 to 3, etc., when used to coat the surface of a three-dimensional resin molded body by insert injection molding to impart anti-reflective and hard-coat properties, had the problem of not being able to sufficiently balance moldability with functionality such as abrasion resistance and anti-reflective properties. Furthermore, in Patent Document 4, the thermoplastic resin sheet, which is integrated by heat-sealing the heat-sealable resin film side of the composite film to a thermoplastic resin sheet, is thermoformed into a predetermined shape, and then the semi-cured resin layer is cured by irradiating it with energy rays, thereby manufacturing a molded product by so-called after-cure. Although it is possible to obtain moldability into three-dimensional shapes and high surface hardness and abrasion resistance, the uncured hard coat layer is easily scratched during handling, and during molding such as insert injection molding, undesirable transfer of shapes such as scratches on the mold, adhesion of the hard coat layer to the mold surface, and peeling of the hard coat layer from the base film layer are likely to occur, so it was not necessarily sufficiently practical. Furthermore, when this after-curing technology was applied to an anti-reflective coating having a thin refractive index adjustment layer on top of a hard coat layer, the uncured hard coat layer and the thin refractive index adjustment layer would mix, resulting in the inability to obtain the desired anti-reflective properties, or problems such as the anti-reflective layer sticking to the mold during molding, surface roughness, whitening, and peeling.

[0006] The present invention has been made in view of the above problems, and provides a functional film for coating resin molded articles, a method for manufacturing the same, a resin molded article, and a method for manufacturing the same, which can provide good abrasion resistance and anti-reflective properties to the resin molded article without causing adhesion to the mold, surface roughness, whitening, or peeling during molding. [Means for solving the problem]

[0007] One or more embodiments of the present invention relate to a functional film for coating resin molded articles, comprising a thermoplastic resin film and a hard coat layer and a low refractive index layer sequentially laminated on at least one side of the thermoplastic resin film, wherein the hard coat layer is formed of a curable resin composition which is at least partially cured, the curable resin composition which comprises at least a thermosetting resin component which is cured and has at least a partially crosslinked structure, the low refractive index layer is formed of an uncured active energy ray curable resin composition, and the refractive index of the low refractive index layer when the active energy ray curable resin composition is cured is lower than the refractive index of the hard coat layer.

[0008] One or more embodiments of the present invention relate to a method for manufacturing a functional film for coating a resin molded article, comprising: step 1, applying a curable resin composition containing at least a thermosetting resin component onto a thermoplastic resin film to form a coating film and curing at least the thermosetting resin component to form a hard coat layer; and step 2, applying an active energy ray curable resin composition onto the hard coat layer to form a low refractive index layer, wherein in step 2 and subsequent steps, the active energy ray curable resin composition constituting the low refractive index layer is not irradiated with active energy rays.

[0009] One or more embodiments of the present invention relate to a resin molded article comprising a thermoplastic resin substrate and a functional film for coating the resin molded article, wherein the functional film for coating the resin molded article covers at least a portion of the thermoplastic resin substrate, and the low refractive index layer on at least one side of the functional film for coating the resin molded article is located on the outermost surface of the resin molded article.

[0010] One or more embodiments of the present invention relate to a method for manufacturing a resin molded article, which includes an injection molding step of placing a functional film for coating the resin molded article in an injection molding die so that at least one low refractive index layer faces the injection molding die, and then injection molding a thermoplastic resin. [Effects of the Invention]

[0011] According to the present invention, there can be provided a functional film for coating a resin molded body, which is excellent in moldability when coating the resin molded body, and can impart good abrasion resistance and antireflection properties to the resin molded body without causing sticking to a mold, surface roughness, whitening, peeling, etc. during molding, and a resin molded body including the same. Further, according to the production method of the present invention, a functional film for coating a resin molded body having good abrasion resistance and antireflection properties can be coated on the resin molded body with good moldability without causing sticking to a mold, surface roughness, whitening, peeling, etc. during molding.

Brief Description of the Drawings

[0014] Specifically, the functional film for coating resin molded articles of one or more embodiments of the present invention (hereinafter also simply referred to as "functional film") is formed by creating a hard coat layer from a curable resin composition that is at least partially cured, and a low refractive index layer from an uncured active energy ray curable resin composition. As a result, when coating a resin molded article with the functional film for coating resin molded articles by molding such as insert injection molding, the film easily conforms to the shape of the resin molded article, especially when coating a resin molded article having a three-dimensional shape, thus resulting in good moldability. Furthermore, during molding such as insert injection molding, adhesion of the low refractive index layer to the mold surface is suppressed, preventing adhesion to the mold and resulting in good moldability. In addition, after coating the resin molded article with the functional film for coating resin molded articles, the low refractive index layer can be post-cured to impart excellent abrasion resistance to the resin molded article. In this specification, a three-dimensional shape means a non-planar shape, such as a shape having irregularities or curved parts on its surface.

[0015] In this specification, when a numerical range is indicated by "~", the numerical range includes both endpoints (upper and lower limits). For example, the numerical range "X~Y" includes both endpoints, X and Y. Furthermore, when multiple numerical ranges are described in this specification, they shall include numerical ranges formed by appropriately combining the upper and lower limits of different numerical ranges.

[0016] (Thermoplastic resin film) The thermoplastic resin film is not particularly limited, but it is preferably a transparent material. Examples include acrylic resin films, polycarbonate resin films, polyester resin films, polyamide resin films, and polyimide resin films. However, it is preferably an acrylic resin film, and more preferably an acrylic resin film composed of an acrylic resin composition containing an acrylic resin and a graft copolymer containing a rubber component. This acrylic resin film has excellent transparency, weather resistance, surface hardness, and secondary moldability, good adhesion to functional layers composed of various curable resin compositions, and is easy to obtain as a functional film for coating resin molded articles that has excellent conformability to the surface shape of various resin molded articles, including three-dimensional shapes.

[0017] <Acrylic resin> As an acrylic resin, for example, an acrylic resin containing 50% by mass or more of methyl methacrylate as a monomer component can be suitably used. From the viewpoint of weather resistance, moldability and heat resistance, it is preferable that the acrylic resin contains 50 to 100% by mass of constituent units derived from methyl methacrylate and 0 to 50% by mass of other constituent units, and more preferably 70 to 100% by mass of constituent units derived from methyl methacrylate and 0 to 30% by mass of other constituent units.

[0018] Other constituent units include, for example, (meth)acrylic acid, alkyl (meth)acrylate esters (excluding methyl methacrylate), aromatic vinyl compounds, vinyl cyanide compounds, and constituent units derived from vinylidene halides, etc. In this specification, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid.

[0019] Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-phenoxyethyl acrylate, benzyl acrylate, 2-(N,N-dimethylamino)ethyl acrylate, and glycidyl acrylate.

[0020] Examples of methacrylic acid esters include ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate, and adamantyl methacrylate.

[0021] Examples of aromatic vinyl compounds include styrene, vinyltoluene, and α-methylstyrene. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. Examples of vinylidene halides include vinylidene chloride and vinylidene fluoride.

[0022] The other constituent units included in the acrylic resin may be one type or a combination of two or more types.

[0023] From the viewpoint of improving the heat resistance of acrylic resins, structural units having a specific structure may be introduced into the acrylic resin by copolymerization, functional group modification, and modification. Examples of such acrylic resins with good heat resistance include the following. 1) Acrylic resins in which an N-substituted maleimide compound is copolymerized as a copolymer component, 2) Glutaric anhydride acrylic resin, 3) Acrylic resin having a lactone ring structure, 4) Glutarimide acrylic resin, 5) Acrylic resins containing hydroxyl groups and / or carboxyl groups, 6) Aromatic vinyl-containing acrylic polymers obtained by polymerizing aromatic vinyl monomers and other monomers copolymerizable thereto (for example, styrene-containing acrylic polymers obtained by polymerizing styrene monomers and other monomers copolymerizable thereto), 7) Hydrogenated aromatic vinyl-containing acrylic polymers obtained by partially or completely hydrogenating the aromatic rings of the aromatic rings of the aromatic rings of the aromatic rings of the aromatic rings of the aromatic acrylic polymers obtained by polymerizing styrene monomers and other monomers copolymerizable thereto, and 8) Acrylic polymers containing repeating cyclic acid anhydride units.

[0024] In particular, from the viewpoint of heat resistance and optical properties, acrylic polymers containing 97 to 100% by mass of constituent units derived from methyl methacrylate and 0 to 3% by mass of constituent units derived from methyl acrylate, and glutarimide acrylic resins are preferred. The glutarimide acrylic resin is not particularly limited, but for example, one produced by the method described in International Publication No. 2005 / 54311 and International Publication No. 2012 / 114718 may be used.

[0025] The glass transition temperature (Tg) of the acrylic resin is preferably 115°C or higher, more preferably 118°C or higher, and even more preferably 120°C or higher, from the viewpoint of heat resistance.

[0026] The method for producing acrylic resins is not particularly limited, and known polymerization methods such as suspension polymerization, bulk polymerization, solution polymerization, emulsion polymerization, and dispersion polymerization can be applied. Furthermore, any of the known radical polymerization, living radical polymerization, anionic polymerization, and cationic polymerization methods can be applied.

[0027] <Graft copolymer> The graft copolymer containing rubber components preferably contains graft copolymer particles (A) having an average particle diameter of 20 to 200 nm, and more preferably contains graft copolymer particles (B) having an average particle diameter larger than that of graft copolymer particles (A). Specifically, in an acrylic resin film, it is preferable that multilayer graft copolymer particles (A) are dispersed in a matrix containing an acrylic resin, or an acrylic resin and other components, and more preferably that multilayer graft copolymer particles (A) and multilayer graft copolymer particles (B) are dispersed in a matrix containing an acrylic resin, or an acrylic resin and other components.

[0028] The graft copolymer particles (A) preferably have a core-shell structure comprising a cross-linked elastomer (Ac), which is a rubber component, and a graft polymer layer (As) located on the surface side of the cross-linked elastomer (Ac).

[0029] The crosslinked elastomer (Ac) contained in the graft copolymer particles (A) may be a known crosslinked elastomer. Preferably, the crosslinked elastomer (Ac) is an acrylic acid ester-based crosslinked elastomer (a crosslinked elastomer consisting of a polymer mainly composed of acrylic acid ester). Here, "main component" means that the content of constituent units derived from acrylic acid ester in the polymer is 50% by mass or more.

[0030] Particles of acrylic acid ester-based cross-linked elastomers (Ac) may have a concentric spherical multilayer structure comprising a hard or semi-hard cross-linked resin layer within the cross-linked elastomer layer. Examples of such hard or semi-hard cross-linked resin layers include hard cross-linked methacrylic resin particles as shown in Japanese Patent Publication No. 55-27576, semi-hard cross-linked particles made of methyl methacrylate-acrylic acid ester-styrene as shown in Japanese Patent Application Publication No. 4-270751, and cross-linked rubber particles with a high degree of cross-linking. By incorporating such a hard or semi-hard cross-linked resin layer, improvements in transparency and color tone can be expected.

[0031] The graft copolymer particles (A) preferably have a core-shell structure formed by graft polymerization of a graft polymer layer (As) in the presence of acrylic acid ester-based crosslinked elastomer (Ac) particles.

[0032] The average particle size of the graft copolymer particles (A) is preferably 20 to 200 nm, more preferably 50 to 150 nm, and particularly preferably 50 to 120 nm. When the average particle size of the graft copolymer particles (A) is within the above range, the impact resistance and transparency of the acrylic resin film are improved.

[0033] As the acrylic acid ester-based crosslinked elastomer (Ac), crosslinked elastomer particles obtained by polymerizing an acrylic acid ester, another vinyl monomer copolymerizable with the acrylic acid ester, and a monomer mixture (Mc) containing a polyfunctional monomer copolymerizable with the acrylic acid ester and having two or more non-conjugated double bonds per molecule are preferably used.

[0034] The acrylic acid ester, other vinyl monomers, and polyfunctional monomers may all be mixed together and polymerized in a single step. Alternatively, to adjust the toughness, whitening resistance, etc., of the acrylic resin film, the composition of the acrylic acid ester, other vinyl monomers, and polyfunctional monomers may be changed as appropriate, or the acrylic acid ester, other vinyl monomers, and polyfunctional monomers may be polymerized in two or more separate steps while maintaining the same composition.

[0035] As for acrylic acid esters, aliphatic esters of acrylic acid are preferred due to their excellent polymerizability and low cost, alkyl acrylates are more preferred, and alkyl acrylates with 1 to 22 carbon atoms in the alkyl group are particularly preferred.

[0036] Specific examples of preferred alkyl acrylates include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dodecyl acrylate, stearyl acrylate, heptadecyl acrylate, and octadecyl acrylate. These may be used individually or in combination of two or more.

[0037] The amount of acrylic acid ester is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more, based on 100% by mass of the monomer mixture (Mc). When the amount of acrylic acid ester is 50% by mass or more, the impact resistance and elongation at tensile break of the acrylic resin film are good, and cracks are less likely to occur during secondary molding.

[0038] Other vinyl monomers include, for example, methacrylic acid esters, vinyl cyanide compounds, aromatic vinyl compounds, vinylidene halides, vinyl halides, vinyl esters, acrylic acid and its salts, methacrylic acid and its salts, acrylic acid derivatives, maleic acid derivatives, etc. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, and dimethylaminoethyl methacrylate. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. Examples of aromatic vinyl compounds include styrene, vinyltoluene, and α-methylstyrene. Examples of vinylidene halides include vinylidene chloride and vinylidene fluoride. Examples of halogenated vinyls include vinyl chloride and vinyl bromide. Examples of vinyl esters include vinyl formate, vinyl acetate, and vinyl propionate. Examples of acrylic acid salts include sodium acrylate and calcium acrylate. Examples of methacrylic acid salts include sodium methacrylate and calcium methacrylate. Examples of acrylic acid derivatives include 2-hydroxyethyl acrylate, phenoxyethyl acrylate, benzyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, acrylamide, and N-methylolacrylamide. Examples of maleic acid derivatives include maleic anhydride, N-alkylmaleimide, and N-phenylmaleimide. These may be used individually or in combination of two or more. Among these, one or more selected from the group consisting of methacrylic acid esters and aromatic vinyl compounds are particularly preferred in terms of weather resistance and transparency.

[0039] The amount of other vinyl monomers is preferably 0 to 49.9% by mass, more preferably 0 to 30% by mass, and particularly preferably 0 to 20% by mass, based on 100% by mass of the monomer mixture (Mc). When the amount of other vinyl monomers is 49.9% by mass or less, the impact resistance and elongation at tensile break of the acrylic resin film are good, and cracks are less likely to occur during secondary molding.

[0040] The polyfunctional monomer can be one that is commonly used as a crosslinking agent and / or graft crossing agent. Examples of polyfunctional monomers that can be used include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl maleate, divinyl adipate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, and dipropylene glycol dimethacrylate. These polyfunctional monomers may be used individually or in combination of two or more.

[0041] The amount of polyfunctional monomer is preferably 0.1 to 10% by mass, and more preferably 1 to 4% by mass, based on 100% by mass of the monomer mixture (Mc). If the amount of polyfunctional monomer is within the above range, it is preferable from the viewpoint of the acrylic resin film's resistance to bending cracking and bending whitening, as well as the fluidity of the resin during molding.

[0042] Furthermore, in acrylic acid ester-based crosslinked elastomers (Ac), the amount of polyfunctional monomers may be varied between the interior and near the surface of the crosslinked elastomer (Ac) in order to improve the graft coating efficiency of the graft polymer layer (As) described later. Specifically, as shown in Japanese Patent Publication No. 1460364 and Japanese Patent Publication No. 1786959, etc., by increasing the content of polyfunctional monomers that function as graft cross-intermediates near the surface of the crosslinked elastomer (Ac) compared to the interior, the coating of graft copolymer particles (A) by the graft polymer layer can be improved, resulting in better dispersibility in acrylic resins and suppression of a decrease in crack resistance due to peeling at the interface between graft copolymer particles (A) and acrylic resins. Furthermore, since sufficient coating can be obtained with a relatively small amount of graft polymer layer (As), the amount of graft copolymer particles (A) required to introduce a predetermined amount of crosslinked elastomer (Ac) into the acrylic resin composition can be reduced. This is expected to improve the melt processability of the acrylic resin film, improve film processing accuracy, and enhance surface hardness due to a decrease in melt viscosity.

[0043] Furthermore, a chain transfer agent may be added to the monomer mixture (Mc) for the purpose of controlling the molecular weight and crosslinking density of the acrylic acid ester-based crosslinked elastomer (Ac), and controlling thermal stability, etc., by reducing the double bond ends of the polymer due to the disproportionation termination reaction during polymerization. The chain transfer agent is selected from those normally used in radical polymerization. Examples of chain transfer agents include mercaptan compounds, mercapto acids, thiophenols, and carbon tetrachloride. The mercaptan compound may be monofunctional or polyfunctional with 2 to 20 carbon atoms, and specifically, examples include n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan. One type of chain transfer agent may be used alone, or two or more types may be used in combination. The amount of chain transfer agent used is preferably 0 to 1.0 parts by mass, and more preferably 0 to 0.2 parts by mass, per 100 parts by mass of the total amount of monomer mixture (Mc).

[0044] The cross-linked elastomer (Ac) particles may be a single layer made of the above-mentioned acrylic acid ester-based cross-linked elastomer (Ac), or a multilayer structure containing two or more layers made of the above-mentioned acrylic acid ester-based cross-linked elastomer (Ac), or a multilayer particle containing a hard or semi-hard cross-linked resin layer with at least one layer made of acrylic acid ester-based cross-linked elastomer (Ac).

[0045] As monomers constituting the hard or semi-hard crosslinked resin layer, alkyl acrylates, aromatic vinyl compounds, vinyl cyanide compounds, maleic acid derivatives, and polyfunctional monomers having two or more non-conjugated double bonds per molecule can be used as appropriate, as described for use in acrylic acid ester-based crosslinked elastomers (Ac).

[0046] Among these, one or more selected from the group consisting of methyl methacrylate, butyl methacrylate, butyl acrylate, ethyl acrylate, styrene, acrylonitrile, etc., are particularly preferred. Furthermore, as the polyfunctional monomer, the same type used for polymerization of acrylic ester-based crosslinked elastomer (Ac) layers can be used. In addition, when polymerization of a rigid or semi-rigid crosslinked resin layer, a chain transfer agent may be used in combination with these monomers for the purpose of controlling thermal stability, etc., by controlling the crosslink density and reducing the double bond ends of the polymer. The same chain transfer agent used for polymerization of acrylic ester-based crosslinked elastomer (Ac) layers can be used. The amount of chain transfer agent used is preferably 0 to 2 parts by mass, and more preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total amount of the rigid or semi-rigid crosslinked resin layer.

[0047] When the graft copolymer particle (A) has a two-layer structure consisting of a crosslinked elastomer particle (Ac) as a core particle and a graft polymer layer (As), the graft copolymer particle (A) can typically be obtained by graft copolymerizing a monomer mixture (Ms) containing 50-100% by mass of a methacrylic acid ester and 0-50% by mass of another vinyl monomer copolymerizable with the methacrylic acid ester in the presence of the crosslinked elastomer particle (Ac) to form the graft polymer layer (As).

[0048] The amount of methacrylic acid ester in the monomer mixture (Ms) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, from the viewpoint of ensuring compatibility with the acrylic resin matrix and preventing a decrease in the toughness of the coating film due to impregnation with organic solvents during coating of the acrylic resin film, as well as whitening and cracking due to stretching during molding.

[0049] In the graft polymer layer (As), examples of methacrylate esters include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, phenyl methacrylate, and benzyl methacrylate. Among these, alkyl methacrylates having 1 to 4 carbon atoms in the alkyl group are preferred.

[0050] In the graft polymer layer (As), other vinyl monomers that can be used include alkyl acrylates with two or more carbon atoms in the alkyl group. The alkyl acrylates with two or more carbon atoms in the alkyl group are preferably one or more selected from the group consisting of ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, dodecyl acrylate, and stearyl acrylate; more preferably one or more selected from the group consisting of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate; and particularly preferably n-butyl acrylate.

[0051] The graft polymer layer (As) is preferably obtained by graft copolymerizing 10 to 95 parts by mass of a monomer mixture (Ms) containing 70 to 99% by mass of an alkyl methacrylate, 0.5 to 30% by mass of an alkyl acrylate with two or more carbon atoms in the alkyl group, and 0 to 19% by mass of other vinyl monomers, in the presence of 5 to 90 parts by mass of crosslinked elastomer particles (Ac), in at least one step. However, the total amount of crosslinked elastomer particles (Ac) and monomer mixture (Ms) should be 100 parts by mass.

[0052] In monomer mixtures (Ms), other vinyl monomers include aromatic vinyl compounds such as styrene and its nuclear-substituted derivatives, vinyl cyanide compounds such as acrylonitrile, methacrylic acid and its derivatives, acrylic acid and its derivatives, N-substituted maleimides, maleic anhydride, methacrylamide, acrylamide, and the like.

[0053] The monomer mixture (Ms) may also contain a reactive UV absorber as another vinyl monomer. In other words, the graft polymer layer (As) may contain constituent units derived from the reactive UV absorber. When the monomer mixture (Ms) contains a reactive UV absorber, it is easier to obtain an acrylic resin film with good weather resistance and chemical resistance. Known reactive UV absorbers can be used as the reactive UV absorber, and are not particularly limited.

[0054] The ratio of constituent units derived from the reactive ultraviolet absorber in the graft polymer layer (As) is preferably 0.01 to 5% by mass, and more preferably 0.1 to 3% by mass.

[0055] In the production of graft copolymer particles (A), when graft copolymerizing monomer mixtures (Ms) in the presence of cross-linked elastomer particles (Ac), such as acrylic ester-based cross-linked elastomer particles (Ac), polymer components that are not grafted to the acrylic ester-based cross-linked elastomer particles (Ac) (free polymers) may be produced. Such free polymers can be used to constitute part or all of the acrylic resin that makes up the matrix phase of an acrylic resin film.

[0056] A chain transfer agent may be added to the monomer mixture (Ms) for the purpose of controlling the molecular weight of the polymer, the grafting rate onto the crosslinked elastomer (Ac), the amount of free polymer not bonded to the crosslinked elastomer (Ac) produced, and thermal stability by reducing the double bond ends of the polymer due to the disproportionation termination reaction during polymerization. Such a chain transfer agent can be the same as the chain transfer agent that can be used for polymerization of the crosslinked elastomer (Ac). The amount of chain transfer agent used is 0 to 2 parts by mass, preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total amount of monomer mixture (Ms).

[0057] The grafting ratio of monomer mixture (Ms) to crosslinked elastomer particles (Ac) is preferably 5 to 250%, more preferably 10 to 200%, and even more preferably 20 to 150%. When the grafting ratio is within the above range, the acrylic resin film exhibits good resistance to bending and whitening, transparency, elongation at tensile break, and moldability.

[0058] Graft copolymer particles (B) are typically preferably comprised of a crosslinked elastomer (Bc) and a graft polymer layer (Bs) located on the surface side of the crosslinked elastomer (Bc), similar to graft copolymer particles (A).

[0059] Regarding graft copolymer particles (B), they are generally the same as graft copolymer particles (A) in terms of raw materials, manufacturing method, etc., except that their average particle diameter is larger than that of graft copolymer particles (A). Particularly preferably, the particles of the acrylic acid ester-based crosslinked elastomer (Bc) have a concentric spherical multilayer structure comprising a hard or semi-hard crosslinked resin layer inside the crosslinked elastomer layer. Examples of such hard or semi-hard crosslinked resin layers include hard crosslinked methacrylic resin particles as shown in Japanese Patent Publication No. 55-27576, etc., and crosslinked particles having a semi-hard layer made of methyl methacrylate-acrylic acid ester-styrene copolymer, etc., as shown in Japanese Patent Application Publication No. 4-270751 and International Publication No. 2014 / 41803, etc. By introducing such a hard or semi-hard crosslinked resin layer, the transparency, resistance to bending whitening, and resistance to bending cracking of graft copolymer particles (B), which have a larger particle diameter than graft copolymer particles (A), can be improved.

[0060] The average particle size of the graft copolymer particles (B) is preferably 150 to 400 nm, and more preferably 200 to 350 nm. Graft copolymer particles (B) with a larger particle size more effectively induce plastic deformation (crazing) in the acrylic resin phase surrounding the graft copolymer particles in response to the action of external forces on the acrylic resin material. For this reason, graft copolymer particles (B) are extremely effective in imparting impact resistance and crack resistance to acrylic resin materials.

[0061] In one or more embodiments of the present invention, the average particle diameter of graft copolymer particles (A) and graft copolymer particles (B) can be measured using a laser diffraction type particle size distribution analyzer such as the Microtrac particle size distribution analyzer MT3000 manufactured by Nikkiso Co., Ltd., using the light scattering method in the latex state.

[0062] The method for producing graft copolymer particles (A) and graft copolymer particles (B) is not particularly limited, and known emulsion polymerization, miniemulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or dispersion polymerization methods can be applied. Emulsion polymerization is particularly preferred because it allows for a wide range of adjustment of the resin structure.

[0063] Known initiators such as organic peroxides, inorganic peroxides, and azo compounds can be used as initiators in the emulsion polymerization of graft copolymer particles (A) or graft copolymer particles (B). Specifically, organic peroxides such as t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, succinate peroxide, t-butyl peroxymaleate, cumene hydroperoxide, benzoyl peroxide, and lauroyl peroxide can be used; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate can be used; and azo compounds such as azobisisobutyronitrile can be used. These may be used individually or in combination of two or more.

[0064] These initiators may be used as pyrolysis-type radical polymerization initiators, or as redox-type polymerization initiator systems in combination with reducing agents such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, hydroxyacetone acid, and ferrous sulfate. Ferrous sulfate may also be used in combination with complexes such as ethylenediaminetetraacetate-2-sodium.

[0065] Among these, from the viewpoint of polymerization stability and particle size control, it is more preferable to use inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate, or to use a redox initiator system that combines organic hydroxylated oxides such as t-butyl hydroperoxide and cumene hydroperoxide with an inorganic reducing agent such as a divalent iron salt and / or an organic reducing agent such as sodium formaldehyde sulfoxylate, reducing sugars, and ascorbic acid.

[0066] The inorganic or organic peroxides mentioned above can be added by known methods such as adding them directly to the polymerization system, adding them mixed with monomers, or adding them dispersed in an aqueous emulsifier solution. From the viewpoint of the transparency of the acrylic resin film, the methods of adding them mixed with monomers and adding them dispersed in an aqueous emulsifier solution are preferred.

[0067] There are no particular limitations on the surfactant (also called an emulsifier) ​​used in the emulsion polymerization of graft copolymer particles (A) or graft copolymer particles (B). A wide range of known surfactants can be used for emulsion polymerization. Preferred surfactants include, for example, anionic surfactants such as alkylsulfonic acid, alkylbenzenesulfonic acid, dioctylsulfosuccinic acid, alkyl sulfate, sodium fatty acid, polyoxyethylene alkyl ether acetate, alkyl phosphoric acid, alkyl ether phosphoric acid, alkylphenyl ether phosphoric acid, and sodium, potassium, and ammonium salts of surfactant, as well as nonionic surfactants such as alkylphenols and reaction products of aliphatic alcohols with propylene oxide and ethylene oxide. For example, polyoxyethylene lauryl ether phosphoric acid and its sodium salt can be suitably used as alkyl ether phosphoric acid and its salts. These surfactants may be used alone or in combination of two or more.

[0068] Graft copolymer particles (A) or graft copolymer particles (B) obtained by emulsion polymerization can be separated and recovered from the latex of either graft copolymer particles (A) or graft copolymer particles (B) by known methods. For example, graft copolymer particles (A) or graft copolymer particles (B) can be separated and recovered by adding a water-soluble electrolyte such as calcium chloride or magnesium sulfate to the latex and allowing it to coagulate, or by freezing and then filtering out the solids, washing, and drying. Alternatively, graft copolymer particles (A) or graft copolymer particles (B) can be separated and recovered by spray drying, freeze-drying, or other treatments of the latex.

[0069] In the acrylic resin composition, i.e., in the acrylic resin film, the content of the rubber component, i.e., the cross-linked elastomer (cross-linked elastomer Ac and / or cross-linked elastomer Bc), is preferably 35% by mass or less, more preferably 25% by mass or less, and particularly preferably 15% by mass or less. When the content of the rubber component in the acrylic resin film is within the above range, the functional film is more likely to meet the high temperature and high humidity shrinkage rate requirements. Furthermore, from the viewpoint of improving the impact resistance of the acrylic resin film, the content of the rubber component, i.e., the cross-linked elastomer (cross-linked elastomer Ac and / or cross-linked elastomer Bc), in the acrylic resin composition, i.e., in the acrylic resin film, is preferably 5% by mass or more, and more preferably 10% by mass or more.

[0070] In the acrylic resin composition, i.e., in the acrylic resin film, it is preferable that the content of the rubber component is within the range described above. The content of the acrylic resin is not particularly limited, but may be 10 to 98.5% by mass, 15 to 90% by mass, 20 to 85% by mass, or 30 to 70% by mass.

[0071] In the acrylic resin composition, i.e., in the acrylic resin film, the content of graft copolymer particles (A) is not particularly limited, but may be, for example, 10 to 90% by mass, 15 to 80% by mass, or 20 to 70% by mass. Similarly, in the acrylic resin composition, i.e., in the acrylic resin film, the content of graft copolymer particles (B) is not particularly limited, but may be, for example, 0.5 to 60% by mass, 1 to 55% by mass, or 2 to 50% by mass.

[0072] <Other ingredients> The acrylic resin film or acrylic resin composition may contain a thermoplastic resin that is at least partially compatible with the acrylic resin, to the extent that it does not impair the objectives of the present invention. Examples of such thermoplastic resins include styrene resins, polyvinyl chloride resins, polycarbonate resins, amorphous saturated polyester resins, polyamide resins, phenoxy resins, polyarylate resins, olefin-methacrylic acid derivative resins, olefin-acrylic acid derivative resins, cellulose derivatives (such as cellulose acylate), vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polylactic acid resins, and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) resins. Examples of styrene resins include styrene-acrylonitrile resins, styrene-methacrylic acid resins, styrene-acrylic acid resins, styrene-maleic anhydride resins, styrene-N-substituted maleimide resins, styrene-unsubstituted maleimide resins, styrene-acrylonitrile-butadiene resins, and styrene-acrylonitrile-acrylic acid ester resins. Among these thermoplastic resins, styrene resins, polycarbonate resins, and cellulose acylate resins are preferred because they exhibit excellent compatibility with acrylic resins and have the potential to improve the bending crack resistance, solvent resistance, and low moisture absorption of acrylic resin films.

[0073] The acrylic resin film or acrylic resin composition may also contain conventionally known additives used in acrylic resin films, to the extent that it does not impair the objectives of the present invention. Examples of such additives include antioxidants, ultraviolet absorbers, light stabilizers, light diffusers, matting agents, lubricants, colorants such as pigments and dyes, fibrous fillers, antiblocking agents consisting of organic or inorganic particles, infrared reflectors consisting of metals or metal oxides, plasticizers, and antistatic agents. The additives are not limited to these. These additives can be used in any amount depending on the type of additive, to the extent that it does not impair the objectives of the present invention, or to enhance the effects of the present invention.

[0074] Acrylic resin films can be manufactured by known processing methods. Specific examples of known processing methods include melt processing, calendering, press molding, and solvent casting. Melt processing methods include inflation and T-die extrusion. In the solvent casting method, an acrylic resin composition is dissolved and dispersed in a solvent, and the resulting dispersion is then poured onto a belt-shaped substrate in a film-like manner. Subsequently, the solvent is evaporated from the poured film-like dispersion to obtain an acrylic resin film. Among these methods, melt processing methods that do not use solvents, particularly T-die extrusion, are preferred. Melt processing methods allow for the production of films with excellent surface properties with high productivity, while also reducing the burden on the natural and working environment caused by solvents, as well as the energy and costs associated with manufacturing.

[0075] In the manufacture of acrylic resin films, if necessary, a film with superior surface properties can be obtained by simultaneously contacting (sandwiching) both sides of the molten film with a cooling roll or cooling belt during the molding process. In this case, it is preferable to simultaneously contact the molten film with a roll or metal belt maintained at a temperature of -5°C or below the glass transition temperature of the acrylic resin composition, preferably -10°C or below.

[0076] More preferably, at least one of the rolls used for such clamping is a roll having an elastic metal sleeve, such as those disclosed in Japanese Patent Publication No. 2000-153547 and Japanese Patent Publication No. 11-235747, and by transferring the mirror surface of the roll using a low clamping pressure, a film with excellent smoothness and less internal distortion can be obtained.

[0077] From the viewpoint of excellent heat resistance, the acrylic resin film preferably has a glass transition temperature of 115°C or higher, more preferably 118°C or higher, and even more preferably 120°C or higher.

[0078] From the viewpoint of excellent heat resistance, the acrylic resin film preferably has a glass transition temperature of 115°C or higher and a rubber component content of 15% by mass or less, more preferably has a glass transition temperature of 118°C or higher and a rubber component content of 15% by mass or less, even more preferably has a glass transition temperature of 118°C or higher and a rubber component content of 14.5% by mass or less, and still more preferably has a glass transition temperature of 120°C or higher and a rubber component content of 14.5% by mass or less.

[0079] The thickness of the acrylic resin film is not particularly limited and can be set appropriately depending on the application of the functional film, but for example, 20 to 500 μm is preferred, and 40 to 300 μm is more preferred. When the thickness of the acrylic resin film is within the above range, it has good moldability, is easy to wind up, and is less prone to wrinkling during winding.

[0080] (Hard coat layer) An acrylic resin film is laminated with a hard coat layer. The hard coat layer only needs to be laminated on at least one side of the acrylic resin film, and may be laminated on both sides if necessary. The hard coat layer provides good chemical resistance and stain resistance.

[0081] The hard coat layer is formed of a curable resin composition that is at least partially cured. In the hard coat layer, the curable resin composition includes at least a thermosetting resin component, which is cured and has at least a partially crosslinked structure. In this specification, the thermosetting resin component is a compound that can be cured (crosslinked) by heat to form a cured product.

[0082] (thermosetting resin component) In the hard coat layer, the curable resin composition preferably includes at least a thermosetting resin component, which is cured and has at least a partially cross-linked structure. Alternatively, the hard coat layer may contain only a thermosetting resin component, which is cured and has at least a partially cross-linked structure. Including a cured product of the thermosetting resin component in the hard coat layer suppresses mixing of the uncured components of the curable resin composition in the low refractive index layer with the components of the hard coat layer, thus preventing the desired anti-reflective function from being impaired. Furthermore, it can suppress adhesion of the low refractive index layer to the mold surface during insert molding, preventing mold adhesion.

[0083] Examples of thermosetting resin components include conventionally known thermosetting resins such as urethane resins, epoxy resins, oxetane resins, phenolic resins, novolac resins, unsaturated polyester resins, vinyl ester resins, alkyd resins, melamine resins, imide resins, silyl resins, styrene-based resins obtained by polymerizing monomers having two or more vinyl polymerizable functional groups, and (meth)acrylate resins.

[0084] Among these thermosetting resins, it is desirable to appropriately control the crosslinking state of the hard coat layer by curing only the thermosetting resin component while leaving the photocurable resin component and low refractive index layer uncured. Therefore, it is desirable to select a resin that cures through a different reaction than the photocurable resin component used in the hard coat layer and low refractive index layer, as described later. For example, when selecting a photocurable resin component, such as a photocurable urethane (meth)acrylate resin, which has a (meth)acrylate functional group and cures by irradiation with active energy rays using a photoradical generator (photoinitiator), it is preferable to use a non-radical curing type thermosetting resin such as urethane resin, epoxy resin, or oxetane resin. Among these, urethane resin is particularly preferred because it has an excellent balance of good affinity with the photocurable resin component, transparency, flexibility, toughness, and hardness.

[0085] Examples of urethane resins preferred for hard coat layers include those obtained by curing a thermosetting resin composition containing, for example, a polyol compound having multiple hydroxyl groups, a polyisocyanate compound having multiple isocyanate groups or a derivative thereof as a curing agent, and, if necessary, a curing reaction catalyst. The urethane resin is preferably one that yields a hard cured product due to its properties as a hard coat.

[0086] The urethane resin is obtained by blending a polyol compound and a polyisocyanate compound or a derivative thereof into a curable resin composition for a hard coat layer, coating it onto a thermoplastic resin film substrate, and then in a drying process in which volatile components containing a solvent are devolved by heating, the polyol compound and the polyisocyanate compound are reacted and cured.

[0087] The reaction curing conditions for the urethane resin in the above drying process should be appropriately set within a temperature range that does not cause softening, deformation, or breakage of the thermoplastic resin film substrate, and that allows the reaction between the polyol compound and the polyisocyanate compound to proceed smoothly. The drying process can be carried out at a temperature of preferably 40°C to 120°C, more preferably 50°C to 110°C, and even more preferably 60°C to 100°C, for preferably 10 seconds to 5 minutes, and more preferably 20 seconds to 3 minutes.

[0088] Furthermore, after the polyol compound and polyisocyanate compound are reacted and cured in the drying process, post-curing may be performed by curing at room temperature or under certain heating conditions for several minutes to several days.

[0089] The polyol compounds used in the aforementioned urethane resin can be conventionally known compounds that are commonly used as raw materials for polyurethane resins. For example, acrylic polyol compounds, polyester polyol compounds, epoxy polyol compounds, polycarbonate polyol compounds, and polyhydric alcohol compounds having a hydrocarbon skeleton can be used. These may be used individually or in combination of two or more as appropriate.

[0090] Among these, the polyol compound is preferably one or more selected from the group consisting of acrylic polyol compounds, epoxy polyol compounds, and polyhydric alcohol compounds with a hydrocarbon skeleton. These polyol compounds are more preferably those with a glass transition temperature (Tg) of room temperature or higher. This can provide a hard urethane resin suitable for hard coat layers and enhance durability such as weather resistance, hydrolysis resistance, and chemical resistance.

[0091] Specifically, the acrylic polyol compound can be a resin obtained by vinyl polymerization, wherein polymerization units containing hydroxyl groups in the side chains are copolymerized. The weight-average molecular weight of the acrylic polyol compound is preferably 5,000 to 100,000, and more preferably 10,000 to 80,000. A weight-average molecular weight of 100,000 or less can increase the hardness of the urethane resin. A weight-average molecular weight of 5,000 or more improves moldability during secondary molding and insert molding.

[0092] Examples of the epoxy polyol compounds include bisphenol-type epoxy resins modified with amine compounds or amino alcohol compounds.

[0093] Examples of polyhydric alcohol compounds with a hydrocarbon skeleton include ethylene glycol, propylene glycol, tetraethylene glycol, cyclohexanediol, cyclohexanedimethanol, glycerin, pentaerythritol, norbornadiol, and adamantanediol.

[0094] The polyol compound may have substituents to appropriately adjust its adhesion to the acrylic resin film, photocurable resin component, and low refractive index layer, as well as its antifouling properties, slipperiness, flame retardancy, and antistatic properties. Examples of substituents include alkoxy groups, ester groups, carbonyl groups, halogen groups (fluorine, chlorine, and bromine, etc.), aromatic groups, heterocyclic groups, amino groups, silyl groups, acidic groups (carboxylic acids, sulfonic acids, phosphoric acid, etc.), and derivatives of these substituents.

[0095] The hydroxyl value of the polyol compound is preferably 5 to 350 mg KOH / g, preferably 10 to 300 mg KOH / g, and more preferably 15 to 250 mg KOH / g. When the hydroxyl value is 5 mg KOH / g or higher, the hardness of the urethane resin increases. When the hydroxyl value is 350 mg KOH / g or lower, the moldability during secondary molding and insert molding is improved.

[0096] As the polyisocyanate compound used in the urethane resin, a compound containing two or more isocyanate groups in one molecule or a derivative thereof, which is a known compound used as a curing agent for urethane resins, can be used.

[0097] Examples of the polyisocyanate compounds include aromatic polyisocyanates such as diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), tolylene diisocyanate (TDI), and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI); and alicyclic polyisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, and norbornene diisocyanate. These polyisocyanate compounds may also be used in the form of derivatives such as adducts, isocyanurates (also simply referred to as nulates), and biuretes. These polyisocyanate compounds and their derivatives may be used individually or in combination of two or more as appropriate.

[0098] (Photocurable resin component) In the hard coat layer, the curable resin composition includes a photocurable resin component in addition to a thermosetting resin component, and either the thermosetting resin component or the photocurable resin component may be cured, but it is preferable that only the thermosetting resin component is cured. Because the hard coat layer includes an uncured photocurable resin component in addition to the cured product of the curable resin composition, the degree of crosslinking of the entire hard coat layer is relatively low, which allows for high flexibility, deformability, and moldability during secondary molding.

[0099] In this specification, a photocurable resin component is a compound that can be cured (crosslinked) by active energy rays such as ultraviolet light or electron beams to form a cured product. Suitable photocurable resin components include, for example, urethane (meth)acrylate compounds commonly used in hard coat layers. In this specification, (meth)acrylate is a general term for acrylate and methacrylate.

[0100] Urethane (meth)acrylate compounds can be obtained, for example, by mixing a polyhydric alcohol, a polyhydric isocyanate, and a hydroxyl group-containing (meth)acrylate, and generating urethane bonds through the reaction of isocyanate groups with hydroxyl groups.

[0101] The various properties of urethane (meth)acrylate compounds can be appropriately adjusted by the structure of the polyhydric alcohol, the type of polyhydric isocyanate, and the number of acryloyl groups or methacryloyl groups (CH2=CH-CO- or CH2=C(CH3)-CO-) derived from the hydroxyl group-containing (meth)acrylate, and are not particularly limited. As urethane (meth)acrylate compounds, commercially available urethane (meth)acrylate resins (including oligomers) used as UV-curable hard coat agents can also be used as appropriate.

[0102] The polyhydric alcohols are not particularly limited, but examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, and polytetramethylene glycol. These polyhydric alcohols may be used individually or in combination of two or more.

[0103] The polyvalent isocyanate is not particularly limited, but for example, a polyvalent isocyanate compound containing two or more isocyanate groups can be used, specifically 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3' -Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane triisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate , bis(2-isocyanate ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, toridine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, 2,5-bis(isocyanate methyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanate methyl)-bicyclo[2. 2.1] Examples include heptane, trimethylolpropane adducts of triethylene diisocyanate, isocyanurates of triethylene diisocyanate, oligomers of diphenylmethane-4,4'-diisocyanate, biuret derivatives of hexamethylene diisocyanate, isocyanurates of hexamethylene diisocyanate, uretdiones of hexamethylene diisocyanate, and isocyanurates of isophorone diisocyanate. These polyisocyanates may be used individually or in combination of two or more.

[0104] The hydroxyl group-containing (meth)acrylate is not particularly limited, but may include, for example, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate having one hydroxyl group, or compounds having an ethylenically unsaturated bond with at least one hydroxyl group, such as 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, trimethylpropane mono(meth)acrylate, trimethylolpropanedi(meth)acrylate, allyl alcohol, ethylene glycol allyl ether, glycerin (mono, di)allyl ether, N-methylol (meth)acrylamide, etc. Furthermore, these hydroxyl group-containing (meth)acrylates may be used individually or in combination of two or more.

[0105] To promote the reaction of polyvalent isocyanates with isocyanate groups, organotin-based urethane catalysts can be suitably used. Suitable organotin-based urethane catalysts include those commonly used in urethane reactions, such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dialkylmalate, tin stearate, and tin octoate. While the amount of these organotin-based urethane catalysts used is not particularly limited, it is desirable to use them within a range of 0.005 to 3% by mass from the viewpoint of reactivity and reaction control.

[0106] The hard coat layer curable resin composition may contain other photocurable resin components in addition to the urethane (meth)acrylate compound. Examples of other photocurable resin components include monomers and resins having radical-reactive functional groups, specifically (meth)acrylate, epoxy acrylate, polyester acrylate, silicone acrylate, polycarbonate acrylate, and polyacrylic acrylate. Furthermore, compositions containing other curable resin components such as hydrolysis condensates of 2-4 functional silane compounds, epoxy groups, and monomers and resins having cationic or anionic curable functional groups such as oxetane groups may also be used.

[0107] A (meth)acrylate only needs to have at least one (meth)acryloyl group, and may be a monofunctional (meth)acrylate having one meth)acryloyl group, or a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups. Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates, aryl (meth)acrylates, phenoxyethyl (meth)acrylates, and alicyclic (meth)acrylates such as isobornyl (meth)acrylates. Examples of polyfunctional (meth)acrylates include polyalkylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, hexanediol di(meth)acrylate, and diethylene glycol di(meth)acrylate. In this specification, (meth)acryloyl group is a general term for methacryloyl group and acryloyl group. There are no particular restrictions on the epoxy acrylate monomer. Specifically, glycidyl ( Examples include meth)acrylate, β-methylglycidyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, and vinylcyclohexene monooxide (i.e., 1,2-epoxy-4-vinylcyclohexane).

[0108] A composition comprising a hydrolysis condensate of a silane compound is preferably a curable resin composition containing a condensate obtained by hydrolyzing and condensing a silane compound (Z) having a hydrolyzable silyl group, represented by the following general formula (1), and, if necessary, a catalyst or curing agent for reacting with a reactive substituent.

[0109] R1 -(SiR 2 a (OR 3 ) 3-a )···(1) In the above general formula (1), R 1 is a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, which may be substituted at at least a part of its terminals with a reactive substituent selected from the group consisting of an epoxy group, an oxetane group, a (meth)acryloyl group, a vinyl group, a hydroxy group, a carboxy group, an amino group, and a functionally protected amino group. R 2 are each independently a monovalent hydrocarbon group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. R 3 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. a is 0, 1 or 2.

[0110] Preferably, the weight average molecular weight of the condensate is 30,000 or less. Also, preferably, the use ratio of the silane compound having a reactive substituent is 10% by mass or more of the whole. When a composition comprising such a hydrolytic condensate of a silane compound is used in combination for the hard coat layer, the cured product as the hard coat layer may be excellent in hardness, chemical resistance, durability, etc.

[0111] The reactive substituent in R 1 in the general formula (1) is preferably an epoxy group or an oxetane group from the viewpoints of less curing shrinkage during the formation of the hard coat layer and easy obtainment of a functional film excellent in durability and suppressed in curl.

[0112] When performing the hydrolytic condensation reaction of the silane compound (Z), it is more preferable to use a neutral salt catalyst. This is because when the reactive substituent is an epoxy group or an oxetane group, it is easy to suppress the decomposition of the reactive substituent during hydrolytic condensation.

[0113] In the curable resin composition for hard coat layers, the other photocurable resin components mentioned above may be used individually or in combination of two or more. Furthermore, commercially available UV-curable hard coat agents can also be used.

[0114] (Other ingredients) The hard coat layer curable resin composition hardens upon irradiation with active energy rays, such as ultraviolet light, forming a cured product. When curing is performed by irradiation with active energy rays, a photopolymerization initiator is used. Furthermore, when a composition containing the above-mentioned hydrolysis condensates of silane compounds, monomers, resins, or mixtures thereof having cationic or anionic curable functional groups such as epoxy groups and oxetane groups is used in combination, a photoanion generator or photocation generator may be added as appropriate.

[0115] Specific examples of photopolymerization initiators include, for example, acetophenone, benzophenone, and benzoyl Examples include methyl ether, benzoyl ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-2-phenylacetophenone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one compounds. Among these, 1-hydroxycyclohexyl-phenyl-ketone is preferred due to its excellent compatibility with urethane (meth)acrylate compounds.

[0116] Specific examples of photocation generators include, for example, CPI-100P and C manufactured by Sunapro Co., Ltd. Examples include PI-101A, CPI-200K, and CPI-200S; WPI-124, WPI-113, WPI-116, WPI-169, WPI-170, and WPI-124 from Wako Pure Chemical Industries; and Rhodia Corporation's Roadsill 2074, among others.

[0117] Specific examples of photoanion generators include, for example, acetophenone o-benzoyloxium, nifedipine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene 2-(9-oxoxanthene2-yl)propionic acid, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, and 1,2-diisopropyl-3-[bis Examples include (dimelamino)methylene]guanidium 2-(3-benzoylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylpyguanidium, and n-butyltriphenylbalate.

[0118] The hard coat layer may be formed by applying a hard coat layer curable resin composition onto a thermoplastic resin film, such as an acrylic resin film, and curing the coating film at least partially. In this case, the hard coat layer curable resin composition may optionally contain additives such as leveling agents, ultraviolet absorbers, light stabilizers, defoamers, antioxidants, light diffusers, matting agents, anti-glare agents, anti-fouling agents, lubricants, colorants such as pigments and dyes, organic particles, inorganic particles, metal particles, and antistatic agents. The additives are not limited to these.

[0119] When a curable resin composition for a hard coat layer contains an anti-glare agent, it can impart light diffusion and anti-glare functions to the hard coat layer. While not particularly limited, examples of anti-glare agents include inorganic particles such as silica particles, alumina particles, titanium oxide particles, zirconia particles, and zinc oxide particles; thermoplastic resin particles such as (meth)acrylic resin particles, polyamide resin particles, polyamide-imide resin particles, and polyacetal resin particles; and organic particles such as cross-linked polyolefin resin particles, cross-linked (meth)acrylic resin particles, cross-linked styrene resin particles, and cross-linked urethane resin particles. Among these, silica particles and cross-linked (meth)acrylic resin particles are preferred. These anti-glare agents may be surface-treated by known methods to adjust their dispersibility, aggregation state, and affinity to the curable resin composition for the hard coat layer. These anti-glare agents may be used individually or in combination of two or more. The amount of anti-glare agent added is adjusted as appropriate according to the design intent for visual properties such as anti-glare, clarity, and matte finish, and is not particularly limited, but for example, it may be 0.5 to 50 parts by mass per 100 parts by mass of the curable resin composition.

[0120] The particles used as the anti-glare agent have an average particle diameter of preferably 0.1 to 20 μm, and more preferably 0.5 to 10 μm.

[0121] As the cross-linked (meth)acrylic resin particles, commercially available cross-linked acrylic monodisperse particles such as MX-80H3wT, MX-150, MX-180TA, MX-300, and MX-500 manufactured by Soken Chemical Co., Ltd. may be used.

[0122] When a curable resin composition for hard coat layers contains a leveling agent, the applicability of the hard coat layer, the scratch resistance and stain resistance of the hard coat layer, etc., can be improved. As the leveling agent, fluorine-based leveling agents, acrylic-based leveling agents, silicone-based leveling agents, and adducts or mixtures thereof can be used. The amount of leveling agent to be added is not particularly limited, but for example, it may be 0.03 to 3.0 parts by mass per 100 parts by mass of the curable resin composition.

[0123] When a curable resin composition for a hard coat layer contains inorganic particles, the hardness, wear resistance, and antistatic properties of the hard coat layer are improved. While not particularly limited, examples of inorganic particles include silica, alumina, titanium oxide, zinc oxide, zirconia, graphene, nanocarbon, carbon black, nanodiamond, mica, barium titanate, boron nitride, metallic silver, and metallic copper. These inorganic particles may be used without surface treatment, or their dispersion state may be controlled by known methods to appropriately control their affinity with the curable resin component. These inorganic particles may be used individually or in combination of two or more types.

[0124] To impart appropriate coatability to a curable resin composition for a hard coat layer, an organic solvent is usually added. The organic solvent is not particularly limited as long as it can impart the desired coatability to the curable resin composition and form a hard coat layer with the desired film thickness and performance. A boiling point of 50 to 150°C is preferred for the organic solvent from the viewpoint of coatability and the drying properties of the formed coating film.

[0125] Specific examples of organic solvents include saturated hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and methylene chloride; alcohol compounds such as methanol, ethanol, isopropyl alcohol, and butanol; ester compounds such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether compounds such as tetrahydrofuran, dioxane, propylene glycol monoethyl ether, methyl cellosolve, and ethyl cellosolve; and amide compounds such as N-methylpyrrolidone and dimethylformamide. Organic solvents may be used individually or in combination of two or more.

[0126] Any method can be used without particular limitation for applying the curable resin composition for the hard coat layer. Examples of application methods include the reverse coat method, gravure coat method, bar coat method, die coat method, spray coat method, kiss coat method, wire bar coat method, and curtain coat method. These application methods may be performed individually or in combination of two or more methods.

[0127] When the curable resin composition for the hard coat layer contains an organic solvent, it can be applied to a thermoplastic resin film, such as an acrylic resin film, and then dried to remove the organic solvent from the coating and cure the thermosetting resin component (e.g., reaction curing). The drying process can be carried out, for example, under the conditions described in the section describing the thermosetting resin component. If the curable resin composition for the hard coat layer contains a photocurable resin component and the photocurable resin component is to be cured, curing may be performed after drying using light, such as ultraviolet irradiation.

[0128] The wavelength of ultraviolet light irradiated during light-induced curing is preferably in the range of 200 to 400 nm. The integrated ultraviolet (UV) light intensity is, for example, 150 to 500 mJ / cm². 2 Preferably, the concentration is 180-450 mJ / cm². 2 Preferably, the concentration is 200-400 mJ / cm². 2 It is even more preferable that the UV integrated light amount is within the above range. When the integrated light amount is within the above range, a hard coat layer with appropriate hardness can be obtained while ensuring moldability. 2 When the above is achieved, the degree of crosslinking of the hard coat layer is improved, resulting in better surface hardness and scratch resistance. (Integrated light intensity: 500 mJ / cm²) 2 The following conditions result in appropriate impregnation of the hard coat layer with the low refractive index curable resin composition, as described later, during coating.

[0129] As an irradiation device for ultraviolet exposure light, for example, an irradiation device equipped with lamp light sources such as high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, electrodeless lamps, and excimer lamps, or pulsed or continuous laser light sources such as argon ion lasers and helium-neon lasers can be used.

[0130] For the hard coat layer curable resin composition, commercially available products containing acrylic polyol compounds as the thermosetting resin component, such as "6AN-3000" and "6AN-4000" from Taisei Fine Chemical Co., Ltd., and commercially available products containing isocyanurate derivatives of polyisocyanates from Mitsui Chemicals, Inc., such as "D131N" (XDI nurate), "D170N" (HDI nurate), and "D370N" (PDI nurate), can be used as the polyisocyanate compound that functions as the thermosetting agent. Furthermore, commercially available hard coat resin compositions containing photocurable urethane (meth)acrylate compounds may be used as hard coat layers, such as "Z-607-27L," "Z-607-9L," and "Z-607-26HL" from Aica Kogyo Co., Ltd., "ENS102" from DIC Corporation, "Beamset 1200W" from Arakawa Chemical Industries, Ltd., "Acrit 8UX-116A" from Taisei Fine Chemical Co., Ltd., "NXD-004AP" from Nippon Chemical Paint Co., Ltd., "P-5820TAH-1" from Daido Chemical Industries, Ltd., and "Rioduras MOL7200" from Toyo Chem Co., Ltd. Since these hard coat resin compositions retain elongation even after curing, the crack elongation of the functional film at 120°C can be further increased.

[0131] The thickness of the hard coat layer is not particularly limited, but is preferably 0.6 to 10.0 μm, more preferably 0.7 to 7.0 μm, and even more preferably 0.8 to 5.0 μm. A hard coat layer thickness of 0.6 to 10.0 μm makes it easier to achieve both wear resistance and moldability.

[0132] The hard coat layer may contain a thermosetting resin component and a photocurable resin component, and may be a partially cured hard coat layer in which only the thermosetting resin component is cured, or it may contain only a thermosetting resin component, and may be a fully cured hard coat layer in which the thermosetting resin component is cured, or it may contain a thermosetting resin component and a photocurable resin component, and may be a fully cured hard coat layer in which both the thermosetting resin component and the photocurable resin component are cured.

[0133] The laminate of the thermoplastic resin film and the hard coat layer preferably has a crack elongation of 80% or more at 120°C, more preferably 90% or more, even more preferably 100% or more, and particularly preferably 120% or more. This makes it easier to obtain a functional film with a crack elongation of 80% or more at 120°C, and thus a functional film with excellent moldability. In this specification, the crack elongation at 120°C can be measured by the method described in the examples.

[0134] (Low refractive index layer) The low refractive index layer is formed from an active energy ray curable resin composition, which is in an uncured state. The low refractive index layer functions as an anti-reflective layer, and the refractive index of the low refractive index layer when the active energy ray curable resin composition is cured is lower than the refractive index of the hard coat layer. As the active energy ray curable resin composition, a curable resin composition for low refractive index layers containing a photocurable resin component and a refractive index adjusting agent can be used as appropriate. By forming a low refractive index layer using an active energy ray curable resin composition containing a photocurable resin component and a refractive index adjusting agent, the refractive index of the low refractive index layer when the active energy ray curable resin composition is cured becomes lower than the refractive index of the hard coat layer.

[0135] As the photocurable resin component, for example, a compound containing a (meth)acryloyl group can be used. Examples of compounds containing a (meth)acryloyl group include urethane (meth)acrylate compounds, monofunctional (meth)acrylates, and polyfunctional (meth)acrylates. These photocurable resin components may be used individually or in combination of two or more.

[0136] As urethane (meth)acrylate compounds, monofunctional (meth)acrylates, and polyfunctional (meth)acrylates, those listed in the section describing the hard coat layer can be used as appropriate.

[0137] As the polyfunctional (meth)acrylate, commercially available products such as the polyfunctional (meth)acrylate resins (UV-curing acrylic polymers) "Acrit 8KX-077", "Acrit 8KX-254B", and "Acrit 8KX-212" manufactured by Taisei Fine Chemical Co., Ltd. can be used as appropriate.

[0138] When a high molecular weight polyfunctional (meth)acrylate resin with a weight-average molecular weight of 40,000 or more is used as the photocurable resin component in the curable resin composition for low refractive index layers, a compound containing a low molecular weight (meth)acryloyl group with a weight-average molecular weight of 11,000 or less may also be used. In the curable resin composition for low refractive index layers, the content of the compound containing a (meth)acryloyl group with a weight-average molecular weight of 11,000 or less may be more than 25% by mass and may be 30% by mass or more, based on 100% by mass of the total photocurable resin components. This makes it easier to improve the wear resistance of the resin molded article after curing the curable resin composition for low refractive index layers in resin molded articles using functional films. The curable resin composition for low refractive index layers may also contain only a compound containing a low molecular weight (meth)acryloyl group with a weight-average molecular weight of 11,000 or less as the photocurable resin component. Compounds containing low molecular weight (meth)acryloyl groups may have a weight-average molecular weight of 4000 or less, 3000 or less, 2000 or less, or 1000 or less.

[0139] The curable resin composition for the low refractive index layer may contain, in addition to compounds containing (meth)acryloyl groups, the photocurable resin components described in the section on the hard coat layer. Alternatively, commercially available coating agents for the low refractive index layer or hard coat layer, such as "Z-624-7L" manufactured by Aica Kogyo Co., Ltd., may be used as the photocurable resin component.

[0140] Refractive index modifiers are used to lower the apparent refractive index of the low refractive index layer after curing compared to the hard coat layer by dispersing a low refractive index substance in the photocurable resin component at a dispersion size smaller than the wavelength of visible light.

[0141] Examples of refractive index modifiers that can be used include silica nanoparticles, silicone nanoparticles, hollow silica nanoparticles, hollow organic particles, and fluoride nanoparticles. Examples of hollow organic particles include those composed of acrylic resins and fluororesins having a cross-linked structure. Examples of fluorides that make up fluoride nanoparticles include fluororesins, magnesium fluoride, lithium fluoride, aluminum fluoride, and calcium fluoride. In particular, from the viewpoint of suppressing the increase in haze and improving transparency, it is preferable that the refractive index modifier includes hollow silica nanoparticles. The above-mentioned refractive index modifiers may be used individually or in combination of two or more types.

[0142] From the viewpoint of transparency, hollow silica nanoparticles preferably have an average particle diameter of 100 nm or less, more preferably 80 nm or less, and even more preferably 60 nm or less. When the particle diameter of hollow silica nanoparticles is less than 100 nm, the transparency is excellent. Furthermore, there is no particular lower limit to the average particle diameter of hollow silica nanoparticles, but from the viewpoint of improving anti-reflective performance, it may be, for example, 10 nm or more, or 20 nm or more. Specifically, hollow silica nanoparticles preferably have an average particle diameter of 10 to 100 nm, more preferably 20 to 80 nm, and even more preferably 20 to 60 nm. From the viewpoint of transparency and anti-reflective properties, the refractive index modifier preferably contains 30% by mass or more of hollow silica nanoparticles, more preferably 40% by mass or more, and even more preferably 50% by mass or more. In this specification, the average particle diameter of hollow silica nanoparticles can be determined by observing the cross-section of the low refractive index layer with an electron microscope and averaging the particle diameters of 10 hollow silica nanoparticles.

[0143] These refractive index modifiers may be surface-treated to enhance the affinity between the particle surface and the photocurable resin component in order to ensure good dispersion within the photocurable resin component. While many known surface treatment methods can be used, for refractive index modifiers made of inorganic materials such as hollow silica nanoparticles, a method of organicizing the surface using a coupling agent such as a silane coupling agent is employed. The coupling agent used may have substituents that have affinity or reactivity with the photocurable resin component.

[0144] In a curable resin composition for a low refractive index layer (low refractive index layer), the content of hollow silica fine particles is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on 100% by mass of the total of the photocurable resin component and hollow silica fine particles. When the content of hollow silica fine particles is 30% by mass or more, the anti-reflective properties are improved. Furthermore, there is no particular upper limit to the content of hollow silica fine particles, but from the viewpoint of improving surface hardness and abrasion resistance, for example, it is preferably 80% by mass or less, and preferably 70% by mass or less, based on 100% by mass of the total of the photocurable resin component and hollow silica fine particles. Specifically, the content of hollow silica fine particles is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, and even more preferably 50 to 70% by mass, based on 100% by mass of the total of the photocurable resin component and hollow silica fine particles.

[0145] The curable resin composition for low refractive index layers (low refractive index layer) contains a photopolymerization initiator for curing a resin molded article formed by laminating functional films by irradiation with active energy rays such as ultraviolet light, as described later, to form a cured product. As the photopolymerization initiator, for example, one or more of the photopolymerization initiators described in the section on hard coat layers can be used as appropriate.

[0146] In a curable resin composition for a low refractive index layer, a portion of the organic material may be replaced with a water-repellent or oil-repellent material to impart antifouling properties to the low refractive index layer. Examples of water-repellent or oil-repellent materials include wax-based materials such as fluorine-based, silicone-based, and aliphatic hydrocarbon-based materials. These water-repellent or oil-repellent materials may contain reactive groups that can react with the photocurable resin component.

[0147] Various additives can be added to the low refractive index layer as other components, as long as they do not impair the effects of the present invention. Examples of such additives include photopolymerization initiators, dispersants, surfactants, light stabilizers, antistatic agents, leveling agents, antifouling agents, and antifingerprint agents.

[0148] To impart appropriate coatability to a curable resin composition for a low refractive index layer, an organic solvent is usually added. As the organic solvent, one or more of those listed in the section describing the hard coat layer can be used as appropriate.

[0149] Any method can be used without particular restriction for applying the curable resin composition for the low refractive index layer, and the methods described in the section describing the hard coat layer can be used as appropriate.

[0150] A low refractive index layer is formed by applying a curable resin composition for low refractive index layers onto a hard coat layer and drying the coating film as appropriate. The organic solvent is removed from the coating film by drying. The drying process is not particularly limited, but for example, it can be carried out under temperature conditions of preferably 40°C to 120°C, more preferably 50°C to 110°C, and even more preferably 60°C to 100°C for preferably 10 seconds to 5 minutes, more preferably 20 seconds to 3 minutes.

[0151] The thickness of the low refractive index layer is preferably, for example, 0.01 to 1 μm, and more preferably 0.05 to 0.5 μm. When the thickness of the low refractive index layer is within the above range, it exhibits excellent anti-reflective performance, facilitates the formation of a uniform coating film, and also provides good adhesion to the hard coat layer.

[0152] In one or more embodiments of the present invention, the functional film has a low refractive index layer formed from an uncured curable resin composition for the low refractive index layer. That is, in the functional film, the low refractive index layer is in an uncured state. As described later, after laminating the functional film onto the surface of a thermoplastic resin substrate to form a resin molded body, the surface of the resin molded body is irradiated with active energy rays to cure the low refractive index layer (curable resin composition for the low refractive index layer), thereby obtaining a resin molded body that has an anti-reflective function and excellent abrasion resistance, surface hardness, chemical resistance, etc.

[0153] (Other functional layers) Functional films may include functional layers other than the hard coat layer and the low refractive index layer. Examples of these other functional layers are not limited to primer layers, but include high refractive index layers, anti-glare layers, anti-fouling layers, anti-fingerprint layers, scratch-resistant layers, antistatic layers, UV shielding layers, infrared shielding layers, surface texture layers, light diffusion layers, matte layers, polarizing layers, colored layers, design layers, embossed layers, conductive layers, gas barrier layers, and gas absorption layers. Functional films may also comprise two or more of these functional layers. Furthermore, a single functional layer may possess two or more functions.

[0154] (Functional film) As described above, one or more embodiments of the present invention provide a functional film comprising a thermoplastic resin film and a hard coat layer and a low refractive index layer laminated sequentially on the thermoplastic resin film (preferably an acrylic resin film). In one or more embodiments of the present invention, for example, as shown in Figure 1, the functional film 1 comprises a thermoplastic resin film 2 and a hard coat layer 3 and a low refractive index layer 4 laminated sequentially on one side of the thermoplastic resin film 1. In one or more embodiments of the present invention, the functional film only needs to have the low refractive index layer on the outermost surface, and may optionally include other functional layers as described above between the thermoplastic resin film and the hard coat layer, and / or between the hard coat layer and the low refractive index layer, as long as they do not hinder the effects of the present invention. Furthermore, a primer layer may be provided on the side opposite to the hard coat layer and low refractive index layer.

[0155] The functional film preferably has a crack elongation at 120°C (hereinafter also simply referred to as "120°C crack elongation") of 80% or more. When the crack elongation at 120°C is 80% or more, it is possible to suppress the occurrence of cracks in the functional film when laminating the functional film onto a thermoplastic resin substrate and coating the thermoplastic resin substrate with the functional film, particularly when vacuum forming, pressure forming, or injection molding (including insert molding), and a resin molded product can be obtained with good moldability. The crack elongation at 120°C of the functional film is more preferably 90% or more, even more preferably 100% or more, and particularly preferably 110% or more. In this specification, the crack elongation at 120°C can be measured by the method described in the examples.

[0156] From the viewpoint of suppressing whitening during molding, the Δhaze of the functional film at 80% stretch at 120°C is preferably 10% or less, more preferably 5% or less, even more preferably 3% or less, even more preferably 1% or less, even more preferably 0.8% or less, and particularly preferably 0.4% or less. In this specification, the Δhaze at 80% stretch at 120°C can be measured by the method described in the examples.

[0157] From the viewpoint of transparency of the resin molded article coated with the functional film, the haze measured after curing the low refractive index layer is preferably 2.0% or less, more preferably 1.5% or less, even more preferably 1.0% or less, even more preferably 0.8% or less, and particularly preferably 0.4% or less. In this specification, the haze can be measured by the method described in the examples.

[0158] From the viewpoint of anti-reflective properties, anti-glare properties, and visibility of the resin molded article coated with the functional film, the luminous reflectance measured after curing the low refractive index layer is preferably 4.0% or less, more preferably 3.5% or less, even more preferably 2.5% or less, even more preferably 2.0% or less, and particularly preferably 1.5% or less. In this specification, the luminous reflectance can be measured by the method described in the examples.

[0159] From the viewpoint of scratch resistance of the resin molded article coated with the functional film, it is preferable that the pencil hardness measured after curing the low refractive index layer is 2H or higher. In this specification, pencil hardness can be measured by the method described in the examples.

[0160] From the viewpoint of the abrasion resistance of the resin molded article coated with the functional film, it is preferable that, after curing the low refractive index layer, a gauze abrasion test is performed on the low refractive index layer side with a weight of 500g and 200 back-and-forth cycles, and that there are 10 or fewer scratches visible to the naked eye, and it is particularly preferable that no scratches are visible to the naked eye.

[0161] (Method of manufacturing functional films) The functional film is not particularly limited, but it can be produced by, in step 1, applying a curable resin composition for a hard coat layer to at least one side of a thermoplastic resin film (preferably an acrylic resin film) to form a coating film and curing it at least partially to form a hard coat layer, and in step 2, applying an active energy ray curable resin composition on the hard coat layer to form an uncured low refractive index layer. In step 2 and subsequent steps, by not irradiating the active energy ray curable resin composition constituting the low refractive index layer with active energy rays, a functional film including a low refractive index layer formed of the uncured active energy ray curable resin composition is obtained.

[0162] When laminating a hard coat layer and a low refractive index layer on both sides of a functional film, step 1 can be performed twice to form hard coat layers on both sides of the functional film, and then step 2 can be performed.

[0163] If the functional film includes other functional layers, and these other functional layers include photocurable resin components, the other functional layers can be formed before step 1, or after step 1 and before step 2.

[0164] When the curable resin composition for the hard coat layer contains both a thermosetting resin component and a photocurable resin component, the thermosetting resin component is cured by not irradiating with active energy rays in steps 1 and beyond, forming a hard coat layer that has at least partially cross-linked structures and where the photocurable resin component remains uncured. If necessary, in step 1, after drying the coating film of the curable resin composition for the hard coat layer, it is also possible to further cure the photocurable resin component by irradiating with active energy rays.

[0165] (Resin molded product) The resin molded article comprises a thermoplastic resin substrate and the functional film, wherein at least a portion of the thermoplastic resin substrate is covered with the functional film, which is positioned such that the low refractive index layer is located on the outermost surface of the resin molded article. That is, at least one side of the low refractive index layer is located on the outermost surface of the resin molded article. The functional film has high crack elongation at 120°C, which allows for the coating of a thermoplastic resin substrate having a non-planar three-dimensional shape in at least a portion with the functional film, thereby suitably obtaining a resin molded article with a three-dimensional shape. The functional film can be used as a surface material that protects the surface of resin molded articles of various shapes while imparting various functions such as anti-reflective properties, abrasion resistance (including scratch resistance), and anti-glare properties.

[0166] The thermoplastic resin substrate may be composed of, for example, polycarbonate resin having a bisphenol-based skeleton, a fluorene-based skeleton, or an isosorbide-based skeleton, acrylic resin, styrene-based resin (AS resin, ABS resin, and MAS resin, styrene-maleimide resin, styrene-maleic anhydride resin, etc.), saturated polyester resin, polyvinyl chloride resin, polyarylate resin, PPS-based resin, POM-based resin, polyamide resin, polylactic acid resin, cellulose acylate resin, and polyolefin resin. Among these, one or more selected from the group consisting of polycarbonate resin, acrylic resin, styrene-based resin, and amorphous polyolefin resin are preferred because they have the excellent transparency required for the display portion, and polycarbonate resin and / or acrylic resin are more preferred because they have good adhesion to the functional film, with polycarbonate resin being even more preferred from the viewpoint of high rigidity, high heat resistance, and high impact resistance.

[0167] The resin molded articles can be used, for example, as automotive interior materials, automotive exterior materials, optical components, and home appliance components. Examples of automotive interior materials are not particularly limited, but include instrument panels, front panels for in-vehicle displays, meter covers, door lock bezels, steering wheels, power window switch bases, center clusters, dashboards, and console boxes. Examples of automotive exterior materials are not particularly limited, but include door mirrors, windows, headlamp covers, taillamp covers, windshield components, weatherstrips, bumpers, bumper guards, side mudguards, body panels, spoilers, front grilles, strut mounts, wheel caps, center pillars, center ornaments, side moldings, door moldings, and window moldings. Examples of optical components are not particularly limited, but include various displays, lenses, mirrors, goggles, and window glass. Examples of home appliance components, though not particularly limited, include display windows, buttons, and housings for portable electronic devices such as smartphones, mobile phones, and tablets; televisions, DVD players, stereo systems, rice cookers, washing machines, refrigerators, air conditioners, humidifiers, dehumidifiers, fans, and other household electronic and electrical appliances; and casings, front panels, buttons, surface decorative materials, and exterior materials for furniture products. Resin molded products can also be used as exterior building materials such as siding, fences, roofs, gates, and gable boards.

[0168] By using the functional film of one or more embodiments of the present invention, a resin molded article with a complex three-dimensional shape and excellent appearance, with controlled surface properties such as scratch resistance, abrasion resistance, anti-reflective properties, and anti-glare properties, can be easily manufactured. For this reason, among the above applications, the resin molded article is preferably used for applications such as the front panel of a display device such as an in-vehicle display, which has various shapes such as planar shapes and three-dimensional shapes such as curved shapes.

[0169] (Method of manufacturing resin molded products) The method for manufacturing a resin molded article is not particularly limited, as long as it is a molding method that can coat a thermoplastic resin substrate with a functional resin film. For example, a resin molded article can be manufactured by insert injection molding. Alternatively, pre-molding may be performed before insert injection molding by methods such as vacuum forming, pressure forming, or compression molding, as needed.

[0170] <Pre-molding> Functional films can be pre-formed by molding methods such as vacuum forming, pressure forming, and compression molding to shape them for use in insert injection molding. For example, when manufacturing a resin molded body with a three-dimensional shape having at least a curved portion, a curved functional film with a predetermined three-dimensional shape can be produced by pre-forming using methods such as vacuum forming, pressure forming, and compression molding, and then the resin molded body can be manufactured by insert injection molding. Depending on the final shape of the resin molded body, pre-forming may not be necessary.

[0171] Pre-forming is preferably carried out by heating the thermoplastic resin film, which is the base film of the functional film, to a temperature above its softening temperature. When the thermoplastic resin film is the acrylic resin film described above, the temperature of the functional film during pre-forming is preferably 90 to 200°C, more preferably 100 to 170°C, and even more preferably 110 to 140°C. If the temperature of the functional film during pre-forming is 90°C or higher, plasticization is sufficient, and the film does not break, crack, whiten, or warp after molding in the stretched portion. If the temperature of the functional film during pre-forming is 200°C or lower, the film does not draw down due to excessive viscosity reduction, foaming or generation of gas components due to thermal decomposition of the resin, and the resulting deterioration of appearance do not occur.

[0172] Pre-forming may be carried out using a molding machine separate from the injection molding die, or, for example, the shape of the injection molding die may be used as is and shaping may be carried out using a known method as appropriate.

[0173] <Insert injection molding> Insert injection molding (also known as film insert molding or IML molding) involves placing a functional film, or a functional film molded into a predetermined shape as needed, on at least one surface of an injection molding die, such that at least one low refractive index layer faces the injection molding die, i.e., at least one low refractive index layer is in contact with the injection molding die surface. After clamping the die, a thermoplastic resin is injected to perform insert injection molding, obtaining a resin molded body in which the functional film is laminated in close contact with the surface of a thermoplastic resin substrate.

[0174] The conditions for insert injection molding are not particularly limited. For example, the molding temperature, injection pressure, injection speed, holding pressure, mold temperature, cooling time, etc., can be appropriately set within a known range so that the thermoplastic resin for molding can be successfully injected.

[0175] Since an uncured low-refractive-index layer is present on the surface of the resin molded body, it is preferable to set the mold temperature as low as possible during cooling after injection molding of the resin molded body, within a range where excessive rapid cooling of the molded body does not cause residual strain or other problems. It is even more preferable to set the temperature lower than the softening temperature of the low-refractive-index layer. Setting the mold temperature low makes it less likely for the low-refractive-index layer to adhere to the mold surface due to softening. Furthermore, when peeling off the low-refractive-index layer that has adhered to the mold surface, peeling of the low-refractive-index layer, surface roughness, whitening, etc. tend to occur, but these problems are avoided because the low-refractive-index layer does not adhere to the mold surface due to softening.

[0176] Furthermore, generally, the area near the gate of an injection molding die is subject to high shear stress during injection, and the injection resin flows in accompanied by shear heat generation. As a result, it tends to become hotter than other areas, and adhesion of the low refractive index layer to the mold surface is particularly likely to occur. For this reason, it is preferable to use methods to suppress shear heat generation near the gate by devising the shape of the gate and the injection profile. Alternatively, methods such as lowering the cooling temperature of the mold near the gate or increasing the cooling capacity of the mold near the gate may be employed.

[0177] (Curing by irradiation with active energy rays) The resin molded article obtained as described above has a functional film disposed on at least one side, and the functional film includes a partially cured (containing a thermosetting resin component and a photocurable resin component, with the thermosetting resin component cured) or fully cured (containing only a thermosetting resin component, with the thermosetting resin component cured, or containing a thermosetting resin component and a photocurable resin component, with both the thermosetting resin component and the photocurable resin component cured) hard coat layer and an uncured low refractive index layer, and the uncured low refractive index layer is formed on the outermost surface of the resin molded article. By irradiating the resin molded body with active energy rays to cure the low refractive index layer (hereinafter also referred to as "post-curing"), a resin molded body can be obtained that has excellent surface hardness, scratch resistance, and chemical resistance based on the high crosslinking density of the photocurable resin component after curing, and also has excellent anti-reflective properties based on the formation of a low refractive index layer with a refractive index lower than that of the hard coat layer. In the case of a functional film, if the hard coat layer is partially cured, the hard coat layer can also be completely cured by post-curing.

[0178] The method for post-curing a resin molded product is not particularly limited, as long as the conditions are such that the curing reaction of the low refractive index layer proceeds sufficiently by irradiation with active energy rays. For example, after insert injection molding, the mold may be opened on one side and cured by irradiating the surface of the resin molded product, or, if the resin molded product is transparent, from the back side, with active energy rays. Alternatively, the resin molded product may be removed from the mold and then irradiated with active energy rays.

[0179] Ultraviolet light is preferred as the active energy ray. Known light sources such as high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, electrodeless lamps, and UV-LEDs can be used as ultraviolet sources. The cumulative irradiation light intensity can be appropriately set according to the characteristics of the photocurable resin component used in the low refractive index layer, for example, 50 to 4000 mJ / cm². 2 Preferably 100-3500 mJ / cm² 2 That is the case.

[0180] While there are no particular limitations on the temperature conditions during active energy ray irradiation, it is preferable to carry out the process at room temperature or at a temperature that does not exceed the softening temperature of the molded article, from the viewpoint of ensuring that the crosslinking reaction proceeds smoothly.

[0181] Furthermore, if it is desirable to prevent warping or cracking of the molded product due to excessive curing shrinkage during post-curing, the process may be carried out at temperatures below room temperature.

[0182] Furthermore, when using a curing system such as a radical curing system that is susceptible to curing inhibition by oxygen, it is preferable to perform active energy ray irradiation under a nitrogen atmosphere or under low oxygen concentration conditions such as reduced pressure.

[0183] In the injection-molded article, from the viewpoint of suppressing adhesion of the functional film to the mold, surface roughness, whitening, and peeling of the functional film during molding, the color difference (ΔE) between the functional film before injection molding (low refractive index layer uncured) and the film portion of the UV-cured resin molded article (low refractive index layer cured) is preferably 1.5 or less, more preferably 1.0 or less, and even more preferably 0.5 or less. In this specification, the color difference can be measured as described in the examples. [Examples]

[0184] The present invention will be described in more detail below based on the examples. The present invention is not limited to these examples. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "percent mass".

[0185] The measurement and evaluation methods used in the examples and comparative examples will be explained.

[0186] (Crack elongation at 120°C) The 120°C crack elongation was measured using a laminate of a functional film or acrylic resin film and a hard coat layer. Specifically, the laminate of the functional film or acrylic resin film and the hard coat layer was cut to 10 mm (width) x 100 mm (length), and a tensile test was performed using a Tensilon tensile testing machine (Shimadzu Corporation, AG-2000D) equipped with a high-temperature chamber set to 120°C, under the conditions of a preheating time of 2 minutes, a chuck distance of 40 mm, and a tensile speed of 200 mm / min. The elongation when cracks occurred in the hard coat layer was measured, and the average value of the test results obtained from measurements of three samples was defined as the 120°C crack elongation. (Δ-haze after 80% stretching at 120°C) The haze difference (Δ-haze) after 80% stretching at 120°C was measured using a functional film. Specifically, a 10mm (width) x 100mm (length) piece was cut, and a tensile test was performed using a Tensilon tensile testing machine (Shimadzu Corporation, AG-2000D) equipped with a high-temperature chamber set to 120°C, under the conditions of a preheating time of 2 minutes, a chuck distance of 40mm, and a tensile speed of 200mm / min. The haze of the functional film after 80% stretching was measured using a haze meter NDH4000 (Nippon Denshoku Industries Ltd.) in accordance with ISO 14782. (Hayes) Haze was measured using a functional film after UV irradiation, in accordance with ISO 14782, using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.). UV irradiation was performed using a high-pressure mercury lamp (model number "H06-L41") manufactured by I-Graphics Co., Ltd., with an integrated light intensity of 230 mJ / cm². 2 I went there. (Luminous reflectance) The luminous reflectance was measured using a functional film after UV irradiation. The opposite sides of the hard coat layer and low refractive index layer were painted black with black marker ink, and black vinyl tape was applied over them. The measurement was performed using a colorimeter SC-P (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS Z 8722:2009. UV irradiation was performed in the same manner as for haze measurement. (Pencil hardness) Pencil hardness was measured using functional films after UV irradiation, in accordance with JIS K 5600-5-4:1999. UV irradiation was performed in the same manner as for haze measurement. (Abrasion test) Abrasion tests were conducted using functional films after UV irradiation, employing a HEIDON Type 14DR surface texture measuring instrument (manufactured by Shinto Kagaku Co., Ltd.). A gauze pad was attached to a 1mm diameter probe, and a 500g weight was placed on top. The gauze was placed on the hard-coated surface of the functional film, and a 200-reciprocal test was performed with a stroke of 100mm and a speed of 6000mm / min. Abrasion resistance was evaluated according to the following criteria. A rating of B or higher indicates good abrasion resistance. A: No visible damage. B: 1 to 10 scratches visible to the naked eye C: More than 10 scratches visible to the naked eye (Mold adhesion) The color difference (ΔE) between the functional film before injection molding (low refractive index layer uncured) and the film portion of the resin molded product after injection molding and curing by UV irradiation (low refractive index layer cured) was measured. The color difference was measured using a spectrophotometer SE7700 under the following conditions. Based on the ΔE value, mold adhesion was evaluated according to the following criteria. Mode: Reflection Backing treatment: Black tape Light source: D65 Viewing angle: 2° Measurement diameter: 28mm No mold adhesion: ΔE is 1.5 or less Mold adhesion present: ΔE is greater than 1.5

[0187] [Manufacturing Example 1: Graft Copolymer Particles (A)] The following substances were charged into an 8L polymerization apparatus equipped with a stirrer. • Deionized water (200 copies) • Sodium dioctyl sulfosuccinate 0.24 parts • Sodium formaldehyde sulfoxylate 0.15 parts • 0.001 parts of ethylenediaminetetraacetic acid-2-sodium • Ferrous sulfate 0.00025 parts Subsequently, the polymerization apparatus was thoroughly purged with nitrogen gas to create a substantially oxygen-free environment. The internal temperature was then set to 60°C, and 30 parts of the following mixture (I) were continuously added at a rate of 10 parts / hour. After the addition was complete, polymerization was continued for another 0.5 hours to obtain latex with crosslinked elastomer (Ac) particles (average particle size 80 nm). The polymerization conversion rate was 99.5%. Mixing ratio of mixture (I): • Vinyl monomer mixture (90% n-butyl acrylate (BA) and 10% methyl methacrylate (MMA)) 10 parts • Allyl methacrylate (AlMA) 1 part • Cumene hydroperoxide (CHP) 0.2 parts

[0188] Subsequently, 0.05 parts of sodium dioctyl sulfosuccinate were charged into the polymerization apparatus, the internal temperature was set to 60°C, and 70 parts of the following mixture (II) were continuously added at a rate of 10 parts / hour to form a graft polymer layer (As). Polymerization was continued for another hour to obtain latex of graft copolymer particles (A). The polymerization conversion rate was 98.2%. The obtained latex was filtered through a stainless steel mesh with a mesh opening of 10 μm, then salted out with calcium chloride, coagulated, washed with water, and dried to obtain powdered graft copolymer particles (A1). The average particle size of the graft copolymer particles (A1) was 80 nm. Mixing ratio of mixture (II): • Vinyl monomer mixture (MMA 99%, BA 1%) 70 parts t-dodecyl mercaptan (t-DM) 0.5 part ·CHP0.5 part

[0189] [Manufacturing Example 2: Graft Copolymer Particles (B)] The following substances were charged into an 8L polymerization apparatus equipped with a stirrer. • Deionized water (180 units) • Polyoxyethylene lauryl ether phosphate 0.002 parts • Boric acid 0.4725 parts • Sodium carbonate 0.04725 parts • Sodium hydroxide 0.0098 parts

[0190] Subsequently, after thoroughly purging the polymerization apparatus with nitrogen gas, the internal temperature was raised to 80°C, and 0.027 parts of potassium persulfate were added in a 2% aqueous solution. Then, a mixture consisting of 27 parts of vinyl monomer mixture (97% MMA and 3% BA) and 0.036 parts of allyl methacrylate was continuously added over 81 minutes. Polymerization was continued for another 60 minutes to obtain polymer particles that would form the first layer of the core (cross-linked elastomer (Bc)). The polymerization conversion rate was 99.0%. Subsequently, 0.0267 parts of sodium hydroxide were added in a 2% aqueous solution, followed by 0.08 parts of potassium persulfate in a 2% aqueous solution. Then, a mixture consisting of 50 parts of vinyl monomer mixture (BA 83%, and styrene (St) 17%) and 0.375 parts of allyl methacrylate was continuously added over 150 minutes. After the addition was complete, 0.015 parts of potassium persulfate were added in a 2% aqueous solution, and polymerization was continued for 120 minutes to obtain a core (crosslinked elastomer particles (Bc)) consisting of the first and second layers. The polymerization conversion rate was 99.0%, and the average particle size of the crosslinked elastomer particles Bc was 230 nm.

[0191] Subsequently, 0.023 parts of potassium persulfate were added in a 2% aqueous solution, and 23 parts of a vinyl monomer mixture (80% MMA and 20% BA) were continuously added over 45 minutes. Polymerization was then continued for another 30 minutes to form a graft polymer layer (Bs) on the surface of a cross-linked elastomer particle (Bc) having a core two-layer structure, thereby obtaining graft copolymer particle (B) latex. The polymerization conversion rate was 100.0%. The obtained latex was salted out with magnesium sulfate, coagulated, washed with water, and dried to obtain white powdery graft copolymer particles. The average particle size of the graft copolymer particles (B) was 230 nm.

[0192] Table 1 below shows the details of the main component of the thermosetting component used in the hard coat layer in the examples and comparative examples, and Table 2 below shows the details of the curing agent of the thermosetting component. Furthermore, Table 3 below shows the details of the photocurable resin component used in the hard coat layer, and Table 4 below shows the details of the photocurable resin component used in the low refractive index layer.

[0193] [Table 1]

[0194] [Table 2]

[0195] [Table 3]

[0196] [Table 4]

[0197] (Example 1) <Fabrication of acrylic resin film> Thirty parts of graft copolymer particles (A) from Production Example 1, four parts of graft copolymer particles (B) from Production Example 2, and 66 parts of acrylic resin (polymethyl methacrylate, manufactured by Kuraray Co., Ltd., product name "Parapet HM") were mixed using a Henschel mixer. Next, using a 58 mmΦ single-screw extruder (manufactured by NSK Ltd.) with the cylinder temperature adjusted to 200°C to 260°C, melt-kneading was performed at a screw rotation speed of 90 rpm and a discharge rate of 130 kg / hour. The mixture was then pulled into strands, cooled in a water bath, and cut using a pelletizer to obtain pellets of the acrylic resin composition.

[0198] The resulting acrylic resin composition pellets were melt-kneaded using a 90mmΦ single-screw extruder with a T-die at a cylinder temperature of 180°C to 240°C and a discharge rate of 130 kg / hr. The mixture was then extruded from the T-die at a die temperature of 240°C and cooled and solidified using a cast roll temperature-controlled to 90°C and a cooling roll temperature-controlled to 60°C to obtain an acrylic resin film with a thickness of 175 μm.

[0199] <Production of functional films> A curable resin composition for a hard coat layer was applied to one side of the obtained acrylic resin film using a #10 bar coater, dried at 80°C for 1 minute to form a hard coat layer (3 μm thick), and cured at room temperature for 3 hours. As a curable resin composition for the hard coat layer, a composition was used which consisted of 50% of a photocurable resin component, a polyfunctional acrylate resin (manufactured by Taisei Fine Chemical Co., Ltd., product name "Acrit 8KX-077"), 46.3% of a thermosetting resin component, an acrylic polyol compound (manufactured by Taisei Fine Chemical Co., Ltd., product name "Acrit 6AN-4000"), and 3.7% of a polyisocyanate resin (manufactured by Mitsui Chemicals, Inc., product name "Takenate D131N") as a thermosetting agent for the acrylic polyol compound, and was diluted with methyl ethyl ketone (MEK) to a solid content concentration of 30%. A hard coat layer (a partially cured hard coat layer in which the thermosetting resin component is cured and the photocurable resin component is not cured) was coated with a curable resin composition for a low refractive index layer using a #3 bar coater, dried at 80°C for 1 minute to form a low refractive index layer (thickness 100 nm), and a functional film was obtained. As a curable resin composition for the low refractive index layer, a composition was used which consisted of 100 parts of a mixture of 40 parts of a urethane acrylate resin (manufactured by Mitsubishi Chemical Corporation, product name "Shiko UV-1700B", weight-average molecular weight Mw: 2000) and 60 parts of hollow silica (manufactured by JGC Catalysts & Chemicals Co., Ltd., product name "Thru-Ria A2SL-02KA", average particle size 50 nm), mixed with 10 parts of a fluorine-based antifouling additive (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KY-1203") and 3 parts of a photoinitiator (manufactured by IGM Resins BV, product name "Omnirad184"), and then diluted with propylene glycol monomethyl ether (PGM) to a solid content of 3%.

[0200] <Fabrication of resin molded body X> A resin molded body X was fabricated by plate injection molding. Specifically, a mold 11 (L1: 120 mm, W1: 120 mm, thickness: 2 mm) having a gate 12 as shown in Figure 2 was used, and as shown in Figure 3, a functional film 13 (L2: 60 mm, W2: 60 mm) was placed so that the low refractive index layer side faced the mold surface and the distance L3 from the gate 12 was 5 mm, and the top edge was covered with polyimide tape 14. PC (H2000: manufactured by Mitsubishi Engineering Plastics) was used as the injection resin, and an 80-ton injection molding machine "FN-1000" manufactured by Nissei Plastic Industrial Co., Ltd. was used as the molding machine, with the temperature conditions as follows: injection speed of 10 mm / sec, injection pressure of 160 MPa, cooling time of 20 seconds, and molding cycle of 40 seconds. Temperature conditions: Nozzle 300°C, H2 290°C, H3 280°C, H4 270°C, under hopper 50°C, mold set to 80°C (actual measurement 78°C). The resulting resin molded body was removed from the mold and exposed to a total light intensity of 230 mJ / cm² using a high-pressure mercury lamp (model number "H06-L41") manufactured by I-Graphics Co., Ltd. at room temperature. 2 The low refractive index layer was cured by irradiating it with ultraviolet light.

[0201] <Fabrication of resin molded body Y> A resin molded body Y having a three-dimensional shape was fabricated. <<Pre-molding>> The functional film was shaped using vacuum pressure forming (film temperature 120°C, mold temperature 90°C, pressure 1 MPa) to obtain a curved film with a three-dimensional shape as shown in Figures 4A and 4B. <Insert injection molding> The curved film obtained above was set in the mold of an injection molding machine (FNX180ECOJECT manufactured by Nissei Plastic Industrial Co., Ltd.), and polycarbonate resin (H2000 manufactured by Mitsubishi Engineering Plastics) was injection molded under conditions of a cylinder temperature of 260-300°C and a mold temperature of 80°C. The curved film and the polycarbonate resin were integrated to obtain a resin molded body having a three-dimensional shape as shown in Figures 5A and 5B. The resulting resin molded body was removed from the mold and exposed to a total light intensity of 230 mJ / cm² using a high-pressure mercury lamp (model number "H06-L41") manufactured by I-Graphics Co., Ltd. at room temperature. 2The low refractive index layer was cured by irradiating it with ultraviolet light.

[0202] (Examples 2-12) Functional films, resin molded articles X and Y were prepared in the same manner as in Example 1, except that the amounts of photocurable resin components and thermosetting resin components in the curable resin composition for hard coat layers were as shown in Tables 5 and 6 below.

[0203] (Example 13) Functional films, resin molded articles X and Y were prepared in the same manner as in Example 1, except that the amounts of the photocurable resin component, thermosetting resin component, and crosslinked acrylic resin particles (manufactured by Soken Chemical Co., Ltd., product name "MX-80H3wT", average particle size 0.8 μm), which are used as an anti-glare agent, were as shown in Table 6 below.

[0204] (Comparative Example 1) Functional films, resin molded articles X and Y were prepared in the same manner as in Example 1, except that an active energy ray curable resin composition was used, which was prepared by diluting the resins shown in Table 7 below, which are photocurable resin components, in methyl ethyl ketone (MEK) to a solid content concentration of 30% as the curable resin composition for the hard coat layer.

[0205] (Comparative Example 2) <Production of functional films> On one surface of an acrylic resin film obtained in the same manner as in Example 1, a coating agent shown in Table 7 below, which is a photocurable resin component, was diluted in propylene glycol monomethyl ether (PGM) to a solid content concentration of 30%. This composition was applied using a #10 bar coater, dried at 80°C for 1 minute, and then cured by ultraviolet irradiation to form a hard coat layer (thickness 3 μm). Ultraviolet irradiation was performed using a high-pressure mercury lamp (model number "H06-L41") manufactured by I-Graphics Co., Ltd., with an integrated light intensity of 230 mJ / cm². 2 I went there. The same low refractive index curable resin composition used in Example 1 was applied to the surface of the hard coat layer using a #3 bar coater and dried at 80°C for 1 minute to form a low refractive index layer (thickness 100 nm). <Fabrication of resin molded bodies X and Y> Resin molded articles X and Y were prepared in the same manner as in Example 1, except that the functional film obtained above was used.

[0206] (Comparative Examples 3-6) Functional films, resin molded articles X and Y were prepared in the same manner as in Comparative Example 2, except that the coating agents shown in Table 7 below, which are photocurable resin components, were used as curable resin compositions for the hard coat layer, each diluted in methyl ethyl ketone (MEK) to a solid content concentration of 30%.

[0207] (Comparative Example 7) <Production of functional films> On one surface of an acrylic resin film obtained in the same manner as in Example 1, a coating agent shown in Table 8 below, which is a photocurable resin component, was diluted in methyl ethyl ketone (MEK) to a solid content concentration of 30% as a hard coat layer curable resin composition. This composition was applied using a #10 bar coater, dried at 80°C for 1 minute, and then cured by ultraviolet irradiation to form a hard coat layer (thickness 3 μm). Ultraviolet irradiation was performed using a high-pressure mercury lamp (model number "H06-L41") manufactured by I-Graphics Co., Ltd., with an integrated light intensity of 230 mJ / cm². 2 I went there. On the surface of the hard coat layer, a coating agent containing a photocurable resin component (manufactured by Aica Kogyo Co., Ltd., product name "Aicatron Z-824-2") was diluted with 2-propanol (IPA) to a solid content concentration of 2.5%. This composition was applied using a #3 bar coater, dried at 80°C for 1 minute, and then cured by ultraviolet irradiation to form a low refractive index layer (thickness 100 nm). Ultraviolet irradiation was performed using a high-pressure mercury lamp (model number "H06-L41") manufactured by I-Graphics Co., Ltd., with an integrated light intensity of 230 mJ / cm². 2 I went there. <Fabrication of resin molded bodies X and Y> Resin molded articles X and Y were prepared in the same manner as in Example 1, except that the functional film obtained above was used.

[0208] (Comparative Examples 8-9) Functional films, resin molded articles X and Y were prepared in the same manner as in Comparative Example 7, except that a coating agent shown in Table 8 below, which is a photocurable resin component, was used as the curable resin composition for the low refractive index layer, and the composition was diluted with 2-propanol (IPA) to a solid content of 2.5%.

[0209] (Comparative Example 10) Functional films, resin molded articles X and Y were prepared in the same manner as in Comparative Example 7, except that a coating agent containing the photocurable resin component shown in Table 8 below (manufactured by Aica Kogyo Co., Ltd., product name "Aicatron Z-607-26HL") was used as the resin composition for the hard coat layer, diluted in methyl ethyl ketone (MEK) to a solid content concentration of 30%.

[0210] (Comparative Example 11) Functional films were prepared in the same manner as in Example 1, except that the curable resin composition for hard coat layer formation and the curable resin composition for low refractive index layer formation were cured by ultraviolet irradiation during coating. Ultraviolet irradiation was performed using a high-pressure mercury lamp (model number "H06-L41") manufactured by I-Graphics Co., Ltd., with an integrated light intensity of 230 mJ / cm². 2 I went there.

[0211] In the examples and comparative examples, the crack elongation at 120°C, Δ haze after 80% stretching at 120°C, haze, reflectance, pencil hardness, and mold adhesion were measured as described above, and the results are shown in Tables 5 to 9 below. In addition, abrasion tests were performed in the examples and comparative examples as described above, and the results are shown in Tables 5 to 9 below.

[0212] [Table 5]

[0213] [Table 6]

[0214] [Table 7]

[0215] [Table 8]

[0216] [Table 9]

[0217] As can be seen from Tables 5-6 above, the functional films of Examples 1-13 exhibited a crack elongation of over 90% at 120°C, a Δ-haze of 10% or less at 80% stretching at 120°C, no mold adhesion, no surface roughness, whitening, or peeling, and good moldability. Furthermore, they had a pencil hardness of 2H or higher, an evaluation of A or higher in abrasion tests, and good abrasion resistance. In addition, their luminous reflectance was 4.0% or less, indicating good anti-reflective and anti-glare properties.

[0218] On the other hand, in Comparative Example 1, where both the hard coat layer and the low refractive index layer were uncured, the resin molded article adhered to the mold during production, resulting in poor moldability. Comparative Examples 2 and 3, where the hard coat layer did not contain thermosetting resin components, had a pencil hardness of H or less and / or a rating of C in the abrasion test, indicating poor abrasion resistance. Comparative Examples 4-6, where the hard coat layer did not contain thermosetting resin components, had a 120°C crack elongation of 70% or less, indicating poor moldability. Comparative Examples 7-9, where both the hard coat layer and the low refractive index layer were cured, had a pencil hardness of H or less and a rating of C in the abrasion test, indicating poor abrasion resistance. Furthermore, Comparative Examples 7, 9, and 10 had a Δ-haze exceeding 10% at 120°C and 80% stretch, resulting in whitening during molding and poor moldability. Comparative Examples 10 and 11, in which both the hard coat layer and the low refractive index layer were cured, had a crack elongation of 60% or less at 120°C, a Δ-haze of over 10% at 80% stretching at 120°C, whitening occurred during molding, and the moldability was poor.

[0219] The embodiments described above are not independent of each other, and as those skilled in the art can combine as appropriate, without needing further explanation. Furthermore, components from different embodiments may be combined as appropriate. [Explanation of Symbols]

[0220] 1. Functional film (for coating resin molded articles) 2 Thermoplastic resin film 3. Hard court layer 4. Low refractive index layer 11 molds Gate 12 13. Functional films (for coating resin molded products) 14 Polyimide Tape 20. Curved film with a three-dimensional shape 30 Resin molded body having a three-dimensional shape

Claims

1. A functional film for coating a resin molded article, comprising a thermoplastic resin film and a hard coat layer and a low refractive index layer sequentially laminated on at least one side of the thermoplastic resin film, The hard coat layer is formed of a curable resin composition which is at least partially cured, and the curable resin composition comprises at least a thermosetting resin component which is cured and has at least a partially crosslinked structure. In the hard coat layer, the thermosetting resin component includes a constituent unit consisting of a reaction product of a polyisocyanate compound and a polyol compound. The low refractive index layer is formed from an uncured active energy ray curable resin composition. The refractive index of the low refractive index layer when the active energy ray curable resin composition is cured is lower than the refractive index of the hard coat layer. In the hard coat layer, if the curable resin composition includes a photocurable resin component in addition to a thermosetting resin component, the photocurable resin component remains uncured, a functional film for coating a resin molded article.

2. The thermoplastic resin film comprises an acrylic resin containing 50% by mass or more of structural units made of methyl methacrylate, and a graft copolymer containing a rubber component, as described in claim 1, for use as a coating for resin molded articles.

3. The functional film for coating a resin molded article according to claim 1 or 2, wherein in the hard coat layer, the curable resin composition includes a photocurable resin component in addition to a thermosetting resin component, and the photocurable resin component is uncured.

4. The functional film for coating a resin molded article according to any one of claims 1 to 3, wherein the hard coat layer comprises a photocurable urethane (meth)acrylate compound in the curable resin composition.

5. In the low refractive index layer, the active energy ray curable resin composition comprises a photocurable resin component and a refractive index adjusting agent, as described in any one of claims 1 to 4, for use as a coating for a resin molded article.

6. The functional film for coating a resin molded article according to claim 5, wherein the refractive index adjusting agent contains hollow silica with an average particle diameter of 100 nm or less, and the low refractive index layer contains 30% by mass or more of hollow silica with an average particle diameter of 100 nm or less, based on 100% by mass of the total of the photocurable resin component and the refractive index adjusting agent.

7. A method for manufacturing a functional film for coating a resin molded article according to any one of claims 1 to 6, Step 1 involves applying a curable resin composition containing at least a thermosetting resin component onto a thermoplastic resin film to form a coating film, and curing the thermosetting resin component to form a hard coat layer that is at least partially cured, and The process includes step 2 of applying an active energy ray curable resin composition onto the hard coat layer to form a low refractive index layer. A method for manufacturing a functional film for coating a resin molded article, wherein in step 2 and subsequent steps, the active energy ray-curable resin composition constituting the low refractive index layer is not irradiated with active energy rays.

8. A method for producing a functional film for coating a resin molded article according to claim 7, wherein the curable resin composition used in step 1 comprises only a thermosetting resin component, and a hard coat layer is formed by curing the thermosetting resin component.

9. The method for producing a functional film for coating a resin molded article according to claim 7 or 8, wherein the curable resin composition used in step 1 includes a thermosetting resin component and a photocurable resin component, and a hard coat layer is formed by curing the thermosetting resin component, and no irradiation with active energy rays is performed in step 1 and subsequent steps.

10. A resin molded article comprising a thermoplastic resin substrate and a functional film for coating a resin molded article according to any one of claims 1 to 6, wherein the functional film for coating a resin molded article covers at least a portion of the thermoplastic resin substrate, and a low refractive index layer on at least one side of the functional film for coating a resin molded article is located on the outermost surface of the resin molded article.

11. The resin molded article according to claim 10, which is used for one or more selected from the group consisting of automotive interior materials, automotive exterior materials, optical components, and home appliance components.

12. A method for manufacturing a resin molded article according to claim 10 or 11, A method for manufacturing a resin molded article, comprising an injection molding step of placing a functional film for coating a resin molded article according to any one of claims 1 to 6 inside an injection molding die so that at least one low refractive index layer faces the injection molding die, and then injection molding a thermoplastic resin.

13. The method for manufacturing a resin molded article according to claim 12, wherein the functional film for coating the resin molded article is heated and molded into a predetermined shape, and then placed in an injection molding die.

14. A method for manufacturing a resin molded article according to claim 12 or 13, further comprising a post-curing step of irradiating the resin molded article obtained in the injection molding step with active energy rays to cure the low refractive index layer.

Images