Film insert molded article and method for producing same

Abstract

According to one embodiment of the present invention, provided is a film insert molded article comprising: an insert film including a base material layer and an after-cure-type uncured hard coat layer; and a thermoplastic resin layer located on the base material layer side of the insert film. The uncured hard coat layer has an uneven shape on a surface thereof on the side opposite the side where the base material layer is located.

Description

Film insert molding and its manufacturing method

[0001] The present invention relates to a film insert molding and a method for producing the same.

[0002] BACKGROUND ART Resin film laminates having a hard coat layer (hard coat films) have been used in various fields, and are useful, for example, as front and back panels of mobile devices, and automobile interior components (Patent Document 1).

[0003] A hard coat layer that serves to protect the surface of a laminate is required to have a certain level of hardness and scratch resistance. However, in a typical hard coat film, there is a trade-off between formability and chemical resistance and / or scratch resistance. That is, usually, increasing formability results in a decrease in chemical resistance and / or scratch resistance, and improving chemical resistance and / or scratch resistance results in a deterioration in formability. To solve this problem, an after-cure type laminate film has been proposed in which a hard coat liquid is applied to a substrate and dried to form a hard coat layer, which is then molded without being cured, and the hard coat layer is cured by UV irradiation or the like after molding (Patent Documents 2 and 3).

[0004] Furthermore, environmentally friendly film insert molding has been attracting attention as a molding method. Film insert molding allows injection of resin from the side opposite the hard coat layer of an insert film previously set in a mold, resulting in a resin molded product with a hard coat layer on its surface. This imparts the properties of the hard coat layer (e.g., chemical resistance and scratch resistance) to the resin molded product. Furthermore, by creating irregularities on the surface of the hard coat layer, a desired pattern can be imparted to the surface of the resin molded product, and various methods for this have been investigated.

[0005] Patent Publication No. 2017-508828 International Publication No. 2020 / 031967 International Publication No. 2021 / 193809

[0006] The present invention aims to provide a film insert molding having an uncured hard coat layer with an uneven surface, which exhibits excellent retention of the uneven surface after the hard coat layer is cured, and a method for producing the same.

[0007] As a result of intensive research, the present inventors have found that in a film insert molding produced using an insert film having an after-cure type uncured hard coat layer, when an uneven shape is imparted to the surface of the hard coat layer while it is in an uncured state, the uneven shape is excellently retained after the hard coat layer is cured. The present invention is, for example, as follows. [1] A film insert molding comprising an insert film having a base layer and an after-cure type uncured hard coat layer, and a thermoplastic resin layer located on the base layer side of the insert film, wherein the uncured hard coat layer has an uneven shape on the surface opposite to the side on which the base layer is located, and the uneven shape satisfies the following conditions (i) and / or (ii): (i) The ten-point region height of the surface having the uneven shape of the hard coat layer after curing the uncured hard coat layer is S10z ０ The uncured hard coat layer was cured and then subjected to an environmental test at a temperature of 85° C. and a humidity of 85% for 1000 hours. The height of the ten-point region of the surface having the concave-convex shape of the hard coat layer after the test was defined as S10z １ In this case, the shape retention rate {(S10z １ / S10z ０ (ii) the ten-point region height of the surface having the uneven shape of the hard coat layer after curing the uncured hard coat layer is S10z ０ The height of the ten-point region of the surface having the concave-convex shape of the hard coat layer after the uncured hard coat layer is cured and then annealed at a temperature of 120° C. for 1 hour is defined as S10z ２ In this case, the shape retention rate {(S10z ２ / S10z ０[2] After the uncured hard coat layer is cured, the ten-point region height (S10z ０ ) is 0.5 μm or more. [3] The film insert molded article according to [1] or [2], wherein the uncured hard coat layer contains an active energy ray-curable resin having a (meth)acryloyl group. [4] The film insert molded article according to [3], wherein the active energy ray-curable resin having a (meth)acryloyl group has a (meth)acrylate skeleton. [5] The film insert molded article according to any one of [1] to [4], wherein the uncured hard coat layer contains nanoparticles. [6] The film insert molded article according to any one of [1] to [5], wherein the uncured hard coat layer contains a leveling agent. [7] After curing the uncured hard coat layer, the nanoindenter hardness of the cured hard coat layer is 400 N / mm ２ The film insert molded article according to any one of [1] to [6], wherein the hard coat layer has a haze of 1% or more after curing the uncured hard coat layer. [8-1] The film insert molded article according to any one of [1] to [8], wherein the base layer comprises a polycarbonate resin. [9] A film insert cured product obtained by curing the hard coat layer in the film insert molded article according to any one of [1] to [8-1].

[10] A method for producing a film insert molding, comprising: preparing an insert film having a base layer and an after-cure type uncured hard coat layer; and injecting a molten thermoplastic resin onto the base layer side of the insert film, and imparting an uneven shape to the surface of the uncured hard coat layer opposite to the side where the base layer is located, to obtain a film insert molding, wherein the uneven shape satisfies the following conditions (i) and / or (ii): (i) The ten-point region height of the surface having the uneven shape of the hard coat layer after curing the uncured hard coat layer is S10z ０The uncured hard coat layer was cured and then subjected to an environmental test at a temperature of 85° C. and a humidity of 85% for 1000 hours. The height of the ten-point region of the surface having the concave-convex shape of the hard coat layer after the test was defined as S10z １ In this case, the shape retention rate {(S10z １ / S10z ０ (ii) the ten-point region height of the surface having the uneven shape of the hard coat layer after curing the uncured hard coat layer is S10z ０ The height of the ten-point region of the surface having the concave-convex shape of the hard coat layer after the uncured hard coat layer is cured and then annealed at a temperature of 120° C. for 1 hour is defined as S10z ２ In this case, the shape retention rate {(S10z ２ / S10z ０ ) × 100} is 80% or more.

[11] The method according to

[10] , further comprising curing the uncured hard coat layer after providing the unevenness on the uncured hard coat layer.

[0008] According to the present invention, it is possible to provide a film insert molding having an uncured hard coat layer with an uneven shape on the surface, which has excellent retention of the uneven shape after the hard coat layer is cured, and a method for producing the same.

[0009] Hereinafter, embodiments of the present invention will be described in detail. According to one embodiment, the film insert molding of the present invention comprises an insert film having a substrate layer and an after-cure type uncured hard coat layer, and a thermoplastic resin layer located on the substrate layer side of the insert film. The uncured hard coat layer has an uneven shape on the surface opposite to the side where the substrate layer is located, and the uneven shape satisfies the following conditions (i) and / or (ii): (i) The ten-point region height of the surface having the uneven shape of the hard coat layer after curing the uncured hard coat layer is S10z ０ The uncured hard coat layer was cured and then subjected to an environmental test at a temperature of 85°C and a humidity of 85% for 1000 hours. The height of the ten-point region on the surface having the concave-convex shape of the hard coat layer was then defined as S10z １In this case, the shape retention rate {(S10z １ / S10z ０ (ii) the ten-point region height of the surface having the uneven shape of the hard coat layer after curing the uncured hard coat layer is S10z ０ The height of the ten-point region of the surface having the uneven shape of the hard coat layer after the uncured hard coat layer is cured and then annealed at a temperature of 120° C. for 1 hour is defined as S10z ２ In this case, the shape retention rate {(S10z ２ / S10z ０ ) × 100} is 80% or more.

[0010] The present inventors have found that in a film insert molding produced using an insert film having an after-cure type uncured hard coat layer, when an uneven shape (pattern) is imparted to the surface of the hard coat layer while the hard coat layer is still uncured, the uneven shape is well retained after the hard coat layer is cured. In particular, it has been found that the uneven shape is largely retained even when the film insert molding after the hard coat layer is cured is placed at a relatively high temperature.

[0011] The reason why such an effect is obtained is unclear, but is presumed to be as follows. When a roughened shape is imparted to a hard coat layer after it has been cured, residual stress is generated by forcibly applying stress to a hard coat layer with a certain hardness to impart the roughened shape. Therefore, when placed under high-temperature conditions such as annealing treatment or environmental testing, the hard coat layer moves in a direction that relieves the residual stress, making it difficult to maintain the roughened shape. On the other hand, when a roughened shape is imparted to a hard coat layer in an uncured state and then cured, the shape is fixed by curing the layer with the roughened shape imparted. Therefore, it is thought that the roughened shape is less susceptible to heat and is maintained even when placed under high-temperature conditions.

[0012] Furthermore, when a film insert molding is produced by injection molding, for example, an insert film having an after-cure uncured hard coat layer is used, and a molten thermoplastic resin is injected onto the side of the insert film opposite the hard coat layer, imparting a textured pattern to the surface of the uncured hard coat layer, thereby obtaining a film insert molding product while successfully transferring a pattern to the hard coat layer surface. Furthermore, since the textured pattern is imparted to the hard coat layer while it is still uncured, there is also the advantage that the textured pattern can be easily imparted with less energy than when the textured pattern is imparted to the hard coat layer after curing.

[0013] The components, manufacturing method, physical properties, uses, etc. of the film insert molding according to the embodiment will be described in detail below. 1. Insert Film The insert film used in the manufacture of the film insert molding according to the embodiment comprises a substrate layer and an after-cure uncured hard coat layer. The insert film may consist of only the substrate layer and the uncured hard coat layer, or may comprise other layers. It is preferable that the hard coat layer and the substrate layer are laminated so as to be in contact with each other, but this is not limited to this embodiment, and other layers may be disposed between the substrate layer and the hard coat layer. Examples of other layers include, but are not limited to, a primer layer.

[0014] An insert film is manufactured as follows. First, a material such as a resin composition is processed into a layer (sheet) using a conventional method to manufacture a substrate layer. For example, this can be a method using extrusion molding, cast molding, or the like. An example of extrusion molding is a method in which pellets, flakes, or powder of the resin composition are melted and kneaded in an extruder, then extruded through a T-die or the like, and the resulting semi-molten sheet is cooled and solidified while being clamped between rolls to form a sheet. For example, in a configuration in which the substrate layer and the hard coat layer are in contact with each other, the insert film is manufactured by applying a hard coat composition to the substrate layer.

[0015] [1] The substrate layer in the substrate layer insert film preferably contains a resin, more preferably a thermoplastic resin. The type of thermoplastic resin is not particularly limited, but various resins such as polycarbonate (PC) resin, acrylic resins such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, and aromatic polyamide are used. Of the above-mentioned thermoplastic resins, the substrate layer preferably contains at least a polycarbonate resin, and more preferably an aromatic polycarbonate resin from the viewpoint of toughness and heat resistance.

[0016] The type of polycarbonate resin is not particularly limited as long as it contains a carbonate bond -[O-R-OCO]- (R is an aliphatic group, an aromatic group, or a group containing both an aliphatic group and an aromatic group, and may have a linear or branched structure) in the molecular main chain. Among these, polycarbonate resins having a bisphenol skeleton are preferred, and bisphenol A polycarbonate resins having a bisphenol A skeleton or bisphenol C polycarbonate resins having a bisphenol C skeleton are particularly preferred. As the polycarbonate resin, a mixture of bisphenol A polycarbonate resin and bisphenol C polycarbonate resin, or a copolymer of bisphenol A and bisphenol C may be used. In order to improve the hardness of the base layer, it is preferable to use a bisphenol C polycarbonate resin (for example, a polycarbonate resin made of bisphenol C, a mixture of bisphenol A polycarbonate resin and bisphenol C polycarbonate resin, or a copolymer of bisphenol A and bisphenol C).

[0017] Acrylic resins are also preferred as thermoplastic resins contained in the substrate layer. Specific examples include, but are not limited to, homopolymers of various (meth)acrylic acid esters, such as polymethyl methacrylate (PMMA) and methyl methacrylate (MMA), or copolymers of PMMA, MMA, or their constituent monomers with one or more other monomers. A mixture of multiple resins can also be used. Among these, (meth)acrylates containing a cyclic alkyl structure, which have low birefringence, low moisture absorption, and excellent heat resistance, are preferred. Examples of such (meth)acrylates include, but are not limited to, ACRYPET (manufactured by Mitsubishi Rayon Co., Ltd.), DELPET (manufactured by Asahi Kasei Chemicals Corporation), and PARAPET (manufactured by Kuraray Co., Ltd.).

[0018] The substrate layer may also be formed of multiple layers having different compositions. For example, a substrate layer consisting of the above-mentioned polycarbonate resin layer and an acrylic resin layer can also be used. The substrate layer consisting of multiple layers is not limited to a two-layer structure and may be three or more layers. For example, a substrate layer including a polycarbonate resin layer and an acrylic resin layer can be used. By using such a substrate layer, it is possible to maintain the thermoformability of the substrate layer while improving the surface hardness of the substrate layer. When a substrate layer including a polycarbonate resin layer and an acrylic resin layer is used, it is preferable that a hard coat layer be laminated on the acrylic resin side. This is because by laminating a hard coat layer on the acrylic resin side, a laminate can be obtained that has improved properties such as pencil hardness in addition to the properties derived from the hard coat layer.

[0019] The viscosity average molecular weight of the thermoplastic resin contained in the substrate layer is preferably 15,000 to 40,000, more preferably 20,000 to 35,000, and even more preferably 22,500 to 25,000.

[0020] The substrate layer may also contain additives as components other than the thermoplastic resin. Examples of additives include heat stabilizers, antioxidants, flame retardants, flame retardant assistants, ultraviolet absorbers, release agents, and colorants. The substrate layer may contain one or more of these additives. Furthermore, the substrate layer may also contain antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, and the like.

[0021] The content of the thermoplastic resin in the substrate layer is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more, relative to the mass of the substrate layer. Furthermore, in a substrate layer primarily composed of polycarbonate resin, the proportion of the polycarbonate resin in the substrate layer is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. In a substrate layer primarily composed of acrylic resin, the proportion of the acrylic resin in the substrate layer is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0022] The thickness of the substrate layer is not particularly limited, but is preferably 0.1 mm to 1.0 mm. The thickness of the substrate layer is more preferably 0.2 mm to 0.8 mm, and even more preferably 0.3 mm to 0.7 mm. By using a substrate layer with such a thickness, a film with excellent formability and hardness can be realized. When the substrate layer is composed of multiple layers, the thickness of each layer may be within the above-mentioned range, or the thickness of the entire substrate layer may be within the above-mentioned range.

[0023] [2] The hard coat layer in the hard coat layer insert film is an after-cure type uncured hard coat layer. The material is not particularly limited as long as it has such properties, but it preferably contains, for example, an active energy ray curable resin or a thermosetting resin. When the hard coat layer contains such a curable resin, it is desirable that the hard coat layer can be cured without using a curing agent. The hard coat layer may further contain various additives to improve its properties, such as nanoparticles, photopolymerization initiators, leveling agents, light stabilizers, polymerization inhibitors, etc.

[0024] (1) The curable resin hard coat layer preferably contains an active energy ray-curable resin or a thermosetting resin, and more preferably contains an active energy ray-curable resin. Any resin having active energy ray curability can be used as the active energy ray-curable resin. Examples of active energy ray-curable resins include (meth)acrylate polymers, more specifically, epoxy (meth)acrylate polymers, urethane (meth)acrylate polymers, and polyester (meth)acrylate polymers. In particular, polymers having a (meth)acryloyl group, such as (meth)acrylate polymers having a (meth)acryloyl group, are preferably used. More specifically, examples include epoxy (meth)acrylate polymers having a (meth)acryloyl group, urethane (meth)acrylate polymers having a (meth)acryloyl group, and polyester (meth)acrylate polymers having a (meth)acryloyl group. Active energy ray-curable resins are readily available from various companies. Hereinafter, polymers having a (meth)acryloyl group will also be referred to as (meth)acryloyl polymers. In this specification, the term "(meth)acrylate" refers to methacrylate and / or acrylate, and the term "(meth)acryloyl group" refers to methacryloyl group and / or acryloyl group. Other similar descriptions are also interpreted as above.

[0025] The epoxy (meth)acrylate polymer active energy ray curable resin may be, for example, an epoxy (meth)acrylate polymer. Among them, an epoxy (meth)acrylate polymer having a (meth)acryloyl group is preferred. A synthesis example of an epoxy (meth)acrylate is shown in formula (1). Epoxy (meth)acrylate can be obtained by adding acrylic acid or methacrylic acid having an unsaturated bond to an epoxy compound. (In formula (1), R is an alkyl group having 1 to 12 carbon atoms or a hydrogen atom, and the alkyl group may be substituted with one or more substituents selected from an epoxy group, a hydroxyl group, an acryloyl group, and a methacryloyl group; and R' is a methyl group or a hydrogen atom.)

[0026] An epoxy (meth)acrylate polymer can be obtained, for example, by copolymerizing (meth)acrylic acid and (meth)acrylic acid glycidyl ether to synthesize an epoxy resin having a (meth)acrylate skeleton, and then adding acrylic acid, methacrylic acid, etc. to the epoxy resin. An example of the synthesis is shown in formula (2).

[0027] Suitable epoxy (meth)acrylate polymers include, for example, those having repeating units represented by formula (I): In formula (I), m is an alkylene group having 1 to 4 carbon atoms or a single bond; n is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom; p is a single bond or an alkylene group having 1 or 2 carbon atoms; and q is an alkyl group having 1 to 12 carbon atoms which may have one or more substituents selected from an epoxy group, a hydroxyl group, an acryloyl group, and a methacryloyl group, or a hydrogen atom.

[0028] In the above formula (I), preferably, m is an alkylene group having 1 or 2 carbon atoms; n is an alkyl group having 1 or 2 carbon atoms; p is a single bond or a methylene group; and q is an alkyl group having 1 to 6 carbon atoms which may have one or more substituents selected from an epoxy group, a hydroxyl group, and an acryloyl group, or a hydrogen atom. More preferably, m is a methylene group; n is a methyl group; p is a single bond; and q is an alkyl group having 5 or less carbon atoms which may have one or more substituents selected from a methyl group and an epoxy group, or an alkyl group having 8 or less carbon atoms which may have one or more substituents selected from a hydroxyl group and an acryloyl group.

[0029] Specific examples of the repeating unit represented by formula (I) include those represented by the following formulae (II-a), (II-b) and (II-c).

[0030] When the epoxy (meth)acrylate polymer contains repeating units of the above formulas (II-a), (II-b), and (II-c), the proportion of repeating units of formula (II-a) is preferably 30 to 85 mol%, more preferably 40 to 80 mol%, based on the total number of moles of repeating units of formula (II-a), repeating units of formula (II-b), and repeating units of formula (II-c). The proportion of repeating units of formula (II-b) is preferably 5 to 30 mol%, more preferably 10 to 25 mol%, based on the total number of moles. Furthermore, the proportion of repeating units of formula (II-c) is preferably 10 to 40 mol%, more preferably 10 to 35 mol%, based on the total number of moles. The molar ratio of the repeating unit of formula (II-a), the repeating unit of formula (II-b), and the repeating unit of formula (II-c) is preferably 4.5 to 5.5:1.5 to 2.5:2.5 to 3.5, for example, about 5:2:3.

[0031] Urethane (meth)acrylate polymer The polymer having a (meth)acryloyl group may be a urethane (meth)acrylate polymer. Specific examples include the urethane (meth)acrylate polymers described below. A preferred specific example of the urethane (meth)acrylate polymer is a urethane (meth)acrylate polymer containing a structural unit derived from an isocyanate compound and a structural unit derived from a compound having a (meth)acryloyloxy group and a hydroxyl group.

[0032] Isocyanate Compound The isocyanate compound is, for example, an aromatic isocyanate which may have an alkyl substituent (such as a methyl group), preferably an aromatic isocyanate having 6 to 16 carbon atoms, more preferably an aromatic isocyanate having 7 to 14 carbon atoms, and particularly preferably an aromatic isocyanate having 8 to 12 carbon atoms. Although aromatic isocyanates are preferred as the isocyanate compound, aliphatic and alicyclic isocyanates can also be used.

[0033] Specific examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethane), Examples of the polyisocyanate include polyisocyanates such as methyl cyclohexane, phenylene diisocyanate, lysine diisocyanate, lysine triisocyanate, and naphthalene diisocyanate, trimer compounds or tetramer compounds of these polyisocyanates, biuret-type polyisocyanates, water-dispersible polyisocyanates (for example, "AQUANATE 100," "AQUANATE 110," "AQUANATE 200," and "AQUANATE 210," manufactured by Nippon Polyurethane Industry Co., Ltd.), and reaction products of these polyisocyanates with polyols.

[0034] Among these isocyanate compounds, particularly preferred are diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, a trimethylolpropane (TMP) adduct of toluene diisocyanate, an isocyanate of toluene diisocyanate, a TMP adduct of xylene diisocyanate, and dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), and the like, which are represented by the following formulas.

[0035] Examples of acrylate compounds for forming a urethane (meth)acrylate polymer containing a molecular structure of an acrylate compound cyclic skeleton include pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPPA), hydroxypropyl (meth)acrylate (hydroxypropyl acrylate; HPA), etc. Furthermore, as the acrylate compound, a compound having a (meth)acryloyloxy group and a hydroxyl group, for example, a monofunctional (meth)acrylic compound having a hydroxyl group, can also be used.

[0036] Examples of the monofunctional (meth)acrylic compound having a hydroxyl group include hydroxyl group-containing mono(meth)acrylates {for example, hydroxyalkyl(meth)acrylates [for example, hydroxy C2-20 alkyl-(meth)acrylates such as 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, and 6-hydroxyhexyl(meth)acrylate, preferably hydroxy C2-12 alkyl-(meth)acrylate, more preferably hydroxy C2-6 alkyl-(meth)acrylate], polyalkylene glycol mono(meth)acrylates [for example, poly C2-4 alkylene glycol mono(meth)acrylates such as diethylene glycol mono(meth)acrylate and polyethylene glycol mono(meth)acrylate], and hydroxyalkylene glycol mono(meth)acrylates having three or more hydroxy groups. Examples of suitable acrylate compounds include mono(meth)acrylates of polyols having a silyl group [e.g., alkane polyol mono(meth)acrylates such as glycerin mono(meth)acrylate and trimethylolpropane mono(meth)acrylate, and mono(meth)acrylates of polymers of alkane polyols such as diglycerin mono(meth)acrylate], N-hydroxyalkyl(meth)acrylamides (e.g., N-hydroxy C1-4 alkyl(meth)acrylamides such as N-methylol(meth)acrylamide and N-(2-hydroxyethyl)(meth)acrylamide), and adducts of these compounds (e.g., hydroxyalkyl(meth)acrylates) to which lactones (e.g., C4-10 lactones such as ε-caprolactone) have been added (e.g., adducts in which about 1 to 5 moles of lactone have been added). These acrylate compounds may be used alone or in combination of two or more.

[0037] A preferred example of the compound for forming a (meth)acryloyloxy group is 2-hydroxy-3-phenoxypropyl acrylate. Among the above, pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPPA), and hydroxypropyl (meth)acrylate (hydroxypropyl acrylate; HPA) are particularly preferred.

[0038] Copolymer of Isocyanate Compound and Acrylate Compound

[0043] Specific preferred examples of a copolymer of an isocyanate compound and an acrylate compound, i.e., a urethane (meth)acrylate polymer, include a copolymer of xylylene diisocyanate (XDI) and pentaerythritol triacrylate (PETA), a copolymer of XDI and dipentaerythritol pentaacrylate (DPPA), a copolymer of dicyclohexylmethane diisocyanate (H12MDI) and PETA, a copolymer of isophorone diisocyanate (IPDI) and PETA, and a copolymer of XDI and hydroxypropyl (meth)acrylate (HPA).

[0039] Further, examples of the urethane (meth)acrylate polymer having a molecular structure with a cyclic skeleton include copolymers using polyol compounds in addition to the above-mentioned isocyanate compounds and acrylate compounds. Polyol compounds (polyhydric alcohols) are compounds having two or more hydroxyl groups in one molecule, and examples thereof include the following:That is, examples of polyol compounds include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyl- Dihydric alcohols such as dimethylmethylene glycol, tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, neopentyl glycol, and hydroxypivalic acid neopentyl glycol ester; and polylactones obtained by adding lactones such as ε-caprolactone to these dihydric alcohols. diols; ester diols such as bis(hydroxyethyl) terephthalate; polyether diols such as alkylene oxide adducts of bisphenol A, polyethylene glycol, polypropylene glycol, and polybutylene glycol; α-olefin epoxides such as propylene oxide and butylene oxide; monoepoxy compounds such as Cardura E10 [manufactured by Shell Chemical Co., Ltd., glycidyl ester of synthetic highly branched saturated fatty acid]; trihydric or higher alcohols such as glycerin, trimethylolpropane, trimethylolethane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, and mannite; polylactone polyols obtained by adding lactones such as ε-caprolactone to these trihydric or higher alcohols; and alicyclic polyhydric alcohols such as 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F.

[0040] As the polyol constituent unit, a urethane (meth)acrylate polymer containing a constituent unit derived from tricyclodidecanedimethanol (TCDDM) represented by the following formula is preferably used.

[0041] Specific preferred examples of the urethane (meth)acrylate polymer containing a polyol structural unit include a copolymer of tricyclodidecanedimethanol (TCDDM), IPDI, and PETA, a copolymer of TCDDM, H12MDI, and PETA, a copolymer of these copolymers in which DPPA is used instead of or together with PETA, and a copolymer of TCDDM, xylylene diisocyanate (XDI), and hydroxypropyl (meth)acrylate (HPA).

[0042] The urethane (meth)acrylate polymer containing a structural unit derived from a polyol compound, in addition to an isocyanate compound and a compound having a (meth)acryloyloxy group and a hydroxyl group, preferably contains at least a component represented by the following formula (i): (A3)-O(OC)HN-A2-HN(OC)-O-A1-O-(CO)NH-A2-NH-(CO)O-(A3) (i) (In formula (i), A1 represents an alkylene group derived from the above-mentioned polyol compound, A2 represents each independently an alkylene group derived from the above-mentioned isocyanate compound, and A3 represents each independently an alkyl group derived from the above-mentioned compound having a (meth)acryloyloxy group and a hydroxyl group. An example of a compound for forming A3 is 2-hydroxy-3-phenoxypropyl acrylate.

[0043] Further specific examples of urethane (meth)acrylate polymers include the following compounds containing structural units derived from ethylene glycol, pentaerythritol triacrylate, and isophorone diisocyanate: In the following formula, n is an integer of 0 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

[0044] In the urethane (meth)acrylate polymer, the ratio of the structural units derived from the compound having a (meth)acryloyloxy group and a hydroxyl group to the structural units derived from the isocyanate compound is preferably 99:1 to 30:70 (weight ratio), more preferably 97:3 to 60:40, and even more preferably 95:5 to 80:20.

[0045] (Acrylate-Containing Urethane (Meth)acrylate Polymer) A preferred example of the urethane (meth)acrylate polymer includes one containing a structural unit derived from a urethane (meth)acrylate and a structural unit derived from a (meth)acrylate. A more preferred example of such a urethane (meth)acrylate polymer includes one containing a structural unit derived from a hexafunctional urethane (meth)acrylate and a structural unit derived from a difunctional (meth)acrylate.

[0046] (Hexafunctional) Urethane Acrylate As described above, the urethane (meth)acrylate polymer preferably contains a structural unit derived from a urethane (meth)acrylate, particularly a hexafunctional urethane (meth)acrylate. Preferred examples of hexafunctional urethane acrylates include those represented by the following formulas: a reaction product of dicyclohexylmethane diisocyanate (H12MDI) and pentaerythritol triacrylate (PETA), a reaction product of isophorone diisocyanate (IPDI) and PETA, and the like. Specific examples of preferred products of these hexafunctional urethane acrylates include UN-3320HC (a reaction product of H12MDI and PETA: manufactured by Negami Chemical Industrial Co., Ltd.), CN-968 (a reaction product of IPDI and PETA: manufactured by Sartomer Japan Co., Ltd.), and CN-975 (manufactured by Sartomer Japan Co., Ltd.).

[0047] (Meth)acrylate (Bifunctional (meth)acrylate, etc.) The (meth)acrylate structural unit that can constitute the urethane (meth)acrylate polymer is preferably a structural unit derived from a compound having 4 to 20 carbon atoms, which contains at least one (meth)acryloyloxy group and at least one vinyl ether group, and which may have a substituent. The number of carbon atoms in the (meth)acrylate is preferably 6 to 18, and more preferably 8 to 16. Examples of the substituent on the (meth)acrylate include alkyl groups. In addition, the (meth)acrylate is preferably bifunctional. For example, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate [2-(2-vinyloxyethoxy)ethyl acrylate: VEEA] of the following formula is suitably used as the (meth)acrylate. (In the above formula, R is a hydrogen atom or a methyl group.)

[0048] In the urethane (meth)acrylate polymer, the ratio of the structural units derived from the urethane acrylate to the structural units derived from the (meth)acrylate is preferably 99:1 to 30:70 (weight ratio), more preferably 97:3 to 60:40, and even more preferably 95:5 to 80:20.

[0049] (Fluorine-Containing Urethane (Meth)acrylate Polymer) A fluorine-containing urethane acrylate polymer may be used as the (meth)acrylate polymer. The fluorine-containing urethane acrylate polymer preferably contains at least a component represented by the following formula (ii): (A3)-O(OC)HN-A2-HN(OC)-O-A1-O-(CO)NH-A2-NH-(CO)O-(A3) (ii) In the above formula (ii), A1 is preferably an optionally substituted alkylene group derived from a fluorine-containing diol having 8 or less carbon atoms, and the number of carbon atoms is preferably 6 or less, for example 1 to 4. Examples of the substituent contained in the alkylene group of A1 include an alkyl group.

[0050] In the above formula (ii), A2 are each independently an alkylene group derived from an aliphatic or alicyclic isocyanate having 4 to 20 carbon atoms, which may have a substituent. The number of carbon atoms in A2 is preferably 6 to 16, and more preferably 8 to 12. Examples of the substituent on the alkylene group in A2 include an alkyl group. Furthermore, examples of the alicyclic isocyanate that forms A2 include isophorone diisocyanate of the following formula:

[0051] In the above formula (ii), A3 is independently an alkyl group having 4 to 30 carbon atoms that contains at least one (meth)acryloyloxy group and may further have a substituent. The number of carbon atoms in A3 is preferably 6 to 20, and more preferably 8 to 16. Examples of the substituent on the alkyl group in A3 include branched alkyl groups. A3 preferably contains at least two (meth)acryloyloxy groups, and may contain, for example, three (meth)acryloyloxy groups. Furthermore, A3 is derived, for example, from pentaerythritol triacrylate of the following formula:

[0052] The fluorine-containing urethane acrylate polymer is preferably one formed from the above-mentioned compounds, and the fluorine-containing urethane acrylate includes, for example, a compound represented by the following formula (IV).

[0053] Polyester (meth)acrylate polymer The polymer having a (meth)acryloyl group may be a polyester (meth)acrylate polymer. Examples of polyester (meth)acrylate polymers include polymers obtained by a dehydration condensation reaction of (meth)acrylic acid, a polybasic carboxylic acid (anhydride), and a polyol. Examples of polybasic carboxylic acid (anhydride) used in such a dehydration condensation reaction include succinic acid (anhydride), adipic acid, maleic acid (anhydride), itaconic acid (anhydride), trimellitic acid (anhydride), pyromellitic acid (anhydride), hexahydrophthalic acid (anhydride), phthalic acid (anhydride), isophthalic acid, and terephthalic acid. Examples of polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0054] Specific examples of polyester (meth)acrylate polymers include Aronix M-6100, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8530, and Aronix M-8050 (all trade names of polyester (meth)acrylate oligomers manufactured by Toagosei Co., Ltd.), Laromer PE44F, Laromer LR8907, Laromer PE55F, Laromer PE46T, and Laromer LR8800 (all trade names of polyester (meth)acrylate oligomers manufactured by BASF), Ebecryl 80, Ebecryl 657, Ebecryl 800, Ebecryl 450, and Ebecryl 657. 1830, Ebecryl 584 (all of which are trade names of polyester (meth)acrylate oligomers manufactured by Daicel U.C.B. Co., Ltd.), Photomer RCC13-429, Photomer 5018 (all of which are trade names of polyester (meth)acrylate oligomers manufactured by San Nopco Ltd.), and the like.

[0055] Other active energy ray-curable resins: As the active energy ray-curable resin, (meth)acrylate polymers other than those mentioned above can be used, such as (meth)acrylate polymers that do not contain a (meth)acryloyl group or (meth)acrylate polymers that do not contain a (meth)acrylate skeleton. Furthermore, as the active energy ray-curable resin, compounds other than (meth)acrylate compounds, such as epoxy compounds and oxetane compounds, can also be used.

[0056] The hard coat layer may contain one type of resin or two or more types of resins. The content of the resin in the hard coat layer is preferably 40 to 99 parts by weight, more preferably 50 to 95 parts by weight, and even more preferably 60 to 90 parts by weight, based on 100 parts by weight of the total of the resin and the nanoparticles.

[0057] When a polymer having a (meth)acryloyl group, preferably a (meth)acrylate polymer having a (meth)acryloyl group, is used as the active energy ray-curable resin, the polymer preferably has a (meth)acrylic equivalent of 200 to 700 g / eq. The (meth)acrylic equivalent of the polymer having a (meth)acryloyl group is more preferably 250 to 700 g / eq, even more preferably 300 to 600 g / eq, and particularly preferably 360 to 550 g / eq. Here, the (meth)acrylic equivalent (g / eq) refers to the molecular weight per (meth)acryloyl group, defined as [molecular weight / number of (meth)acryloyl groups]. For example, using a polymer having a (meth)acrylic equivalent of 250 to 700 g / eq can provide a hard coat layer that is excellent in both fingerprint wiping ability and scratch resistance. The (meth)acrylate polymer as the active energy ray-curable resin preferably has a weight average molecular weight of 5,000 to 200,000. The weight average molecular weight of the (meth)acrylate polymer is preferably 10,000 to 150,000, more preferably 15,000 to 100,000, and even more preferably 20,000 to 50,000.

[0058] The weight-average molecular weight can be measured based on the description in paragraphs

[0061] to

[0064] of JP-A-2007-179018. Details of the measurement method are shown below.

[0059] That is, first, a calibration curve showing the relationship between elution time and molecular weight of the polymer is prepared by a universal calibration method using polystyrene as a standard polymer. Then, the elution curve (chromatogram) of the (meth)acrylate polymer is measured under the same conditions as in the case of the above-mentioned calibration curve. Furthermore, the weight average molecular weight (Mw) is calculated from the elution time (molecular weight) of the polycarbonate resin and the peak area (number of molecules) at that elution time. The weight average molecular weight is expressed by the following formula (A), where Ni means the number of molecules having a molecular weight Mi. Mw = Σ(NiMi ２ ) / Σ(NiMi)...(A)

[0060] A hard coat layer containing a (meth)acrylate polymer having the above-described (meth)acrylic equivalent and weight-average molecular weight exhibits excellent tack-free properties before curing and excellent scratch resistance after curing, and also allows for successful curing and polymerization reactions. Furthermore, the use of a polymer having a (meth)acryloyl group in the hard coat layer improves tack-free properties (anti-stickiness), preventing deterioration of the appearance even when thermoforming is performed with a protective film attached. This is because the protective film can be easily peeled from the laminate after thermoforming. Such polymers having a (meth)acryloyl group are commercially available and easily available. They are available, for example, from Dai Nippon Ink, Kyoeisha Chemical, and DSP Gokyo Food & Chemical.

[0061] (2) Polyfunctional Acrylate Compound The hard coat layer may contain a pentaerythritol-based polyfunctional acrylate compound. Examples of polyfunctional acrylate compounds having multiple acrylate groups, preferably three or more acrylate groups, include pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, which are represented by the following formulas (3) and (4), respectively. Other examples include pentaerythritol triacrylate.

[0062] The content of the polyfunctional acrylate compound in the hard coat layer is preferably 70 parts by weight or less, more preferably 50 parts by weight or less, and even more preferably 30 parts by weight or less, when the total of the curable resin and the polyfunctional acrylate compound contained in the hard coat layer is 100 parts by weight. In this way, by adding the polyfunctional acrylate compound to the hard coat composition and reacting it with the acryloyl group, glycidyl group (epoxy group), hydroxyl group, etc. contained in the side chain of the resin (e.g., (meth)acrylate polymer), a hard coat layer having higher scratch resistance can be formed.

[0063] (3) The nanoparticle hard coat layer may contain nanoparticles. This can improve the scratch resistance and hardness of the hard coat layer. The nanoparticles may be inorganic or organic particles, but are preferably inorganic nanoparticles, and more preferably inorganic oxide nanoparticles. For example, metal oxide nanoparticles such as nanosilica, nanoalumina, nanotitania, and nanozirconia may be used. Nanodiamonds may also be used.

[0064] The hard coat layer preferably contains silica particles as nanoparticles. The nanoparticles contained in the hard coat layer are preferably treated with a surface treatment agent. The surface treatment allows the inorganic nanoparticles to be stably dispersed in the hard coat composition, particularly in a resin (e.g., a (meth)acrylate polymer).

[0065] As a surface treatment agent for nanoparticles, a compound having a substituent that can bond to the surface of the nanoparticles and a substituent that is highly compatible with the components of the hard coat layer in which the nanoparticles are dispersed (e.g., a (meth)acrylate polymer, a polymer having a (meth)acryloyl group, etc.) is preferably used. For example, a silane compound, an alcohol, an amine, a carboxylic acid, a sulfonic acid, a phosphonic acid, etc. may be used as the surface treatment agent.

[0066] The inorganic nanoparticles preferably have polymerizable groups on their surfaces. The polymerizable groups can be introduced by surface treatment of the inorganic nanoparticles. Specific examples of polymerizable groups include vinyl groups, meth(acrylic) groups, and free-radical polymerizable groups. The average particle size of the nanoparticles is preferably 5 to 300 nm, more preferably 5 to 200 nm, 5 to 180 nm, 5 to 90 nm, 10 to 80 nm, and 20 to 70 nm. The average particle size of the nanoparticles can be measured by observing the cross-section of the hard coat layer using an electron microscope. For example, a TEM image of the cross-section of a particle created by FIB processing or the like is taken, and the diameters of 50 observed particles are measured and averaged to determine the average particle size. If the particles are not spherical, the average of the major and minor axes is considered to be the particle diameter. For example, using nanoparticles with an average particle size of 5 to 200 nm can produce a hard coat layer that is easy to wipe off fingerprints and has high nanoindenter hardness (uncured).

[0067] The hard coat layer preferably contains 1 to 60 parts by weight of nanoparticles, for example, inorganic nanoparticles, when the total of the resin and nanoparticles contained in the uncured hard coat layer is 100 parts by weight, more preferably 5 to 55 parts by weight of inorganic nanoparticles, and even more preferably 10 to 50 parts by weight of inorganic nanoparticles.

[0068] (4) Leveling Agent The hard coat layer may contain a leveling agent. This improves the leveling properties, antifouling properties, and abrasion resistance of the hard coat layer. Fluorine-based additives are preferably used as the leveling agent. Examples of fluorine-based compounds contained in fluorine-based additives include compounds having perfluoropolyether bonds. Fluorine-based additives can be synthesized by yourself, but commercially available products are also easily available. For example, the Megafac RS series from DIC, the KY series from Shin-Etsu Chemical, and the Optool series from Daikin can be used.

[0069] The content of the leveling agent is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, even more preferably 0.001 to 4 parts by weight, and particularly preferably 0.001 to 3 parts by weight, when the total of the resin and nanoparticles contained in the uncured hard coat layer is 100 parts by weight.

[0070] (5) Photopolymerization Initiator As described above, the resin contained in the hard coat layer is preferably active energy ray-curable or thermosetting, more preferably active energy ray-curable, and particularly preferably ultraviolet ray-curable. Therefore, the hard coat layer may further contain a photopolymerization initiator. Examples of photopolymerization initiators that can be used include IRGACURE 184 (1-hydroxycyclohexylphenyl ketone), IRGACURE 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one), IRGACURE TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), IRGACURE 819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), and EsacureONE (oligo(2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone). Of these, EsacureONE is preferred as the photopolymerization initiator from the viewpoint of heat resistance.

[0071] The content of the photopolymerization initiator in the hard coat layer is preferably 1 to 6 parts by weight, more preferably 2 to 5 parts by weight, and particularly preferably 2 to 4 parts by weight, when the total amount of the resin and nanoparticles contained in the uncured hard coat layer is 100 parts by weight.

[0072] (6) Light Stabilizer: The hard coat layer may contain a light stabilizer. This can suppress resin deterioration due to ultraviolet irradiation during weather resistance testing. Examples of light stabilizers that can be used include hindered amine compounds such as Tinuvin 123 (manufactured by BASF), Tinuvin 770DF (manufactured by BASF), Tinuvin 144 (manufactured by BASF), and LA-81 (manufactured by ADEKA). The content of the light stabilizer in the hard coat layer is preferably 0.1 to 15 parts by weight, more preferably 0.1 to 7 parts by weight, and particularly preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the total resin and nanoparticles contained in the uncured hard coat layer.

[0073] (7) Polymerization Inhibitor The hard coat layer may contain a polymerization inhibitor. The polymerization inhibitor suppresses polymerization of the curable resin due to light or heat, improving storage stability. Examples of polymerization inhibitors that can be used include hydroxy aromatics, quinone compounds, nitrogen-containing compounds, and sulfur-based compounds. More specifically, examples of polymerization inhibitors that can be used include phenothiazine, 2-hydroxynaphthoquinone, N-isopropyl-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, and 2-mercaptobenzimidazole.

[0074] (8) Other Additives The hard coat layer may contain other additives such as a heat stabilizer, an antioxidant, a flame retardant, a flame retardant assistant, an ultraviolet absorber, a release agent, a colorant, etc. As long as the desired physical properties are not significantly impaired, an antistatic agent, a fluorescent brightener, an antifogging agent, a flow improver, a plasticizer, a dispersant, an antibacterial agent, etc. may also be added to the hard coat layer.

[0075] The dilution solvent used in preparing the hard coat composition is used to adjust the viscosity, and any non-polymerizable solvent can be used without particular limitation. By using the dilution solvent, the hard coat composition can be easily applied onto the substrate layer.

[0076] Examples of dilution solvents include toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, heptane, octane, decane, dodecane, propylene glycol monomethyl ether, and 3-methoxybutanol.

[0077] <Production of Hard Coat Layer> The hard coat layer is produced by applying a hard coat composition containing the above-mentioned materials onto a layer (e.g., a substrate layer) adjacent to the hard coat layer. For example, the hard coat composition can be prepared by mixing the materials and further stirring them with a disper.

[0078] Examples of methods for applying the hard coat composition include methods using a bar coater, gravure coater, die coater, dip coating, spray coating, etc. In this case, after the hard coat composition is applied, it is dried at a predetermined temperature. The drying temperature is preferably 30 to 150°C, more preferably 60 to 130°C. Drying at a temperature within the above range makes it possible to remove the organic solvent from the hard coat layer and also to prevent deformation of other layers due to heating.

[0079] The thickness of the hard coat layer is not particularly limited, but is preferably 1 to 10 μm, more preferably 2 to 7 μm. By setting the thickness within the above range, the desired performance of the hard coat layer can be obtained, and problems in adhesion and formability are unlikely to occur.

[0080] 2. Film insert molding product The film insert molding product according to the embodiment comprises an insert film having the above-described substrate layer and uncured hard coat layer, and a thermoplastic resin layer located on the substrate layer side of the insert film, and the uncured hard coat layer has an uneven shape (pattern) on the surface opposite to the side where the substrate layer is located. Thus, the hard coat layer has an uneven shape on its surface in an uncured state. The type of uneven shape is not limited and can be appropriately selected depending on the application and desired decoration of the molded product.

[0081] For example, when a film insert molding is produced by injection molding, a molten thermoplastic resin can be injected onto the side of the insert film opposite the hard coat layer, and the uncured hard coat layer surface can be imparted with a concave-convex shape. This method allows a film insert molding to be obtained while successfully transferring a pattern onto the hard coat layer surface.

[0082] More specifically, the method for producing the film insert molding includes a shaping step of shaping the insert film into a predetermined shape and a resin layer forming step of forming a thermoplastic resin layer in contact with the insert film. Any method for shaping the insert film can be used as long as it involves heating and molding the film. For example, the insert film can be shaped into the desired shape by pressure forming, in which the base layer of the insert film is heated and molded under air pressure, vacuum pressure forming, or TOM molding, in which the insert film is molded under vacuum conditions.

[0083] Shaping an insert film means changing the shape of the insert film to suit the intended use of the molded product, and typically involves providing irregularities, bent regions, etc. to a sheet-like insert film. The shape of the bent region achieved by shaping is generally expressed by the height (H) and radius (R) of the mold. The larger H, the greater the stretched width, and the smaller R, the more acute the angle, making it difficult to follow the shape.

[0084] The molding temperature in the shaping process of the insert film is determined primarily by the Tg (glass transition temperature) of the thermoplastic resin in the substrate layer. The molding temperature is primarily determined by the Tg (glass transition temperature) of the thermoplastic resin contained in the substrate layer. The molding temperature is preferably about 0 to 70°C higher, more preferably about 20 to 40°C higher, than the Tg of the thermoplastic resin contained in the substrate layer. For example, when the laminate has a substrate layer containing a typical bisphenol A-type polycarbonate resin, molding is optimally performed in the range of 170 to 190°C.

[0085] A thermoformed after-cure type insert film can be fixed in a predetermined injection mold, for example, and a thermoplastic resin can be injected to form a thermoplastic resin layer, thereby obtaining a film insert molded article. More specifically, it is preferable to provide a thermoplastic resin layer by injecting a thermoplastic resin onto the surface of the insert film fixed in the mold opposite the hard coat layer. In addition to forming the thermoplastic resin layer in this manner, it is also preferable to impart an uneven shape to the surface of the uncured hard coat layer. The uneven shape can be imparted, for example, by using a mold having a desired uneven shape (pattern) on the surface of the mold that fixes the insert film and contacts the hard coat layer. Using such a mold, it is possible to impart an uneven shape to the surface of the uncured hard coat layer while injecting the thermoplastic resin.

[0086] Examples of the thermoplastic resin to be injected include polyethylene, polypropylene, polystyrene, polyvinyl chloride, ABS resin, AS resin, polyethylene terephthalate, acrylic resin (PMMA), polycarbonate, polyethylene terephthalate (PET), polyacetal, polyamide, etc. Among these, polycarbonate resin is preferred from the viewpoint of excellent transparency, impact resistance, etc.

[0087] The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 0.5 mm to 20 mm, for example, 0.5 mm to 20 mm, preferably 0.8 mm to 15 mm, and more preferably 1 mm to 10 mm.

[0088] The mold temperature during injection molding is, for example, 20 to 100°C, desirably 30 to 90°C, and more preferably 40 to 80°C. This temperature range can prevent the uncured hard coat layer material from fusing to the mold, resulting in poor appearance, and can ensure the fluidity of the thermoplastic resin. By setting the mold temperature to a relatively low temperature, the hard coat layer can be molded in an uncured state, and the occurrence of cracks or breakage in the hard coat layer can be suppressed even when subjected to the pressure of the injected thermoplastic resin.

[0089] Furthermore, it is preferable that the nanoindenter hardness of the uncured hard coat layer in the state in which the mold is heated in the thermoplastic resin layer forming step is within a predetermined range. For example, in the temperature range of 40 to 100°C in the thermoplastic resin layer forming step, the nanoindenter hardness of the uncured hard coat layer at 40°C is 100 N / mm ２ or more and the nanoindenter hardness at 80°C is 10 N / mm ２ Furthermore, the nanoindenter hardness at 40°C is preferably 120 N / mm ２ or more and the nanoindenter hardness at 80°C is 12 N / mm ２ More preferably, the nanoindenter hardness at 40°C is 150 N / mm ２ or more and the nanoindenter hardness at 80°C is 15 N / mm ２ It is particularly preferable that the nanoindenter hardness of the uncured hard coat layer when heated in the thermoplastic resin layer forming step is adjusted in this way, so that the strength of the uncured hard coat layer is maintained at an appropriate level in the step, and damage to the uncured hard coat layer is prevented. The nanoindenter hardness value is a value in accordance with ISO 14577-1.

[0090] According to one embodiment of the present invention, there is provided a method for producing a film insert molding, comprising: preparing an insert film having a substrate layer and an after-cure uncured hard coat layer; injecting a molten thermoplastic resin onto the substrate layer side of the insert film and imparting a textured pattern to the surface of the uncured hard coat layer opposite to the substrate layer side, thereby obtaining a film insert molding. The method may further comprise curing the uncured hard coat layer after imparting the textured pattern to the uncured hard coat layer.

[0091] 3. Film Insert Cured Product The above-described production method may further include curing the uncured hard coat layer after imparting a textured pattern to the uncured hard coat layer. Thus, according to one embodiment, a film insert cured product is provided, which is obtained by curing the hard coat layer in the above-described film insert molding. The means for curing the hard coat layer can be appropriately determined depending on the composition of the hard coat layer. When ultraviolet light is used for curing, the cumulative light dose is approximately 100 to 1,000 mJ, preferably 200 to 800 mJ, more preferably 300 to 700 mJ, for example, approximately 500 mJ. The obtained cured product can be suitably used, for example, in mobile devices, automotive interior components, home appliances, etc.

[0092] The film insert cured product produced as described above can retain the uneven shape imparted to the hard coat layer surface to a high degree even when placed under relatively high temperatures. For example, the uneven shape retention rate after an environmental test (temperature 85°C, humidity 85%, 1000 hours) is preferably 80% or more (e.g., 80 to 100%), more preferably 85% or more (e.g., 85 to 100%), and particularly preferably 90% or more (e.g., 90 to 100%). The shape retention rate after the environmental test is calculated by measuring the ten-point region height of the uneven surface of the hard coat layer after curing the uncured hard coat layer by S10z ０ The height of the ten-point region on the surface of the hard coat layer having the irregular shape after the uncured hard coat layer is cured and then subjected to the environmental test is defined as S10z １ As such, {(S10z １ / S10z０ ) × 100}. Details of the measurement method etc. will be described in the examples below.

[0093] The retention rate of the uneven shape after annealing (at 120°C for 1 hour) is preferably 80% or more (e.g., 80 to 100%), more preferably 85% or more (e.g., 85 to 100%), and particularly preferably 90% or more (e.g., 90 to 100%). The shape retention rate after annealing is calculated by S10z, which is the ten-point region height of the uneven surface of the hard coat layer after curing the uncured hard coat layer. ０ The height of the ten-point region of the surface having the uneven shape of the hard coat layer after the uncured hard coat layer is cured and then annealed is S10z ２ As such, {(S10z ２ / S10z ０ ) × 100}. Details of the measurement method etc. will be described in the examples below.

[0094] After the uncured hard coat layer is cured, the ten-point region height (S10z ０ ) is preferably 0.5 μm or more (for example, 0.5 to 20 μm), more preferably 1.0 μm or more (for example, 1.0 to 15 μm), and particularly preferably 2.0 μm or more (for example, 2.0 to 12 μm). ０ Such a value means that a firm uneven shape is imparted to the surface of the hard coat layer.

[0095] The hard coat layer after curing has a preferred hardness. That is, when the nanoindenter hardness of the hard coat layer after curing is measured, the nanoindenter hardness at room temperature (25° C.) is preferably 400 N / mm ２ or more, for example, 400 to 700 N / mm ２ The nanoindenter hardness is more preferably 400 to 600 N / mm ２ , particularly preferably 405 N / mm ２ or more (for example, 405 to 550 N / mm ２ The specific method for measuring the nanoindenter hardness is as described in the Examples below.

[0096] The haze of the hard coat layer after curing is preferably 1% or more (e.g., 1 to 100%), more preferably 10% or more (e.g., 10 to 100%), and particularly preferably 40% or more (e.g., 40 to 100%). A haze value of this range can improve antiglare properties. The appearance and texture of the molded article can also be changed by adjusting the haze value.

[0097] The present invention will be described in detail below using examples, but the scope of the present invention is not limited thereto. (Examples 1 to 3) An after-cure type insert film CRF08U (product number: 4P0, manufactured by Mitsubishi Gas Chemical Company, Inc.) was preheated at 190°C for approximately 40 seconds. Immediately thereafter, pressure molding (shaping) was performed using 1.5 MPa high-pressure air. The mold used here was a mold with a deep-draw height and a right-angled protrusion (a rectangular mold measuring 60 mm in length, 150 mm in width, and 10 mm in height). The insert film CRF08U is an after-cure type insert film that has a substrate layer consisting of two layers of bisphenol A polycarbonate resin and PMMA resin, and a polymer acrylate paint is applied to the PMMA side as a hard coat layer.

[0098] The shaped insert film was placed in contact with the hard coat layer on the cavity surface of an injection mold similar to that used for the pressure molding described above, and a molten thermoplastic resin was then injected into the substrate layer side of the insert film to produce a film insert molded article. Polycarbonate resin (Iupilon H-3000, manufactured by Mitsubishi Engineering Plastics) was used as the injection resin. The mold temperature was 60°C. The cavity surface of the injection mold was textured, and molds with the textures of Honing No. 3 (Example 1), Honing No. 6S (Example 2), and Honing No. 9S (Example 3) were used.

[0099] The film insert molding obtained above was irradiated with UV (accumulated light amount 1350 mJ / cm ２ ) was performed to UV-cure the hard coat layer of the insert film.

[0100] Examples 4 to 6 Film insert moldings were produced in the same manner as in Examples 1 to 3, except that the insert film was changed to an after-cure type CRF08U (product number: 4P2, manufactured by Mitsubishi Gas Chemical Company, Inc.).

[0101] Comparative Examples 1 to 3 A pre-cured insert film MRF08U (product number: D51, manufactured by Mitsubishi Gas Chemical Company, Inc.) was pressure molded in the same manner as in Examples 1 to 3. The shaped insert film was placed on the cavity surface of an injection mold similar to that used in the pressure molding, with the hard coat layer in contact with the cavity surface. A molten thermoplastic resin was then injected into the substrate layer side of the insert film to produce a film insert molded article. A polycarbonate resin (manufactured by Mitsubishi Engineering Plastics: Iupilon H-3000) was used as the injection resin. The mold temperature at this time was 100°C. The grain pattern of the injection mold was the same as in Examples 1 to 3.

[0102] Comparative Examples 4 to 6 Film insert moldings were produced in the same manner as in Comparative Examples 1 to 3, except that the insert film was changed to DF02U (manufactured by Mitsubishi Gas Chemical Company, Inc.), which is a two-layer product of bisphenol A polycarbonate and PMMA.

[0103] <Evaluation of Physical Properties> The molded articles (after hard coating layer curing) according to the Examples and Comparative Examples prepared as described above were evaluated for various physical properties as follows. (1) Shape retention rate (environmental test) The environmental test was carried out using a thermo-hygrostat PL-3KPH (manufactured by Espec Corporation) under conditions of a temperature of 85°C, a humidity of 85%, and a test time of 1000 hours. The ten-point region height (S10z) of the grained surface of the hard coating layer before the environmental test was ０ ), and the ten-point area height (S10z １ The measurement was performed using a white light interference microscope (VS-1550, manufactured by Hitachi High-Technologies Corporation), and the average value (arithmetic mean) of the ten-point area heights (three values) measured in three different areas was calculated as S10z ０ and S10z １ The shape retention rate (%) of the uneven shape (grain pattern) on the surface of the hard coat layer was calculated using the formula {(S10z １ / S10z ０ ) × 100}. In Table 3 below, values ​​calculated by the above formula that exceeded 100% are marked as "100%." ​​This is due to errors and variations that arise from the selection of the three measurement points, etc., and is calculated by the ten-point region height (S10z １ ) is the ten-point region height before the test (S10z ０ ) and therefore, in any case, it can be said that the uneven shape is well maintained.

[0104] (2) Shape Retention Rate (Annealing Treatment) The annealing treatment was carried out using a constant temperature incubator DKN402 (manufactured by Yamato Scientific Co., Ltd.) at a temperature of 120°C for 1 hour. The ten-point region height (S10z) of the grained surface of the hard coat layer before the annealing treatment was ０ ), and the ten-point region height (S10z ２ The measurement was carried out in the same manner as in the environmental test, and the average value was calculated in the same manner to obtain S10z ０ and S10z ２ The shape retention rate (%) of the grain pattern (uneven shape) on the surface of the hard coat layer was calculated using the formula {(S10z ２ / S10z ０ ) × 100}. As with the shape retention rate after the environmental test, in Table 3 below, values ​​calculated by the above formula that exceeded 100% are represented as "100%."

[0105] (3) Nanoindenter Hardness For the insert film molded article after hard coating layer curing, the nanoindenter hardness of the hard coating layer after curing in the thickness direction of the insert film was measured using an ultra-microindentation hardness tester (ENT-NEXUS, manufactured by Elionix) under the following conditions. The measurement position was the center of the film, and the average value of 30 points close to the center in the thickness direction of the center was calculated as the indentation hardness (N / mm ２) Temperature: 25°C (room temperature) Indenter: Berkovich indenter (vertical angle 65.03°) Surface detection: The applied load was set so that the displacement was 1 / 10 of the after-cure hard coat layer (0.5 mN) Load curve: 0.5 mN over 10 seconds (linear) Creep: 0.5 mN for 50 seconds Unloading curve: 0 mN over 10 seconds (linear) The nanoindenter hardness value of the insert film was calculated in accordance with ISO14577-1 2002-10-01 Part 1 (calculation using the built-in software of the device).

[0106] (4) Chemical Resistance Neutrogena SPF100 was applied to the grained surface of the cured hard coat layer and allowed to stand at 80°C for 1 hour. Thereafter, the appearance was visually observed and rated as follows: A: No abnormality on the surface B: The grained pattern became faint C: Whitening was observed

[0107] (5) Haze The haze value of the hard coat layer after curing was measured using a haze meter (HM-150N, manufactured by Murakami Color Co., Ltd.) in accordance with JIS K 7136:2000.

[0108] The configurations and evaluation results of the film insert moldings according to the examples and comparative examples are summarized in Tables 2 and 3 below.

[0109] Table 3 shows that when a grain pattern is applied to a hard coat layer in an uncured state and then cured (Examples 1 to 6), the uneven shape (grain pattern) is well maintained even after environmental testing and annealing. This effect is more pronounced than when a pre-cured hard coat layer (cured before applying the grain pattern) is used (Comparative Examples 1 to 3). Furthermore, the molded articles of Examples 1 to 6 also have excellent hardness and chemical resistance.

[0110] Although several embodiments of the present invention have been described, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be embodied in various other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their modifications are included within the scope and spirit of the invention, and are also included in the scope of the invention and its equivalents as defined in the claims.

Claims

1. A film insert molding comprising an insert film having a base layer and an after-cure type uncured hard coat layer, and a thermoplastic resin layer located on the base layer side of the insert film, wherein the uncured hard coat layer has an uneven shape on the surface opposite to the side on which the base layer is located, and the uneven shape satisfies the following conditions (i) and / or (ii): (i) The ten-point region height of the surface having the uneven shape of the hard coat layer after curing the uncured hard coat layer is S10z ０ The uncured hard coat layer was cured and then subjected to an environmental test at a temperature of 85° C. and a humidity of 85% for 1000 hours. The height of the ten-point region of the surface having the concave-convex shape of the hard coat layer after the test was defined as S10z １ In this case, the shape retention rate {(S10z １ / S10z ０ (ii) the ten-point region height of the surface having the uneven shape of the hard coat layer after curing the uncured hard coat layer is S10z ０ The height of the ten-point region of the surface having the concave-convex shape of the hard coat layer after the uncured hard coat layer is cured and then annealed at a temperature of 120° C. for 1 hour is defined as S10z ２ In this case, the shape retention rate {(S10z ２ / S10z ０ ) × 100} is 80% or more.

2. After the uncured hard coat layer is cured, the ten-point region height (S10z ０ 2. The film insert molding according to claim 1, wherein the thickness of the film insert molding is 0.5 μm or more.

3. The film insert molding according to claim 1 or 2, wherein the uncured hard coat layer contains an active energy ray-curable resin having a (meth)acryloyl group.

4. A film insert molding according to claim 3, wherein the active energy ray curable resin having a (meth)acryloyl group has a (meth)acrylate skeleton.

5. The film insert molding according to any one of claims 1 to 4, wherein the uncured hard coat layer contains nanoparticles.

6. The film insert molding according to any one of claims 1 to 5, wherein the uncured hard coat layer contains a leveling agent.

7. After curing the uncured hard coat layer, the nanoindenter hardness of the cured hard coat layer is 400 N / mm ２ The film insert molding according to any one of claims 1 to 6.

8. The film insert molding according to any one of claims 1 to 7, wherein after the uncured hard coat layer is cured, the haze of the cured hard coat layer is 1% or more.

9. A film insert cured product obtained by curing the hard coat layer in the film insert molding according to any one of claims 1 to 8.

10. A method for producing a film insert molding, comprising: preparing an insert film having a base layer and an after-cure type uncured hard coat layer; and injecting a molten thermoplastic resin onto the base layer side of the insert film, and simultaneously imparting a concave-convex shape to the surface of the uncured hard coat layer opposite to the side where the base layer is located, to obtain a film insert molding, wherein the concave-convex shape satisfies the following conditions (i) and / or (ii): (i) The ten-point region height of the surface having the concave-convex shape of the hard coat layer after curing the uncured hard coat layer is S10z ０ The uncured hard coat layer was cured and then subjected to an environmental test at a temperature of 85° C. and a humidity of 85% for 1000 hours. The height of the ten-point region of the surface having the concave-convex shape of the hard coat layer after the test was defined as S10z １ In this case, the shape retention rate {(S10z １ / S10z ０ (ii) the ten-point region height of the surface having the uneven shape of the hard coat layer after curing the uncured hard coat layer is S10z ０ The height of the ten-point region of the surface having the concave-convex shape of the hard coat layer after the uncured hard coat layer is cured and then annealed at a temperature of 120° C. for 1 hour is defined as S10z ２ In this case, the shape retention rate {(S10z ２ / S10z ０ ) × 100} is 80% or more.

11. The method of claim 10, further comprising curing the uncured hard coat layer after imparting the texture onto the uncured hard coat layer.

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