Thermoforming laminate and method for forming laminate

Abstract

Provided is a thermoforming laminate, etc., having excellent thermoforming properties as well as exceptional chemical resistance and abrasion resistance.　Examples of solutions to the abovementioned problem include, inter alia, a thermoforming laminate having (a) a base material layer that contains a thermoplastic resin, (b) an after-cure hard coating layer that contains an active-energy-ray-curable resin having a (meth)acryloyl group, the hard coating layer also containing a polymerization inhibitor, and (c) a protective film, the thermoforming laminate being such that: the (a) base material layer, the (b) hard coating layer, and the (c) protective film are laminated in the stated order; and the polymerization inhibitor includes at least one from among quinone-based compounds, sulfur-containing compounds, and nitrogen-containing compounds.

Description

[Technical Field]

[0001] The present invention relates to a laminate for thermoforming and a method for forming a thermoformable laminate. [Background technology]

[0002] For home appliances and automotive molded products, it has been common to coat plastic molded products, but due to the large environmental impact, a method of insert molding with thermoformable decorative film is also being used. In recent years, there has been a growing demand for chemical resistance and scratch resistance, so there is a great demand for thermoforming films with hard coatings. Thermoforming films with hard coatings are generally manufactured by applying a hard coating liquid to a substrate and then curing it with UV light.

[0003] There is a trade-off between moldability and chemical resistance and scratch resistance. In other words, increasing moldability usually results in a decrease in chemical resistance and scratch resistance, while improving chemical resistance and scratch resistance results in a decrease in moldability. To solve these problems, an after-cure type has been proposed, in which the hard coat is applied, molded without curing, and then cured by UV irradiation or other methods after molding.

[0004] Some after-cure type hard coat films for thermoforming have a protective film attached to prevent scratches and foreign matter from getting caught in them. If foreign matter gets caught in them during the molding process, it can cause a significant decrease in yield, so it is desirable to mold the hard coat film in a clean environment with the protective film attached. However, in order to perform thermoforming, the hard coat film needs to be softened by heating to a temperature equal to or higher than the Tg of the substrate. In the case of conventional after-cure type hard coat films, if heating is performed with a protective film attached, the hardening proceeds, resulting in a problem of significant impairment of thermoformability.

[0005] Furthermore, in the case of conventional after-cure type hard coat films, if thermoforming is carried out with the protective film attached, the pattern of the protective film may be transferred, resulting in a poor appearance. For these reasons, conventional hard coat films are generally formed after peeling off the protective film.

[0006] As described above, it was not easy to obtain a molded product having excellent chemical resistance, scratch resistance, etc. by performing thermoforming on a hard-coated film for thermoforming with a protective film attached while ensuring the thermoformability of the film and without deteriorating the appearance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Special Publication No. 2017-508828 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0008] A main object of the present invention is to provide a thermoformable laminate or the like which has good thermoformability and excellent chemical resistance and abrasion resistance. [Means for solving the problem]

[0009] The present invention includes the following. (1) A laminate for thermoforming, (a) a substrate layer containing a thermoplastic resin; (b) an after-cure hard coat layer containing an active energy ray-curable resin having a (meth)acryloyl group, the hard coat layer containing a polymerization inhibitor; and (c) Protective film and the (a) substrate layer, the (b) hard coat layer, and the (c) protective film are laminated in the order described above; The thermoforming laminate, wherein the polymerization inhibitor contains at least one of a quinone compound, a sulfur-containing compound, and a nitrogen-containing compound. (2) The thermoforming laminate according to (1) above, wherein the polymerization inhibitor comprises a quinone compound selected from 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, phenothiazine, and 2-mercaptobenzimidazole. (3) The thermoforming laminate according to (2) above, wherein the polymerization inhibitor comprises a quinone compound selected from N-isopropyl-N'-phenyl-p-phenylenediamine, phenothiazine, and 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl. (4) The thermoforming laminate according to any one of (1) to (3) above, wherein the hard coat layer contains 0.0001 to 5% by weight of the polymerization inhibitor. (5) The thermoforming laminate according to any one of (1) to (4) above, wherein the active energy ray-curable resin having a (meth)acryloyl group has a (meth)acrylate skeleton. (6) The thermoforming laminate according to any one of (1) to (5) above, wherein the hard coat layer contains nanoparticles. (7) The thermoforming laminate according to any one of (1) to (6) above, wherein the hard coat layer contains a leveling agent. (8) A thermoforming laminate according to any one of (1) to (7), wherein the adhesive surface of the protective film, which is the surface on the hard coat layer side, has a surface free energy of 30.0 (mN / m) or more, calculated based on the OWRK method from the values of the average contact angle of water and the average contact angle of diiodomethane, before being attached to the hard coat layer. (9) The laminate for thermoforming according to any one of (1) to (8) above, wherein the adhesive surface of the protective film has a surface roughness Sa of 0.1 μm or less. (10) The thermoforming laminate according to any one of the above (1) to (9), wherein the hard coat layer is UV-curable. (11) The thermoforming laminate according to any one of (1) to (10) above, wherein the thermoplastic resin contains an aromatic polycarbonate. (12) The thermoforming laminate according to (11) above, wherein the aromatic polycarbonate comprises a bisphenol A polycarbonate. (13) The thermoforming laminate according to any one of (1) to (12) above, wherein the substrate layer comprises at least two layers, an acrylic resin layer and an aromatic polycarbonate layer. (14) A method for molding a thermoforming laminate, comprising a heat molding step of heating the thermoforming laminate according to any one of (1) to (13) above with the protective film attached. (15) A molded product obtained by molding the thermoforming laminate according to any one of (1) to (13) above. (16) An article obtained by irradiating the molded product of (15) above with active energy rays. [Effects of the Invention]

[0010] In the thermoforming laminate of the present invention, as described above, the curable hard coat layer laminated between the substrate layer and the protective film contains a polymerization inhibitor. With such a thermoforming laminate, even when thermoforming is performed with the protective film still laminated, curing of the hard coat layer is reliably suppressed, good processability is achieved, and the inclusion of fine foreign matter in the hard coat layer is prevented, resulting in a good surface appearance. Therefore, such a thermoforming laminate is particularly suitable for thermoforming with the protective film still attached.

[0011] Furthermore, after being thermoformed into a predetermined shape, the thermoformable laminate is cured and the protective film is removed, resulting in a resin film laminate having a hard coat layer on the surface that has excellent chemical resistance and abrasion resistance. The thermoforming laminate of the present invention having such excellent characteristics is particularly suitable as a material for resin film laminates used in applications such as mobile devices and automobile interior components. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a cross-sectional view showing a specific example of a laminate for thermoforming. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below. Note that the present invention is not limited to the following embodiments, and can be modified as desired within the scope of the effects of the invention.

[0014] [Thermoforming laminate] The thermoforming laminate of the present invention comprises (a) a substrate layer containing a thermoplastic resin, (b) a curable hard coat layer, and (c) a protective film, and these layers are laminated in the order of (a) substrate layer, (b) hard coat layer, and (c) protective film. That is, the laminate of the present invention includes not only a laminate in which the (a) substrate layer is directly laminated on one surface of the (b) hard coat layer and the (c) protective film is directly laminated on the other surface, but also a laminate having layers other than the above (a) to (c).

[0015] The structure of a laminate for thermoforming is, for example, as shown in Fig. 1. In the laminate 10 illustrated in Fig. 1, a protective film 12, which is the outermost layer, is laminated on a hard coat layer 16. Therefore, the surface of the hard coat layer 16 on the side of the protective film 12 is protected by the protective film 12. The hard coat layer 16 is laminated on the surface on the PMMA layer side of a base layer having, for example, a polymethyl methacrylate layer (PMMA resin layer) 20 and a polycarbonate layer (PC resin layer) 22. Each layer of the thermoforming laminate will now be described.

[0016] [Base material layer] The substrate layer is preferably laminated so as to be in contact with the surface of the hard coat layer opposite to the protective film, although other layers may be disposed between the substrate layer and the hard coat layer.

[0017] The substrate layer contains a thermoplastic resin. The type of thermoplastic resin is not particularly limited, but various resins such as polycarbonate (PC) resin, acrylic resin 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 can be used. Of these options, the thermoplastic resin of the substrate layer preferably contains at least a polycarbonate resin. Furthermore, from the viewpoint of toughness and heat resistance, it is desirable to use an aromatic polycarbonate.

[0018] The type of polycarbonate resin contained in the substrate layer is not particularly limited as long as it contains an -[OR-OCO]- unit containing a carbonate bond in the molecular main chain (where R contains an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear or branched structure). However, polycarbonates having a bisphenol skeleton are preferred, and bisphenol A polycarbonates having a bisphenol A skeleton or bisphenol C polycarbonates having a bisphenol C skeleton are particularly preferred. As the polycarbonate resin, a mixture or copolymer of bisphenol A and bisphenol C may be used. The hardness of the substrate layer can be improved by using a bisphenol C-based polycarbonate resin, for example, a polycarbonate resin containing only bisphenol C, or a polycarbonate resin that is a mixture or copolymer of bisphenol C and bisphenol A. The viscosity average molecular weight of the thermoplastic resin such as polycarbonate resin is preferably 15,000 to 40,000, more preferably 20,000 to 35,000, and even more preferably 22,500 to 25,000.

[0019] The substrate layer preferably contains an acrylic resin. The acrylic resin contained in the substrate layer is not particularly limited, but examples include homopolymers of various (meth)acrylic acid esters, such as polymethyl methacrylate (PMMA) and methyl methacrylate (MMA), copolymers of PMMA or MMA with one or more other monomers, and mixtures of multiple types of these resins. 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)acrylic resins include, but are not limited to, ACRYPET (manufactured by Mitsubishi Rayon), DELPET (manufactured by Asahi Kasei Chemicals), and PARAPET (manufactured by Kuraray).

[0020] As the substrate layer, a multilayer product containing the above-mentioned polycarbonate resin layer and the above-mentioned acrylic resin layer can also be used. In this way, for example, in a multilayer product containing at least two layers, an acrylic resin layer and an aromatic polycarbonate layer, a hard coat layer is preferably provided on the acrylic resin side. By using a multilayer product containing a polycarbonate resin and an acrylic resin, it is possible to improve the surface hardness while maintaining the thermoformability of the substrate.

[0021] The substrate layer may also contain additives other than the thermoplastic resin. For example, at least one additive selected from the group consisting of a heat stabilizer, an antioxidant, a flame retardant, a flame retardant aid, an ultraviolet absorber, a release agent, and a colorant. Additionally, the substrate layer may contain additives such as an antistatic agent, a fluorescent brightener, an antifogging agent, a flow improver, a plasticizer, a dispersant, and an antibacterial agent.

[0022] The base layer preferably contains 80% by mass or more of thermoplastic resin, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of thermoplastic resin. The base layer also contains 80% by mass or more of polycarbonate resin, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of polycarbonate resin. Of the base layers, those containing acrylic resin as the main component preferably contain 80% by mass or more of acrylic resin, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of acrylic resin.

[0023] The thickness of the substrate layer is not particularly limited, but is preferably 0.10 mm to 1.0 mm, for example, 0.15 mm to 0.80 mm, 0.18 mm to 0.60 mm, or 0.25 mm to 0.40 mm. Furthermore, when the base layer has a plurality of layers, the thickness of each layer may be within the above range, and the thickness of the entire base layer may be within the above range.

[0024] [Hard coat layer] The hard coat layer contains a polymerization inhibitor and an active energy ray-curable resin. Thus, the energy ray-curable hard coat layer can be cured even without a curing agent. However, the hard coat layer can further contain a photopolymerization initiator and various additives to improve the function of the hard coat layer.

[0025] <Polymerization inhibitor> The hard coat composition forming the hard coat layer contains a polymerization inhibitor, which inhibits polymerization of the active energy ray-curable resin caused by light or heat, thereby improving storage stability.

[0026] As the polymerization inhibitor used in the hard coat layer of the laminate of the present invention, hydroxy aromatic compounds, quinone compounds, nitrogen-containing compounds, sulfur-based compounds, etc. are used, as will be described later.

[0027] Examples of hydroxy aromatics include phenols such as hydroquinone and p-methoxyphenol (4-methoxyphenol), cresol, t-butylcatechol, di(t-butyl)hydroxytoluenes such as 3,5-di-t-butyl-4-hydroxytoluene, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-butylphenol), and 4,4'-thiobis(3-methyl-6-t-butylphenol).

[0028] Examples of quinone compounds include benzoquinone, naphthoquinone, 2-t-butyl-1,4-benzoquinone, and 2-hydroxynaphthoquinone.

[0029] Known nitrogen-containing compounds include amine compounds and nitroso compounds. Examples of amine compounds include p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline. Examples of nitroso compounds include N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, and α-nitroso-β-naphthol. Further, examples of the nitrogen-containing compound other than those mentioned above include nitroxides such as piperidine-1-oxyl, pyrrolidine-1-oxyl, 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, and 2,2,6,6-tetramethylpiperidine-1-oxyl. These nitrogen-containing compounds act as radical scavengers.

[0030] Examples of sulfur-based compounds include phenothiazine, distearyl thiodipropionate, and 2-mercaptobenzimidazole.

[0031] Other polymerization inhibitors include transition metal salts, such as copper salt compounds and manganese salt compounds. Examples of such compounds include copper salts such as copper dialkyldithiocarbamate (wherein the alkyl group is a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different), copper acetate, copper salicylate, copper thiocyanate, copper nitrate, copper chloride, copper carbonate, copper hydroxide, and copper acrylate; manganese dialkyldithiocarbamate (wherein the alkyl group is a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different), manganese diphenyldithiocarbamate, manganese formate, manganese acetate, manganese octanoate, manganese naphthenate, manganese permanganate, and manganese salt of ethylenediaminetetraacetic acid.

[0032] Among these polymerization inhibitors, quinone compounds, nitrogen-containing compounds, and sulfur-based compounds are preferred. These polymerization inhibitors function even in the absence of oxygen, and therefore can effectively suppress polymerization hardening due to heat when thermoforming is performed with a protective film attached.

[0033] Furthermore, as the polymerization inhibitor, 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, 2-mercaptobenzimidazole, etc. are desirable, and it is particularly desirable to use phenothiazine, N-isopropyl-N'-phenyl-p-phenylenediamine, 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, etc.

[0034] The amount of polymerization inhibitor added is preferably 0.0001 to 5 wt %, more preferably 0.0003 to 1 wt %, even more preferably 0.0005 to 0.5 wt %, and particularly preferably 0.001 to 0.1 wt % (10 to 1000 ppm by weight) based on the total weight of the hard coat composition forming the hard coat layer. Addition of an excessive amount of polymerization inhibitor may adversely affect the physical properties of the hard coat layer or cause coloration. On the other hand, if the amount of polymerization inhibitor added is too small, curing of the hard coat layer during heating may proceed, making it impossible to suppress deterioration of thermoformability.

[0035] <Active energy ray curable resin> Any compound having active energy ray curability can be used as the active energy ray curable resin. As the active energy ray curable compound, a (meth)acrylate compound having a (meth)acryloyl group ((meth)acrylate polymer / (meth)acrylate resin) is preferably used. The (meth)acrylate compound having a (meth)acryloyl group desirably has a (meth)acrylate skeleton. As the (meth)acrylate compound, for example, epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, etc. are used. These active energy ray curable resins are also easily available from various companies.

[0036] Epoxy (meth)acrylate Among the active energy ray-curable compounds described above, epoxy (meth)acrylate derived from an epoxy compound is preferable. A synthesis example of 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. [ka] (In formula (1), R represents an alkyl group having a total of 1 to 12 carbon atoms which may contain at least one substituent selected from the group consisting of an epoxy group, a hydroxyl group, an acryloyl group, and a methacryloyl group, or hydrogen, and R' represents a methyl group or hydrogen.)

[0037] Epoxy (meth)acrylate having a (meth)acrylate skeleton can be obtained, for example, by copolymerizing (meth)acrylic acid and (meth)acrylic acid glycidyl ether to synthesize an epoxy compound having a (meth)acrylate skeleton, and then adding acrylic acid, methacrylic acid, etc. to this. A synthesis example is shown in Scheme 2. [ka]

[0038] Epoxy (meth)acrylates used in the hard coat composition include those having a repeating unit represented by the following formula (I): [ka] 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 hydrogen, p is a single bond or an alkylene group having 1 or 2 carbon atoms, and q is an alkyl group having a total of 1 to 12 carbon atoms which may contain at least one substituent selected from the group consisting of an epoxy group, a hydroxyl group, an acryloyl group, and a methacryloyl group, or hydrogen.

[0039] The epoxy (meth)acrylate polymer more preferably contains the following repeating unit, that is, a repeating unit in which, in the above formula (I), 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 a total of 1 to 6 carbon atoms which may contain at least one substituent selected from the group consisting of a glycidyl group, a hydroxyl group, and an acryloyl group, or hydrogen. For example, in the above formula (I), m is a methylene group, n is a methyl group, p is a single bond, and q is a methyl group, an alkyl group having 5 or less carbon atoms and containing a glycidyl group (epoxy group), an alkyl group having 8 or less carbon atoms and containing a hydroxyl group and an acryloyl group, or the like.

[0040] Specific examples of repeating units contained in the epoxy (meth)acrylate polymer include those represented by the following formulae (II-a), (II-b), and (II-c). [ka] In the epoxy (meth)acrylate polymer, the repeating unit of the formula (II-a) preferably accounts for 30 to 85 mol %, more preferably 40 to 80 mol %, based on the total number of moles of the repeating unit of the formula (II-a), the repeating unit of the formula (II-b), and the repeating unit of the formula (II-c). The repeating unit of the formula (II-b) preferably accounts for 5 to 30 mol %, more preferably 10 to 25 mol %, based on the total number of moles. The repeating unit of the formula (II-c) preferably accounts for 10 to 40 mol %, more preferably 10 to 35 mol %, based on the total number of moles. The molar ratio of the repeating units of the above formula (II-a), the repeating units of the above formula (II-b), and the repeating units of the above formula (II-c) is preferably 4.5-5.5:1.5-2.5:2.5-3.5, for example, 5:2:3.

[0041] Urethane (meth)acrylate As described above, the following urethane (meth)acrylate can also be used as the active energy ray-curable resin having a (meth)acryloyl group.

[0042] (Urethane acrylate containing a cyclic skeleton molecular structure) The urethane acrylate resin is preferably a urethane acrylate having a molecular structure of a cyclic skeleton. More specifically, a polymer of an isocyanate compound and an acrylate compound having a cyclic skeleton is a specific example of a preferred urethane acrylate. The urethane acrylate resin that may have a molecular structure of a cyclic skeleton is preferably an active energy ray curable type.

[0043] Isocyanate compounds The isocyanate compound is, for example, an aromatic isocyanate which may have a substituent, such as an alkyl group such as a methyl group, and is preferably an aromatic isocyanate having a total of 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. The isocyanate compound is preferably an aromatic isocyanate, but aliphatic or alicyclic isocyanates may also be used.

[0044] For example, preferred structural units of urethane (meth)acrylate 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(isocyanate), Examples of the polyisocyanate include polyisocyanates such as (anatomethyl)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. Among these isocyanate compounds, preferred specific examples include 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), and xylylene diisocyanate (XDI), which are represented by the following formulas. [ka]

[0045] Acrylate Compounds Examples of the above-mentioned acrylate compound, that is, the acrylate compound for forming a urethane acrylate preferably containing a molecular structure of a cyclic skeleton, include pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPPA), and hydroxypropyl (meth)acrylate (hydroxypropyl acrylate: HPA). Furthermore, as the acrylate compound, a compound having a (meth)acryloyloxy group and a hydroxy group, for example, a monofunctional (meth)acrylic compound having a hydroxyl group, can also be used. 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, 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, polyethylene glycol mono(meth)acrylate], and compounds having three or more hydroxyl groups. mono(meth)acrylates of polyols having the formula (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 in which lactones (e.g., C4-10 lactones such as ε-caprolactone) are added to the hydroxyl groups of these compounds (e.g., hydroxyalkyl(meth)acrylates) (e.g., adducts in which about 1 to 5 moles of lactone are added). These (meth)acrylic compounds may be used alone or in combination of two or more. A preferred specific example of a compound for forming a (meth)acryloyloxy group is 2-hydroxy-3-phenoxypropyl acrylate. Among the above-mentioned acrylate compounds, particularly preferred specific examples include pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPPA), and hydroxypropyl (meth)acrylate (hydroxypropyl acrylate: HPA).

[0046] Polymer of isocyanate compound and acrylate compound Preferred specific examples of the polymer of the above-mentioned isocyanate compound and acrylate compound, i.e., urethane acrylate polymer, include a polymer of xylylene diisocyanate (XDI) and pentaerythritol triacrylate (PETA), a polymer of XDI and dipentaerythritol pentaacrylate (DPPA), a polymer of dicyclohexylmethane diisocyanate (H12MDI) and PETA, a polymer of isophorone diisocyanate (IPDI) and PETA, and a polymer of XDI and hydroxypropyl (meth)acrylate (HPA).

[0047] Further, examples of urethane acrylates containing a cyclic skeleton include polymers containing a polyol compound as a constituent unit in addition to the above-mentioned isocyanate compound and acrylate compound. A polyol compound (polyhydric alcohol) is a compound 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-dimethyltrimethylol, and 2,3-dimethyl-1,2-butanediol. Dihydric alcohols such as ethylene 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; polylactone diols obtained by adding lactones such as ε-caprolactone to these dihydric alcohols; 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, and monoepoxy compounds such as Cardura E10 [trade name, glycidyl ester of synthetic highly branched saturated fatty acid, manufactured by Shell Chemical Co., Ltd.]; trihydric or higher alcohols such as glycerin, trimethylolpropane, trimethylolethane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, and mannitol; 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.

[0048] For example, the polyol compound may be a urethane acrylate represented by the following formula, which contains tricyclodidecanedimethanol (TCDDM) as a constituent unit. [ka]

[0049] Specific preferred examples of the above-mentioned urethane acrylate polymer include a polymer of tricyclodidecanedimethanol (TCDDM), IPDI, and PETA, a polymer of TCDDM, H12MDI, and PETA, a polymer of these polymers containing DPPA as a structural unit in place of or together with PETA, and a polymer of xylylene diisocyanate (XDI) and hydroxypropyl (meth)acrylate (HPA).

[0050] (Urethane acrylate containing a specific structural unit) Preferred specific examples of urethane acrylate resins include urethane acrylate resins having a structural unit derived from an isocyanate and a structural unit derived from a compound having a (meth)acryloyloxy group and a hydroxy group, as shown below. Preferred structural units of the above-mentioned urethane (meth)acrylate include the following.

[0051] Isocyanate compounds The isocyanate compound forming the above-mentioned structural unit is, for example, an aromatic isocyanate which may have a substituent which is an alkyl group such as a methyl group, and is preferably an aromatic isocyanate having a total of 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. The isocyanate preferably has a cyclic skeleton. Therefore, specific preferred examples of the isocyanate include aromatic isocyanates and alicyclic isocyanates (alicyclic isocyanates), but aliphatic isocyanates (non-cyclic aliphatic isocyanates) that do not have a cyclic skeleton can also be used.

[0052] For example, compounds forming a preferred structural unit of urethane (meth)acrylate 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(2-methyl-2-propanol), ... Examples of the polyisocyanate include polyisocyanates such as (isocyanatomethyl)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. Among these isocyanates, 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 the like are preferred.

[0053] Compounds having a (meth)acryloyloxy group and a hydroxy group A preferred specific example of the compound having a (meth)acryloyloxy group and a hydroxy group, which is used to form the above-mentioned structural unit, is a monofunctional (meth)acrylic compound having a hydroxyl group. 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, 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, polyethylene glycol mono(meth)acrylate], and compounds having three or more hydroxyl groups. mono(meth)acrylates of polyols having the formula (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 in which lactones (e.g., C4-10 lactones such as ε-caprolactone) are added to the hydroxyl groups of these compounds (e.g., hydroxyalkyl(meth)acrylates) (e.g., adducts in which about 1 to 5 moles of lactone are added). These (meth)acrylic compounds may be used alone or in combination of two or more. A preferred example of a compound for forming an alkyl group containing a (meth)acryloyloxy group (A3 described below) is 2-hydroxy-3-phenoxypropyl acrylate.

[0054] Examples of urethane (meth)acrylates containing the above-mentioned specific structural units include polymers containing a polyol compound as a structural unit in addition to an isocyanate compound and a compound having a (meth)acryloyloxy group and a hydroxy group. A polyol compound (polyhydric alcohol) is a compound 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-dimethyltrimethyl-1,2-but ...4-dimethyltrimethyl-1,2-butanediol, 1,4-pentanediol, 2,4-dimethyltrimethyl-1,2-butanediol, 1,3-butanediol, 1,3-butanediol, 2,3-dimethyltrimethyl-1,2-butanediol, 1,4-butanediol, 1,3- Dihydric alcohols such as ethylene 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; polylactone diols obtained by adding lactones such as ε-caprolactone to these dihydric alcohols; 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, and monoepoxy compounds such as Cardura E10 [trade name, glycidyl ester of synthetic highly branched saturated fatty acid, manufactured by Shell Chemical Co., Ltd.]; trihydric or higher alcohols such as glycerin, trimethylolpropane, trimethylolethane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, and mannitol; 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.

[0055] The urethane (meth)acrylate containing a polyol compound as a constituent unit in addition to an isocyanate compound and a compound having a (meth)acryloyloxy group and a hydroxy 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 is an alkylene group derived from the polyol compound described above, Each A2 is independently an alkylene group derived from the isocyanate compound described above, Each A3 is independently an alkyl group derived from the above-mentioned compound having a (meth)acryloyloxy group and a hydroxy group.

[0056] Preferred specific examples of the urethane (meth)acrylate contained in the resin material include the following compounds containing structural units derived from ethylene glycol, pentaerythritol triacrylate, and isophorone diisocyanate: In the following formula, the value of n is 0 to 10, preferably 1 to 5, and more preferably 1 to 3. [ka]

[0057] In the urethane acrylate resin, the ratio of the compound having a (meth)acryloyloxy group and a hydroxy group, or a constituent unit derived from such a compound, to the isocyanate, or a constituent unit derived from the isocyanate, 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.

[0058] (urethane acrylate containing acrylate) A preferred example of the urethane acrylate resin is one containing a urethane acrylate and an acrylate. A more preferred example of such a urethane acrylate resin is one containing a mixture of a hexafunctional urethane acrylate and a difunctional acrylate.

[0059] (Hexafunctional) urethane acrylate As described above, the urethane acrylate resin preferably contains a urethane acrylate, in particular, a hexafunctional urethane acrylate. Preferred hexafunctional urethane acrylate compounds include those represented by the following formulas: a polymer of dicyclohexylmethane diisocyanate (H12MDI) and pentaerythritol triacrylate (PETA), a polymer of isophorone diisocyanate (IPDI) and PETA, etc. Specific examples of preferred products of these hexafunctional urethane acrylates include UN-3320HC (a polymer of H12MDI and PETA: manufactured by Negami Chemical Industrial Co., Ltd.), CN-968 (a polymer of IPDI and PETA: manufactured by Sartomer Japan Co., Ltd.), and CN-975 (manufactured by Sartomer Japan Co., Ltd.). [ka] [ka]

[0060] (Meth)acrylate (difunctional (meth)acrylate, etc.) As described above, the (meth)acrylate preferably contained in the urethane acrylate resin is preferably a compound having 4 to 20 carbon atoms, which contains at least one (meth)acryloyloxy group and at least one vinyl ether group, and 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 in the (meth)acrylate include an alkyl group. Moreover, the (meth)acrylate is preferably bifunctional. As the (meth)acrylate, for example, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate [2-(2-vinyloxyethoxy)ethyl acrylate: VEEA] of the following formula is preferably used. [ka] (In the above formula, R is hydrogen or a methyl group.)

[0061] In the urethane acrylate resin, the ratio of urethane acrylate to (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.

[0062] (Fluorine-containing urethane acrylate) The (meth)acrylate polymer may be a fluorine-containing urethane acrylate, which 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 may have a substituent and is preferably an alkylene group derived from a fluorine-containing diol having a total carbon number of 8 or less, and the total carbon number is preferably 6 or less, for example 4. Examples of the substituent contained in the alkylene group of A1 include an alkyl group.

[0063] In the formula (ii), A2 are each independently an alkylene group derived from an aliphatic or alicyclic isocyanate, which may have a substituent and has a total of 4 to 20 carbon atoms. 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. As the alicyclic isocyanate forming A2, for example, isophorone diisocyanate of the following formula is used. [ka]

[0064] In the above formula (ii), A3 each independently represents an alkyl group containing at least one (meth)acryloyloxy group and optionally having a substituent, the total number of carbon atoms of which is 4 to 30. The total number of carbon atoms of A3 is preferably 6 to 20, and more preferably 8 to 16. Examples of the substituent of the alkyl group of A3 include branched alkyl groups. A3 preferably contains at least two (meth)acryloyloxy groups, for example, three (meth)acryloyloxy groups. Furthermore, as a compound that forms A3, for example, pentaerythritol triacrylate of the following formula is used. [ka]

[0065] The fluorine-containing urethane acrylate 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). [ka]

[0066] Polyester (meth)acrylate As the (meth)acrylate compound having a (meth)acryloyl group, the above-mentioned polyester (meth)acrylate can also be used. Polyester (meth)acrylates include polymers (resins) obtained by the dehydration condensation reaction of (meth)acrylic acid, a polybasic carboxylic acid (anhydride), and a polyol. Examples of polybasic carboxylic acid (anhydrides) used in such dehydration condensation reactions 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.

[0067] Specific examples of polyester (meth)acrylates include Aronix M-6100, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8530, and Aronix M-8050 (trade names of polyester (meth)acrylate oligomers manufactured by Toagosei Co., Ltd.), Laromer PE44F, Laromer LR8907, Laromer PE55F, Laromer PE46T, and Laromer LR8800 (trade names of polyester (meth)acrylate oligomers manufactured by BASF), Ebecryl 80, Ebecryl 657, Ebecryl 800, Ebecryl 450, Ebecryl 1830, and Ebecryl Examples include 584 (all trade names of polyester (meth)acrylate oligomers manufactured by Daicel-UCB Ltd.), Photomer RCC13-429, and Photomer 5018 (all trade names of polyester (meth)acrylate oligomers manufactured by San Nopco Ltd.).

[0068] The (meth)acrylate polymer as the active energy ray-curable resin preferably has a (meth)acrylic equivalent of 200 to 500 g / eq. The (meth)acrylic equivalent of the (meth)acryloyl polymer is preferably 220 to 450 g / eq, more preferably 250 to 400 g / eq. Furthermore, 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.

[0069] The weight-average molecular weight value can be measured based on the description in paragraphs 0061 to 0064 of JP-A No. 2007-179018. Details of the measurement method are shown below. [Table 1] That is, first, a calibration curve showing the relationship between elution time and the molecular weight of polycarbonate is created by the universal calibration method using polystyrene as the standard polymer. Then, the elution curve (chromatogram) of the polycarbonate is measured under the same conditions as for the above-mentioned calibration curve. Furthermore, the weight-average molecular weight (Mw) is calculated from the elution time (molecular weight) of the polycarbonate 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 represents the number of molecules having a molecular weight Mi. Mw=Σ(NiMi 2 ) / Σ(NiMi)····(A) In this specification, (meth)acrylic includes both acrylic and methacrylic.

[0070] As described above, hard coat compositions containing (meth)acrylate polymers having a (meth)acrylic equivalent and weight-average molecular weight within a specified range exhibit excellent tack-free properties before curing and excellent scratch resistance after curing, and also facilitate the curing and polymerization reaction. In other words, the use of a (meth)acrylate compound (polymer) having a (meth)acryloyl group in a hard coat composition provides excellent tack-free properties (anti-stickiness) and prevents 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 polymer (meth)acrylate compounds having a (meth)acryloyl group are commercially available and easily available. They are available from, for example, Dainippon Ink, Kyoeisha Chemical, and DSP Gokyo Food & Chemical.

[0071] Other active energy ray curable resins As the active energy ray-curable resin, (meth)acrylate compounds ((meth)acrylate polymer resins) other than those mentioned above, for example, (meth)acrylate compounds that do not contain a (meth)acryloyl group or a (meth)acrylate skeleton, can also be used. 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.

[0072] In addition, the hard coat composition may contain a single or multiple types of active energy ray-curable resins. The content of the active energy ray-curable resin in the hard coat composition is preferably 40% by weight or more, more preferably 60% by weight or more, and even more preferably 80% by weight or more, based on the total weight of the hard coat composition.

[0073] (Polyfunctional acrylate compound) For example, a pentaerythritol-based polyfunctional acrylate compound may be added to the (meth)acrylate compound. Examples of polyfunctional acrylate compounds having multiple acrylate groups, preferably three or more acrylate groups, include pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, as well as pentaerythritol triacrylate, which are represented by the following formulas (3) and (4), respectively. [ka] [ka]

[0074] The polyfunctional acrylate compound is preferably contained in an amount of 70% by weight or less, more preferably 50% by weight or less, and even more preferably 30% by weight or less, based on the total weight of the polyfunctional acrylate compound and the (meth)acrylate compound. 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 (meth)acrylate polymer, a hard coat layer with higher scratch resistance can be formed.

[0075] (nanoparticles) Nanoparticles can be added to improve the scratch resistance and hardness of the hard coat composition. The nanoparticles can be inorganic or organic, but inorganic nanoparticles are preferred. For example, metal oxide nanoparticles such as nanosilica, nanoalumina, nanotitania, and nanozirconia can be used. Nanodiamonds can also be used.

[0076] The inorganic nanoparticles contained in the hard coat composition preferably include silica particles. The nanoparticles contained in the hard coat 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 the (meth)acrylate resin ((meth)acrylate polymer).

[0077] As a surface treatment agent for nanoparticles such as inorganic nanoparticles, a compound having a substituent capable of bonding to the surface of the nanoparticles and a substituent highly compatible with the components of the hard coat composition in which the nanoparticles are dispersed, particularly with (meth)acryloyl polymers, is preferably used. For example, a silane compound, alcohol, amine, carboxylic acid, sulfonic acid, phosphonic acid, etc. are used as the surface treatment agent.

[0078] The inorganic nanoparticles preferably have copolymerizable groups on their surfaces, which can be introduced by surface treatment of the inorganic nanoparticles. Specific examples of the copolymerizable groups include vinyl groups, meth(acrylic) groups, and free-radical polymerizable groups. The average particle size of the nanoparticles is preferably 5 to 500 nm, more preferably 10 to 300 nm, and even more preferably 20 to 100 nm. The average particle size of the nanoparticles is measured using, for example, a Zetasizer Nano ZS manufactured by Malvern Panalytical in accordance with a particle size measurement method using dynamic light scattering.

[0079] The hard coat composition preferably contains 20 to 80 wt % of nanoparticles, such as inorganic nanoparticles, based on the total weight of the hard coat composition, more preferably 30 to 70 wt % of inorganic nanoparticles, and even more preferably 40 to 60 wt % of inorganic nanoparticles.

[0080] (Leveling agent) To impart leveling properties, antifouling properties, and abrasion resistance to the hard coat composition, a silicone-based compound can be added as a leveling agent. Silicone-based compounds having polyalkylsiloxane bonds are used. While synthetic products can be used, commercially available products are readily available. For example, Shin-Etsu Silicone's KP series, BYK Japan's BYK series, and EVONIK's TEGO Glide series can be used.

[0081] To impart leveling properties, antifouling properties, and abrasion resistance to the hard coat composition, a fluorine-based compound can be added as a leveling agent. The fluorine-based compound used has a perfluoropolyether bond. While synthetic products can be used, commercially available products are readily available. For example, DIC's Megafac RS series, Shin-Etsu Chemical's KY series, and Daikin's Optool series can be used.

[0082] The hard coat composition preferably contains 0.1 wt % or more and 10 wt % or less of a leveling agent based on the total weight of the hard coat composition, and the content of the leveling agent in the hard coat composition is more preferably 0.5 wt % or more and 7 wt % or less, and even more preferably 1 wt % or more and 5 wt % or less.

[0083] (Curability of hard coat composition) The hard coat composition is preferably energy ray-curable or heat-curable, more preferably energy ray-curable, and even more preferably ultraviolet-curable. Therefore, the hard coat composition preferably further contains 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). Among these, IRGACURE TPO is preferred as the photopolymerization initiator from the viewpoint of heat resistance.

[0084] The hard coat composition contains, for example, 1 to 6% by weight of a photopolymerization initiator based on the total weight of the hard coat composition. The content of the photopolymerization initiator in the hard coat composition is more preferably 2 to 5% by weight, and even more preferably 3 to 4% by weight.

[0085] (Other additives) The hard coat composition may contain other additives, such as at least one additive selected from the group consisting of a heat stabilizer, an antioxidant, a flame retardant, a flame retardant aid, an ultraviolet absorber, a release agent, and a colorant. As long as the desired physical properties are not significantly impaired, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, etc. may also be added to the hard coat composition. In the hard coat composition, the active energy ray curable resin such as a (meth)acrylate polymer and the nanoparticles are contained in a total amount of preferably 60% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Therefore, the content of components other than the above two main components in the hard coat composition is preferably less than 40% by mass, more preferably less than 20% by mass, and particularly preferably less than 10% by mass.

[0086] The dilution solvent used in preparing the hard coat composition for forming a hard coat layer is used to adjust the viscosity, and is not particularly limited as long as it is non-polymerizable. The dilution solvent mainly allows the hard coat composition for forming a hard coat layer to be easily applied onto a transparent substrate.

[0087] 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.

[0088] <Production of hard coat layer> The hard coat layer is produced, for example, by applying a composition containing an active energy ray-curable resin such as the above-mentioned (meth)acrylate polymer, a polymerization inhibitor, etc. For example, the components such as the (meth)acrylate polymer are mixed and further stirred with a disper to produce a hard coat composition.

[0089] The hard coat composition can be coated onto the surface of the substrate layer using a bar coater, gravure coater, die coater, dip coater, spray coater, etc. In this case, after the hard coat liquid (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 120°C. If the temperature is below 30°C, the organic solvent will likely remain and affect the physical properties of the hard coat, and if the temperature is above 150°C, the substrate may be deformed.

[0090] The thickness of the hard coat layer is preferably in the range of 1 μm to 10 μm, more preferably in the range of 2 μm to 7 μm. If it is less than 1 μm, the desired performance cannot be obtained, and if it exceeds 10 μm, adhesion and moldability may deteriorate.

[0091] <Properties of the hard coat layer> (i) Tack-free property The hard coat layer contained in the laminate of the present invention has excellent tack-free properties. Although it does not have the adhesive properties of a typical adhesive layer, a protective film can be easily attached to the hard coat layer, which has high tack-free properties. In a moldable laminate in which such a hard coat layer is covered with a protective film, even if the uncured hard coat layer comes into contact with other substances, such as an operator's hand, it can maintain its predetermined shape, and adhesion of part of the hard coat layer to the surface of the contacted substance is suppressed. A moldable laminate with such excellent characteristics can be easily molded into shapes suitable for various applications and then cured. Furthermore, the moldable laminate in its uncured state can be easily stored or distributed in its predetermined shape.

[0092] In contrast, resin compositions with poor tack-free properties require a curing step before being molded into shapes suitable for various uses, and therefore tend to have poor moldability.

[0093] (ii) Gloss (appearance) after peeling off the protective layer In the hard coat layer, when processed into a film in an uncured state and a protective film is laminated and peeled off, the occurrence of unevenness on the film surface can be suppressed and good gloss can be maintained. In such evaluation tests, it was confirmed that the hard coat layer contained in the laminate of the present invention can keep the surface smooth and maintain good gloss after peeling off the protective film.

[0094] (iii) Formability (pressure formability) The hard coat layer of the moldable laminate of the present invention also has excellent moldability in an uncured state. The moldability of the hard coat composition can be evaluated, for example, as follows. That is, after applying the hard coat composition to the surface of the substrate layer and drying it, the resulting laminate is placed on a mold having convex portions and heated to perform pressure moldability. The moldability can be evaluated by determining whether the sheet-like hard coat composition is appropriately stretched while following the convex portions, and whether cracks occur. Although details are omitted, it was confirmed in such evaluation tests that the hard coat layer can be stretched while conforming to the convex portions without causing cracks during pressure forming.

[0095] (iv) Scratch resistance For evaluation tests, when the hard coat layer is cured without the protective film, high scratch resistance is achieved. As will be described in detail later, when a molding laminate having a hard coat layer is cured, it has been confirmed that the scratch resistance of the surface of the hard coat layer is superior to that of cured PMMA resin (polymethyl methacrylate resin) and lens resin.

[0096] (v)Hardness The hard coat layer cured without the protective film for evaluation testing has high hardness. Specifically, it can achieve a pencil hardness of B or higher according to the evaluation method of JIS K 5600-5-4:1999. The surface of the cured hard coat layer preferably achieves a pencil hardness of F or higher, and particularly preferably 2H or higher.

[0097] (vi) Adhesion The cured hard coat composition also has excellent adhesion, specifically, a hard coat composition that has an evaluation result of 0 as determined by the evaluation method of JIS K 5600-5-6 is obtained.

[0098] Furthermore, after a protective film is applied to a hard coat layer formed from a (meth)acrylate polymer, a pressure of 30 kg / m2 is applied from above the masking film under conditions of a temperature of 23±2°C and a relative humidity of 50±5%, and after 24 hours the masking film is peeled off. The Sa value of the hard coat layer surface is then preferably 0.0300 μm or less, more preferably 0.0200 μm or less, and even more preferably 0.0150 μm or less. The conditions for peeling the protective film from the surface of the hard coat layer were a peel angle, i.e., the angle between the masking film and the surface of the hard coat layer during peeling, of 90 degrees, and a peel speed of 600 mm / min.

[0099] [Protection film] After the hard coat layer has dried, a protective film is attached to the hard coat surface to prevent scratches. The surface of the protective film that contacts the hard coat layer is an adhesive surface with appropriate adhesive strength, and is attached to the surface of the hard coat layer. The protective film may be a single layer consisting of only an adhesive layer, but preferably has a two-layer structure consisting of a substrate and an adhesive layer. In a two-layer protective film, the adhesive surface of the adhesive layer is laminated on the hard coat layer so that it contacts the hard coat layer. The protective film may have a multilayer structure that further includes layers other than the substrate and adhesive layer described above. The protective film may also have a single-layer structure, and even in a protective film with a single-layer structure, the adhesive surface that is the surface on the hard coat layer side has appropriate adhesive strength.

[0100] The substrate of the protective film is preferably formed from a thermoplastic resin, and more preferably contains a polyolefin resin. Examples of the polyolefin resin contained in the protective film include polyethylene and polypropylene, and may be a homopolymer or a copolymer. Among polyolefin resins, polyethylene is preferred. As the polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), etc. can be used, but low-density polyethylene is preferred.

[0101] The polyolefin copolymer may be a copolymer of ethylene or propylene with a monomer copolymerizable therewith, such as α-olefins, styrenes, dienes, cyclic compounds, and oxygen-containing compounds.

[0102] Examples of the α-olefins include 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Examples of the styrenes include styrene, 4-methylstyrene, and 4-dimethylaminostyrene. Examples of the dienes include 1,3-butadiene, 1,5-hexadiene, 1,4-hexadiene, and 1,7-octadiene. Examples of the cyclic compounds include norbornene and cyclopentene. Examples of oxygen-containing compounds include hexenol, hexenoic acid, and methyl octenoate. These copolymerizable monomers may be used alone or in combination. Furthermore, copolymers of ethylene and propylene may also be used. The copolymer may be an alternating copolymer, a random copolymer, or a block copolymer.

[0103] The polyolefin resin contained in the base material of the protective film may contain a modified polyolefin resin modified with a small amount of a carboxyl group-containing monomer such as acrylic acid, maleic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, etc. The modification can usually be achieved by copolymerization or graft modification.

[0104] The substrate of the protective film preferably contains 80% by weight or more of polyolefin resin, more preferably 90% by weight or more of polyolefin resin, and even more preferably 95% by weight or more of polyolefin resin, based on the total weight of the substrate.

[0105] The adhesive layer of the protective film is preferably formed from an elastomer or a thermoplastic resin. Examples of the thermoplastic resin contained in the adhesive layer include polyolefin resins such as polypropylene and modified polyolefin. Examples of the polyolefin resin contained in the protective film (masking film) include polyethylene and polypropylene, and may be either a homopolymer or a copolymer. Among polyolefin resins, polyethylene is preferred.

[0106] The adhesive layer of the protective film preferably contains 80% by weight or more of an elastomer or thermoplastic resin, more preferably 90% by weight or more of an elastomer or thermoplastic resin, and even more preferably 95% by weight or more of an elastomer or thermoplastic resin, based on the total weight of the adhesive layer.

[0107] In the formable laminate, the thickness of the protective film is preferably 10 μm to 100 μm, and more preferably 20 μm to 80 μm.

[0108] The adhesive surface of the protective film, i.e., the adhesive surface in contact with the surface of the hard coat layer, preferably has a surface free energy of 30.0 (mN / m) or more before being attached to the hard coat layer. The surface free energy value is determined by measuring the average contact angle of 1 μL of water and the average contact angle of 1 μL of diiodomethane (CH2I2) placed on the adhesive surface using the θ / 2 method, and calculating the surface free energy value from these average contact angles using the OWRK (Owens-Wendt-Rabel-Kaelble) method. The surface free energy value of the adhesive surface is preferably 31.0 (mN / m) or more.

[0109] On the adhesive surface of the protective film that comes into contact with the surface of the hard coat layer, the average contact angle when 1 μl of the above-mentioned diiodomethane is left standing is preferably 64° or less, more preferably 60° or less, and even more preferably 58° or less. As described above, a protective film having a high surface free energy or an adhesive surface with a small contact angle of a stationary diiodomethane droplet can be said to have high wettability. When the surface of a hard coat layer is covered with a protective film having high wettability, it becomes possible to easily maintain the surface of the hard coat layer smooth without generating minute irregularities. Furthermore, such a protective film reliably protects the surface of the hard coat layer even when it is in an uncured, soft state, and therefore it is easy to improve the formability of the hard coat layer.

[0110] The protective film preferably has a surface roughness Sa (ISO 25178) of 0.100 μm or less on the adhesive surface that comes into contact with the hard coat layer before (before) it is attached to the hard coat layer. The surface roughness Sa of the adhesive surface of the protective film in the unattached state is more preferably 0.090 μm or less, even more preferably 0.080 μm or less, and particularly preferably 0.070 μm or less.

[0111] The adhesive strength value of the adhesive surface of the protective film is preferably 5 (mN / 25mm) or more and 5000 (mN / 25mm) or less against the surface of the PMMA (polymethyl methacrylate resin layer), and more preferably 9 (mN / 25mm) or more and 3000 (mN / 25mm) or less.

[0112] <Method of manufacturing a thermoforming laminate> A laminate for thermoforming is produced as follows. First, a material such as a resin composition is processed into a layer (sheet) by a conventional method to produce a base layer. For example, this can be done by extrusion molding or cast molding. An example of extrusion molding is a method in which pellets, flakes, or powder of a resin composition are melted and kneaded in an extruder, then extruded from 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. The hard coat composition prepared as described above is then applied to the outer surface of the substrate layer having a single layer or multiple layers to form a hard coat layer. The above-mentioned protective film is laminated to the surface of the hard coat layer side of the thus obtained intermediate body of the base layer and hard coat layer to produce a laminate for thermoforming.

[0113] [Thermoforming of laminated bodies] The thermoforming laminate can be made by any method that involves heating and molding a film, such as pressure forming, which involves heating the substrate and molding it under air pressure, vacuum pressure forming, which involves molding under vacuum conditions, or TOM molding, which allows the film to be thermoformed into the desired shape.

[0114] The molding temperature of the thermoformable laminate is determined mainly by the Tg (glass transition temperature) of the thermoplastic resin of the base layer. The molding temperature is preferably 0°C to 70°C higher than the Tg of the thermoplastic resin of the base layer, more preferably in the range of 20°C to 40°C. For example, in the case of a laminate including a base layer made of a general bisphenol A-type polycarbonate, molding is optimally carried out in the range of 170°C to 190°C.

[0115] Since the polymerization reaction of the hard coat layer can be suppressed by heating, the thermoforming laminate can be molded with the protective film attached. That is, the molding method for the thermoforming laminate of the present invention includes a heat molding step of heating the laminate with the protective film attached. By performing the series of operations with the protective film attached, it is possible to not only suppress the occurrence of scratches but also to suppress the inclusion of foreign matter.

[0116] [Manufacturing of molded products and articles] As described above, a molded product such as a cured film can be obtained by removing the protective film from a laminate that has been thermoformed into a predetermined shape and then curing the laminate. The surface of the hard coat layer side of the molded product, such as a cured film, produced in this manner has excellent properties. That is, the surface of the hard coat layer side of the molded product achieves high pencil hardness, preferably a pencil hardness of B or higher based on JISK 5600-5-4:1999, high scratch resistance, and excellent adhesion, for example, adhesion evaluated as level 0 in JISK 5600-5-6. Furthermore, the molded product thus obtained can be irradiated with active energy rays such as ultraviolet rays to produce a cured article. Examples of the above-mentioned molded products and articles include resin film laminates used in mobile devices, automobile interior materials, and the like. [Example]

[0117] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples and can be practiced with any modifications within the scope of the present invention.

[0118] Heat resistance test (heat resistance test): The thermoforming laminates obtained in each example described below were heated at 200°C for 2 minutes with a protective film attached, and after peeling off the protective film, 1 ml of methyl ethyl ketone was dropped onto the surface of the hard coat layer that had been in contact with the protective film. After 1 minute, the appearance was checked. Those that showed improved chemical resistance were judged to have undergone crosslinking, i.e., the polymerization reaction of the hard coat composition had progressed.

[0119] Thermoforming properties (including deep drawing and right-angle forming): The thermoforming laminate obtained in each example was cut to A4 size, and the obtained sample with a protective film attached was preheated at 190°C for approximately 40 seconds. Immediately afterwards, pressure forming was performed using a mold with a right-angled protrusion at a deep drawing height using high-pressure air at 1.5 MPa. For pressure forming, a right-angled mold with dimensions of 30 mm in both length and width was used, with a radius R of 1 mm in the area in contact with the right-angled portion of the mold and heights of 5 mm and 11 mm. Visual inspection of the edges of the thermoformed laminate, i.e., the area bent along the mold, was evaluated as good if there was no whitening or cracking, and as poor if there was either whitening or cracking.

[0120] Preparation Example 1 A mixture was prepared by adding the photopolymerization initiator IRGACURE TPO (2,4,6-trimethylbenzoyl-diphenyl phosphine oxide; 3% by weight based on solids) and the leveling agent BYK-UV3500 (a polyether-modified polydimethylsiloxane with acrylic functional groups; 1% by weight based on solids) to Artcure RA-3602MI manufactured by Negami Chemical Industries, a polymer acrylate type paint (an acrylic polymer with (meth)acryloyl groups (reactive groups) in the side chains of the acrylic skeleton) as a photopolymerizable compound. The resulting mixture was diluted with propylene glycol monoethyl ether as a solvent to a solids concentration of 30%.

[0121] Example 1 A hard coat composition was prepared by adding 500 ppm by weight of phenothiazine (solids content) to the photopolymerizable compound obtained in Preparation Example 1. A two-layer product of bisphenol A polycarbonate and PMMA, DF02U (manufactured by Mitsubishi Gas Chemical Company, thickness 0.254 mm), was used as the substrate layer. The hard coat composition was applied to the PMMA surface of the substrate layer using a bar coater to a film thickness of 3 μm. After drying at 120°C for 5 minutes, a protective film (PAC-3-50THK manufactured by San-A Chemical Co., Ltd.) was attached to the surface of the resulting hard coat layer opposite the substrate. Subsequently, a thermoforming test was performed using the method described above, and the results were good at both 5 mm and 11 mm heights. Furthermore, heat reactivity and chemical resistance tests showed no change in the surface of the hard coat layer, indicating good heat reactivity. [Polymerization inhibitor 1] Phenothiazine [ka]

[0122] Example 2 A thermoforming laminate was obtained in the same manner as in Example 1, except that phenothiazine was replaced with N-isopropyl-N'-phenyl-p-phenylenediamine. A thermoforming test was conducted, and the results were good at both 5 mm and 11 mm heights. Furthermore, a heat reactivity test was conducted, and no changes were observed on the surface of the hard coat layer, demonstrating good heat resistance and reactivity. [Polymerization inhibitor 2] N-isopropyl-N'-phenyl-p-phenylenediamine [ka]

[0123] Example 3 A laminate for thermoforming was obtained in the same manner as in Example 1, except that phenothiazine was replaced with 2-hydroxynaphthoquinone. A thermoforming test was carried out, and the result was good, with a height of 5 mm. Furthermore, a heat reactivity test was also carried out, but no change was observed, indicating good heat resistance and reactivity. [Polymerization inhibitor 3] 2-hydroxynaphthoquinone [ka]

[0124] Example 4 A laminate for thermoforming was obtained in the same manner as in Example 1, except that phenothiazine was replaced with 2-mercaptobenzimidazole. A thermoforming test was carried out, and the result was good, with a height of 5 mm. Furthermore, a heat reactivity test was also carried out, but no change was observed, indicating good heat resistance and reactivity. [Polymerization inhibitor 4] 2-mercaptobenzimidazole [ka]

[0125] Example 5 A laminate for thermoforming was obtained in the same manner as in Example 1, except that phenothiazine was replaced with 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline. A thermoforming test was conducted, and the result was good, with a height of 5 mm. Furthermore, a heat reactivity test was conducted, but no change was observed, indicating good heat resistance and reactivity. [Polymerization inhibitor 5] 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline [ka]

[0126] Example 6 A laminate for thermoforming was obtained in the same manner as in Example 1, except that phenothiazine was replaced with 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl. A thermoforming test was conducted, and the result was good, with a height of 5 mm. Furthermore, a heat reactivity test was conducted, but no change was observed, indicating good heat resistance and reactivity. [Polymerization inhibitor 6] 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl [ka]

[0127] Example 7 The photopolymerizable compound obtained in Preparation Example 1 was mixed with nanosilica particles (Nissan Chemical Industries, Ltd., organosilica sol MEK-AC-2140Z) at a weight ratio of polymer:nanosilica particles = 80:20, and 500 ppm by weight of phenothiazine (solids equivalent) was added to prepare a hard coat composition. A thermoforming laminate was obtained from the resulting composition using the same method as in Example 1. A thermoforming test was performed, and the results were good at both 5 mm and 11 mm heights. Furthermore, a heat reactivity test was performed, but no change was observed, indicating good heat resistance and reactivity.

[0128] Comparative Example 1 A laminate for thermoforming was obtained in the same manner as in Example 1, except that phenothiazine was not added. A thermoforming test was carried out, and the result was poor at a height of 5 mm. Furthermore, a heat reactivity test confirmed the progress of crosslinking in the hard coat composition.

[0129] Comparative Example 2 A laminate for thermoforming was obtained in the same manner as in Example 1, except that phenothiazine was replaced with di(tert-butyl)hydroxytoluene. A thermoforming test was conducted, and the result was poor at a height of 5 mm. Furthermore, a heat reactivity test confirmed the progress of crosslinking in the hard coat composition. [Polymerization inhibitor 7] Di(tert-butyl)hydroxytoluene [ka]

[0130] Comparative Example 3 A thermoforming laminate was obtained in the same manner as in Example 1, except that phenothiazine was replaced with 4-methoxyphenol. A thermoforming test was performed, and the result was poor at 5 mm height. Furthermore, a heat reactivity test confirmed the progress of crosslinking in the hard coat composition. [Polymerization inhibitor 8] 4-Methoxyphenol [ka] [Table 2]

[0131] Examples 8 to 11 Hard coat compositions were obtained in the same manner as in Example 1, except that the amount of phenothiazine added was changed under the conditions shown in Table 3 below. The results of the thermoforming test carried out under each condition are shown in Table 3. Table 3 also includes the results of Example 1 above.

[0132] [Table 3]

[0133] Example 12 A laminate for thermoforming was obtained in the same manner as in Example 1, except that the substrate used was changed from DF-02U to FE-2000 (manufactured by Mitsubishi Gas Chemical Company), a bisphenol A polycarbonate single layer film. A thermoforming test was carried out, and the results were good for both the 5 mm height and the 11 mm height.

[0134] Comparative Example 4 Except for not adding phenothiazine, a laminate for thermoforming was obtained in the same manner as in Example 12. As a result of carrying out a thermoforming test, it was found to be defective at a height of 5 mm.

[0135] As described above, although some examples showed poor results in terms of moldability, all of the examples showed good results in the heat reactivity resistance test. Thus, according to the above-mentioned examples, even if the hard coat layer is thermoformed while the protective film is still laminated, the progress of the polymerization reaction is suppressed, and it is possible to form the desired shape without deteriorating the appearance. Furthermore, by curing the hard coat film of each example after thermoforming, it is possible to obtain a molded product excellent in chemical resistance, scratch resistance, etc.

[0136] Next, the hard coat layers of the above-mentioned Examples and Comparative Examples were cured using a Fusion H bulb (Fusion UV Systems) at 90% output while blowing air at 1.8 m / min. The ultraviolet irradiation conditions were 1000 mJ / cm. 2 It was.

[0137] [Evaluation of laminate properties] The properties of the laminate thus obtained after curing by ultraviolet (UV) irradiation and the laminate in a state before the hard coat layer was cured (uncured laminate) were evaluated as follows.

[0138] <Tack-free in uncured state> The tack-free properties of the uncured laminate were evaluated by touch evaluation.

[0139] <Gloss (appearance) after removing masking in uncured state> A test piece having a substrate layer in which polycarbonate resin and PMMA resin were laminated was prepared, and the hard coat composition was applied to the surface of the substrate layer of the test piece on the PMMA resin side so as to form a hard coat layer with a thickness of 7 μm, followed by drying at 120°C for 5 minutes. A 30 μm thick masking film (protective film) made of polypropylene was then attached to the surface of the uncured hard coat layer, and a pressure of 30 kg / m was applied to the masking film. 2 After applying this pressure for 24 hours, the masking film was peeled off and the surface roughness Sa (in accordance with ISO25178) of the surface of the hard coat layer was measured using a scanning white light interference microscope VS1530 manufactured by Hitachi High-Technologies Corporation. The examples and comparative examples in which the surface roughness Sa was less than 0.01 μm were evaluated as having good appearance.

[0140] <Scratch resistance after curing> After curing, 100gf / cm of #0000 steel wool was applied to the surface of the hard coat layer. 2 The test piece was scratched by moving it back and forth 15 times under a pressure of 1.0 MPa. The absolute value of the haze change (ΔH), which is the difference between the haze value measured before the scratch test and the haze value measured after the scratch test according to JIS K 7136:2000, was calculated and evaluated according to JIS K 7136:2000. Examples and comparative examples with a ΔH value of less than 3.0% were evaluated as having good scratch resistance.

[0141] <Chemical resistance after curing> Neutrogena SPF100 was applied to the surface of the cured hard coat layer, and the appearance was visually observed after 1 hour at 80° C. Examples and comparative examples with no abnormalities on the surface were evaluated as having good chemical resistance.

[0142] <Pencil hardness after curing> Measurements were carried out based on the conditions of JIS K 5600-5-4:1999, and the hardness was evaluated based on the hardest pencil that did not cause scratches. <Adhesion> The evaluation was carried out according to the evaluation method of JIS K5600-5-6: 1999. For Examples and Comparative Examples with an evaluation result of 0, the adhesion was evaluated as good. The measurement results of the film properties of the laminates of each of the Examples and Comparative Examples are shown in Table 4. [Table 4]

[0143] As described above, it was confirmed that the examples in which the active energy ray-curable hard coat composition containing the (meth)acrylate resin having a (meth)acryloyl group was cured exhibited excellent properties in terms of tack-free property and appearance before curing, and scratch resistance, chemical resistance, pencil hardness, and adhesion after curing. [Explanation of symbols]

[0144] 10. Molding laminate 12 Protective film 16 Hard coat layer 20 Polymethyl methacrylate layer (base layer) 22 Polycarbonate layer (base layer)

Claims

1. A laminate for thermoforming, comprising: (a) a substrate layer containing a thermoplastic resin; (b) an after-cure hard coat layer containing an active energy ray-curable resin having a (meth)acryloyl group, the hard coat layer containing a polymerization inhibitor; and (c) Protective film and The (a) substrate layer, the (b) hard coat layer, and the (c) protective film are laminated in the order described above, A thermoforming laminate, wherein the polymerization inhibitor is selected from 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, phenothiazine, and 2-mercaptobenzimidazole.

2. 2. The thermoforming laminate of claim 1, wherein the polymerization inhibitor is selected from N-isopropyl-N'-phenyl-p-phenylenediamine, phenothiazine, and 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl.

3. 3. The thermoforming laminate according to claim 1, wherein the hard coat layer contains 0.0001 to 5% by weight of the polymerization inhibitor.

4. The thermoforming laminate according to any one of claims 1 to 3, wherein the active energy ray-curable resin having a (meth)acryloyl group has a (meth)acrylate skeleton.

5. The thermoforming laminate according to any one of claims 1 to 4, wherein the hard coat layer comprises nanoparticles.

6. The thermoforming laminate according to any one of claims 1 to 5, wherein the hard coat layer contains a leveling agent.

7. The thermoforming laminate according to any one of claims 1 to 6, wherein an adhesive surface of the protective film that is the surface on the hard coat layer side has a surface free energy of 30.0 (mN / m) or more, calculated based on the OWRK method from the values of the average contact angle of water and the average contact angle of diiodomethane, before being attached to the hard coat layer.

8. 8. The thermoforming laminate according to claim 1, wherein the adhesive surface of the protective film has a surface roughness Sa of 0.1 μm or less.

9. The thermoforming laminate according to any one of claims 1 to 8, wherein the hard coat layer is UV-curable.

10. The thermoforming laminate according to any one of claims 1 to 9, wherein the thermoplastic resin contains an aromatic polycarbonate.

11. 11. The thermoforming laminate of claim 10, wherein the aromatic polycarbonate comprises a bisphenol A type polycarbonate.

12. The thermoforming laminate according to any one of claims 1 to 11, wherein the substrate layer comprises at least two layers of an acrylic resin layer and an aromatic polycarbonate layer.

13. A method for molding a thermoforming laminate, comprising a heat molding step of heating the thermoforming laminate according to any one of claims 1 to 12 with the protective film attached.

14. A molded product obtained by molding the thermoforming laminate according to any one of claims 1 to 12.

15. An article obtained by irradiating the molded product according to claim 14 with active energy rays.

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