Laminated resin sheet for molding and molded product using same

Abstract

To provide a laminated resin sheet for molding which is excellent in adhesion and has easy moldability while having high hardness and scratch resistance, and a resin molded article using the same.SOLUTION: A laminated resin sheet for molding has a high hardness resin layer containing a high hardness resin, a base material layer containing a polycarbonate resin (a1) arranged on one surface side of the high hardness resin layer, and a hard coat layer arranged on the other surface side of the high hardness resin layer, wherein a plastic deformation ratio of the hard coat layer is 34-60%, and the hard coat layer is formed of a hard coating composition containing (A) a 2-15 functional (meth)acrylate oligomer, (B) a 1-2 functional (meth)acrylate monomer having a molecular weight of 250 or less and viscosity at 25°C of 15 cps or less, (C) a photopolymerization initiator, and (D) a surface modifier.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a moldable laminated resin sheet and a molded article using the same. [Background technology]

[0002] Resin molded articles are used for automobile interior parts such as instrument covers, housings for home appliances, office automation equipment, personal computers, and small portable devices, and touch panel display surfaces for mobile phone terminals, etc. Resin molded articles used for such applications are produced by molding a molding resin sheet.

[0003] Polycarbonate (PC) resin has attracted attention as a resin suitable for the above-mentioned applications. PC resin is known as an engineering plastic (engineering plastic) that is excellent in transparency, lightness, and impact resistance, and is suitably used for the above-mentioned applications.

[0004] For example, Patent Document 1 describes an invention relating to a polycarbonate resin laminate with a hard coating layer for hot bending, which is characterized by having a hard coating layer laminated on at least one surface of a polycarbonate resin. The invention described in Patent Document 1 provides a method for producing a bending member that is excellent in abrasion resistance, hot bending property, and adhesion after hot bending.

[0005] However, as described in Patent Document 1, the outermost surface of a polycarbonate resin molded product does not have sufficient pencil hardness, and is therefore prone to scratches when it comes into contact with hard members. This poses a problem in that it cannot be used for applications requiring high surface hardness, such as the housings of small portable devices or touch panel display surfaces of mobile phone terminals. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] WO2021 / 070632 Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, an object of the present invention is to provide a moldable laminated resin sheet that has high hardness and scratch resistance, excellent adhesion, and easy moldability. [Means for solving the problem]

[0008] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by providing a high-hardness resin layer on a polycarbonate layer and further providing a hard coat layer containing a specific component on the high-hardness resin layer. <1> a high-hardness resin layer containing a high-hardness resin; a substrate layer containing a polycarbonate resin (a1) disposed on one surface side of the high-hardness resin layer; a hard coat layer disposed on the other surface side of the high-hardness resin layer, The plastic deformation rate of the hard coat layer is 34 to 60%, The hard coat layer is (A) a 2- to 15-functional (meth)acrylate oligomer, (B) a mono- or di-functional (meth)acrylate monomer having a molecular weight of less than 200 and a viscosity of 15 cps or less at 25°C; (C) a photoinitiator, and (D) Surface modifier a hard coating composition comprising the content of the component (A) is 40 to 80 mass% based on the total content of the components (A) and (B), the content of the component (B) is 20 to 60 mass% based on the total content of the components (A) and (B), the content of the component (C) is 0.1 to 10 parts by mass per 100 parts by mass of the total of the components (A) and (B), In the moldable laminate resin sheet, the content of the component (D) is 0.1 to 10 parts by mass per 100 parts by mass of the total of the components (A) and (B). <2> The polycarbonate resin (a1) is an aromatic polycarbonate resin. <1> 1. The molding laminate resin sheet according to claim 1. <3> The aromatic polycarbonate resin is represented by the following formula (3a): [ka] The above-mentioned structural unit represented by <2> 1. The molding laminate resin sheet according to claim 1. <4> The content of the polycarbonate resin (a1) is 75 to 100% by mass based on the total mass of the base layer. <1> ~ <3> 1. The molding laminate resin sheet according to claim 1, wherein the resin is a fluororesin. <5> The high-hardness resin is The following general formula (1): [ka] (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group having 1 to 18 carbon atoms. and a (meth)acrylic acid ester structural unit (a) represented by the following general formula (2): [ka] (In the formula, R 3 is a hydrogen atom or a methyl group, and R 4 is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms. and a copolymer (B1) containing an aliphatic vinyl structural unit (b) represented by the formula: a resin (B2) which is a copolymer containing 6 to 77% by mass of (meth)acrylic acid ester structural units, 15 to 71% by mass of styrene structural units, and 8 to 23% by mass of unsaturated dicarboxylic acid structural units; The following formula (5): [ka] a resin (B3) that is a polymer containing a structural unit (c) represented by the following formula: Resin (B4) is a copolymer containing 5 to 20 mass% of styrene structural units, 60 to 90 mass% of (meth)acrylic acid ester structural units, and 5 to 20 mass% of N-substituted maleimide structural units; The following formula (7): [ka] Resin (B5) is a polymer containing a structural unit (e) represented by the formula: a resin (B6) which is a copolymer containing 50 to 95% by mass of styrene structural units and 5 to 50% by mass of unsaturated dicarboxylic acid units; The above, comprising at least one selected from the group consisting of <1> ~ <4> 1. The molding laminate resin sheet according to claim 1, wherein the resin is a fluororesin. <6> The resin (B3) is represented by the following formula (6): [ka] The copolymer further contains a structural unit (d) represented by <5> 1. The molding laminate resin sheet according to claim 1. <7> The content of the high-hardness resin is 70 to 100% by mass with respect to the total mass of the high-hardness resin layer. <1> ~ <6> 1. The molding laminate resin sheet according to claim 1, wherein the resin is a fluororesin. <8> the total thickness of the base layer and the high-hardness resin layer is 0.5 to 3.5 mm; <1> ~ <7> 1. The molding laminate resin sheet according to claim 1, wherein the resin is a fluororesin. <9> The ratio of the thickness of the base material layer to the total thickness of the base material layer and the high-hardness resin layer is 75% to 99%. <1> ~ <8> 1. The molding laminate resin sheet according to claim 1, wherein the resin is a fluororesin. <10> The viscosity of the hard coating composition is 400 cps or less at 25°C. <1> ~ <9> 1. The molding laminate resin sheet according to claim 1, wherein the resin is a fluororesin. <11> The pencil hardness of the surface of the hard coat layer is 2H or more. <1> ~ <10> 1. The molding laminate resin sheet according to claim 1, wherein the resin is a fluororesin. <12> the above <1> ~ <11> 1. A molded article molded using the moldable laminate resin sheet according to any one of the preceding items. [Effects of the Invention]

[0009] According to the present invention, there are provided a laminated resin sheet for molding which has high hardness and scratch resistance, is less likely to cause abnormal appearance during molding, and has excellent adhesion, and a resin molded product using the same. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram of an aluminum hot press mold used when hot press molding a moldable laminate resin sheet in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, the present invention will be described in detail by way of examples and working examples, but the present invention is not limited to the illustrated examples and working examples, and can be carried out by any method as long as it does not significantly deviate from the content of the present invention.

[0012] The moldable laminate resin sheet of the present invention (hereinafter also simply referred to as "resin sheet") includes a high-hardness resin layer containing a high-hardness resin, a substrate layer containing a polycarbonate resin (a1) arranged on one side of the high-hardness resin layer, and a hard coat layer arranged on the other side of the high-hardness resin layer. That is, the substrate layer, the high-hardness resin layer, and the hard coat layer are arranged in this order. Additional layers may be present between the substrate layer and the high-hardness resin layer, and between the high-hardness resin layer and the hard coat layer. Examples of additional layers include, but are not limited to, an adhesive layer and a primer layer. Additional layers may not be present. According to one embodiment, the substrate layer, the high-hardness resin layer, and the hard coat layer are laminated together. That is, according to one embodiment, the molding laminate resin sheet has a high-hardness resin layer containing a high-hardness resin, a base layer containing a polycarbonate resin (a1) laminated on one surface of the high-hardness resin layer, and a hard coat layer laminated on the other surface of the high-hardness resin layer.

[0013] The high-hardness resin layer and the hard coat layer may be provided on at least one side of the substrate layer, and there is no particular limitation on the configuration of the other side. Also, the high-hardness resin layer may be provided on both sides of the substrate layer, and in this case, a hard coat layer may be provided on one or both of the high-hardness resin layers. When the high-hardness resin layer is provided on both sides of the substrate layer, it is desirable to use the same high-hardness resin for the two high-hardness resin layers in order to obtain a stable resin sheet with little warping.

[0014] In the present invention, the plastic deformation ratio of the hard coat layer is 34 to 60%, preferably 36 to 57%, and more preferably 38 to 55%. This makes it possible to prevent the occurrence of abnormal appearance such as cracks during molding while maintaining sufficient hardness. In the present invention, the plastic deformation ratio of the hard coat layer is a value measured using a Fischer HM2000LT, specifically a value measured by the method described in the examples below.

[0015] The above-mentioned moldable laminate resin sheet can be suitably used to manufacture molded products having a curved shape that requires high hardness. For example, it can be used to successfully manufacture components having a flat portion and a continuous curved portion, thereby providing products with novel designs and functions.

[0016] When conventional resin sheets were used to manufacture molded products with the above-mentioned shapes, problems such as cracks occurring during thermoforming, such as heat press molding, vacuum molding, pressure molding, and TOM molding, were common. Therefore, in order to prevent cracks from occurring during thermoforming, it was necessary to devise measures such as reducing the hardness of the hard coat. However, while reducing the hardness of the hard coat improved thermoformability, new problems arose: the hard coat became soft, making it more susceptible to scratches, and its chemical resistance was reduced.

[0017] In contrast, according to the present invention, since the occurrence of cracks is suppressed as described above, it is possible to provide a thermoformable resin sheet without reducing the hardness of the hard coat. The moldable laminate resin sheet of the present invention has a hard hard coat layer on the surface, making it scratch-resistant and highly chemical-resistant. By utilizing these properties, the moldable laminate resin sheet of the present invention can be used for components for display surfaces of personal computers and mobile phones, automobile exterior and interior components, and curved housings and front panels for mobile phone terminals, personal computers, tablet PCs, car navigation systems, etc.

[0018] Hereinafter, each of the constituent members of the resin sheet according to the present invention will be described. <Base material layer> The substrate layer contains a polycarbonate resin (a1) and may further contain other resins, additives, and the like.

[0019] (Polycarbonate resin (a1)) The polycarbonate resin (a1) is not particularly limited as long as it contains a carbonate bond, i.e., an -[OR-OCO]- unit (where R may contain an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and may have a linear or branched structure), in the molecular main chain. However, an aromatic polycarbonate resin is preferred, and it is particularly preferred to use a polycarbonate resin containing a structural unit of the following formula (3a):

[0020] [ka]

[0021] Specifically, aromatic polycarbonate resins (for example, Iupilon S-2000, Iupilon S-1000, Iupilon E-2000; manufactured by Mitsubishi Engineering-Plastics Corporation) can be used as the polycarbonate resin (a1). By using such a polycarbonate resin, a resin sheet having superior impact resistance can be obtained.

[0022] In recent years, polycarbonate resins to which a monohydric phenol represented by the following general formula (3) has been added as a terminal terminator have been used for the purpose of controlling the glass transition temperature of the polycarbonate resin. In the present invention, polycarbonate resins to which such a terminal terminator has been added can also be used.

[0023] [ka]

[0024] In the formula, R 5 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms; R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms; and n is an integer from 0 to 4; here, the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In this specification, the "alkyl group" and the "alkenyl group" may be linear or branched, and may have a substituent.

[0025] The monohydric phenol represented by the general formula (3) is preferably one represented by the following general formula (4).

[0026] [ka]

[0027] In the formula, R 5 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.

[0028] R in general formula (3) or general formula (4) 5 It is more preferable that the number of carbon atoms in R is within a specific numerical range. 5 The upper limit of the number of carbon atoms in R is preferably 36, more preferably 22, and particularly preferably 18. 5The lower limit of the number of carbon atoms is preferably 8, and more preferably 12.

[0029] R in general formula (3) or general formula (4) 5 When the upper limit of the carbon number is appropriate, the solubility of the monohydric phenol (end terminator) in organic solvents tends to be high, which is preferable since it increases the productivity during the production of polycarbonate resin.

[0030] As an example, R 5 If the number of carbon atoms in R is 36 or less, the productivity and economy of producing polycarbonate resin are high. 5 When the carbon number of the monohydric phenol is 22 or less, the monohydric phenol has particularly excellent solubility in organic solvents, and can significantly increase the productivity in producing the polycarbonate resin, thereby improving the economic efficiency. An example of a polycarbonate resin using such a monohydric phenol is Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Company).

[0031] R in general formula (3) or general formula (4) 5 When the lower limit of the number of carbon atoms is appropriate, the glass transition point of the polycarbonate resin is not too high, and the polycarbonate resin has favorable thermoformability, which is preferable.

[0032] For example, in general formula (4), R 5 When a monohydric phenol in which the alkyl group has 16 carbon atoms is used as an end terminator, a polycarbonate resin excellent in glass transition temperature, melt fluidity, moldability, drawdown resistance, etc. can be obtained, and the monohydric phenol also has excellent solvent solubility during the production of the polycarbonate resin, making it particularly preferred.

[0033] Among the monohydric phenols represented by general formula (3) or general formula (4), it is particularly preferable to use either or both of parahydroxybenzoic acid hexadecyl ester and parahydroxybenzoic acid 2-hexyldecyl ester as the end terminator.

[0034] The weight-average molecular weight of the polycarbonate resin (a1) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and even more preferably 20,000 to 65,000. A weight-average molecular weight of 15,000 or more of the polycarbonate resin (a1) is preferred because it can improve impact resistance. On the other hand, a weight-average molecular weight of 75,000 or less is preferred because it allows the substrate layer to be formed with a small heat source and maintains thermal stability even under high-temperature molding conditions. In this specification, the weight-average molecular weight is the weight-average molecular weight measured by gel permeation chromatography (GPC) and converted into standard polystyrene.

[0035] The Tg of the polycarbonate resin (a1) is preferably 90 to 190°C, more preferably 100 to 170°C, and even more preferably 110 to 150°C. The Tg of the polycarbonate resin (a1) can be controlled by appropriately adjusting the type and combination of structural units of the polycarbonate resin (a1), the weight-average molecular weight, etc. In this specification, the glass transition point is the temperature calculated by the midpoint method using a differential scanning calorimeter to measure a 10 mg sample at a heating rate of 10°C / min.

[0036] The polycarbonate resin (a1) contained in the substrate layer may be one type or two or more types.

[0037] The content of the polycarbonate resin (a1) in the substrate layer is preferably 75 to 100 mass %, more preferably 90 to 100 mass %, and particularly preferably 100 mass %, based on the total mass of the substrate layer. If the content of the polycarbonate resin is 75 mass % or more, impact resistance can be further improved, which is preferable.

[0038] (other resins) The other resin that may be contained in the base layer is not particularly limited, but examples thereof include polyester resins. The polyester resin preferably contains terephthalic acid as the dicarboxylic acid component, but may contain a dicarboxylic acid component other than terephthalic acid.

[0039] For example, a polyester resin (so-called "PETG") obtained by polycondensation of a glycol component containing 80 to 60 mol % of ethylene glycol as the main component and 20 to 40 mol % of 1,4-cyclohexanedimethanol (total 100 mol %) is preferred. The other resins may be used alone or in combination of two or more.

[0040] When other resins are contained, the content thereof is preferably 0 to 25 mass %, more preferably 0 to 10 mass %, and particularly preferably 0 mass %, relative to the total mass of the base layer.

[0041] (additives) The additives that may be contained in the base layer can be those commonly used in resin sheets. Specific examples include antioxidants, anti-coloring agents, anti-static agents, release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, and reinforcing materials such as organic fillers and inorganic fillers. These additives can be used alone or in combination of two or more.

[0042] The amount of the additive is preferably 0 to 10% by mass, more preferably 0 to 7% by mass, and particularly preferably 0 to 5% by mass, relative to the total mass of the base layer.

[0043] The method for mixing the additive and the resin is not particularly limited, and methods such as compounding the entire amount, dry blending a master batch, and dry blending the entire amount can be used.

[0044] (base material layer) The thickness of the substrate layer is preferably 0.3 to 3.5 mm, more preferably 0.3 to 3.0 mm, and even more preferably 1.0 to 3.0 mm.

[0045] <High hardness resin layer> The high-hardness resin layer contains a high-hardness resin. Other resins, additives, and the like may be further contained as necessary. In this specification, a high-hardness resin refers to a resin that is harder than the polycarbonate resin used as the base material, and has a pencil hardness of HB or higher, preferably HB to 3H, more preferably H to 3H, and even more preferably 2H to 3H. The pencil hardness of the high-hardness resin layer is evaluated by a pencil scratch hardness test in accordance with JIS K 5600-5-4:1999. Specifically, pencils of gradually increasing hardness were pressed against the surface of the high-hardness resin layer at an angle of 45 degrees and a load of 750 g, and the hardness of the hardest pencil that did not leave a scratch was evaluated as the pencil hardness.

[0046] [High hardness resin] The high-hardness resin is not particularly limited, but preferably contains at least one selected from the group consisting of resins (B1) to (B6).

[0047] (Resin (B1)) Resin (B1) is a copolymer containing (meth)acrylic acid ester structural units (a) represented by general formula (1) and aliphatic vinyl structural units (b) represented by general formula (2). In this case, the resin (B1) may further contain other structural units. In this specification, (meth)acrylic refers to methacrylic and / or acrylic.

[0048] [ka]

[0049] In the formula, R 1 is a hydrogen atom or a methyl group, preferably a methyl group. Also, R 2is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group, and an isobornyl group. Of these, R 2 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0050] In addition, R 2 is a methyl group or an ethyl group, the (meth)acrylate structural unit (a) represented by general formula (1) becomes a (meth)acrylate structural unit, and R 1 is a methyl group and R 2 When is a methyl group, the (meth)acrylic acid ester structural unit (a) represented by general formula (1) becomes a methyl methacrylate structural unit.

[0051] The (meth)acrylic acid ester structural unit (a) represented by the general formula (1) may be contained in the resin (B1) either alone or in combination of two or more.

[0052] [ka]

[0053] In the formula, R 3 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom. R 4 is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms, and is preferably a cyclohexyl group having no substituent.

[0054] R 3 is a hydrogen atom, and R 4 is a cyclohexyl group, the aliphatic vinyl structural unit (b) represented by general formula (2) is a vinylcyclohexane structural unit.

[0055] The aliphatic vinyl structural unit (b) represented by general formula (2) may be contained in the resin (B1) either alone or in combination of two or more.

[0056] In this specification, the "hydrocarbon group" may be straight-chain, branched-chain, or cyclic, and may have a substituent.

[0057] The other structural units are not particularly limited, but examples thereof include structural units derived from aromatic vinyl monomers containing unhydrogenated aromatic double bonds, which are generated in the process of producing resin (B1) by polymerizing a (meth)acrylic acid ester monomer with an aromatic vinyl monomer and then hydrogenating the aromatic double bonds derived from the aromatic vinyl monomer.Specific examples of the other structural units include styrene structural units. The resin (B1) may contain only one type of other structural unit, or two or more types.

[0058] The total content of the (meth)acrylic acid ester structural units (a) and the aliphatic vinyl structural units (b) is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, and particularly preferably 98 to 100 mol %, based on all structural units of the resin (B1).

[0059] The content of the (meth)acrylic acid ester structural unit (a) represented by general formula (1) is preferably 65 to 80 mol %, more preferably 70 to 80 mol %, based on the total structural units of the resin (B1). A proportion of the (meth)acrylic acid ester structural unit (a) of 65 mol % or more is preferred because it allows for a resin layer that has excellent adhesion to the substrate layer and surface hardness. On the other hand, a proportion of the (meth)acrylic acid ester structural unit (a) of 80 mol % or less is preferred because it reduces the risk of warping of the resin sheet due to water absorption.

[0060] The content of the aliphatic vinyl structural unit (b) represented by general formula (2) is preferably 20 to 35 mol %, more preferably 20 to 30 mol %, based on the total structural units of the resin (B1). A content of the aliphatic vinyl structural unit (b) of 20 mol % or more is preferred because warping under high temperature and high humidity conditions can be prevented. On the other hand, a content of the aliphatic vinyl structural unit (b) of 35 mol % or less is preferred because peeling at the interface with the base layer can be prevented.

[0061] Furthermore, the content of other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less, based on all structural units of the resin (B1).

[0062] In this specification, the term "copolymer" may have any of the structures of a random copolymer, a block copolymer, and an alternating copolymer.

[0063] There are no particular restrictions on the weight average molecular weight of the resin (B1), but from the viewpoints of strength and moldability, it is preferably from 50,000 to 400,000, and more preferably from 70,000 to 300,000.

[0064] The glass transition point of the resin (B1) is preferably 110 to 140°C, more preferably 110 to 135°C, and particularly preferably 110 to 130°C. A glass transition point of 110°C or higher is preferred because the resin sheet is less likely to deform or crack in a hot or humid heat environment. On the other hand, a glass transition point of 140°C or lower is preferred because it provides excellent processability when molded by continuous thermal shaping using a mirrored roll or a shaping roll, or batch-type thermal shaping using a mirrored mold or a shaping mold.

[0065] Specific examples of the resin (B1) include Optimus 7500 and 6000 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) The above-mentioned resin (B1) may be used alone or in combination of two or more kinds.

[0066] When resin (B1) is used as the high-hardness resin, it is preferable to use Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as the polycarbonate resin (a1).

[0067] In addition, as a high-hardness resin, a structural unit represented by general formula (1) (R 1 , R 2 methyl methacrylate) at 75 mol %, and a structural unit represented by general formula (2) (R 3 is a hydrogen atom, R 4 The resin (B1) is a copolymer containing 25 mol % of a cyclohexyl group; vinylcyclohexane, and the polycarbonate resin (a1) is a polycarbonate resin containing a structural unit of formula (3a). The polycarbonate resin (a1) is a polycarbonate resin containing a monohydric phenol (R 5 A particularly preferred embodiment is one in which the carbon number is 8 to 22.

[0068] The method for producing the resin (B1) is not particularly limited, but a resin obtained by polymerizing at least one (meth)acrylic acid ester monomer and at least one aromatic vinyl monomer, and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer, is suitable.

[0069] The aromatic vinyl monomer is not particularly limited, but examples thereof include styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Among these, the aromatic vinyl monomer is preferably styrene.

[0070] The polymerization of the (meth)acrylic acid ester monomer and the aromatic vinyl monomer can be carried out by a known method, for example, a bulk polymerization method or a solution polymerization method. The bulk polymerization method is carried out by continuously supplying a monomer composition containing the above-mentioned monomers and a polymerization initiator to a complete mixing tank and continuously polymerizing the monomers at 100 to 180° C. The above-mentioned monomer composition may contain a chain transfer agent as needed.

[0071] The polymerization initiator is not particularly limited, but examples thereof include organic peroxides such as t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, t-hexylpropoxyisopropyl monocarbonate, t-amylperoxy normal octoate, t-butylperoxyisopropyl monocarbonate, and di-t-butyl peroxide, and azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile). These may be used alone or in combination of two or more.

[0072] The chain transfer agent is not particularly limited, but examples thereof include α-methylstyrene dimer.

[0073] Examples of solvents used in solution polymerization include hydrocarbon solvents such as toluene, xylene, cyclohexane, and methylcyclohexane; ester solvents such as ethyl acetate and methyl isobutyrate; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; and alcohol solvents such as methanol and isopropanol. These solvents may be used alone or in combination of two or more.

[0074] The solvent used in the hydrogenation reaction for hydrogenating the aromatic double bonds derived from the aromatic vinyl monomer after polymerizing the (meth)acrylic acid ester monomer and the aromatic vinyl monomer may be the same as or different from the above-mentioned polymerization solvent. Examples thereof include hydrocarbon solvents such as cyclohexane and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran and dioxane, and alcohol solvents such as methanol and isopropanol.

[0075] The hydrogenation method is not particularly limited, and known methods can be used. For example, the hydrogenation can be carried out in a batch or continuous flow system at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250°C. A reaction temperature of 60°C or higher is preferred because the reaction time is not too long. On the other hand, a reaction temperature of 250°C or lower is preferred because side reactions such as scission of molecular chains and hydrogenation of ester moieties do not occur or occur very little.

[0076] Examples of catalysts used in hydrogenation reactions include solid catalysts in which metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium, or oxides, salts, or complex compounds of these metals, are supported on porous supports such as carbon, alumina, silica, silica-alumina, and diatomaceous earth.

[0077] It is preferable that 70% or more of the aromatic double bonds derived from the aromatic vinyl monomer are hydrogenated by the hydrogenation reaction. That is, the unhydrogenated ratio of the aromatic double bonds contained in the structural units derived from the aromatic vinyl monomer is preferably less than 30%, more preferably less than 10%, and even more preferably less than 5%. An unhydrogenated ratio of less than 30% is preferable because a resin with excellent transparency can be obtained. The structural units of the unhydrogenated portion can become other structural units in the resin (B1).

[0078] (Resin (B2)) Resin (B2) is a copolymer containing 6 to 77 mass% of (meth)acrylic acid ester structural units, 15 to 71 mass% of styrene structural units, and 8 to 23 mass% of unsaturated dicarboxylic acid structural units, and may further contain other structural units.

[0079] The (meth)acrylic acid ester monomer constituting the (meth)acrylic acid ester structural unit in the resin (B2) is not particularly limited, but examples thereof include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate. Of these, the (meth)acrylic acid ester monomer is preferably methyl methacrylate. The above-mentioned (meth)acrylic acid ester monomer may be contained alone or in combination of two or more as the (meth)acrylic acid ester structural unit.

[0080] The content of the (meth)acrylic acid ester structural unit is from 6 to 77% by mass, and preferably from 20 to 70% by mass, based on the total mass of the resin (B2).

[0081] The styrene structural unit in the resin (B2) is not particularly limited, and any known styrene-based monomer can be used. Examples of the styrene-based monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and t-butylstyrene, from the viewpoint of availability. Among these, styrene is preferred as the styrene-based monomer from the viewpoint of compatibility. The above-mentioned styrene-based monomers may be contained alone as the styrene structural unit, or two or more types may be contained in combination.

[0082] The content of styrene structural units is from 15 to 71 mass %, and preferably from 20 to 66 mass %, based on the total mass of the resin (B2).

[0083] The unsaturated dicarboxylic acid anhydride monomer constituting the unsaturated dicarboxylic acid structural unit in the resin (B2) is not particularly limited, but examples thereof include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Among these, from the viewpoint of compatibility with styrene-based monomers, the unsaturated dicarboxylic acid anhydride monomer is preferably maleic acid anhydride. The unsaturated dicarboxylic acid anhydride monomers described above may be contained alone or in combination of two or more as the unsaturated dicarboxylic acid structural unit.

[0084] The content of the unsaturated dicarboxylic acid constituent units is from 8 to 23 mass %, and preferably from 10 to 23 mass %, based on the total mass of the resin (B2).

[0085] Examples of other structural units in the resin (B2) include N-phenylmaleimide.

[0086] The content of other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less, based on all structural units of the resin (B2).

[0087] The total content of the (meth)acrylic acid ester structural units, styrene structural units, and unsaturated dicarboxylic acid structural units is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, and particularly preferably 98 to 100 mol %, based on all structural units of the resin (B2).

[0088] There are no particular restrictions on the weight average molecular weight of the resin (B2), but it is preferably from 50,000 to 300,000, and more preferably from 80,000 to 200,000.

[0089] The glass transition point of the resin (B2) is preferably from 90 to 150°C, more preferably from 100 to 150°C, and particularly preferably from 115 to 150°C.

[0090] Specific examples of the resin (B2) include Resistify R100, R200, and R310 (manufactured by Denka), Delpet 980N (manufactured by Asahi Kasei), and hw55 (manufactured by Daicel-Evonik), etc. The above-mentioned resin (B2) may be used alone or in combination of two or more.

[0091] When resin (B2) is used as the high-hardness resin, a preferred embodiment is to use a polycarbonate resin containing the structural unit of formula (3a) as polycarbonate resin (a1). Furthermore, a monohydric phenol (R 5 It is particularly preferred to use a polycarbonate resin having a carbon number of 8 to 22. Examples of such polycarbonate resins include Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and Iupilon E-2000 (manufactured by Mitsubishi Engineering Plastics Corporation).

[0092] Furthermore, when a copolymer (R100 or R200; manufactured by Denka) consisting of 6 to 26 mass% of methyl methacrylate structural units, 55 to 21 mass% of styrene structural units, and 15 to 23 mass% of maleic anhydride structural units is used as the high-hardness resin (B2), a preferred embodiment is to use Iupizeta T-1380 as the polycarbonate resin (a1).

[0093] Furthermore, when resin (B2) is used as the high-hardness resin, which is a copolymer (R310; manufactured by Denka) composed of 6% by mass of methyl methacrylate structural units, 71% by mass of styrene structural units, and 23% by mass of maleic anhydride structural units, it is particularly preferable to use Iupizeta T-1380 as polycarbonate resin (a1).

[0094] The method for producing the resin (B2) is not particularly limited, but examples thereof include bulk polymerization and solution polymerization.

[0095] (Resin (B3)) Resin (B3) is a polymer containing a structural unit (c) represented by formula (5). In this case, the polymer preferably further contains a structural unit (d) represented by formula (6). The polymer may further contain other structural units.

[0096] [ka]

[0097] The content of the structural unit (c) represented by formula (5) is preferably 50 to 100 mol %, more preferably 60 to 100 mol %, and particularly preferably 70 to 100 mol %, based on all structural units of the resin (B3).

[0098] [ka]

[0099] The content of the structural unit (d) represented by formula (6) is preferably 0 to 50 mol %, more preferably 0 to 40 mol %, and particularly preferably 0 to 30 mol %, based on all structural units of the resin (B3).

[0100] The content of other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less, based on all structural units of the resin (B3).

[0101] The total content of the structural units (c) and (d) is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, and even more preferably 98 to 100 mol %, based on all structural units in the resin (B3).

[0102] The weight average molecular weight of the resin (B3) is preferably from 15,000 to 75,000, more preferably from 20,000 to 70,000, and particularly preferably from 25,000 to 65,000.

[0103] The glass transition point of the resin (B3) is preferably from 105 to 150°C, more preferably from 110 to 140°C, and particularly preferably from 110 to 135°C.

[0104] Specific examples of the resin (B3) include Iupilon KH3410UR, KH3520UR, and KS3410UR (manufactured by Mitsubishi Engineering-Plastics Corporation), etc. The above-mentioned resin (B3) may be used alone or in combination of two or more kinds.

[0105] When resin (B3) is used as the high-hardness resin, a preferred embodiment is to use a polycarbonate resin containing the structural unit of formula (3a) as polycarbonate resin (a1). Furthermore, a monohydric phenol (R 5 A particularly preferred embodiment is one in which a polycarbonate resin (a1) having 8 to 22 carbon atoms is used. An example of such a polycarbonate resin is Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Company). In particular, it is preferred to use Iupilon KS3410UR (manufactured by Mitsubishi Engineering Plastics Corporation) as the resin (B3) and Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Company) as the polycarbonate resin (a1).

[0106] When resin (B3) is used as the high-hardness resin, it is preferable that it contains a resin other than resins (B1) to (B6). In this case, the resin other than resins (B1) to (B6) is preferably a resin that does not contain structural unit (c) but contains structural unit (d), and more preferably a resin consisting only of structural unit (d). Specifically, aromatic polycarbonate resins (e.g., Iupilon S-2000, Iupilon S-1000, Iupilon E-2000; manufactured by Mitsubishi Engineering-Plastics Corporation) can be used.

[0107] When resins other than the resins (B1) to (B6) are contained, the resin (B3) is contained in an amount of preferably 45% by mass or more, more preferably 55% by mass or more, based on the total resins contained in the high-hardness resin layer.

[0108] The method for producing resin (B3) is not particularly limited, but it can be produced by the same method as the method for producing polycarbonate resin (a1) described above, except that bisphenol C is used as the monomer.

[0109] (Resin (B4)) Resin (B4) is a copolymer containing 5 to 20 mass% of styrene structural units, 60 to 90 mass% of (meth)acrylic acid ester structural units, and 5 to 20 mass% of N-substituted maleimide structural units. Resin (B4) may further contain other structural units.

[0110] The styrene structural unit in the resin (B4) is not particularly limited, and any known styrene-based monomer can be used. Examples of the styrene-based monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and t-butylstyrene, from the viewpoint of availability. Among these, styrene is preferred as the styrene-based monomer from the viewpoint of compatibility. The above-mentioned styrene-based monomers may be contained alone as the styrene structural unit, or two or more types may be contained in combination.

[0111] The content of styrene structural units is from 5 to 20% by mass, preferably from 5 to 15% by mass, and more preferably from 5 to 10% by mass, relative to the total mass of the resin (B4).

[0112] The (meth)acrylic acid ester monomer constituting the (meth)acrylic acid ester structural unit in the resin (B4) is not particularly limited, but examples thereof include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate. Of these, the (meth)acrylic acid ester monomer is preferably methyl methacrylate. The above-mentioned (meth)acrylic acid ester monomer may be contained alone or in combination of two or more as the (meth)acrylic acid ester structural unit.

[0113] The content of the (meth)acrylic acid ester structural unit is 60 to 90 mass %, preferably 70 to 90 mass %, and more preferably 80 to 90 mass %, based on the total mass of the resin (B4).

[0114] Examples of the N-substituted maleimide structural unit in the resin (B4) include structural units derived from N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide. Among these, structural units derived from N-phenylmaleimide are preferred from the viewpoint of compatibility with acrylic resins. The structural units derived from the above-mentioned N-substituted maleimides may be contained alone as N-substituted maleimide structural units, or two or more types may be contained in combination.

[0115] The content of the N-substituted maleimide structural units is from 5 to 20% by mass, preferably from 5 to 15% by mass, and more preferably from 5 to 10% by mass, relative to the total mass of the resin (B4).

[0116] Examples of the other structural units include a (meth)acrylic acid ester structural unit represented by general formula (1) and an aliphatic vinyl structural unit represented by general formula (2), where general formula (1) and general formula (2) are the same as those of the resin (B1) described above.

[0117] The content of other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less, based on all structural units of the resin (B4).

[0118] The total content of the styrene structural units, (meth)acrylic acid ester structural units, and N-substituted maleimide structural units is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, and even more preferably 98 to 100 mol %, based on all structural units of the resin (B4).

[0119] The weight average molecular weight of the resin (B4) is preferably from 50,000 to 250,000, more preferably from 100,000 to 200,000.

[0120] The glass transition point of the resin (B4) is preferably from 110 to 150°C, more preferably from 115 to 140°C, and particularly preferably from 115 to 135°C.

[0121] A specific example of the resin (B4) is Delpet PM120N (manufactured by Asahi Kasei Corp.) The above-mentioned resins (B4) may be used alone or in combination of two or more.

[0122] When resin (B4) is used as the high-hardness resin, a preferred embodiment is to use a polycarbonate resin containing the structural unit of formula (3a) as polycarbonate resin (a1). Furthermore, a monohydric phenol (R 5 A particularly preferred embodiment uses a polycarbonate resin having 8 to 22 carbon atoms. An example of such a polycarbonate resin is Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Company). In particular, it is preferred to use Delpet PM-120N, which is composed of 7% by mass of styrene structural units, 86% by mass of (meth)acrylic acid ester structural units, and 7% by mass of N-substituted maleimide structural units, as the resin (B4), and Iupizeta T-1380 as the polycarbonate resin (a1).

[0123] The method for producing the resin (B4) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, or the like.

[0124] (Resin (B5)) Resin (B5) is a polymer containing a structural unit (e) represented by formula (7). In this case, resin (B5) may further contain other structural units.

[0125] [ka]

[0126] The content of the structural unit (e) represented by formula (7) is preferably 80 to 100 mol %, more preferably 90 to 100 mol %, and particularly preferably 95 to 100 mol %, based on all structural units of the resin (B5).

[0127] Examples of other structural units include structural units represented by formula (5) and structural units represented by formula (6), where formula (5) and formula (6) are the same as those in the resin (B3) described above.

[0128] The content of other structural units is preferably 20 mol % or less, more preferably 10 mol % or less, and particularly preferably 5 mol % or less, based on all structural units of the resin (B5).

[0129] The weight average molecular weight of the resin (B5) is preferably from 10,000 to 1,000,000, and more preferably from 15,000 to 50,000.

[0130] The glass transition point of the resin (B5) is preferably from 120 to 200°C, more preferably from 130 to 190°C, and particularly preferably from 140 to 190°C.

[0131] A specific example of the resin (B5) is Iupizeta FPC0220 (manufactured by Mitsubishi Gas Chemical Company, Inc.) The above-mentioned resin (B5) may be used alone or in combination of two or more kinds.

[0132] When resin (B5) is used as the high-hardness resin, a preferred embodiment is to use a polycarbonate resin containing the structural unit of formula (3a) as polycarbonate resin (a1). An example of such a polycarbonate resin is Iupilon E-2000 (manufactured by Mitsubishi Engineering Plastics). In particular, it is preferred to use Iupizeta FPC0220 (manufactured by Mitsubishi Gas Chemical Company) as resin (B5) and Iupilon E-2000 (manufactured by Mitsubishi Engineering Plastics) as polycarbonate resin (a1).

[0133] When resin (B5) is used as the high-hardness resin, it is preferable that it contains a resin other than resins (B1) to (B6). In this case, the resin other than resins (B1) to (B6) is preferably a resin that does not contain structural unit (c) but contains structural unit (d), and more preferably a resin consisting of structural unit (d). Specifically, aromatic polycarbonate resins (e.g., Iupilon S-2000, Iupilon S-1000, Iupilon E-2000; manufactured by Mitsubishi Engineering-Plastics Corporation) can be used.

[0134] When resins other than the resins (B1) to (B6) are contained, the resin (B5) is contained in an amount of preferably 45% by mass or more, more preferably 55% by mass or more, based on the total resins contained in the high-hardness resin layer.

[0135] The method for producing resin (B5) is not particularly limited, but it can be produced by the same method as the above-mentioned method for producing polycarbonate resin (a1), except that bisphenol AP is used as the monomer.

[0136] (Resin (B6)) The resin (B6) is a copolymer containing 50 to 95% by mass of styrene structural units and 5 to 50% by mass of unsaturated dicarboxylic acid structural units.

[0137] As the styrene structural unit, the styrene-based monomers described in the resin (B4) can be used. The resin (B6) may use these styrene structural units alone or in combination of two or more.

[0138] The content of styrene structural units is preferably from 50 to 95 mass %, more preferably from 60 to 90 mass %, and even more preferably from 65 to 87 mass %, relative to the total mass of the resin (B6).

[0139] Examples of the unsaturated dicarboxylic acid anhydride monomer constituting the unsaturated dicarboxylic acid structural unit include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Among these, maleic anhydride is preferred from the viewpoint of compatibility with styrene-based monomers. The above-mentioned unsaturated dicarboxylic acid anhydride monomers may be used alone or in combination of two or more.

[0140] The content of the unsaturated dicarboxylic acid structural unit is preferably from 5 to 50 mass %, more preferably from 10 to 40 mass %, and even more preferably from 13 to 35 mass %, relative to the total mass of the resin (B6).

[0141] Resin (B6) may contain structural units other than the above-mentioned structural units. Examples of the structural units include a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

[0142] [ka] In the formula, R 1 and R 2 is the same as above.

[0143] [ka] In the formula, R 3 and R 4 is the same as above.

[0144] The content of other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, and even more preferably 2 mol % or less, based on all structural units of the resin (B6).

[0145] The weight average molecular weight of the resin (B6) is preferably from 50,000 to 250,000, more preferably from 50,000 to 100,000.

[0146] The glass transition point of the resin (B6) is preferably from 110 to 150°C, more preferably from 120 to 150°C, and particularly preferably from 130 to 150°C.

[0147] Specific examples of the resin (B6) include XIBOND140 and XIBOND160 (manufactured by Polyscope Co., Ltd.) The above-mentioned resin (B6) may be used alone or in combination of two or more kinds.

[0148] When resin (B6) is used as the high-hardness resin, a preferred embodiment is to use a polycarbonate resin containing the structural unit of formula (3a) as polycarbonate resin (a1). Furthermore, a monohydric phenol (R 5 A particularly preferred embodiment uses a polycarbonate resin having 8 to 22 carbon atoms. An example of such a polycarbonate resin is Iupizeta T-1380 (manufactured by Mitsubishi Gas Chemical Company). It is particularly preferred to use an alloy of XIBOND160, which is composed of 78% by mass of styrene structural units and 22% by mass of maleic anhydride structural units, and an acrylic resin as resin (B6), and to use Iupizeta T-1380 as polycarbonate resin (a1).

[0149] The method for producing the resin (B6) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, or the like.

[0150] At least one selected from the group consisting of the above resins (B1) to (B6) may be contained as an alloy.

[0151] The alloy is not particularly limited, but examples thereof include an alloy of two types of resin (B1), an alloy of two types of resin (B2), an alloy of two types of resin (B3), an alloy of two types of resin (B4), an alloy of two types of resin (B5), an alloy of two types of resin (B6), an alloy of resin (B1) and resin (B2), an alloy of resin (B2) and resin (B4), an alloy of resin (B2) and other high-hardness resin, an alloy of resin (B2) and acrylic resin, an alloy of resin (B6) and acrylic resin, and the like.

[0152] Examples of the other high hardness resins include methyl methacrylate-styrene copolymers and acrylonitrile-butadiene-styrene copolymers.

[0153] Examples of the acrylic resin include polymethyl methacrylate, copolymers of methyl methacrylate and methyl acrylate or ethyl acrylate, etc. Commercially available products include ACRYPET (manufactured by Mitsubishi Chemical Corporation), SUMIPEX (manufactured by Sumitomo Chemical Co., Ltd.), and PARAPET (manufactured by Kuraray Co., Ltd.).

[0154] When two types of resins are alloyed, it is preferable to use an alloy of resins having a higher glass transition temperature. The above alloys may be used alone or in combination of two or more.

[0155] The alloy may be produced by any method, including, but not limited to, melt-kneading the mixture at a cylinder temperature of 240°C using a twin-screw extruder with a screw diameter of 26 mm, extruding the mixture in the form of strands, and pelletizing the strands with a pelletizer.

[0156] The high-hardness resin layer may contain one type of high-hardness resin or two or more types of high-hardness resins. When two or more types of high-hardness resins are selected from the resins (B1) to (B6), they may be selected from the same or different categories, and may further contain a high-hardness resin other than the resins (B1) to (B6).

[0157] The content of the high-hardness resin in the high-hardness resin layer is preferably 70 to 100 mass %, more preferably 80 to 100 mass %, and particularly preferably 100 mass %, based on the total mass of the high-hardness resin layer.

[0158] [Other resins] The high-hardness resin layer may contain a resin other than the high-hardness resin. Examples of the other resin include methyl methacrylate-styrene copolymer, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co)polymer resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and various elastomers. These other resins may be used alone or in combination of two or more.

[0159] The content of the other resin is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 0% by mass, based on the total mass of the high-hardness resin layer.

[0160] [Additives] The high-hardness resin layer may contain additives, etc. As the additives, those described above can be used.

[0161] [High hardness resin layer] The thickness of the high-hardness resin layer is preferably 10 to 250 μm, more preferably 30 to 200 μm, and particularly preferably 60 to 150 μm. A thickness of 10 μm or more is preferable because the surface hardness is high. On the other hand, a thickness of 250 μm or less is preferable because the impact resistance is high.

[0162] [Lamination of high-hardness resin layer onto base layer] As described above, an additional layer may exist between the substrate layer and the high-hardness resin layer, but here, a case where a high-hardness resin layer is laminated on the substrate layer will be described.

[0163] The method for laminating the high-hardness resin layer on the base layer is not particularly limited, and examples thereof include a method of overlapping a separately formed base layer and a high-hardness resin layer and bonding them together under heat and pressure; a method of overlapping a separately formed base layer and a high-hardness resin layer and bonding them together with an adhesive; a method of co-extrusion molding the base layer and the high-hardness resin layer; a method of in-mold molding the base layer into a pre-formed high-hardness resin layer to integrate them, etc. Of these, the co-extrusion molding method is preferred from the viewpoints of production cost and productivity.

[0164] The co-extrusion method is not particularly limited. For example, in the feed block method, a high-hardness resin layer is placed on one side of a substrate layer in a feed block, and the layer is extruded into a sheet using a T-die, and then cooled while passing through a forming roll to form a desired laminate. In the multi-manifold method, a high-hardness resin layer is placed on one side of a substrate layer in a multi-manifold die, and then extruded into a sheet, and then cooled while passing through a forming roll to form a desired laminate. The above method can be used in the same manner when laminating a high-hardness resin layer on a layer other than the substrate layer.

[0165] The total thickness of the base layer and the high-hardness resin layer is preferably 0.5 to 3.5 mm, more preferably 0.5 to 3.0 mm, and even more preferably 1.2 to 3.0 mm. A total thickness of 0.5 mm or more is preferable because it allows the rigidity of the sheet to be maintained. On the other hand, a total thickness of 3.5 mm or less is preferable because it prevents the sensitivity of the touch sensor from being reduced when a touch panel is installed under the sheet.

[0166] The ratio of the thickness of the base layer to the total thickness of the base layer and the high-hardness resin layer is preferably 75% to 99%, more preferably 80% to 99%, and particularly preferably 85% to 99%. By setting the ratio within the above range, both hardness and impact resistance can be achieved.

[0167] <Hard coat layer> In this specification, the term "hard coat" refers to a coating film in which a crosslinked structure is formed by polymerizing a hard coating composition containing a monomer, oligomer, or prepolymer containing a (meth)acryloyl group as a polymerizable group.

[0168] In the present invention, the hard coating composition contains (A) a di- to penta-functional (meth)acrylate oligomer, (B) a mono- or di-functional (meth)acrylate monomer having a molecular weight of less than 200 and a viscosity of 15 cps or less at 25°C, (C) a photopolymerization initiator, and (D) a surface modifier. In this specification, the photopolymerization initiator refers to a photoradical generator.

[0169] The content of the (meth)acrylate oligomer as component (A) is 40 to 80 mass %, preferably 50 to 75 mass %, and more preferably 55 to 75 mass %, based on the total content of components (A) and (B).

[0170] The content of the (meth)acrylate monomer as component (B) is 20 to 60 mass %, preferably 20 to 50 mass %, more preferably 25 to 45 mass %, based on the total content of components (A) and (B).

[0171] The content of the photopolymerization initiator as component (C) is 0.1 to 10 parts by mass, preferably 0.5 to 7 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the total of components (A) and (B).

[0172] The content of the surface modifier as component (D) is 0.1 to 10 parts by mass, preferably 0.5 to 7 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the total of components (A) and (B).

[0173] The viscosity of a hard coating composition containing components (A) to (D) at 25°C is preferably 400 cps or less, more preferably 300 cps or less, and most preferably 250 cps or less. The lower limit is usually around 30 cps. If the viscosity of a hard coating composition at 25°C exceeds 400 cps, the coating film becomes thick during application, cracks are more likely to occur after thermoforming, and processability during cutting may be significantly reduced. The viscosity of the hard coating composition can be measured at 25°C using a Sekonic VM-100A-L vibration viscometer.

[0174] <Component (A)> [(Meth)acrylate oligomer] The (meth)acrylate oligomer used as component (A) in the present invention is a polyfunctional (meth)acrylate oligomer having 2 to 15 functionalities, preferably 2 to 9 functionalities, and more preferably 2 to 6 functionalities. The oligomer referred to here is a polymer having preferably 2 or more structural units, more preferably about 2 to 20 structural units, and the lower limit of the molecular weight is about 400 or more, more preferably 1200 or more. The upper limit of the molecular weight of the oligomer is preferably 6000 or less, more preferably 4000 or less.

[0175] Specific examples of the component (A) include the polyfunctional (meth)acrylate oligomers (1) to (4) shown below. (1) Polyfunctional polyol (meth)acrylate oligomers, i.e., polyacrylate or polymethacrylate oligomers obtained by reacting a polyhydric alcohol (a polyol or a polyhydroxy-containing compound) with a compound selected from the group consisting of acrylic acid, methacrylic acid, and derivatives thereof. (2) Polyfunctional polyester (meth)acrylate oligomers, i.e., oligomers of saturated or unsaturated polyester polyacrylates or polymethacrylates obtained from polyhydric alcohols (polyols), polycarboxylic acids (polybasic acids or polybasic carboxylic acids) or their anhydrides, and acrylic acid, methacrylic acid, or derivatives thereof. (3) Polyfunctional urethane (meth)acrylate oligomers, i.e., oligomers of urethane polyacrylate or urethane polymethacrylate obtained from polyisocyanate and a compound having active hydrogen and an acryloyloxy group or a methacryloyloxy group. (4) Polyfunctional polyglycidyl ether (meth)acrylate oligomers, i.e., oligomers of polyacrylates or polymethacrylates obtained from polyglycidyl ethers and acrylic acid, methacrylic acid, or derivatives thereof.

[0176] Examples of the polyhydric alcohol (polyol) used in the production of the above (1) polyfunctional polyol (meth)acrylate oligomer include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols having a number average molecular weight of 300 to 1000, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,2'-thiodiethanol, and 1,4-cyclohexanedimethanol; trihydric alcohols such as trimethylolethane, trimethylolpropane, pentaglycerol, glycerol, 1,2,4-butanetriol, and 1,2,6-hexanetriol; and tetrahydric or higher alcohols such as pentaerythritol, diglycerol, and dipentaerythritol.

[0177] The above-mentioned (2) polyfunctional polyester (meth)acrylate oligomer can be obtained by reacting (meth)acrylic acid, a polybasic carboxylic acid (anhydride), and a polyol (a polyhydroxy-containing compound or a polyhydric alcohol). More specifically, a polyester polyol is produced by a dehydration condensation reaction between a dibasic carboxylic acid (anhydride) and a polyol, and then the reaction product is reacted with acrylic acid or methacrylic acid to obtain a polyfunctional polyester (meth)acrylate oligomer.

[0178] The polyhydroxy-containing compounds, also referred to as "polyols," used in the preparation of polyester polyols are preferably compounds having three or more hydroxy groups. Generally, polyols that can be used in the present invention are compounds having 3 to 6 hydroxy groups, preferably 3 to 4 hydroxy groups, and 2 to about 36 carbon atoms. Such polyols include branched or straight-chain aliphatic polyols, alicyclic polyols, aromatic polyols, and polyether polyols. Aliphatic polyols can include triols such as glycerin, trimethylolpropane, and trimethylolethane; tetraols such as pentaerythritol and di-trimethylolpropane; and hexaols such as dipentaerythritol. Additionally, aliphatic and cycloaliphatic polyols can be reacted with various amounts of ethylene oxide and / or propylene oxide to produce ethoxylated and / or propoxylated polyols. Examples of ethoxylated and / or propoxylated polyols include ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated glycerin, propoxylated glycerin, ethoxylated pentaerythritol, and propoxylated pentaerythritol.

[0179] Examples of aromatic polyols include bisphenol A diacrylate. The polyether polyols that can be used in the present invention include both aromatic polyethers and aliphatic polyethers. The aliphatic groups of the polyether polyols can be linear, branched, or cyclic. Examples of polyether polyols include triglycols, such as triethylene glycol, polyethylene glycol, polypropylene glycol, and polybutylene glycol, as well as mixed polyethers, such as poly(propylene-ethylene) glycol.

[0180] Examples of dibasic carboxylic acids (anhydrides) used in the production of polyester polyols include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, and sebacic acid; alicyclic dicarboxylic acids such as tetrahydrophthalic acid and 3,6-endomethylenetetrahydrophthalic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; trimellitic acid; pyromellitic acid; thiodiglycolic acid; thiodivaleric acid; diglycolic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Chlorides, anhydrides, or esters of these compounds can also be used. Anhydrides of these dibasic carboxylic acids are preferred. Alicyclic dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride are particularly preferred. Polyester polyols are polyols containing ester bonds. For example, excess polyol is reacted with a dibasic acid (anhydride) to obtain a low-molecular-weight compound containing about 1 to about 6 ester bonds and reactive hydroxy groups. The above polyols can be used alone or in combination to produce polyester polyols. The polyester polyols may also be further reacted with various amounts of ethylene oxide and / or propylene oxide to provide ethoxylated and / or propoxylated polyester polyols.

[0181] The (2) multifunctional polyester (meth)acrylate oligomer used in the present invention can be obtained by reacting the polyester polyol obtained in this manner with a compound selected from the group consisting of acrylic acid, methacrylic acid, and derivatives thereof. Among the compounds selected from the group consisting of acrylic acid, methacrylic acid and derivatives thereof, it is more preferable to use acrylic acid.

[0182] In the above (2) multifunctional polyester (meth)acrylate oligomer, the polyol (polyhydroxy-containing compound) can be used alone or in combination with other polyhydroxy-containing compounds. Furthermore, compounds selected from the group consisting of acrylic acid, methacrylic acid, and their derivatives can be used alone or in combination with each other. When a mixture of polyhydroxy-containing compounds is used, a mixed ester product is obtained. Similarly, when a mixture of acrylic acid and methacrylic acid is used, the product is a mixed acrylate oligomer.

[0183] A preferred polyester (meth)acrylate oligomer is a di- to tetra-functional acrylate oligomer obtained by esterifying tetrahydrophthalic anhydride, trimethylolpropane, and acrylic acid by a conventional method.

[0184] Examples of the (3) polyfunctional urethane (meth)acrylate oligomer include a urethane reaction product of a (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule with a polyisocyanate, and a urethane reaction product of an isocyanate compound obtained by reacting a polyol with a polyisocyanate with a (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule.

[0185] In the production of a polyfunctional urethane (meth)acrylate oligomer, examples of the polyisocyanate used in the urethanization reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates (for example, diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate), di- or triisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, and polyisocyanates obtained by cyanurating a diisocyanate.

[0186] In the production of a polyfunctional urethane (meth)acrylate oligomer, examples of polyols used in the production of an isocyanate compound include the compounds exemplified above as the polyhydric alcohols used in the production of (1) a polyfunctional polyol (meth)acrylate oligomer. Specific examples of isocyanate compounds obtained by reacting the above polyols with polyisocyanate include trimethylolpropane toluylene diisocyanate. The "compound containing active hydrogen and an acryloyloxy group (or a methacryloyloxy group)" used in the production of the polyfunctional urethane (meth)acrylate oligomer is a compound containing a hydroxyl group and an acryloyloxy group (or a methacryloyloxy group). Specific examples include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

[0187] Specific examples of polyfunctional urethane (meth)acrylate oligomers that are particularly preferably used in the present invention include trimethylolpropane toluylene diisocyanate, or a reaction product of an isocyanurate group-containing polyisocyanate with a compound containing active hydrogen and a (meth)acryloyloxy group. More specifically, examples thereof include a triacrylate oligomer, trimethacrylate oligomer, diacrylate oligomer, or dimethacrylate oligomer of tris(2-hydroxyethyl)isocyanurate; a triacrylate oligomer, trimethacrylate oligomer, diarylate oligomer, or dimethacrylate oligomer of di(2-hydroxyethyl)mono(2-hydroxyheptane)isocyanurate; and a compound (molecular weight of 1,200 or more) containing (meth)acryloyloxy groups at both ends connected by a urethane bond. Commercially available polyfunctional urethane (meth)acrylate oligomers can be used. Specific examples of commercially available products include UN-3320HC (Negami Chemical Co., Ltd.), UA-510H (Kyoeisha Chemical Co., Ltd.), CN968 (Sartomer Co., Ltd.), Eb-220 (Daicel Cytec Co., Ltd.), and U6HA (Shin-Nakamura Chemical Co., Ltd.), but are not limited thereto. In the present invention, hexafunctional urethane acrylate oligomers are particularly preferred.

[0188] The hard coat layer may contain one or more types of (meth)acrylate oligomers as the component (A).

[0189] <Component (B)> [(Meth)acrylate monomer] The (meth)acrylate monomer used as component (B) in the present invention is one in which a (meth)acryloyl group exists as a functional group within the molecule, and may be a monofunctional or bifunctional monomer. The upper limit of the molecular weight of the monomer is less than 200, preferably 190 or less, and more preferably 180 or less. If the molecular weight of the monomer is 200 or more, adhesion to the high-hardness resin layer may be significantly reduced. The viscosity of the monomer at 25°C is 15 cps, preferably 10 cps or less, more preferably 7 cps or less, and particularly preferably 5 cps or less. The viscosity of the monomer can be measured at 25°C using a Sekonic VM-100A-L vibration viscometer.

[0190] Examples of monofunctional monomers having a molecular weight of less than 200 include (meth)acrylic acid and (meth)acrylic acid esters. Specific examples of (meth)acrylate monomers include ethyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-(allyloxymethyl)methyl acrylate, diethylene glycol monoethyl ether acrylate, and 3,3,5-trimethylcyclohexyl acrylate acrylic acid.

[0191] Specific examples of bifunctional (meth)acrylate monomers having a molecular weight of less than 200 include 1,4-butanediol diacrylate and ethylene glycol di(meth)acrylate.

[0192] The hard coat layer may contain one or more types of (meth)acrylate monomers as the component (B).

[0193] <Component (C)> [Photopolymerization initiator] The photopolymerization initiator can be a monofunctional photopolymerization initiator.Specific examples include acetophenone-based initiators such as 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone [Darocure 2959: manufactured by Merck]; α-hydroxy-α,α'-dimethylacetophenone [Darocure 1173: manufactured by Merck]; methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure 651: manufactured by BASF], 1-hydroxy-cyclohexylphenyl ketone [Irgacure 184: manufactured by BASF]; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; and other halogenated ketones, acylphosphinoxides, acylphosphonates, etc.

[0194] <Component (D)> [Surface modifier] The surface modifiers are agents that change the surface properties of the hard coat layer, such as leveling agents, antistatic agents, surfactants, water and oil repellents, inorganic particles, and organic particles.

[0195] Examples of the leveling agent include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyester-modified hydroxyl group-containing polyalkylsiloxane, polyether-modified polydimethylsiloxane having an alkyl group, modified polyether, and silicon-modified acrylic.

[0196] Examples of the antistatic agent include glycerin fatty acid ester monoglycerides, glycerin fatty acid ester organic acid monoglycerides, polyglycerin fatty acid esters, sorbitan fatty acid esters, cationic surfactants, and anionic surfactants.

[0197] Examples of the surfactant and the water / oil repellent agent include fluorine-containing surfactants and water / oil repellents such as an oligomer containing a fluorine-containing group and a lipophilic group, and an oligomer containing a fluorine-containing group, a hydrophilic group, a lipophilic group, and a UV-reactive group.

[0198] Examples of the inorganic particles include silica particles, alumina particles, zirconia particles, and glass particles.

[0199] Examples of the organic particles include acrylic particles and silicon particles.

[0200] The hard coat layer may contain one or more types of surface modifiers.

[0201] [Method for forming hard coat layer] The method for forming the hard coat layer is not particularly limited. For example, the hard coat layer can be formed by applying a hard coating composition onto a layer (e.g., a high-hardness resin layer) located below the hard coat layer, followed by photopolymerization.

[0202] The method for applying the hard coating composition (polymerizable composition) is not particularly limited, and known methods can be used, such as spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, beat coating, and sieving.

[0203] The lamp used for light irradiation in photopolymerization has an emission distribution with a light wavelength of 420 nm or less. Examples include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps. Among these, high-pressure mercury lamps and metal halide lamps are preferred because they efficiently emit light in the active wavelength range of the initiator and do not emit much short-wavelength light that would reduce the viscoelastic properties of the resulting polymer due to crosslinking, or much long-wavelength light that would heat and evaporate the reaction composition.

[0204] The irradiation intensity of the lamp is a factor that determines the degree of polymerization of the resulting polymer, and is appropriately controlled depending on the performance of the target product. When a typical cleavage-type initiator having an acetophenone group is blended, the irradiance is 0.1 to 300 mW / cm. 2 In particular, when a metal halide lamp is used, the illuminance is set to 10 to 40 mW / cm. 2 It is preferable to set the following.

[0205] The photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the hard coating composition. Therefore, it is desirable to perform light irradiation using a method that can eliminate reaction inhibition by oxygen. One such method is to cover the hard coating composition with a film made of polyethylene terephthalate or Teflon to prevent contact with oxygen, and then irradiate the hard coating composition with light through the film. Alternatively, the composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen has been replaced with an inert gas such as nitrogen gas or carbon dioxide gas.

[0206] When light irradiation is performed in an inert atmosphere, a certain amount of inert gas is always introduced to maintain a low oxygen concentration in the atmosphere. The introduction of this inert gas generates an airflow on the surface of the hard coating composition, causing monomer evaporation. To suppress the level of monomer evaporation, the airflow velocity of the inert gas is preferably 1 m / sec or less, more preferably 0.1 m / sec or less, relative to the laminate coated with the hard coating liquid moving under the inert gas atmosphere. By setting the airflow velocity within the above range, monomer evaporation due to the airflow can be substantially suppressed.

[0207] In order to improve the adhesion of the hard coat layer, the coated surface may be pretreated by known methods such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment with a resin composition.

[0208] The hard coat layer may be further modified. For example, it may be subjected to one or more of anti-glare treatment, anti-reflection treatment, antifouling treatment, anti-static treatment, weather resistance treatment, and anti-glare treatment. The treatment method is not particularly limited, and known methods can be used. For example, a method of applying a reflection-reducing coating, a method of depositing a dielectric thin film, a method of applying an anti-static coating, etc. may be mentioned.

[0209] The anti-glare treatment is not particularly limited, but may involve the use of an anti-glare mold. For example, a high-hardness resin layer, a coating film obtained by applying a hard coating composition, and an anti-glare mold are laminated in this order. The hard coating composition is then photopolymerized, and the anti-glare mold is demolded. The photopolymer (hard coat layer) of the hard coating composition has a shape that reflects the rough surface of the anti-glare mold at the contact surface with the anti-glare mold. The material of the anti-glare mold is not particularly limited as long as it transmits UV light, and glass, transparent resin, etc. can be used. Other anti-glare treatment methods include adding particles to the hard coating composition and treating the surface of the resulting hard coat layer. The haze of the hard coat layer can be adjusted by controlling the type of anti-glare mold used (surface haze, thickness, etc.) and the amount of particles added.

[0210] <Molding laminated resin sheet> The pencil hardness of the laminated resin sheet for molding is preferably 2H or higher, more preferably 2H to 4H, and even more preferably 3H to 4H. This is because a pencil hardness of 5H or higher would cause cracks after thermoforming, so by setting the pencil hardness to 2H to 4H, both moldability and hardness can be achieved. The pencil hardness of the laminated resin sheet for molding means the hardness of the hardest pencil that does not leave a scratch when a pencil of gradually increasing hardness is pressed against the surface of the hard coat layer at an angle of 45 degrees and with a load of 750 g (pencil scratch hardness test in accordance with JIS K 5600-5-4:1999).

[0211] <Molded products> According to one embodiment of the present invention, there is provided a molded article molded using the above-described moldable laminate resin sheet.

[0212] Although the molding method is not particularly limited, thermoforming is suitable due to the characteristics of the moldable laminate resin sheet. Thermoforming can be carried out by a method commonly used in the field. Specific thermoforming methods include, for example, heat press molding, pressure molding, vacuum molding, and TOM molding.

[0213] The molding temperature is preferably 100 to 200°C. [Example]

[0214] Examples of the present invention will be described below, but the present invention is not limited to the embodiments of the examples.

[0215] For the purposes of the examples, the following materials were used as the methacrylic resin (C-1) and the styrene copolymer (D-1), but the present invention is not limited to these.

[0216] Methacrylic resin (C-1): ALTUGLAS (registered trademark) V020 manufactured by Arkema Inc. (weight average molecular weight: 127,000, glass transition temperature: 134°C, melt flow rate at 230°C under a load of 3.8 kg: 1.8 g / 10 min, refractive index: 1.49, mm / mr / rr = 7.4 mol% / 37.4 mol% / 55.2 mol%) Styrene copolymer (D-1): XIBOND160 manufactured by Polyscope ((d1) / (d2) = styrene / maleic anhydride = 78% by mass / 22% by mass, weight average molecular weight: 69,500, glass transition temperature: 143°C, melt flow rate at 230°C under a 3.8 kg load: 7.6 g / 10 min, refractive index: 1.58) (equivalent to resin (B6))

[0217] The following materials were used as components constituting the hard coating composition, and were used in the compounding ratios (parts by mass) shown in Table 1 below. CN968 (Component (A)): Sartomer, hexafunctional urethane acrylate oligomer AOMA (component (B)): Nippon Shokubai, 2-(allyloxymethyl)methyl acrylate (monofunctional) [ka] THF (1000) (component (B)): tetrahydrofurfuryl methacrylate (monofunctional), manufactured by Kyoeisha Chemical [ka] EG (component (B)): Kyoeisha Chemical Co., Ltd., ethylene glycol dimethacrylate (bifunctional) [ka] 4-EGA: Kyoeisha Chemical Co., Ltd., PEG200# diacrylate (bifunctional) [ka] 1.6HX: Kyoeisha Chemical Co., Ltd., 1,6-hexanediol dimethacrylate (bifunctional) [ka] 2EG: Kyoeisha Chemical Co., Ltd., diethylene glycol dimethacrylate (bifunctional) [ka] IB-X: Kyoeisha Chemical, isobornyl methacrylate (monofunctional) [ka] TBCHA: 4-tert-butylcyclohexyl acrylate (monofunctional), manufactured by KJ Chemicals [ka] #200: Osaka Organic Chemical Industry Co., Ltd., cyclic trimethylolpropane formal acrylate (monofunctional) [ka] Irgacure 184 (component (C)): BASF Ltd., 1-hydroxycyclohexyl phenyl ketone RS-90 (component (D)): Manufactured by DIC Corporation, oligomer containing fluorine-containing groups, hydrophilic groups, lipophilic groups, and UV-reactive groups.

[0218] <Measurement of adhesion of laminated resin sheet for molding (hard coat layer)> In accordance with JIS-K5400-5-6, 25 squares were cut with a cutter blade, six lines vertically and six lines horizontally at 1 mm intervals. Nichiban cellophane tape was firmly adhered to the cuts and then peeled off at a 60° angle toward the user. A pass (○) was given if no coating peeling occurred, and a fail (×) was given if even one square peeled off.

[0219] <Measurement of Scratch Resistance of Laminated Resin Sheet for Molding (Hard Coat Layer)> Scratch resistance: 100g / cm with #0000 steel wool 2 The test piece was reciprocated 15 times under a load of 0.05g, and a test piece with less than five scratches was rated as passing (◯), and a test piece with five or more scratches was rated as failing (×).

[0220] <Measurement of pencil hardness of moldable laminated resin sheet (hard coat layer)> The moldable laminated resin sheets produced in the examples and comparative examples were evaluated by a pencil scratch hardness test in accordance with JIS K 5600-5-4:1999. Pencils of gradually increasing hardness were pressed against the surface of the hard coat layer at an angle of 45 degrees and with a load of 750 g, and the hardness of the hardest pencil that did not leave a scratch was evaluated as the pencil hardness. A hardness of 2H or higher was considered acceptable.

[0221] <Measurement of plastic deformation rate of laminated resin sheet for molding (hard coat layer)> The plastic deformation rate of the hard coat layer was measured using a Fischer HM2000 LT under the following conditions: Maximum load: 3mN Hold time when maximum load is reached: 5 seconds Loading speed, unloading speed: 10mN / sec Calculation method: 100 - Elastic deformation rate (%) = Plastic deformation rate (%)

[0222] <Evaluation of crack occurrence in hard coat layer (formability)> The moldable laminated resin sheets manufactured in the Examples and Comparative Examples were thermoformed, and the presence or absence of cracks was checked in the 50 mm R portion, the 75 mm R portion, and the 100 mm R portion, respectively. Those in which no cracks were visually observed were evaluated as passing (◯), and those in which cracks were observed were evaluated as failing (×).

[0223] Example 1 [Production of high-hardness resin (B-1) pellets] To a total of 100 parts by mass of 50 parts by mass of the methacrylic resin (C-1) and 50 parts by mass of the styrene copolymer (D-1), 500 ppm of phosphorus additive PEP-36 (ADEKA Corporation) and 0.2% by mass of stearic acid monoglyceride (product name: H-100, Riken Vitamin Co., Ltd.) were added, and after mixing for 20 minutes in a blender, the mixture was melt-kneaded at a cylinder temperature of 240 ° C using a twin-screw extruder (Toshiba Machine Co., Ltd., TEM-26SS, L / D ≒ 40) with a screw diameter of 26 mm and equipped with a polymer filter with a 10 μm opening, extruded into strands, and pelletized using a pelletizer. Pellets of high-hardness resin (B-1) were produced stably. The pellets of high-hardness resin (B-1) had an appearance of ◯ (transparent), a glass transition temperature of 121°C, a melt flow rate of 2.5 g / 10 min under a load of 3.8 kg at 230°C, and a refractive index of 1.54.

[0224] (Manufacturing of laminated resin sheets for molding) A laminate consisting of a substrate layer and a high-hardness resin layer was molded using a multi-layer extrusion device having a single-screw extruder with a shaft diameter of 35 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to each extruder, and a T-die connected to the feed block.

[0225] Specifically, the high-hardness resin (B-1) obtained above was continuously introduced into a single-screw extruder with a shaft diameter of 35 mm and extruded at a cylinder temperature of 230°C and a discharge rate of 2.6 kg / h. Also, a polycarbonate resin (Iupizeta T-1380; manufactured by Mitsubishi Gas Chemical Company, Tg: 125°C, weight-average molecular weight (Mw): 44,500) was continuously introduced into a single-screw extruder with a shaft diameter of 65 mm and extruded at a cylinder temperature of 240°C and a discharge rate of 50.0 kg / h.

[0226] The extruded high-hardness resin and polycarbonate resin were introduced into a feed block equipped with two-type, two-layer distributor pins, and the high-hardness resin and polycarbonate resin were laminated at a temperature of 240°C. The extruded material was then introduced into a T-die at a temperature of 240°C and extruded into a sheet. The sheet was then cooled while transferring a mirror finish using three mirror-finished rolls set at temperatures of 120°C, 130°C, and 190°C from the upstream side, yielding a laminate of a high-hardness resin layer and a polycarbonate resin layer (substrate layer). The thickness of the resulting laminate was 2.0 mm, and the thickness of the high-hardness resin layer near the center was 60 μm.

[0227] On the high-hardness resin layer side of the laminate obtained above, each hard coating composition prepared according to the composition (parts by mass) in Table 1 below was used to form a cured coating film (hard coat layer) on the polycarbonate resin layer (substrate layer) according to the following procedure, thereby obtaining each moldable laminate resin sheet. The hard coating composition was applied to a laminate consisting of a high-hardness resin layer and a polycarbonate resin layer (substrate layer) heated in a hot-air circulating dryer set at 100°C, and then coated with a bar coater to a thickness of 5-10 μm after curing. A 100 μm-thick PET film was then placed on top and leveled with a hand roller. A cured coating (hard coat layer) was formed by irradiating the laminate with ultraviolet light from a metal halide lamp with a power density of 120 W / cm at a conveyor speed of 1.0 m / min, positioned 14 cm below the light source. After curing, the PET film was peeled off, yielding a moldable laminate resin sheet bearing a cured coating of the hard coating composition.

[0228] (Production of Molded Body) The moldable laminated resin sheet produced above was heat-pressed to produce a molded body. The heat press used was a servomotor-driven mold clamping machine, and the maximum mold clamping force was 3000 kgf. The produced laminated resin sheet for molding was placed in a tray dryer set at 120°C and preheated for 3 minutes. The temperature of the sheet when taken out of the tray dryer was 80°C. After removing the laminated resin sheet for molding from the tray dryer, it was placed in the lower die of an aluminum hot press die (Fig. 1) within 50 seconds. The laminated resin sheet for molding was heat-press molded using an aluminum heat-press mold (Figure 1) with a clearance (the gap between the upper and lower molds that sandwich the molded sheet) of 2 mm and a lower mold with a curvature radius R of 50 mm. The temperature of both the upper and lower molds was 122°C, the mold clamping force was 200 kgf, and the pressing time was 3 minutes.

[0229] The evaluation results of the obtained moldable laminate resin sheets are shown in the following Table 2. The moldable laminate resin sheets of Examples 1 to 6 satisfied all the performance requirements. On the other hand, the moldable laminate resin sheets of Comparative Examples 1 to 6 did not satisfy all the performance requirements and were overall judged to be unacceptable.

[0230] [Table 1]

[0231] [Table 2]

[0232] 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 high-hardness resin layer containing a high-hardness resin; a substrate layer containing a polycarbonate resin (a1) disposed on one surface side of the high-hardness resin layer; a hard coat layer disposed on the other surface side of the high-hardness resin layer, the hard coat layer has a plastic deformation rate of 34 to 60%; The hard coat layer is (A) a di- to penta-functional (meth)acrylate oligomer, (B) a mono- or di-functional (meth)acrylate monomer having a molecular weight of less than 200 and a viscosity of 15 cps or less at 25°C; (C) a photopolymerization initiator, and (D) Surface modifier a hard coating composition comprising the content of the component (A) is 50 to 75 mass% based on the total content of the components (A) and (B), the content of the component (B) is 20 to 50 mass% based on the total content of the component (A) and the component (B), the content of the component (C) is 0.1 to 10 parts by mass per 100 parts by mass of the total of the components (A) and (B), The moldable laminate resin sheet, wherein the content of the component (D) is 0.1 to 10 parts by mass per 100 parts by mass of the total of the components (A) and (B).

2. The moldable laminate resin sheet according to claim 1, wherein the polycarbonate resin (a1) is an aromatic polycarbonate resin.

3. The aromatic polycarbonate resin is represented by the following formula (3a): 【Chemistry 1】 The molding laminate resin sheet according to claim 2, comprising a structural unit represented by the formula:

4. The moldable laminate resin sheet according to any one of claims 1 to 3, wherein the content of the polycarbonate resin (a1) is 75 to 100 mass% relative to the total mass of the base material layer.

5. The high-hardness resin is The following general formula (1): 【Chemistry 2】 (In the formula, R １ is a hydrogen atom or a methyl group, and R ２ is an alkyl group having 1 to 18 carbon atoms. and a (meth)acrylic acid ester structural unit (a) represented by the following general formula (2): 【Transformation 3】 (In the formula, R ３ is a hydrogen atom or a methyl group, and R ４ is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms. and a copolymer (B1) containing an aliphatic vinyl structural unit (b) represented by the formula: a resin (B2) which is a copolymer containing 6 to 77% by mass of (meth)acrylic acid ester structural units, 15 to 71% by mass of styrene structural units, and 8 to 23% by mass of unsaturated dicarboxylic acid structural units; The following formula (5): 【Chemistry 4】 a resin (B3) which is a polymer containing a structural unit (c) represented by the following formula: a resin (B4) which is a copolymer containing 5 to 20% by mass of styrene structural units, 60 to 90% by mass of (meth)acrylic acid ester structural units, and 5 to 20% by mass of N-substituted maleimide structural units; The following formula (7): 【Transformation 5】 Resin (B5) is a polymer containing a structural unit (e) represented by the formula: a resin (B6) which is a copolymer containing 50 to 95% by mass of styrene structural units and 5 to 50% by mass of unsaturated dicarboxylic acid units; The molding laminate resin sheet according to any one of claims 1 to 4, comprising at least one selected from the group consisting of:

6. The resin (B3) is represented by the following formula (6): 【Transformation 6】 6. The moldable laminate resin sheet according to claim 5, which is a copolymer further comprising a structural unit (d) represented by the following formula:

7. 7. The moldable laminate resin sheet according to claim 1, wherein the content of the high-hardness resin is 70 to 100% by mass based on the total mass of the high-hardness resin layer.

8. 8. The moldable laminate resin sheet according to claim 1, wherein the total thickness of the base material layer and the high-hardness resin layer is 0.5 to 3.5 mm.

9. The molding laminate resin sheet according to any one of claims 1 to 8, wherein the ratio of the thickness of the base material layer to the total thickness of the base material layer and the high-hardness resin layer is 75% to 99%.

10. 10. The moldable laminate resin sheet according to claim 1, wherein the viscosity of the hard coating composition is 400 cps or less at 25°C.

11. The moldable laminate resin sheet according to any one of claims 1 to 10, wherein the pencil hardness of the surface of the hard coat layer is 2H or more.

12. A molded article molded using the moldable laminate resin sheet according to any one of claims 1 to 11.

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