Laminated resin sheet for molding and molded product using same

Abstract

The present invention can provide a laminated resin sheet for molding, having: a high-hardness resin layer that includes a high-hardness resin; a substrate layer that includes a polycarbonate resin (a1) and is positioned on one surface side of the high-hardness resin layer; and a hard coating anti-glare layer that is positioned on another surface side of the high-hardness resin layer, wherein the glass transition temperature (Tg1) of the high-hardness resin, the glass transition temperature (Tg2) of the polycarbonate resin (a1), and the glass transition temperature (Tg3) of the hard coating anti-glare layer satisfy mathematical expressions (1) and (2), and the indentation hardness (HIT) of the hard coating anti-glare layer is 400 N / mm2 or less.

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] Conventionally, various modifications have been made to the molding resin sheet to impart properties according to the application, such as laminating a hard coat layer or decorating. One such modification is to provide an anti-glare layer on the resin sheet. The anti-glare layer is subjected to an anti-glare treatment that imparts a fine structure or shape to the surface of the layer, thereby preventing light reflection (anti-glare properties), thereby improving visibility and making fingerprints less noticeable.

[0004] Meanwhile, 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 applied to the above-mentioned applications.

[0005] For example, Patent Document 1 describes an invention relating to a multilayer film for simultaneous injection molding and lamination, characterized in that a layer (B) made of methacrylic resin and acrylic rubber particles is laminated on at least one surface of a layer (A) made of polycarbonate resin. Patent Document 1 also describes that polycarbonate resin was selected as a resin film with high heat resistance. The invention described in Patent Document 1 also describes that layer (B) is used as a surface decoration film, and that blending organic or inorganic fine particles into layer (A) and / or layer (B) results in a light-diffusing matte layer. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-234184 Summary of the Invention [Problem to be solved by the invention]

[0007] However, for example, when a layer having different physical properties is laminated on a polycarbonate (PC) resin layer to form a laminate resin sheet, as in Patent Document 1, abnormal appearance may occur during molding. Also, when an anti-glare treated layer is laminated on a polycarbonate (PC) resin layer, haze increases, and the transparency of the polycarbonate (PC) resin may be impaired.

[0008] Therefore, an object of the present invention is to provide a moldable laminate resin sheet that is less likely to cause abnormal appearance during molding and has excellent transparency despite having an anti-glare layer, and a molded article using the same. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that the above-mentioned problems can be solved by providing a hard coat antiglare layer, which is formed by performing a predetermined antiglare treatment on a polycarbonate (PC) resin layer, and by providing a predetermined high-hardness resin layer between the PC resin layer and the hard coat antiglare layer, thereby completing the present invention. That is, the present invention is, for example, as follows. <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 antiglare layer disposed on the other surface of the high-hardness resin layer; and The glass transition point (Tg1) of the high-hardness resin, the glass transition point (Tg2) of the polycarbonate resin (a1), and the glass transition point (Tg3) of the hard coat anti-glare layer satisfy the following relationship:

number

number

[0010] According to the present invention, there are provided a moldable laminate resin sheet which is less likely to cause abnormal appearance during molding and which has an anti-glare layer but is excellent in transparency, and a resin molded product using the same. [Brief explanation of the drawings]

[0011] [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

[0012] 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.

[0013] The moldable laminate resin sheet of the present invention (hereinafter also simply referred to as "resin sheet") has 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 anti-glare 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 anti-glare 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 anti-glare 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 anti-glare layer are laminated together. That is, 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 side of the high-hardness resin layer, and a hard coat anti-glare layer laminated on the other side of the high-hardness resin layer.

[0014] The high-hardness resin layer and the hard-coat anti-glare 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, the hard-coat anti-glare 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.

[0015] The glass transition point (Tg1) of the high-hardness resin and the glass transition point (Tg2) of the polycarbonate resin (a1) satisfy the following relationship:

[0016]

number

[0017] That is, (Tg1-Tg2) is -10 to 40°C, preferably -5 to 30°C, and more preferably 0 to 30°C. This prevents appearance defects such as cracks and flow marks from occurring during molding. Specifically, the molding temperature during molding is usually set to match the molding temperature of the resin contained in the largest amount in the layer. In the case of a resin sheet using a polycarbonate resin as the substrate layer, polycarbonate resin is usually contained in the largest amount, so thermoforming is performed at a molding temperature matched to the polycarbonate resin. If the Tg of the high-hardness resin is extremely lower than the Tg of the polycarbonate resin (a1) at the molding temperature set in this way, the high-hardness resin will become rubbery or molten during thermoforming and become more mobile. In this case, the hard coat anti-glare layer, which remains hard even when heated, will be unable to follow the movement of the high-hardness resin, which has become more mobile, and cracks will easily occur. On the other hand, if the Tg of the high-hardness resin is too high compared to the Tg of the polycarbonate resin (a1), the difference in viscosity between the high-hardness resin and the polycarbonate resin becomes large, causing the interface to become rough when they are laminated, which can lead to the occurrence of flow marks. In the present invention, the glass transition point (Tg1) of the high-hardness resin and the glass transition point (Tg2) of the polycarbonate resin (a1) are values ​​measured using a differential scanning calorimeter DSC7020 manufactured by Hitachi High-Tech Science, specifically, values ​​measured by the method described in the examples below.

[0018] Incidentally, it is preferable to interpose a high-hardness resin layer between the substrate layer and the hard-coat anti-glare layer, since the resulting laminated resin sheet can have high hardness. The presence of the high-hardness resin layer prevents or suppresses buckling of the hard-coat layer, which has a relatively low elastic modulus, thereby achieving high hardness.

[0019] Since the anti-glare treatment is applied to the hard coat layer, the moldable laminate resin sheet can have high scratch resistance.

[0020] The glass transition temperature (Tg3) of the hard coat anti-glare layer satisfies the following relationship:

[0021]

number

[0022] That is, Tg3 is 120°C or less, preferably 110°C or less, and more preferably 100°C or less. This makes it possible to prevent appearance abnormalities such as cracks from occurring during molding. In the present invention, the glass transition point (Tg3) of the hard coat anti-glare layer is a value measured using a DMS-6100 manufactured by SII NanoTechnology Inc., specifically, a value measured by the method described in the Examples below.

[0023] The indentation hardness (HIT) of the hard coat anti-glare layer is 400N / mm 2 or less, preferably 375N / mm 2 or less, more preferably 350 N / mm 2 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 indentation hardness of the hard coat anti-glare layer is a value measured using a Fischer HM2000 LT, specifically, a value measured by the method described in the examples below.

[0024] 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.

[0025] 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.

[0026] In contrast, according to the present invention, cracking is suppressed as described above, making it 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 anti-glare layer on the surface, making it scratch-resistant and highly chemical-resistant. Taking advantage of 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, exterior and interior components of automobiles, and curved housings and front panels for mobile phone terminals, personal computers, tablet PCs, car navigation systems, etc.

[0027] Hereinafter, each of the constituent members of the resin sheet according to the present invention will be described.

[0028] <Base material layer> The substrate layer contains a polycarbonate resin (a1) and may further contain other resins, additives, and the like.

[0029] (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):

[0030] [ka]

[0031] 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).

[0032] By using such a polycarbonate resin, a resin sheet having superior impact resistance can be obtained.

[0033] 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.

[0034] [ka]

[0035] 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.

[0036] The monohydric phenol represented by the general formula (3) is preferably one represented by the following general formula (4).

[0037] [ka]

[0038] 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.

[0039] 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. 5 The lower limit of the number of carbon atoms is preferably 8, and more preferably 12.

[0040] 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.

[0041] 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).

[0042] 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.

[0043] For example, in general formula (4), R 5When 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] The polycarbonate resin (a1) contained in the substrate layer may be one type or two or more types.

[0048] 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.

[0049] (other resins) The other resin is not particularly limited, but examples thereof include polyester resin.

[0050] The polyester resin preferably contains terephthalic acid as the dicarboxylic acid component, but may contain a dicarboxylic acid component other than terephthalic acid.

[0051] 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.

[0052] The other resins may be used alone or in combination of two or more.

[0053] 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.

[0054] (additives) The additives may 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 and inorganic fillers. These additives may be used alone or in combination of two or more.

[0055] 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.

[0056] 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.

[0057] (base material layer) The thickness of the substrate layer is preferably 0.3 to 10 mm, more preferably 0.3 to 5 mm, and even more preferably 0.3 to 3.5 mm.

[0058] <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.

[0059] [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).

[0060] (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.

[0061] [ka]

[0062] In the formula, R 1 is a hydrogen atom or a methyl group, preferably a methyl group.

[0063] Also, R 2 is 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.

[0064] In addition, R 2 When R 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.

[0065] 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.

[0066] [ka]

[0067] In the formula, R 3 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] In this specification, the "hydrocarbon group" may be straight-chain, branched-chain, or cyclic, and may have a substituent.

[0072] 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.

[0073] The resin (B1) may contain only one type of other structural unit, or two or more types.

[0074] 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).

[0075] 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.

[0076] 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 substrate can be prevented.

[0077] 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).

[0078] In this specification, the term "copolymer" may have any of the structures of a random copolymer, a block copolymer, and an alternating copolymer.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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).

[0083] 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.

[0084] 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.

[0085] 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.

[0086] For the polymerization of the (meth)acrylic acid ester monomer and the aromatic vinyl monomer, a known method can be used, and for example, the production can be carried out by a bulk polymerization method or a solution polymerization method.

[0087] 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.

[0088] 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.

[0089] The chain transfer agent is not particularly limited, but examples thereof include α-methylstyrene dimer.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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).

[0095] (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.

[0096] 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.

[0097] 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).

[0098] 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 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 monomer from the viewpoint of compatibility. The above-mentioned styrene monomers may be contained alone as the styrene structural unit, or two or more types may be contained in combination.

[0099] 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).

[0100] 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.

[0101] 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).

[0102] Examples of other structural units in the resin (B2) include N-phenylmaleimide.

[0103] 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).

[0104] 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).

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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).

[0109] 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).

[0110] 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).

[0111] The method for producing the resin (B2) is not particularly limited, but examples thereof include bulk polymerization and solution polymerization.

[0112] (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.

[0113] [ka]

[0114] 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).

[0115] [ka]

[0116] 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).

[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 (B3).

[0118] 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).

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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). It is particularly 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).

[0123] 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.

[0124] 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.

[0125] 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.

[0126] (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.

[0127] 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 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 monomer from the viewpoint of compatibility. The above-mentioned styrene monomers may be contained alone as the styrene structural unit, or two or more types may be contained in combination.

[0128] 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).

[0129] 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.

[0130] 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).

[0131] 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.

[0132] 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).

[0133] 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.

[0134] 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).

[0135] 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).

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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).

[0140] The method for producing the resin (B4) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, or the like.

[0141] (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.

[0142] [ka]

[0143] 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).

[0144] 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.

[0145] 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 (B5).

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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).

[0150] 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.

[0151] 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.

[0152] 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.

[0153] (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.

[0154] 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.

[0155] 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 %, based on the total mass of the resin (B6).

[0156] 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.

[0157] 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).

[0158] 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).

[0159] [ka]

[0160] In the formula, R 1 and R 2 is the same as above.

[0161] [ka]

[0162] In the formula, R 3 and R 4 is the same as above.

[0163] 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).

[0164] The weight average molecular weight of the resin (B6) is preferably from 50,000 to 250,000, and more preferably from 100,000 to 200,000.

[0165] The glass transition point of the resin (B6) is preferably from 110 to 150°C, more preferably from 115 to 140°C, and particularly preferably from 115 to 137°C.

[0166] 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.

[0167] 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).

[0168] The method for producing the resin (B6) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, or the like.

[0169] At least one selected from the group consisting of the above resins (B1) to (B6) may be contained as an alloy.

[0170] 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.

[0171] Examples of the other high hardness resins include methyl methacrylate-styrene copolymers and acrylonitrile-butadiene-styrene copolymers.

[0172] 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.).

[0173] When two types of resins are alloyed, it is preferable to use an alloy of resins having a higher glass transition temperature.

[0174] The above alloys may be used alone or in combination of two or more.

[0175] 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.

[0176] 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).

[0177] 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.

[0178] [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.

[0179] 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.

[0180] [Additives] The high-hardness resin layer may contain additives, etc. As the additives, those described above can be used.

[0181] [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.

[0182] [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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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 it within the above range, both hardness and impact resistance can be achieved.

[0188] <Hard coat anti-glare layer> The hard coat antiglare layer is not particularly limited, but is preferably prepared by antiglare treating an acrylic hard coat. In this specification, the term "acrylic hard coat" refers to a coating film formed by polymerizing a monomer, oligomer, or prepolymer containing a (meth)acryloyl group as a polymerizable group to form a crosslinked structure.

[0189] The acrylic hard coat preferably contains a (meth)acrylic monomer, a (meth)acrylic oligomer, and a surface modifier. In this case, the acrylic hard coat may further contain a photopolymerization initiator. In this specification, the photopolymerization initiator refers to a photoradical generator.

[0190] The content of the (meth)acrylic monomer is preferably 2 to 98 mass %, more preferably 5 to 50 mass %, and even more preferably 20 to 40 mass %, based on the total mass of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier.

[0191] The content of the (meth)acrylic oligomer is preferably 2 to 98 mass %, more preferably 50 to 94 mass %, and even more preferably 60 to 78 mass %, relative to the total mass of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier.

[0192] Furthermore, the content of the surface modifier is preferably 0 to 15 mass %, more preferably 1 to 10 mass %, and even more preferably 2 to 5 mass %, relative to the total mass of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier.

[0193] Furthermore, when a photopolymerization initiator is contained, the content of the photopolymerization initiator is preferably 0.001 to 7 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier.

[0194] [(Meth)acrylic monomers] Any (meth)acrylic monomer can be used as long as it has a (meth)acryloyl group as a functional group in the molecule, specifically, a monofunctional monomer, a difunctional monomer, or a trifunctional or higher functional monomer.

[0195] Examples of the monofunctional monomer include (meth)acrylic acid and (meth)acrylic acid esters.

[0196] Specific examples of bifunctional and / or trifunctional or higher (meth)acrylic monomers include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, polyethylene Examples of the copolymer include ethylene glycol diacrylate, 1,4-butanediol oligoacrylate, neopentyl glycol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane propoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glyceryl propoxy tri(meth)acrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, and pentaerythritol tetraacrylate.

[0197] The hard coat anti-glare layer may contain one or more types of (meth)acrylic monomers.

[0198] [(Meth)acrylic oligomer] Examples of the (meth)acrylic oligomer include difunctional or higher polyfunctional urethane (meth)acrylate oligomers (hereinafter also referred to as polyfunctional urethane (meth)acrylate oligomers), difunctional or higher polyfunctional polyester (meth)acrylate oligomers (hereinafter also referred to as polyfunctional polyester (meth)acrylate oligomers), and difunctional or higher polyfunctional epoxy (meth)acrylate oligomers (hereinafter also referred to as polyfunctional epoxy (meth)acrylate oligomers).

[0199] Examples of the 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 and a polyisocyanate; and a urethane reaction product of an isocyanate compound obtained by reacting a polyol with a polyisocyanate and a (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule.

[0200] Examples of the (meth)acrylate monomer having at least one (meth)acryloyloxy group and one hydroxyl group per molecule used in the urethanization reaction include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0201] Examples of polyisocyanates used in the urethanization reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates (for example, diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate), di- or tri-polyisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, and polyisocyanates obtained by polymerizing diisocyanates.

[0202] Polyols used in the urethanization reaction generally include aromatic, aliphatic and alicyclic polyols, as well as polyester polyols and polyether polyols.

[0203] Typical aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerin, hydrogenated bisphenol A, and the like.

[0204] The polyester polyol may be obtained by a dehydration condensation reaction between the above-mentioned polyols and a polycarboxylic acid. Specific examples of the polycarboxylic acid include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides.

[0205] Examples of polyether polyols include polyalkylene glycols, as well as polyoxyalkylene-modified polyols obtained by reacting the above-mentioned polyols or phenols with alkylene oxides.

[0206] The polyfunctional polyester (meth)acrylate oligomer is obtained by a dehydration condensation reaction using (meth)acrylic acid, a polycarboxylic acid, and a polyol. Examples of polycarboxylic acids used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may also be anhydrides. Examples of polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0207] The polyfunctional epoxy (meth)acrylate oligomer is obtained by an addition reaction between a polyglycidyl ether and (meth)acrylic acid. Examples of the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.

[0208] The hard coat anti-glare layer may contain one or more types of (meth)acrylic oligomers.

[0209] [Surface modifier] The surface modifiers are agents that change the surface performance of the hard coat anti-glare layer, such as leveling agents, antistatic agents, surfactants, water and oil repellents, inorganic particles, and organic particles.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] Examples of the inorganic particles include silica particles, alumina particles, zirconia particles, silicon particles, silver particles, and glass particles.

[0214] Examples of the organic particles include acrylic particles and silicon particles.

[0215] The hard coat anti-glare layer may include one or more surface modifiers.

[0216] [Photopolymerization initiator] The photopolymerization initiator may 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], and 1-hydroxy-cyclohexylphenyl ketone; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; and other halogenated ketones, acylphosphinoxides, and acylphosphonates.

[0217] [Method for forming hard coat anti-glare layer] The method for forming the hard coat antiglare layer is not particularly limited. For example, the hard coat antiglare layer can be formed by applying a hard coat liquid onto a layer (e.g., a high-hardness resin layer) located below the hard coat antiglare layer, and then photopolymerizing the applied liquid.

[0218] The method for applying the hard coat liquid (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 spraying.

[0219] 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.

[0220] 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.

[0221] Photopolymerization reactions are inhibited by oxygen in the air or oxygen dissolved in the reactive 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 reactive composition with a film made of polyethylene terephthalate or Teflon to prevent contact with oxygen, and then irradiate the reactive 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.

[0222] 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 reactive 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 coat 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.

[0223] In order to improve the adhesion of the hard coat anti-glare 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.

[0224] 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 reactive composition, and an anti-glare mold are laminated in this order. The reactive composition is then photopolymerized, and the anti-glare mold is demolded. The photopolymer of the reactive composition (hard-coat anti-glare layer) 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 reactive composition and treating the surface of the resulting hard-coat anti-glare layer. The haze of the hard-coat anti-glare layer can be adjusted by controlling the type of anti-glare mold used (surface haze, thickness, etc.) and the amount of particles added.

[0225] The hard coat anti-glare layer may be further modified. For example, it may be subjected to one or more of 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 used.

[0226] <Molding laminated resin sheet> The pencil hardness of the moldable laminate resin sheet is preferably 2H or higher, more preferably H to 4H, and even more preferably 3H to 4H. The pencil hardness of the moldable laminate resin sheet means the hardness of the hardest pencil that does not leave a scratch when pencils of gradually increasing hardness are pressed against the surface of the hard coat anti-glare 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).

[0227] The haze of the moldable laminate resin sheet is preferably 2 to 30, and more preferably 4 to 12. In the present invention, the haze of the moldable laminate resin sheet is a value measured using HR-100 model manufactured by Murakami Color Research Laboratory, and specifically, a value measured by the method described in the examples below.

[0228] <Molded products> According to one aspect of the present invention, there is provided a molded article molded using the above-described moldable laminate resin sheet.

[0229] 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.

[0230] The molding temperature is preferably 100 to 200°C. [Example]

[0231] Examples of the present invention will be described below, but the present invention is not limited to the embodiments of the examples.

[0232] <Measurement of pencil hardness of laminated resin sheet for molding (hard coat anti-glare layer)> The moldable laminate 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 anti-glare 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. A hardness of 2H or higher was considered acceptable.

[0233] <Measurement of indentation hardness of molding laminated resin sheet (hard coat anti-glare layer)> The indentation hardness of the hard coat anti-glare layer was measured using a Fischer HM2000 LT under the following measurement conditions: Maximum load: 3mN Hold time when maximum load is reached: 5 seconds Loading speed, unloading speed: 10mN / sec

[0234] <Measurement of the glass transition temperature (Tg) of high-hardness resin and polycarbonate resin> The glass transition temperatures of the polycarbonate resins and high-hardness resins used in the examples and comparative examples were measured using a Hitachi High-Tech Science DSC7020 differential scanning calorimeter at a heating rate of 10°C / min under a nitrogen atmosphere. The weight of the resin used for the measurement was 10 to 20 mg.

[0235] <Glass transition temperature (Tg) of hard coat anti-glare layer> The hard coat anti-glare layer forming material used in the examples and comparative examples was applied to a PET substrate for the base layer so that the thickness after curing was 0.2 mm. Then, another PET substrate for the cover layer was pressed onto the applied photocurable resin, and ultraviolet light of 1000 mJ / cm was applied using a metal halide lamp. 2 After curing, the PET for the base layer and the PET for the cover layer were each peeled off to obtain a film having only the hard coat antiglare layer. The glass transition temperature of only the hard coat anti-glare layer used in the examples and comparative examples was measured using a DMS-6100 manufactured by SII Nanotechnology Inc. in a tensile measurement mode with a heating rate of 2°C / min, a frequency of 1 Hz, and a measurement temperature range of 0 to 150°C to calculate the loss coefficient (tan δ), and the maximum value thereof was taken as the glass transition temperature.

[0236] <Evaluation of the occurrence of cracks in the hard coat anti-glare layer> The moldable laminated resin sheets manufactured in the Examples and Comparative Examples were thermoformed, and the presence or absence of cracks was confirmed in the 50 mmR portion, the 75 mmR portion, and the 100 mmR portion.

[0237] <Measurement of haze of laminated resin sheet for molding> The evaluation was carried out in accordance with JIS K 7136 using the HR-100 model manufactured by Murakami Color Research Laboratory.

[0238] Example 1 (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.

[0239] Specifically, high-hardness resin (B2) (a copolymer of 21% by mass of methyl methacrylate structural units, 64% by mass of styrene structural units, and 15% by mass of maleic anhydride structural units; Resisfy R100 (manufactured by Denka), Tg: 124°C, weight-average molecular weight (Mw): 171,000) 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, 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.

[0240] 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.

[0241] A hard coat anti-glare layer was formed on the high-hardness resin layer side of the laminate obtained above. The hard coat anti-glare layer was made from 60% by weight of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer), 35% by weight of SR206NS (Sartomer, ethylene glycol dimethacrylate), 5% by weight of RS-90 (DIC Corporation, oligomer containing fluorine-containing groups, hydrophilic groups, lipophilic groups, and UV-reactive groups), and 1 part by weight of photopolymerization initiator I-184 (BASF, compound name: 1-hydroxycyclohexylphenyl ketone) per 100 parts by weight of the mixture of CN9010NS, SR206NS, and RS-90.

[0242] This hard coat anti-glare layer forming material was applied to the laminate, and the uneven surface of a 2 mm thick frosted glass plate with a haze of 10% was placed on top of it, and a metal halide lamp (20 mW / cm) was used to illuminate the surface. 2 The hard coat was cured by applying a heat of 10000 W for 5 seconds to form an anti-glare layer. The frosted glass plate was then peeled off to produce a resin sheet. The anti-glare layer had a thickness of 6 μm, a haze of 9%, and a Tg of 85°C.

[0243] (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 clamping machine. The maximum clamping force was 3000 kgf.

[0244] 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.

[0245] After removing the laminated resin sheet for molding from the tray dryer, it was placed in the lower mold of an aluminum hot press mold (Fig. 1) within 50 seconds.

[0246] 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.

[0247] <Example 2> A moldable laminate resin sheet and a molded article were produced in the same manner as in Example 1, except that the materials for the hard coat anti-glare layer were changed from "60% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)" to "70% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 25% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)." The Tg of the hard coat anti-glare layer was 90°C.

[0248] Example 3 A moldable laminate resin sheet and a molded article were produced in the same manner as in Example 1, except that the materials for the hard coat anti-glare layer were changed from "60% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)" to "60% by mass of CN9006NS (Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR562NS (Sartomer, alkoxylated hexanediol diacrylate)." The Tg of the hard coat anti-glare layer was 65°C.

[0249] Example 4 A moldable laminate resin sheet and a molded article were produced in the same manner as in Example 1, except that the materials for the hard coat anti-glare layer were changed from "60% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)" to "70% by mass of CN9006NS (Sartomer, aliphatic urethane acrylate oligomer) and 25% by mass of SR562NS (Sartomer, alkoxylated hexanediol diacrylate)." The Tg of the hard coat anti-glare layer was 69°C.

[0250] <Example 5> A moldable laminate resin sheet and a molded article were produced in the same manner as in Example 1, except that the materials for the hard coat anti-glare layer were changed from "60% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)" to "60% by mass of CN9025 (Sartomer, urethane acrylate) and 35% by mass SR259NS (Sartomer, polyethylene glycol (200) diacrylate)." The Tg of the hard coat anti-glare layer was 46°C.

[0251] Example 6 A moldable laminate resin sheet and a molded article were produced in the same manner as in Example 1, except that the materials for the hard coat anti-glare layer were changed from "60% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)" to "70% by mass of CN9025 (Sartomer, urethane acrylate) and 25% by mass of SR259NS (Sartomer, polyethylene glycol (200) diacrylate)." The Tg of the hard coat anti-glare layer was 52°C.

[0252] Example 7 A moldable laminate resin sheet and a molded article were produced in the same manner as in Example 1, except that the materials for the hard coat anti-glare layer were changed from "60% by mass of CN9010NS (manufactured by Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR206NS (manufactured by Sartomer, ethylene glycol dimethacrylate)" to "60% by mass of CN9030 (manufactured by Sartomer, urethane acrylate oligomer) and 35% by mass of SR344NS (manufactured by Sartomer, polyethylene glycol (400) diacrylate)." The Tg of the hard coat anti-glare layer was 23°C.

[0253] Example 8 A moldable laminate resin sheet and a molded article were produced in the same manner as in Example 1, except that the materials for the hard coat anti-glare layer were changed from "60% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)" to "70% by mass of CN9030 (Sartomer, urethane acrylate oligomer) and 25% by mass of SR344NS (Sartomer, polyethylene glycol (400) diacrylate)." The Tg of the hard coat anti-glare layer was 31°C.

[0254] Example 9 FPC0220(Tg184℃) / E2000(Tg147℃) / 2.0mmt A laminate consisting of a base layer and a high-hardness resin layer was molded using the same multilayer extrusion apparatus as in Example 1. Specifically, a high-hardness resin (B5) (a polycarbonate resin containing a structural unit represented by formula (7); Iupizeta FPC0220 (manufactured by Mitsubishi Gas Chemical Company, Ltd.); Tg: 184°C) was continuously introduced into a single-screw extruder with a shaft diameter of 35 mm and extruded at a cylinder temperature of 300°C and a discharge rate of 2.6 kg / h. A polycarbonate resin (Iupilon E2000; manufactured by Mitsubishi Gas Chemical Company, Ltd.; Tg: 147°C) was continuously introduced into a single-screw extruder with a shaft diameter of 65 mm and extruded at a cylinder temperature of 280°C and a discharge rate of 50.0 kg / h.

[0255] 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 280°C. The extruded material was then extruded into a sheet using a T-die at 280°C. The sheet was then cooled while transferring a mirror surface using three mirror-finish 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. A hard coat anti-glare layer was formed on the high-hardness resin layer side of the resulting laminate in the same manner as in Example 1, to produce a moldable laminate resin sheet. Furthermore, a molded product was produced in the same manner as in Example 1.

[0256] Example 10 MS-H(Tg115℃) / Low TgPC(Tg125℃) / 2.0mmt A laminate consisting of a base layer and a high-hardness resin layer was molded using the same multi-layer extrusion device as in Example 1. Specifically, a high-hardness resin (B1) (R in general formula (1)) was extruded into a single-screw extruder having a shaft diameter of 35 mm. 1 and R 2 are both methyl groups, and R in general formula (2) 3 is a hydrogen atom, and R 4 A resin (75 mol% (meth)acrylate structural unit, 25 mol% aliphatic vinyl structural unit, weight average molecular weight 120,000; Tg: 115°C) in which the unit is a cyclohexyl group was continuously introduced and extruded at a cylinder temperature of 240°C and a discharge rate of 2.6 kg / h. A polycarbonate resin (Iupizeta T-1380; manufactured by Mitsubishi Gas Chemical Company; Tg: 125°C) 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.

[0257] Thereafter, the mixture was extruded using a T-die in the same manner as in Example 1 to obtain a laminate of a high-hardness resin layer and a polycarbonate resin layer (substrate layer). The thickness of the obtained laminate was 2.0 mm, and the thickness of the high-hardness resin layer was 60 μm near the center. A hard coat anti-glare layer was formed on the high-hardness resin layer side of the obtained laminate in the same manner as in Example 1 to produce a moldable laminate resin sheet. Furthermore, a molded product was produced in the same manner as in Example 1.

[0258] <Comparative Example 1> A moldable laminate resin sheet and a molded article were produced in the same manner as in Example 1, except that the materials for the hard coat anti-glare layer were changed from "60% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)" to "40% by mass of CN9030 (Sartomer, urethane acrylate oligomer) and 55% by mass of SR833NS (Sartomer, tricyclodecane dimethanol diacrylate)." The Tg of the hard coat anti-glare layer was 134°C.

[0259] <Comparative Example 2> The material for the hard coat anti-glare layer was changed from "60% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)" to "40% by mass of CN9030 (Sartomer, urethane acrylate oligomer) and 55% by mass of SR833NS (Sartomer, tricyclodecane dimethanol diacrylate)," and the lamp was heated with a metal halide lamp (120 mW / cm 2 ) for 2.5 seconds to cure the laminated resin sheet and molded article were produced in the same manner as in Example 1. The Tg of the hard coat anti-glare layer was 134°C.

[0260] <Comparative Example 3> The material for the hard coat anti-glare layer was changed from "60% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)" to "60% by mass of CN9025 (Sartomer, urethane acrylate) and 35% by mass of SR833NS (Sartomer, tricyclodecane dimethanol diacrylate)," and the lamp was heated with a metal halide lamp (120 mW / cm 2 A moldable laminate resin sheet and a molded article were produced in the same manner as in Example 1, except that the hard coat anti-glare layer was cured by exposing it to a UV lamp for 10 seconds. The Tg of the hard coat anti-glare layer was 115°C.

[0261] <Comparative Example 4> The materials for the hard coat anti-glare layer were changed from "60% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 35% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)" to "70% by mass of CN9010NS (Sartomer, aliphatic urethane acrylate oligomer) and 25% by mass of SR206NS (Sartomer, ethylene glycol dimethacrylate)," and the lamp was heated with a metal halide lamp (120 mW / cm 2 A moldable laminate resin sheet and a molded article were produced in the same manner as in Example 1, except that the hard coat anti-glare layer was cured by exposing it to a UV light source (UV-IR) for 10 seconds. The Tg of the hard coat anti-glare layer was 90°C.

[0262] For the moldable laminate resin sheets produced in the Examples and Comparative Examples, the Tg, indentation hardness, and pencil hardness of the hard coat anti-glare layer were measured. Furthermore, the molded articles were evaluated for the presence or absence of cracks in the hard coat anti-glare layer. The results are shown in Table 1 below.

[0263] [Table 1]

[0264] It is clear that the moldable laminate resin sheets of Examples 1 to 10 do not cause abnormalities in appearance during molding, despite having a hard coat anti-glare layer.Furthermore, it is clear that they have high hardness.

[0265] 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 having a pencil hardness of HB to 3H as measured in a pencil scratch hardness test in accordance with JIS K 5600-5-4:1999; a substrate layer containing a polycarbonate resin (a1) disposed on one surface side of the high-hardness resin layer; a hard coat antiglare layer disposed on the other surface of the high-hardness resin layer; and The glass transition point (Tg1) of the high-hardness resin, the glass transition point (Tg2) of the polycarbonate resin (a1), and the glass transition point (Tg3) of the hard coat anti-glare layer satisfy the following relationship: [Equation 1] [Equation 2] Fulfilling The indentation hardness (HIT) of the hard coat anti-glare layer is 400 N / mm ２ The following is a molding laminate resin sheet.

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. The moldable laminate resin sheet according to any one of claims 1 to 9, wherein the moldable laminate resin sheet has a haze of 2 to 30.

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 antiglare 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.