WO2021033483A1 - Anti-glare layered body - Google Patents

Anti-glare layered body Download PDF

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Publication number
WO2021033483A1
WO2021033483A1 PCT/JP2020/028358 JP2020028358W WO2021033483A1 WO 2021033483 A1 WO2021033483 A1 WO 2021033483A1 JP 2020028358 W JP2020028358 W JP 2020028358W WO 2021033483 A1 WO2021033483 A1 WO 2021033483A1
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resin
mass
layer
copolymer
high hardness
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PCT/JP2020/028358
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French (fr)
Japanese (ja)
Inventor
帰心 小澤
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三菱瓦斯化学株式会社
Ｍｇｃフィルシート株式会社
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Priority to JP2021540683A priority Critical patent/JPWO2021033483A1/ja
Priority to CN202080057972.8A priority patent/CN114270226A/en
Publication of WO2021033483A1 publication Critical patent/WO2021033483A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Definitions

  • the present invention relates to an antiglare laminate. More specifically, the present invention has a front plate of an in-vehicle liquid crystal display device, a mobile phone terminal, a personal computer, a tablet PC, which has high scratch resistance and excellent shape stability while having antiglare performance. With respect to the antiglare laminate used as.
  • the liquid crystal display device is provided with a front plate for the purpose of protecting the liquid crystal panel and the like.
  • Examples of the material used for the front plate of the conventional liquid crystal display device include (meth) acrylic resin typified by polymethyl methacrylate (PMMA).
  • a sheet made of polycarbonate resin has been used as a front plate because it has high impact resistance, heat resistance, secondary workability, light weight and transparency.
  • the front plate obtained by applying a hard coat on a multilayer sheet in which an acrylic resin is laminated on the surface layer of a polycarbonate resin sheet has a surface hardness and scratch resistance comparable to those of a conventional acrylic resin with a hard coat, and the polycarbonate resin. It is widely used as a front plate because it has excellent impact resistance, heat resistance, workability and transparency.
  • the front plate of the liquid crystal display device provided with the above-mentioned polycarbonate resin sheet is generally formed by a melt extrusion method together with an acrylic resin.
  • an optical laminate for antireflection is generally provided on the outermost surface.
  • Such an optical laminate for antireflection suppresses the reflection of an image or reduces the reflectance by scattering or interference of light.
  • an antiglare film in which an antiglare layer having an uneven shape is formed on the surface of a transparent base material is known.
  • This antiglare film can scatter external light due to the uneven shape of the surface to prevent deterioration of visibility due to reflection of external light and reflection of an image.
  • this optical laminate is usually installed on the outermost surface of the liquid crystal display device, it is also required to impart hard coat property so as not to be scratched during handling.
  • a mixture of fine particles and a binder resin or a curable resin is usually applied to a base material to form fine irregularities on the surface. It prevents reflection and prevents reflection of the image.
  • a concavo-convex shape is added to prevent the image from being reflected, the scattering of the transmitted light traveling straight increases, the outline of the pixel becomes ambiguous, and character blurring occurs.
  • the front panel of in-vehicle liquid crystal display devices, mobile phone terminals, personal computers, and tablet PCs has both excellent impact resistance, heat resistance, and performance of suppressing character blur while preventing image reflection.
  • fine particles are added in order to improve the transparency and reduce the blurring of characters. The addition of fine particles improves the hardness of the pencil, but reduces the scratch resistance, which is not preferable.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2010-160398
  • An object of the present invention is to solve at least one of the above-mentioned conventional problems. Further, the present invention provides an antiglare laminate having both anti-glare performance for preventing image reflection and suppression of character blurring, high scratch resistance, and excellent shape stability. That is the issue.
  • the present invention is as follows. ⁇ 1> A layer containing the resin (A) containing the polycarbonate resin (a1) and A layer containing the high hardness resin (B) provided on at least one surface of the layer containing the resin (A) containing the polycarbonate resin (a1), and a layer containing the high hardness resin (B). Further, a hard coat layer provided on a layer containing a high hardness resin (B) and having an uneven shape, and a hard coat layer.
  • the layer containing the high hardness resin (B) has a thickness of 10 to 250 ⁇ m, and the layer containing the resin (A) containing the polycarbonate resin (a1) and the layer containing the high hardness resin (B).
  • the total thickness of is 100-3,000 ⁇ m;
  • the transmission sharpness when light is transmitted using an optical comb having a width of 2.0 mm is measured at an incident angle of 45 ° using T1 and an optical comb having a width of 2.0 mm.
  • the antiglare laminate has T1 / T2 of 2.0 or more.
  • the transmission sharpness T1 when light is transmitted using a 2.0 mm wide optical comb satisfies 30% ⁇ T1 ⁇ 50%, and the incident angle of light 45 using a 2.0 mm wide optical comb.
  • the high hardness resin (B) contains at least one selected from the group consisting of the following resins (B1) to (B5).
  • the resin (B1) is A copolymer resin containing a (meth) acrylic acid ester structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (b) represented by the following general formula (2).
  • the total ratio of the (meth) acrylic acid ester constituent unit (a) and the aliphatic vinyl constituent unit (b) is 90 to 100 mol% of the total constituent units of the copolymer resin, and the (meth) acrylic The copolymer resin: the ratio of the acid ester structural unit (a) is 65 to 80 mol% of the total structural units of the copolymer resin.
  • R1 is a hydrogen atom or a methyl group
  • R2 is an alkyl group having 1 to 18 carbon atoms.
  • R3 is a hydrogen atom or a methyl group
  • R4 is a cyclohexyl group which may have a hydrocarbon group having 1 to 4 carbon atoms.
  • the resin (B2) is The resin (B1) is 35 to 65% by mass, the styrene-unsaturated dicarboxylic acid copolymer (C) is 35 to 65% by mass, and the styrene-unsaturated dicarboxylic acid copolymer (C) is styrene-based.
  • the resin (B3) is The resin (D) containing a vinyl monomer contains 55 to 10% by mass, the styrene-unsaturated dicarboxylic acid-based copolymer (E) contains 45 to 90% by mass, and the styrene-unsaturated dicarboxylic acid-based copolymer weight.
  • the coalescence (E) contains 50 to 80% by mass of the styrene-based monomer unit (e1), 10 to 30% by mass of the unsaturated dicarboxylic acid monomer unit (e2), and a vinyl-based monomer unit (e3). It is a resin contained in an amount of 5 to 30% by mass.
  • the resin (B4) is Resin copolymer (G) or resin containing 5 to 20% by mass of styrene constituent unit, 60 to 90% by mass of (meth) acrylic acid ester constituent unit, and 5 to 20% by mass of N-substituted maleimide monomer.
  • the resin (B5) is A copolymer containing a structural unit (H) represented by the following formula (3) and a structural unit (J) optionally represented by the following formula (4).
  • ⁇ 4> The antiglare laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the hard coat layer having an uneven shape does not contain inorganic particles or organic particles.
  • the hard coat layer having an uneven shape has at least one of antireflection performance, antifouling performance, antistatic performance, and weather resistance, according to any one of ⁇ 1> to ⁇ 4>.
  • ⁇ 6> The antiglare laminate according to any one of ⁇ 1> to ⁇ 5>, which comprises a second hard coat layer on a surface opposite to the hard coat layer having the unevenness.
  • R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms
  • R 2 to R 5 each independently have a hydrogen atom, a halogen, or a substituent.
  • a method for producing an antiglare laminate which comprises a step of transferring an uneven shape to the hard coat layer by crimping a grained PET film.
  • an antiglare laminate can be provided.
  • the antiglare laminate of the present invention may be referred to as "resin sheet" may be referred to as a layer containing a resin (A) containing a polycarbonate resin (al) (hereinafter, may be referred to as a "base material layer”).
  • a layer containing the high-hardness resin (B) (hereinafter, may be referred to as a "high-hardness resin layer” or a “high-hardness layer”) and a hard coat layer having an uneven shape are provided on at least one surface.
  • the base material layer may be a layer made of a resin (A) containing a polycarbonate resin (al).
  • the high hardness layer may be a layer made of a high hardness resin (B).
  • the high hardness resin layer exists between the base material layer and the hard coat layer, and the outermost surface of the hard coat layer, which is the outermost layer, is provided with an uneven shape.
  • the other surface of the layer containing the resin (A) containing the polycarbonate resin (al) is not particularly specified, but both the high hardness resin layer and the hard coat layer, or any one of the layers may be provided.
  • the high-hardness resin layer it is desirable to use a resin selected from the high-hardness resin (B), and when the high-hardness resin layer is provided on both sides of the base material layer, the same high-hardness resin (on both sides). It is more desirable to use B) for shape stability.
  • the hard coat layer has an uneven shape.
  • the antiglare laminate is, for example, a car navigation system, a center information display (CID), a rear seat entertainment (RSE), a cluster, etc. as an in-vehicle display device, a touch panel full protection plate, and an OA device. It can be used as a front plate for a device, a portable electronic device, or a television. Further, for example, the front plate can be used alone as the front plate of the liquid crystal display device, but may be combined and used as the front plate, for example, by laminating with another substrate such as a touch sensor.
  • the resin (A) containing the polycarbonate resin (a1) used in the present invention is a resin mainly containing the polycarbonate resin (a1).
  • the content of the polycarbonate resin (a1) in the resin (A) is 75% by mass or more, but it is more preferably 90% by mass or more because the impact resistance is improved by increasing the content. Is 100% by mass.
  • the polycarbonate resin (al) has a carbonic acid ester bond in the main chain of the molecule, that is,-[OR-OCO] -unit (R is an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group. It is not particularly limited as long as it contains, and further has a linear structure or a branched structure), but it is particularly preferable to use a polycarbonate resin containing the structural unit of the following formula (4). By using such a polycarbonate resin, an antiglare laminate having excellent impact resistance can be obtained.
  • polycarbonate resin (a1) an aromatic polycarbonate resin (for example, manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade names: Iupiron S-2000, Iupiron S-1000, Iupilon E-2000) and the like can be used. However, it is not limited to these.
  • R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms
  • R 2 to R 5 each independently have a hydrogen atom, a halogen, or a substituent. It represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the substituent may be a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. is there.
  • the monohydric phenol represented by the general formula (5) is represented by the following general formula (6).
  • R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.
  • the carbon number of R 1 in the general formula (5) or the general formula (6) is within a specific numerical range. Specifically, as the upper limit of the number of carbon atoms of R 1 , 36 is preferable, 22 is more preferable, and 18 is particularly preferable. Further, as the lower limit of the number of carbon atoms of R 1 , 8 is preferable, and 12 is more preferable.
  • one or both of the parahydroxybenzoic acid hexadecyl ester and the parahydroxybenzoic acid 2-hexyldecyl ester are terminated. It is particularly preferable to use it as an agent.
  • R 1 in the general formula (6) for example, when using a monohydric phenol which is alkyl group of 16 carbon atoms (terminating agent), a glass transition temperature, melt flowability, moldability, drawdown resistance, polycarbonate
  • the monohydric phenol has excellent solvent solubility during resin production, and is particularly preferable as a terminal terminator used for the polycarbonate resin in the present invention.
  • the productivity is high and the economy is good in producing the polycarbonate resin.
  • the carbon number of R 1 is 22 or less, the monohydric phenol is particularly excellent in organic solvent solubility, and the productivity can be made very high in the production of the polycarbonate resin, and the economic efficiency is also improved.
  • the weight average molecular weight of the polycarbonate resin (al) affects the impact resistance and molding conditions of the antiglare laminate. That is, if the weight average molecular weight is too small, the impact resistance of the antiglare laminate is lowered, which is not preferable. If the weight average molecular weight is too high, an excessive heat source may be required when laminating the layer containing the polycarbonate resin (al), which is not preferable. In addition, since a high temperature is required depending on the molding method, the polycarbonate resin (al) is exposed to a high temperature, which may adversely affect its thermal stability.
  • the weight average molecular weight of the polycarbonate resin (al) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000. More preferably, it is 25,000 to 65,000.
  • the weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
  • the resin (A) may further contain additives and the like.
  • additives those usually used in the resin sheet can be used.
  • Additives include, for example, antioxidants, anticolorants, antichargers, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers and inorganic fillers. Such as reinforcing materials can be mentioned.
  • the method of mixing the additive and the resin is not particularly limited, and a method of compounding the entire amount, a method of dry-blending the masterbatch, a method of dry-blending the entire amount, and the like can be used.
  • 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 with respect to the total mass of the base material layer.
  • the high-hardness resin (B) used in the present invention includes a high-hardness resin (B1), a high-hardness resin (B2), a high-hardness resin (B3), a high-hardness resin (B4), and a high-hardness resin (B5). Includes at least one selected from the group consisting of.
  • the high-hardness resin (B1) used in the present invention includes a (meth) acrylic acid ester structural unit (a) represented by the general formula (1) and an aliphatic vinyl composition represented by the general formula (2).
  • R1 is a hydrogen atom or a methyl group
  • R2 is an alkyl group having 1 to 18 carbon atoms.
  • R3 is a hydrogen atom or a methyl group
  • R4 is a cyclohexyl group which may have a hydrocarbon group having 1 to 4 carbon atoms.
  • hydrocarbon group may be linear, branched or cyclic, or may have a substituent.
  • R2 is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and carbon. More preferably, it is an alkyl group having the number 1 to 6. Specific examples thereof include a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group, and an isobornyl group.
  • R2 is a methyl group or an ethyl group (meth) acrylic acid ester structural unit, and more preferably R1 is a methyl group and R2 is It is a building block of methyl methacrylate, which is a methyl group.
  • R3 is a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • R4 is a cyclohexyl group having a cyclohexyl group or a hydrocarbon group having 1 to 4 carbon atoms.
  • R3 is a hydrogen atom and R4 is a cyclohexyl group.
  • the high-hardness resin (B1) may contain one or more of the (meth) acrylic acid easter constituent unit (a), and one or more of the aliphatic vinyl constituent unit (b). It may be contained.
  • the total ratio of the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is preferably 90 to 100 mol% with respect to the total of all the structural units of the copolymer resin. Is 95 to 100 mol%, more preferably 98 to 100 mol%.
  • the high hardness resin (B1) may contain a structural unit other than the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b).
  • the amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less, based on all the constituent units of the resin (B1).
  • Examples of the structural unit other than the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) include the aromatic vinyl after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer.
  • Examples thereof include a structural unit derived from an aromatic vinyl monomer containing an unhydrogenated aromatic double bond, which is generated in the process of producing a resin (B1) by hydrogenating an aromatic double bond derived from the monomer.
  • the content of the (meth) acrylic acid ester structural unit (a) represented by the general formula (1) is preferably 65 to 80 mol% with respect to all the structural units in the high hardness resin (B1). , More preferably 70-80 mol%.
  • the ratio of the (meth) acrylic acid ester structural unit (a) to all the structural units in the resin (B1) is 65 mol% or more, a resin layer having excellent adhesion to the base material layer and surface hardness can be obtained. Can be done. Further, if it is 80 mol% or less, warpage due to water absorption of the resin sheet is unlikely to occur.
  • the content of the aliphatic vinyl constituent unit (b) represented by the general formula (2) is preferably 20 to 35 mol% with respect to all the constituent units in the high hardness resin (B1), more preferably. Is 20 to 30 mol%. If the content of the aliphatic vinyl constituent unit (b) is 20 mol% or more, warpage under high temperature and high humidity can be prevented, and if it is 35 mol% or less, at the interface with the base material layer. Can be prevented from peeling off.
  • the "copolymer” may have any structure of random, block, and alternating copolymers.
  • the method for producing the high-hardness resin (B1) is not particularly limited, but after polymerizing at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer, the fragrance derived from the aromatic vinyl monomer is used. Those obtained by hydrogenating the group double bond are preferable.
  • the (meth) acrylic acid means methacrylic acid and / or acrylic acid.
  • Specific examples of the aromatic vinyl monomer used at this time include styrene, ⁇ -methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene is preferred.
  • a known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer, and for example, it can be produced by a massive polymerization method, a solution polymerization method, or the like.
  • the massive polymerization method is carried out by a method in which a monomer composition containing the above-mentioned monomer and a polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ° C.
  • the monomer composition may contain a chain transfer agent, if necessary.
  • the polymerization initiator is not particularly limited, but is t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di (t-hexyl).
  • azo compounds include lonitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile). These can be used alone or in combination of two or more.
  • the chain transfer agent is used as needed, and examples thereof include ⁇ -methylstyrene dimer.
  • Examples of the solvent used in the solution polymerization method 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, tetrahydrofuran, and the like.
  • Examples thereof include ether solvents such as dioxane and alcohol solvents such as methanol and isopropanol.
  • the solvent used for the hydrogenation reaction after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer may be the same as or different from the solvent used in the above solution polymerization method.
  • 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
  • alcohol solvents such as methanol and isopropanol.
  • solvents include solvents.
  • the high hardness resin used in the present invention is obtained by polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer as described above, and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer. (B1) is obtained.
  • the method of hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out in a batch system or a continuous flow system at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. When the temperature is 60 ° C. or higher, the reaction time does not take too long, and when the temperature is 250 ° C. or lower, the molecular chain is less likely to be cleaved or the ester site is hydrogenated.
  • Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobal, ruthenium, and rhodium, or oxides, salts, or complex compounds of these metals, and carbon, alumina, silica, and silica. Examples thereof include a solid catalyst supported on a porous carrier such as alumina and diatomaceous earth.
  • the high hardness resin (B1) is preferably one in which 70% or more of the aromatic double bonds derived from the aromatic vinyl monomer are hydrogenated. That is, the proportion of the unhydrogenated portion of the aromatic double bond in the structural unit derived from the aromatic vinyl monomer is preferably 30% or less. If it exceeds 30%, the transparency of the high hardness resin (B1) may decrease.
  • the proportion of unhydrogenated sites is more preferably less than 10% and even more preferably less than 5%.
  • the weight average molecular weight of the high hardness resin (B1) is not particularly limited, but is preferably 50,000 to 400,000, preferably 70,000 to 300,000 from the viewpoint of strength and moldability. More preferred.
  • the weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
  • the high hardness resin (B1) can be blended with other resins as long as the transparency is not impaired.
  • examples thereof include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, polycarbonate, cycloolephine (co) polymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, and various elastomers. ..
  • the glass transition temperature of the high hardness resin (B1) is preferably in the range of 110 to 140 ° C.
  • the laminate provided in the present invention is less likely to be deformed or cracked in a thermal environment or a moist heat environment, and when it is 140 ° C. or lower, it depends on a mirror surface roll or a shaping roll. It has excellent workability such as continuous heat shaping, or batch type heat shaping using a mirror surface mold or a shaping mold.
  • the glass transition temperature in the present invention is a temperature calculated by the midpoint method when measured at a sample of 10 mg and a heating rate of 10 ° C./min using a differential scanning calorimetry device.
  • Examples of the high hardness resin (B1) include, but are not limited to, Optimus 7500, 6000 (manufactured by Mitsubishi Gas Chemical Company).
  • the high hardness resin (B2) used in the present invention contains 35 to 65% by mass of the high hardness resin (B1) and 35 to 65% by mass of the styrene-unsaturated dicarboxylic acid-based copolymer (C).
  • the styrene-unsaturated dicarboxylic acid-based copolymer (C) contains 65 to 90% by mass of the styrene-based monomer unit (c1) and the unsaturated dicarboxylic acid anhydride monomer unit (c2). It is a resin containing 10 to 35% by mass.
  • the styrene-unsaturated dicarboxylic acid-based copolymer (C) will be described below.
  • the styrene-unsaturated dicarboxylic acid-based copolymer (C) used in the present invention contains a styrene-based monomer unit (c1) and an unsaturated dicarboxylic acid anhydride monomer unit (c2).
  • the styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used, but from the viewpoint of easy availability, styrene, a-methylstyrene, o-methylstyrene, m- Examples thereof include methyl styrene, p-methyl styrene and t-butyl styrene. Of these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these styrene-based monomers may be mixed.
  • the unsaturated dicarboxylic acid anhydride monomer include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferable from the viewpoint of compatibility with vinyl-based monomers. .. Two or more kinds of these unsaturated dicarboxylic acid anhydride monomers may be mixed.
  • composition ratio of styrene-unsaturated dicarboxylic acid copolymer (C) was 65 to 90% by mass (preferably 70 to 85% by mass) of the styrene-based monomer unit (c1), and the unsaturated dicarboxylic acid anhydride alone.
  • the unit of measure (c2) is 10 to 35% by mass (preferably 15 to 30% by mass).
  • copolymer (C) examples include, but are not limited to, POLYSCOPE POLYMERS BV XIBOND140 and XIBOND160.
  • the high hardness resin (B3) used in the present invention includes 55 to 10% by mass (preferably 50 to 20% by mass) of the resin (D) containing a vinyl-based monomer, and styrene-unsaturated dicarboxylic.
  • the weight unit (e1) is 50 to 80% by mass
  • the unsaturated dicarboxylic acid anhydride monomer unit (e2) is 10 to 30% by mass
  • the vinyl-based monomer unit (e3) is 5 to 30% by mass. It is a resin containing.
  • the resin (D) containing the vinyl-based monomer and the styrene-unsaturated dicarboxylic acid-based copolymer (E) will be sequentially described below.
  • Resin (D) containing vinyl-based monomer examples include acrylonitrile, methacrylic acid, acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like. Examples thereof include those obtained by homopolymerizing vinyl-based monomers such as methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate, and methyl methacrylate is particularly preferable as the monomer unit. .. Further, a copolymer containing two or more kinds of the monomer units may be used.
  • the weight average molecular weight of the resin (D) containing the vinyl tea monomer is preferably 10,000 to 500,000, more preferably 50,000 to 300,000.
  • the styrene-unsaturated dicarboxylic acid-based copolymer (E) used in the present invention includes a styrene-based monomer unit (e1), an unsaturated dicarboxylic acid anhydride monomer unit (e2), and a vinyl-based monomer. Includes unit (e3).
  • the styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used, but from the viewpoint of easy availability, styrene, a-methylstyrene, o-methylstyrene, m- Examples thereof include methyl styrene, p-methyl styrene and t-butyl styrene. Of these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these styrene-based monomers may be mixed.
  • the unsaturated dicarboxylic acid anhydride monomer include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferable from the viewpoint of compatibility with vinyl-based monomers. .. Two or more kinds of these unsaturated dicarboxylic acid anhydride monomers may be mixed.
  • the vinyl-based monomer includes, for example, acrylonitrile, metaacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, and the like.
  • vinyl-based monomers such as n-butyl methacrylate and 2-ethylhexyl methacrylate.
  • Methyl methacrylate (MMA) is preferable from the viewpoint of compatibility with the resin (D) containing a vinyl-based monomer. Two or more kinds of these vinyl-based monomers may be mixed.
  • composition ratio of styrene-unsaturated dicarboxylic acid copolymer (E) was 50 to 80% by mass (preferably 50 to 75% by mass) of the styrene-based monomer unit (e1), and the unsaturated dicarboxylic acid anhydride alone.
  • the unit of measure (e2) is 10 to 30% by mass (preferably 10 to 25% by mass)
  • the vinyl-based monomer unit (e3) is 5 to 30% by mass (preferably 7 to 27% by mass).
  • the weight average molecular weight of the styrene-unsaturated dicarboxylic acid-based copolymer (E) is preferably 50,000 to 200,000, more preferably 80,000 to 200,000.
  • the weight average molecular weight of the resin (D) and the copolymer (E) is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
  • copolymer (E) examples include, but are not limited to, Regisphi R100, R200, R310 (manufactured by Denki Kagaku Kogyo), Delpet 980N (manufactured by Asahi Kasei Chemical Co., Ltd.), and the like.
  • the high-hardness resin (B4) used in the present invention includes 5 to 20% by mass of a styrene constituent unit, 60 to 90% by mass of a (meth) acrylic acid ester constituent unit, and an N-substituted maleimide monomer. It is a resin copolymer (G) containing 5 to 20% by mass, or an alloy of the resin copolymer (G) and the copolymer (E).
  • N-substituted maleimide monomer in the resin copolymer (G) examples include N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, and N-methoxyphenyl.
  • N-arylmaleimide such as maleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide
  • N-phenylmaleimide is preferable from the viewpoint of compatibility with acrylic resin. Two or more kinds of these N-substituted maleimide monomers may be mixed.
  • the content of the N-substituted maleimide monomer is 5 to 20% by mass, preferably 5 to 15% by mass, and 5 to 10% by mass with respect to the total amount of the high hardness resin (B4). Is more preferable.
  • the styrene constituent unit is not particularly limited, and any known styrene-based monomer can be used, but from the viewpoint of easy availability, styrene, methylstyrene, o-methylstyrene, m-methylstyrene, p. -Methylstyrene, t-butylstyrene and the like can be mentioned. Of these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these styrene-based monomers may be mixed.
  • the content of the styrene constituent unit is 5 to 20% by mass, preferably 5 to 15% by mass, and more preferably 5 to 10% by mass with respect to the total mass of the high hardness resin (B4). ..
  • the (meth) acrylic acid ester constituent unit is, for example, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n methacrylate.
  • -Butyl, 2-ethylhexyl methacrylate and the like can be mentioned, and methyl methacrylate is particularly preferable as the monomer unit.
  • a copolymer containing two or more kinds of the monomer units may be used.
  • the content of the (meth) acrylic acid ester structural unit is 60 to 90% by mass, preferably 70 to 90% by mass, and 80 to 90% by mass with respect to the total mass of the high hardness resin (B4). More preferably.
  • the method for producing the resin copolymer (G) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, or the like.
  • Examples of the resin copolymer (G) include, but are not limited to, Delpet PM120N (manufactured by Asahi Kasei Chemical Co., Ltd.).
  • the weight average molecular weight of the resin copolymer (G) is preferably 50,000 to 250,000, more preferably 100,000 to 200,000.
  • the high hardness resin (B5) is a copolymer containing a structural unit (H) represented by the following formula (3) and optionally a structural unit (J) represented by the following formula (4).
  • the high hardness resin (B5) may or may not contain the structural unit (J), but is preferably contained.
  • the ratio of the structural unit (H) to all the structural units of the high hardness resin (B5) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and 70 to 100 mol%. Is particularly preferred.
  • the ratio of the structural unit (J) to all the structural units of the high hardness resin (B5) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and 0 to 30 mol%. Is particularly preferred.
  • the total content of the structural unit (H) and the structural unit (J) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 95 to 100 mol% with respect to the high hardness resin (B5). It is 98 to 100 mol%.
  • the high hardness resin (B5) may contain a structural unit other than the structural unit (H) and the structural unit (J). When other structural units are included, the amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and 2 mol% or less with respect to all the structural units of the high hardness resin (B5). Is particularly preferable.
  • the method for producing the high hardness resin (B5) is not particularly limited, but it can be produced by the same method as the above-mentioned method for producing the polycarbonate resin (a1) except that bisphenol C is used as the monomer.
  • Examples of the high hardness resin (B5) include, but are not limited to, Iupiron KH3410UR, KH3520UR, KS3410UR (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and the like.
  • the weight average molecular weight of the high hardness resin (B5) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and particularly preferably 25,000 to 65,000.
  • the high hardness resins (B1) to (B5) may contain additives and the like.
  • the additive those usually used in a resin sheet can be used, and such an additive includes, for example, an antioxidant, an anticolorant, an anticharge agent, a release agent, a lubricant, a dye, and the like. Examples thereof include pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, and reinforcing materials such as organic fillers and inorganic fillers.
  • the method of mixing the additive and the resin is not particularly limited, and a method of compounding the entire amount, a method of dry-blending the masterbatch, a method of dry-blending the entire amount, and the like can be used.
  • 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 with respect to the total mass of the high hardness resin layer. ..
  • the thickness of the high hardness resin layer affects the surface hardness and impact resistance. That is, if the high hardness resin layer is too thin, the surface hardness will be low, and if it is too thick, the impact resistance will be lowered.
  • the thickness of the high hardness resin layer is preferably 10 to 250 ⁇ m, more preferably 30 to 200 ⁇ m, and particularly preferably 60 to 150 ⁇ m.
  • a further layer may exist between the polycarbonate layer and the high-hardness resin layer, but here, a case where the high-hardness resin layer is laminated on the base material layer will be described.
  • the laminating method is not particularly limited, and laminating can be performed in the same manner when other layers are present. For example, a method in which an individually formed base material layer and a high hardness resin layer are superposed and heat-bonded to each other; a individually formed base material layer and a high hardness resin layer are superposed and both are bonded by an adhesive.
  • Various methods such as a method of co-extruding a base material layer and a high-hardness resin layer; a method of in-molding a base material layer into a pre-formed high-hardness resin layer and integrating them. There is. Of these, the coextrusion molding method is preferable from the viewpoint of manufacturing cost and productivity.
  • the coextrusion molding method is not particularly limited.
  • a high-hardness resin layer is placed on one side of a base material layer with a feed block, extruded into a sheet shape with a T-die, and then cooled while passing through a molding roll to form a desired laminate.
  • a high-hardness resin layer is arranged on one side of the base material layer in the multi-manifold die, extruded into a sheet shape, and then cooled while passing through a molding roll to form a desired laminated body. ..
  • the total thickness of the base material layer and the high hardness resin layer is preferably 100 to 3,000 ⁇ m, more preferably 500 to 3,000 ⁇ m, and particularly preferably 1,000 to 3,000 ⁇ m.
  • 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 preferably 75% to 99%, more preferably 80 to 99%, and particularly preferably 85 to 99%. is there. Within the above range, both hardness and impact resistance can be achieved.
  • the antiglare laminate (resin sheet) of the present invention includes a hard coat layer.
  • An additional layer may be present between the hard coat layer and the high hardness resin layer, but preferably the hard coat layer is laminated on the high hardness resin layer.
  • the hard coat layer is preferably an acrylic hard coat.
  • acrylic hard coat means a coating film formed by polymerizing a monomer or oligomer or prepolymer containing a (meth) acryloyl group as a polymerization group to form a crosslinked structure.
  • the composition of the acrylic hard coat preferably contains 2 to 98% by mass of the (meth) acrylic monomer, 2 to 98% by mass of the (meth) acrylic oligomer, and 0 to 15% by mass of the surface modifier. It is preferable to contain 0.001 to 7 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer and the surface modifier.
  • the hard coat layer more preferably contains 5 to 50% by mass of the (meth) acrylic monomer, 50 to 95% by mass of the (meth) acrylic oligomer, and 1 to 10% by mass of the surface modifier, and is particularly preferably. , 20-40% by mass of (meth) acrylic monomer, 60-80% by mass of (meth) acrylic oligomer, and 2-5% by mass of surface modifier.
  • the amount of the photopolymerization initiator is more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer and the surface modifier. It is particularly preferably 0.1 to 3 parts by mass.
  • the (meth) acrylic monomer can be used as long as the (meth) acryloyl group is present as a functional group in the molecule, and is a monofunctional monomer, a bifunctional monomer, or a trifunctional monomer. It may be the above monomer.
  • Examples of the monofunctional monomer include (meth) acrylic acid and (meth) acrylic acid ester.
  • Specific examples of the bifunctional and / or trifunctional or higher (meth) acrylic monomer include diethylene glycol di (meth) acrylate and di. Propropylene 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 , Hydroxypivalate neopentyl glycol diacrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, Polyethylene glycol diacrylate, 1,4-butanediol oligo acryl
  • the hard coat layer may contain one type or two or more types of (meth) acrylic monomers.
  • the (meth) acrylic oligomer is a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer (hereinafter, also referred to as “polyfunctional urethane (meth) acrylate oligomer”), which is bifunctional or higher.
  • Polyfunctional polyester (meth) acrylate oligomer hereinafter, also referred to as “polyfunctional polyester (meth) acrylate oligomer”
  • bifunctional or higher polyfunctional epoxy (meth) acrylate oligomer hereinafter, “polyfunctional epoxy (meth) acrylate oligomer”
  • the hard coat layer may contain one or more (meth) acrylic oligomers.
  • polyfunctional urethane (meth) acrylate oligomer a urethanization reaction product of a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule and polyisocyanate; polyols are polyisocyanates. Examples thereof include a urethanization reaction product of an isocyanate compound obtained by reacting with and a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule.
  • Examples of the (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule used in the urethanization reaction include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
  • Examples include (meth) acrylate.
  • the polyisocyanate used in the urethanization reaction includes hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diisocyanate obtained by hydrogenating aromatic isocyanates among these diisocyanates.
  • diisocyanate such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate
  • di or tri polyisocyanate such as triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate, or polyisocyanate obtained by increasing the amount of diisocyanate.
  • polyols used in the urethanization reaction in addition to aromatic, aliphatic and alicyclic polyols, polyester polyols, polyether polyols and the like are generally used.
  • aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptan, and di. Examples thereof include methylolpropionic acid, dimethylolbutylionic acid, glycerin, and hydrogenated bisphenol A.
  • polyester polyol examples include those obtained by a dehydration condensation reaction between the above-mentioned polyols and a polycarboxylic acid.
  • Specific compounds of the polycarboxylic acid include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid and the like. These polycarboxylic acids may be anhydrides.
  • examples of the polyether polyol include the above-mentioned polyols or polyoxyalkylene-modified polyols obtained by reacting phenols with alkylene oxides.
  • the polyfunctional polyester (meth) acrylate oligomer is obtained by a dehydration condensation reaction using (meth) acrylic acid, a polycarboxylic acid and a polyol.
  • the polycarboxylic acid 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 be anhydrides.
  • the polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptan, dimethylolpropionic acid, and dimethylol.
  • Examples thereof include butyric acid, trimethylolpropane, trimethylolpropane, pentaerythritol, and dipentaerythritol.
  • the polyfunctional epoxy (meth) acrylate oligomer is obtained by an addition reaction between polyglycidyl ether and (meth) acrylic acid.
  • 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.
  • Modifier used in the present invention changes the performance of a hard coat layer such as a leveling agent, an antistatic agent, a surfactant, a water-repellent oil-repellent agent, and a UV absorber.
  • leveling agent examples 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.
  • antistatic agent examples include glycerin fatty acid ester monoglyceride, glycerin fatty acid ester organic acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, cationic surfactant, and anionic surfactant.
  • surfactant and the water- and oil-repellent agent examples include fluorine-containing surfactants such as fluorine-containing group / lipophilic group-containing oligomers, fluorine-containing groups / hydrophilic groups, lipophilic groups, and UV-reactive group-containing oligomers. And water and oil repellents.
  • UV absorbers examples include hydroxyphenyltriazine-based, benzotriazole-based, and bengophenone-based.
  • the hard coat layer may contain a photopolymerization initiator.
  • the photopolymerization initiator refers to a photoradical generator.
  • Examples of the monofunctional photopolymerization initiator that can be used in the present invention include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [Darocure 2959: manufactured by Merck]; ⁇ -hydroxy.
  • Benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; other examples include halogenated ketones, acylphosphinoxides, and acylphosphonates.
  • the method for forming the hard coat layer is not particularly limited, but for example, it can be formed by applying a hard coat liquid on a layer (for example, a high hardness resin layer) located below the hard coat layer and then photopolymerizing the hard coat layer. ..
  • the method of applying the hard coat paint in the present invention is not particularly limited, and a known method can be used.
  • spin coating method dip method, spray method, slide coating method, bar coating method, roll coating method, gravure coating method, meniscus coating method, flexographic printing method, screen printing method, beat coating method, and handling method can be mentioned. ..
  • a lamp having a light emission distribution with a light wavelength of 420 nm or less is used, and examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, and a black light lamp. , Microwave-excited mercury lamp, metal halide lamp, etc.
  • high-pressure mercury lamps or metal halide lamps efficiently emit light in the active wavelength region of the initiator and heat short-wavelength light or reaction compositions that reduce the viscoelastic properties of the obtained polymer by cross-linking. This is preferable because it does not emit a large amount of long-wavelength light that causes evaporation.
  • the irradiation intensity of the lamp is a factor that affects the degree of polymerization of the obtained polymer, and is appropriately controlled for each performance of the target product.
  • the illuminance is preferably in the range of 0.1 to 300 mW / cm 2.
  • the photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to carry out light irradiation using a method that can eliminate the reaction inhibition due to oxygen.
  • One such method is to cover the reactive composition with a film made of polyethylene terephthalate or Teflon to cut off contact with oxygen and irradiate the reactive composition with light through the film. Further, the composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen is replaced by an inert gas such as nitrogen gas or carbon dioxide gas.
  • the airflow velocity of the inert gas is preferably 1 m / sec or less as a relative velocity with respect to the laminate coated with the hard coat liquid moving under the atmosphere of the inert gas. More preferably, it is 0.1 m / sec or less.
  • the coated surface may be pretreated for the purpose of improving the adhesion of the hard coat layer.
  • Known treatment examples include 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. Can be mentioned.
  • the hard coat layer preferably has a pencil hardness of 2H or more when irradiated with ultraviolet rays using a metal halide lamp having an irradiation output of UV light (254 nm) of 20 mW / cm 2.
  • the film thickness of the hard coat layer is preferably 1 ⁇ m or more and 40 ⁇ m or less, and more preferably 2 ⁇ m or more and 10 ⁇ m or less. Sufficient hardness can be obtained when the film thickness is 1 ⁇ m or more. Further, when the film thickness is 40 ⁇ m or less, the occurrence of cracks during bending can be suppressed.
  • the film thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and actually measuring from the coating film interface to the surface.
  • the hard coat layer having an uneven shape may have at least one of antireflection performance, antifouling performance, antistatic performance, and weather resistance.
  • the method of applying the antireflection treatment, the antifouling treatment, the antistatic treatment, the weather resistance treatment and the like to the hard coat layer is not particularly limited, and a known method can be used. For example, a method of applying a reflection-reducing paint, a method of depositing a dielectric thin film, a method of applying an antistatic paint, and the like can be mentioned.
  • Molding by a mold can be produced by a method of producing a mold having a shape complementary to an uneven surface and curing it with ultraviolet rays in a state where a transparent base material coated with a hard coat is in close contact with the mold.
  • the optical comb widths are 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm.
  • the optical comb width is preferably 2.0 mm.
  • the transmission sharpness can be measured by the method described in Examples described later.
  • the optical comb widths are 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm.
  • the optical comb width is preferably 2.0 mm.
  • the reflection sharpness measured at an incident angle of light of 45 ° indicates that the larger the value, the easier the image is reflected, and the smaller the value, the less likely the image is reflected.
  • the reflection sharpness can be measured by the method described in Examples described later.
  • the transmission sharpness when light is transmitted using an optical comb having a width of 2.0 mm is T1, 2.0 mm width.
  • T1 / T2 is preferably 2.0 or more, more preferably 3.0 or more, 3 It is particularly preferable that it is 0.0 to 4.0.
  • the reflection sharpness can be measured by suppressing the back surface reflection by attaching a black tape to the back surface of the uneven surface.
  • the transmission sharpness T1 when light is transmitted using an optical comb having a width of 2.0 mm satisfies 30% ⁇ T1 ⁇ 50%, and more preferably 40% ⁇ T1 ⁇ 50%.
  • the reflection sharpness T2 measured at an incident angle of light of 45 ° using a 0.0 mm wide optical comb preferably satisfies 10% ⁇ T2 ⁇ 20%, and more preferably 10% ⁇ T2 ⁇ 15%. ..
  • the hard coat layer having an uneven shape preferably does not contain inorganic particles or organic particles.
  • the uneven shape in the present invention is provided by transfer.
  • the scratch resistance can be improved by not containing the inorganic particles or the organic particles in the hard coat layer.
  • the second hard coat layer may be provided on the surface opposite to the uneven hard coat layer.
  • the second hard coat layer has at least one of antireflection performance, antifouling performance, antistatic performance, and weather resistance.
  • Another embodiment of the present invention comprises the step of transferring the uneven shape to the hard coat layer by pressing a patterned PET film onto the photocurable resin composition on the layer containing the high hardness resin (B).
  • a method for producing the antiglare laminate including the above.
  • the patterned PET film for example, PTH, PTHA, PTHZ of Unitika emblem, PF11 or PF23 of Daicel's low-glare AG film can be used.
  • T1> ⁇ Transparency clarity (T1)> Using "ICM 1T” manufactured by Suga Test Instruments Co., Ltd., measurement was performed by installing the antiglare laminate so that the flow direction and the direction of the optical comb teeth were parallel to each other based on JIS K7374. Of the optical combs, a 2.0 mm wide optical comb was used, and the sharpness transmitted from the light source was defined as the transmitted sharpness.
  • ⁇ Reflective sharpness (T2)> Using "ICM 1T” manufactured by Suga Test Instruments Co., Ltd., measurement was performed by installing the antiglare laminate so that the flow direction and the direction of the optical comb teeth were parallel to each other based on JIS K7374. Among the optical combs, an optical comb having a width of 2.0 mm was used, and the image sharpness of reflection measured at an incident angle of light of 45 ° was defined as the reflection sharpness. The measurement was carried out by suppressing the reflection on the back surface by attaching a black tape (black vinyl tape model number 117BLA manufactured by 3M Japan Ltd.) to the back surface of the uneven surface.
  • a black tape black vinyl tape model number 117BLA manufactured by 3M Japan Ltd.
  • ⁇ SW hardness> The degree of scratches on the antiglare laminate when 15 reciprocations were made using steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd. under a load of 100 g / cm 2 was visually evaluated on a 10-point scale. It is described by RANK1 to RANK10. RANK1: No scratches (similar to inorganic glass) RANK10: Many scratches (similar to polycarbonate)
  • the test piece was cut out to a size of 100 mm ⁇ 60 mm.
  • the cut out test piece was set in a two-point support type holder and put into an environmental tester set at a temperature of 23% and a relative humidity of 50% for 24 hours or more to adjust the state, and then the warp was measured (before treatment).
  • the test piece was set in a holder and placed in an environmental tester set at a temperature of 85 ° C. and a relative humidity of 85%, and held in that state for 120 hours. Further, the holder was moved into an environmental tester set at a temperature of 23% and a relative humidity of 50%, and the warp was measured again after holding for 4 hours in that state (after treatment).
  • Example 1 ⁇ Laminated body (X-1)> Synthetic resin using 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 all extruders, and a multi-layer extruder having a T-die connected to the feed block.
  • the laminate was molded.
  • Optimas 7500 manufactured by Mitsubishi Gas Chemical Company was continuously introduced as a high-hardness resin (B1) into a single-screw extruder having a shaft diameter of 35 mm, and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.6 kg / h.
  • polycarbonate resin manufactured by Mitsubishi Engineering Plastics, trade name: Iupiron S-1000
  • Iupiron S-1000 polycarbonate resin
  • the feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a high hardness resin (B1) and a polycarbonate resin were introduced and laminated at a temperature of 270 ° C.
  • a laminate (X-1) of the layer (B1) and the polycarbonate resin layer was obtained.
  • the thickness of the obtained laminate (X-1) was 1.0 mm, and the thickness of the high hardness resin (B1) layer was 60 ⁇ m near the center.
  • the Optimas 7500 manufactured by Mitsubishi Gas Chemicals Co., Ltd. used as the high-hardness resin (B1) is represented by the (meth) acrylic acid ester structural unit (a) represented by the general formula (1) and the general formula (2).
  • the copolymer resin is 99 mol% of all the constituent units of the above, and the ratio of the (meth) acrylic acid ester constituent unit (a) is 75 mol% of all the constituent units of the copolymer resin.
  • ⁇ PET film with pattern (Z-1)> As a PET film for transferring the uneven shape, C-50 G-100-1 manufactured by Nakajima Kogyo was used.
  • the photocurable resin composition (Y-1) is applied onto the high hardness resin (B1) layer of the laminate (X-1) using a bar coater so that the coating thickness after curing is 5 to 10 ⁇ m. Then, the handle surface of the patterned PET film (Z-1) was covered and crimped so as to come into contact with the coating liquid. After that, a metal halide lamp (20 mW / cm) with a light source distance of 12 cm was irradiated for 30 seconds to cure, the patterned PET film was peeled off, and an antiglare antiglare provided with an uneven hard coat layer on a high hardness resin (B1) layer. A sex laminate was obtained.
  • Example 2 An antiglare laminate was obtained in the same manner as in Example 1 except that C-50 G-100-2 (Z-2) manufactured by Nakajima Kogyo Co., Ltd. was used for the patterned PET film.
  • Example 3 An antiglare laminate was obtained in the same manner as in Example 1 except that C-50 G-100-3 (Z-3) manufactured by Nakajima Kogyo Co., Ltd. was used for the patterned PET film.
  • Example 4 ⁇ Manufacturing of high hardness resin (B2)> 40% by mass of the high hardness resin (B1) used in Example 1 and 60% by mass of XIBOND140 manufactured by POLYSCOPE POLYMERS BV as a styrene-unsaturated dicarboxylic acid-based copolymer (C) were charged and mixed in a blender for 30 minutes. After that, using an extruder with a screw diameter of 26 mm (manufactured by Toshiba Machine Co., Ltd., TEM-26SS, L / D ⁇ 40), it is melt-kneaded at a cylinder temperature of 230 ° C., extruded into strands, pelletized with a pelletizer, and made into a high-hardness resin.
  • XIBOND140 manufactured by POLYSCOPE POLYMERS BV
  • C styrene-unsaturated dicarboxylic acid-based copolymer
  • the POLYSCOPE POLYMERS BV XIBOND140 used as the styrene-unsaturated dicarboxylic acid-based copolymer (C) contained 85% by mass of the styrene-based monomer unit (c1) and the unsaturated dicarboxylic acid anhydride monomer unit ( It is a resin containing c2) in an amount of 15% by mass.
  • the laminate was molded.
  • polycarbonate resin manufactured by Mitsubishi Engineering Plastics, trade name: Iupiron S-1000
  • Iupiron S-1000 polycarbonate resin
  • the feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a high hardness resin (B2) and a polycarbonate resin were introduced and laminated at a temperature of 270 ° C.
  • a laminate (X-2) of the layer (B2) and the polycarbonate resin layer was obtained.
  • the thickness of the obtained laminate (X-2) was 1.0 mm, and the thickness of the high hardness resin (B2) layer was 60 ⁇ m near the center.
  • the photocurable resin composition (Y-1) is applied onto the high hardness resin (B2) layer of the laminate (X-2) using a bar coater so that the coating thickness after curing is 5 to 10 ⁇ m. Then, the handle surface of the patterned PET film (Z-1) was covered and crimped so as to come into contact with the coating liquid. After that, a metal halide lamp (20 mW / cm) with a light source distance of 12 cm was irradiated for 30 seconds to cure, the patterned PET film was peeled off, and an antiglare antiglare provided with an uneven hard coat layer on a high hardness resin (B2) layer. A sex laminate was obtained.
  • Example 5 ⁇ Manufacturing of high hardness resin (B3)>
  • Regisphi R100 manufactured by Denka
  • a styrene-unsaturated dicarboxylic acid-based copolymer (E) is 75% by mass
  • methyl methacrylate resin parapet HR-L manufactured by Kuraray
  • the resin was melt-kneaded in 1 and extruded into a strand to be pelletized with a pelletizer to obtain a high hardness resin (B3). Pelletization was stable.
  • the Regisphi R100 manufactured by Denka
  • the styrene-unsaturated dicarboxylic acid-based copolymer (E) has 21% by mass of methyl methacrylate constituent unit, 64% by mass of styrene constituent unit, and 15 mass% of maleic anhydride constituent unit. % Is a copolymer.
  • the laminate was molded.
  • polycarbonate resin manufactured by Mitsubishi Engineering Plastics, trade name: Iupiron S-1000
  • Iupiron S-1000 polycarbonate resin
  • the feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a high hardness resin (B3) and a polycarbonate resin were introduced and laminated at a temperature of 270 ° C.
  • a laminate (X-3) of the layer (B3) and the polycarbonate resin layer was obtained.
  • the thickness of the obtained laminate (X-3) was 1.0 mm, and the thickness of the high hardness resin (B3) layer was 60 ⁇ m near the center.
  • the photocurable resin composition (Y-1) is applied onto the high hardness resin (B3) layer of the laminate (X-3) using a bar coater so that the coating thickness after curing is 5 to 10 ⁇ m. Then, the handle surface of the patterned PET film (Z-1) was covered and crimped so as to come into contact with the coating liquid. After that, a metal halide lamp (20 mW / cm) with a light source distance of 12 cm was irradiated for 30 seconds to cure, the patterned PET film was peeled off, and an antiglare antiglare provided with an uneven hard coat layer on a high hardness resin (B3) layer. A sex laminate was obtained.
  • Example 6 Manufacturing of high hardness resin (B4)>
  • the styrene-unsaturated dicarboxylic acid-based copolymer (E) used in Example 5 was 75% by mass, and the resin copolymer (G) was 7% by mass of the styrene constituent unit and 86% by mass of the methyl methacrylate constituent unit.
  • Delpet PM-120N manufactured by Asahi Kasei Chemical Co., Ltd.
  • Delpet PM-120N manufactured by Asahi Kasei Chemical Co., Ltd.
  • TEM-26SS manufactured by Toshiba Machinery Co., Ltd.
  • L / D ⁇ 40 melt-kneaded at a cylinder temperature of 230 ° C.
  • the laminate was molded.
  • polycarbonate resin manufactured by Mitsubishi Engineering Plastics, trade name: Iupiron S-1000
  • Iupiron S-1000 polycarbonate resin
  • the feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a high hardness resin (B4) and a polycarbonate resin were introduced and laminated at a temperature of 270 ° C.
  • a laminate (X-4) of the layer (B4) and the polycarbonate resin layer was obtained.
  • the thickness of the obtained laminate (X-4) was 1.0 mm, and the thickness of the high hardness resin (B4) layer was 60 ⁇ m near the center.
  • the photocurable resin composition (Y-1) is applied onto the high hardness resin (B4) layer of the laminate (X-4) using a bar coater so that the coating thickness after curing is 5 to 10 ⁇ m. Then, the handle surface of the patterned PET film (Z-1) was covered and crimped so as to come into contact with the coating liquid. After that, a metal halide lamp (20 mW / cm) with a light source distance of 12 cm was irradiated for 30 seconds to cure, the patterned PET film was peeled off, and an antiglare antiglare provided with an uneven hard coat layer on a high hardness resin (B4) layer. A sex laminate was obtained.
  • Example 7 ⁇ Laminated body (X-5)> Synthetic resin using 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 all extruders, and a multi-layer extruder having a T-die connected to the feed block.
  • the laminate was molded.
  • Iupiron KH3410UR manufactured by Mitsubishi Engineering Plastics
  • B5 high hardness resin
  • polycarbonate resin manufactured by Mitsubishi Engineering Plastics, trade name: Iupiron S-1000
  • Iupiron S-1000 polycarbonate resin
  • the feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a high hardness resin (B5) and a polycarbonate resin were introduced and laminated at a temperature of 270 ° C.
  • a laminate (X-5) of the layer (B5) and the polycarbonate resin layer was obtained.
  • the thickness of the obtained laminate (X-5) was 1.0 mm, and the thickness of the high hardness resin (B5) layer was 60 ⁇ m near the center.
  • the photocurable resin composition (Y-1) is applied onto the high hardness resin (B5) layer of the laminate (X-5) using a bar coater so that the coating thickness after curing is 5 to 10 ⁇ m. Then, the handle surface of the patterned PET film (Z-1) was covered and crimped so as to come into contact with the coating liquid. After that, a metal halide lamp (20 mW / cm) with a light source distance of 12 cm was irradiated for 30 seconds to cure, the patterned PET film was peeled off, and an antiglare antiglare provided with an uneven hard coat layer on a high hardness resin (B5) layer. A sex laminate was obtained.
  • Comparative Example 1 An antiglare laminate was obtained in the same manner as in Example 1 except that PS-27 (Z-4) manufactured by Daicel was used for the patterned PET film.
  • Comparative Example 2 50 parts by mass of acrylic ultraviolet curable resin (100% solid content: light acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), silica fine particles (octylsilane treated fumed silica, average primary particle diameter 12 nm) with respect to 50 parts by mass of MEK , Nippon Aerozil Co., Ltd.) 0.5 parts by mass, acrylic silane treated silica (average particle size 1.9 ⁇ m, trade name: SE-6050-SYB Admatex Co., Ltd.) 1 part by mass, and photoinitiator (trade name Omnirad184IGM)
  • a coating liquid (i) was prepared by mixing and stirring 3 parts by mass (manufactured by Resins).
  • the coating liquid (i) is applied to a PET (polyethylene terephthalate) film so as to have a dry film thickness of 2.5 ⁇ m, dried at 80 ° C. for 2 minutes, and then equipped with a high-pressure mercury lamp having a light source distance of 12 cm and an output of 80 W / cm.
  • Anti-glare lamination in the same manner as in Example 1 except that a patterned PET film (Z-5) produced by irradiating and curing ultraviolet rays at a line speed of 1.5 m / min on a conveyor was used. I got a body.
  • Comparative Example 3 50 parts by mass of acrylic ultraviolet curable resin (100% solid content product: light acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), silica fine particles (octylsilane treated fumed silica, average primary particle size 1.) With respect to 50% by mass of MEK. 9 ⁇ m, trade name: SE6050-SYB manufactured by Admatex Co., Ltd. 1.5 parts by mass and photoinitiator (brand name IrgaCure 184 manufactured by Toyotsu Chemiplas Co., Ltd.) 3 parts by mass are mixed and stirred to form a coating liquid (Y-). 2) was prepared.
  • acrylic ultraviolet curable resin 100% solid content product: light acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.
  • silica fine particles octylsilane treated fumed silica, average primary particle size 1.
  • SE6050-SYB trade name
  • photoinitiator brand name IrgaC
  • a coating liquid (Y-2) is applied to the laminate (X-1) according to Example 1 so as to have a dry film thickness of 2.5 ⁇ m, dried at 80 ° C. for 2 minutes, and then a metal halide lamp is purged with nitrogen. (20 mW / cm) was irradiated for 30 seconds and cured to obtain an antiglare laminate.
  • Comparative Example 4 Example 1 except that a laminate (X-6) obtained by using a methyl methacrylate resin parapet HR-L (manufactured by Kuraray, weight average molecular weight: 90,000) was used instead of the high hardness resin (B1). A hard coat layer was formed in the same manner as in the above, and an antiglare laminate was obtained.
  • a laminate (X-6) obtained by using a methyl methacrylate resin parapet HR-L manufactured by Kuraray, weight average molecular weight: 90,000
  • a hard coat layer was formed in the same manner as in the above, and an antiglare laminate was obtained.
  • the antiglare laminates obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were evaluated for transmission sharpness, 45 ° reflection sharpness, SW hardness, and shape stability. The results are shown in the table below.
  • the present invention has high scratch resistance and excellent shape stability while having antiglare properties that both prevent image reflection and suppress character blurring. It was found that an antiglare laminate was obtained.

Abstract

The present invention provides an anti-glare layered body comprising: a layer that includes a resin (A) containing a polycarbonate resin (a1); a layer that includes a high hardness resin (B) and that is provided on at least one side of the layer that includes the resin (A) containing the polycarbonate resin (a1); and a hard coating layer that has recesses and projections, and that is provided on the layer including the high hardness resin (B). The anti-glare layered body satisfies conditions (i) and (ii):　(i) The thickness of the layer including a high hardness resin (B) is 10-250 μm, and the combined thickness of the layer that includes the resin (A) containing the polycarbonate resin (a1) and the layer containing the high hardness resin (B) is 100-3,000 μm. (ii) In a case where T1 is the transmission clarity obtained when light is transmitted through an optical frequency comb having a slit width of 2.0 mm and T2 is the reflection clarity measured using an optical frequency comb having a slit width of 2.0 mm at a light incidence angle of 45°, T1/T2 is 2.0 or greater.

Description

防眩性積層体Anti-glare laminate
　本発明は、防眩性積層体に関する。より詳細には、本発明は、防眩性能を有しつつ、高い耐擦傷性を有し、形状安定性にも優れた、車載用液晶表示装置や携帯電話端末、パソコン、タブレットＰＣの前面板として用いられる防眩性積層体に関する。 The present invention relates to an antiglare laminate. More specifically, the present invention has a front plate of an in-vehicle liquid crystal display device, a mobile phone terminal, a personal computer, a tablet PC, which has high scratch resistance and excellent shape stability while having antiglare performance. With respect to the antiglare laminate used as.
　液晶パネルなどの保護を目的として、液晶表示装置には前面板が設けられている。従来の液晶表示装置の前面板に用いられる材料としては、ポリメタクリル酸メチル（ＰＭＭＡ）に代表される（メタ）アクリル樹脂が挙げられる。 The liquid crystal display device is provided with a front plate for the purpose of protecting the liquid crystal panel and the like. Examples of the material used for the front plate of the conventional liquid crystal display device include (meth) acrylic resin typified by polymethyl methacrylate (PMMA).
　また近年、高い耐衝撃性、耐熱性、２次加工性、軽量性及び透明性などを有する点から、ポリカーボネート樹脂からなるシートが前面板として用いられている。特に、ポリカーボネート樹脂シートの表層にアクリル樹脂を積層した多層シートの上にハードコートを施した前面板は、従来のハードコート付きアクリル樹脂に匹敵する表面硬度及び耐擦傷性を有しつつ、ポリカーボネート樹脂の優れた耐衝撃性、耐熱性、加工性及び透明性を併せ持つため、前面板として広く採用されている。 In recent years, a sheet made of polycarbonate resin has been used as a front plate because it has high impact resistance, heat resistance, secondary workability, light weight and transparency. In particular, the front plate obtained by applying a hard coat on a multilayer sheet in which an acrylic resin is laminated on the surface layer of a polycarbonate resin sheet has a surface hardness and scratch resistance comparable to those of a conventional acrylic resin with a hard coat, and the polycarbonate resin. It is widely used as a front plate because it has excellent impact resistance, heat resistance, workability and transparency.
　上記ポリカーボネート樹脂シートを備える液晶表示装置の前面板については、アクリル樹脂と共に溶融押出法によって形成されることが一般的である。 The front plate of the liquid crystal display device provided with the above-mentioned polycarbonate resin sheet is generally formed by a melt extrusion method together with an acrylic resin.
　液晶表示装置においては、一般に最表面には反射防止のための光学積層体が設けられている。このような反射防止用の光学積層体は、光の散乱や干渉によって、像の映り込みを抑制したり反射率を低減したりするものである。 In a liquid crystal display device, an optical laminate for antireflection is generally provided on the outermost surface. Such an optical laminate for antireflection suppresses the reflection of an image or reduces the reflectance by scattering or interference of light.
　反射防止用光学積層体の１つとして、透明性基材の表面に凹凸形状を有する防眩層を形成した防眩性フィルムが知られている。この防眩性フィルムは、表面の凹凸形状によって外光を散乱させて外光の反射や像の映り込みによる視認性の低下を防止することができる。また、この光学積層体は、通常、液晶表示装置の最表面に設置されるものであるため、取り扱い時に傷がつかないように、ハードコート性を付与することも要求される。 As one of the antireflection optical laminates, an antiglare film in which an antiglare layer having an uneven shape is formed on the surface of a transparent base material is known. This antiglare film can scatter external light due to the uneven shape of the surface to prevent deterioration of visibility due to reflection of external light and reflection of an image. Further, since this optical laminate is usually installed on the outermost surface of the liquid crystal display device, it is also required to impart hard coat property so as not to be scratched during handling.
　液晶表示装置や有機エレクトロルミネッサンス（ＥＬ）表示装置などの表示面では、通常、微粒子とバインダー樹脂又は硬化性樹脂との混合物を基材に塗布し、表面に微細な凹凸を形成することにより正反射を防ぎ、像の映り込みを防止している。しかし、像の映り込みを防止するために凹凸形状を付与すると直進する透過光の散乱が増加して、画素の輪郭が曖昧となって文字ボケが発生する。 On display surfaces such as liquid crystal display devices and organic electroluminescence (EL) display devices, a mixture of fine particles and a binder resin or a curable resin is usually applied to a base material to form fine irregularities on the surface. It prevents reflection and prevents reflection of the image. However, if a concavo-convex shape is added to prevent the image from being reflected, the scattering of the transmitted light traveling straight increases, the outline of the pixel becomes ambiguous, and character blurring occurs.
　また、表面凹凸を発現させるために微粒子を添加すると、耐擦傷試験中に最表面の微粒子が脱落して研磨剤として働くため、微粒子を添加しない場合と比較して著しく耐擦傷性が低下するため好ましくない。 In addition, when fine particles are added to develop surface irregularities, the finest particles on the outermost surface fall off during the scratch resistance test and act as an abrasive, so that the scratch resistance is significantly reduced as compared with the case where no fine particles are added. Not preferred.
　以上のように、車載用液晶表示装置や携帯電話端末、パソコン、タブレットＰＣの前面板では、優れた耐衝撃性、耐熱性、像の映り込みを防止しつつ、文字ボケを抑制する性能を両立した防眩性を有しつつ、高い耐擦傷性を有し、形状安定性にも優れた前面板はなかった。
　特許文献１では、透過鮮明度の向上と文字ボケを低減するために微粒子を添加している。微粒子を添加すると鉛筆硬度は向上するが、耐擦傷性が低下するため好ましくない。 As described above, the front panel of in-vehicle liquid crystal display devices, mobile phone terminals, personal computers, and tablet PCs has both excellent impact resistance, heat resistance, and performance of suppressing character blur while preventing image reflection. There was no front plate that had high scratch resistance and excellent shape stability while having excellent anti-glare properties.
In Patent Document 1, fine particles are added in order to improve the transparency and reduce the blurring of characters. The addition of fine particles improves the hardness of the pencil, but reduces the scratch resistance, which is not preferable.
　特許文献１：特開２０１０－１６０３９８ Patent Document 1: Japanese Patent Application Laid-Open No. 2010-160398
　本発明は、上記従来における問題の少なくとも一つを解決することを課題とする。更に、本発明は、像の映り込み防止性能と文字ボケの抑制を両立した防眩性能を有し、高い耐擦傷性を有し、形状安定性にも優れた防眩性積層体を提供することを課題とする。 An object of the present invention is to solve at least one of the above-mentioned conventional problems. Further, the present invention provides an antiglare laminate having both anti-glare performance for preventing image reflection and suppression of character blurring, high scratch resistance, and excellent shape stability. That is the issue.
　上記課題は、以下の本発明によって解決することができる。すなわち、本発明は以下の通りである。
＜１＞ポリカーボネート樹脂（ａ１）を含む樹脂（Ａ）を含む層と、
　ポリカーボネート樹脂（ａ１）を含む樹脂（Ａ）を含む層の少なくとも一方の面に設けられた、高硬度樹脂（Ｂ）を含む層と、
　更に高硬度樹脂（Ｂ）を含む層上に設けられ、凹凸形状を有するハードコート層と、
を備え、下記条件（ｉ）および（ｉｉ）を満たす防眩性積層体：
　（ｉ）前記高硬度樹脂（Ｂ）を含む層の厚みが１０～２５０μｍであり、前記ポリカーボネー樹脂（ａ１）を含む樹脂（Ａ）を含む層と前記高硬度樹脂（Ｂ）を含む層との合計厚みが１００～３，０００μｍであり；
　（ｉｉ）前記積層体は、２．０ｍｍ幅の光学くしを用いて光を透過させたときの透過鮮明度をＴ１、２．０ｍｍ幅の光学くしを用いて光の入射角４５°で測定される反射鮮明度をＴ２とした場合、Ｔ１/Ｔ２が２．０以上である防眩性積層体。 The above problems can be solved by the following invention. That is, the present invention is as follows.
<1> A layer containing the resin (A) containing the polycarbonate resin (a1) and
A layer containing the high hardness resin (B) provided on at least one surface of the layer containing the resin (A) containing the polycarbonate resin (a1), and a layer containing the high hardness resin (B).
Further, a hard coat layer provided on a layer containing a high hardness resin (B) and having an uneven shape, and a hard coat layer.
An antiglare laminate that satisfies the following conditions (i) and (ii):
(I) The layer containing the high hardness resin (B) has a thickness of 10 to 250 μm, and the layer containing the resin (A) containing the polycarbonate resin (a1) and the layer containing the high hardness resin (B). The total thickness of is 100-3,000 μm;
(Ii) In the laminated body, the transmission sharpness when light is transmitted using an optical comb having a width of 2.0 mm is measured at an incident angle of 45 ° using T1 and an optical comb having a width of 2.0 mm. When the reflection sharpness is T2, the antiglare laminate has T1 / T2 of 2.0 or more.
＜２＞２．０ｍｍ幅の光学くしを用いて光を透過させたときの透過鮮明度Ｔ１が３０％≦Ｔ１≦５０％を満たし、２．０ｍｍ幅の光学くしを用いて光の入射角４５°で測定される反射鮮明度Ｔ２が１０％≦Ｔ２≦２０％を満たす、＜１＞に記載の防眩性積層体。
＜３＞高硬度樹脂（Ｂ）が以下の樹脂（Ｂ１）から（Ｂ５）からなる群より選択される少なくとも一つを含む、
　前記樹脂（Ｂ１）は、
　下記一般式（１）で表される（メタ）アクリル酸エステル構成単位（ａ）と、下記一般式（２）で表される脂肪族ビニル構成単位（ｂ）とを含む共重合樹脂であって、前記（メタ）アクリル酸エステル構成単位（ａ）と前記脂肪族ビニル構成単位（ｂ）との合計割合が前記共重合樹脂の全構成単位の９０～１００モル％であり、前記（メタ）アクリル酸エステル構成単位（ａ）の割合が前記共重合樹脂の全構成単位の６５～８０モル％である、共重合樹脂：
Figure JPOXMLDOC01-appb-C000006
 　（式中、Ｒ１は水素原子またはメチル基であり、Ｒ２は炭素数１～１８のアルキル基である。）
Figure JPOXMLDOC01-appb-C000007
 　（式中、Ｒ３は水素原子またはメチル基であり、Ｒ４は炭素数１～４の炭化水素基を有しても良いシクロヘキシル基である。）
であり、
　前記樹脂（Ｂ２）は、
　前記樹脂（Ｂ１）を３５～６５質量％、スチレン－不飽和ジカルボン酸系共重合体（Ｃ）を３５～６５質量％含み、前記スチレン－不飽和ジカルボン酸共重合体（Ｃ）が、スチレン系単量体単位（ｃ１）を６５～９０質量％、不飽和ジカルボン酸無水物単量体単位（ｃ２）を１０～３５質量％で含む樹脂であり、
　前記樹脂（Ｂ３）は、
　ビニル系単量体を含有する樹脂（Ｄ）を５５～１０質量％、スチレン－不飽和ジカルボン酸系共重合体（Ｅ）を４５～９０質量％含み、前記スチレン－不飽和ジカルボン酸系共重合体（Ｅ）が、スチレン系単量体単位（e１）を５０～８０質量％、不飽和ジカルボン酸単量体単位（e２）を１０～３０質量％、ビニル系単量体単位（e３）を５～３０質量％で含む樹脂であり、
　前記樹脂（Ｂ４）は、
　スチレン構成単位を５～２０質量％、（メタ）アクリル酸エステル構成単位を６０～９０質量％、Ｎ－置換型マレイミド単量体を５～２０質量％含む樹脂共重合体（Ｇ）、または樹脂共重合体（Ｇ）と前記共重合体（Ｅ）のアロイである樹脂であり、
　前記樹脂（Ｂ５）は、
　下記式（３）で表される構成単位（Ｈ）と、任意に下記式（４）で表される構成単位（Ｊ）とを含む共重合体である、
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
 ＜１＞または＜２＞に記載の防眩性積層体。 <2> The transmission sharpness T1 when light is transmitted using a 2.0 mm wide optical comb satisfies 30% ≤ T1 ≤ 50%, and the incident angle of light 45 using a 2.0 mm wide optical comb. The antiglare laminate according to <1>, wherein the reflection sharpness T2 measured at ° satisfies 10% ≦ T2 ≦ 20%.
<3> The high hardness resin (B) contains at least one selected from the group consisting of the following resins (B1) to (B5).
The resin (B1) is
A copolymer resin containing a (meth) acrylic acid ester structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (b) represented by the following general formula (2). The total ratio of the (meth) acrylic acid ester constituent unit (a) and the aliphatic vinyl constituent unit (b) is 90 to 100 mol% of the total constituent units of the copolymer resin, and the (meth) acrylic The copolymer resin: the ratio of the acid ester structural unit (a) is 65 to 80 mol% of the total structural units of the copolymer resin.
Figure JPOXMLDOC01-appb-C000006
 (In the formula, R1 is a hydrogen atom or a methyl group, and R2 is an alkyl group having 1 to 18 carbon atoms.)
Figure JPOXMLDOC01-appb-C000007
 (In the formula, R3 is a hydrogen atom or a methyl group, and R4 is a cyclohexyl group which may have a hydrocarbon group having 1 to 4 carbon atoms.)
And
The resin (B2) is
The resin (B1) is 35 to 65% by mass, the styrene-unsaturated dicarboxylic acid copolymer (C) is 35 to 65% by mass, and the styrene-unsaturated dicarboxylic acid copolymer (C) is styrene-based. A resin containing 65 to 90% by mass of the monomer unit (c1) and 10 to 35% by mass of the unsaturated dicarboxylic acid anhydride monomer unit (c2).
The resin (B3) is
The resin (D) containing a vinyl monomer contains 55 to 10% by mass, the styrene-unsaturated dicarboxylic acid-based copolymer (E) contains 45 to 90% by mass, and the styrene-unsaturated dicarboxylic acid-based copolymer weight. The coalescence (E) contains 50 to 80% by mass of the styrene-based monomer unit (e1), 10 to 30% by mass of the unsaturated dicarboxylic acid monomer unit (e2), and a vinyl-based monomer unit (e3). It is a resin contained in an amount of 5 to 30% by mass.
The resin (B4) is
Resin copolymer (G) or resin containing 5 to 20% by mass of styrene constituent unit, 60 to 90% by mass of (meth) acrylic acid ester constituent unit, and 5 to 20% by mass of N-substituted maleimide monomer. A resin that is an alloy of the copolymer (G) and the copolymer (E).
The resin (B5) is
A copolymer containing a structural unit (H) represented by the following formula (3) and a structural unit (J) optionally represented by the following formula (4).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
 The antiglare laminate according to <1> or <2>.
＜４＞前記凹凸形状を有するハードコート層は、無機粒子または有機粒子を含まない、＜１＞～＜３＞のいずれかに記載の防眩性積層体。
＜５＞前記凹凸形状を有するハードコート層は、反射防止性能、防汚性能、帯電防止性能、および耐候性のうち少なくとも１つの特性を有する、＜１＞～＜４＞のいずれかに記載の防眩性積層体。
＜６＞前記凹凸を有するハードコート層とは反対の面に第２のハードコート層を備える、＜１＞～＜５＞のいずれかに記載の防眩性積層体。
＜７＞前記第２のハードコート層が、反射防止性能、防汚性能、帯電防止性能、および耐候性のうち少なくとも１つの特性を有する、＜６＞に記載の防眩性積層体。
＜８＞ポリカーボネート樹脂（ａ１）として、下記一般式（５）で表される１価フェノール由来の成分を含む、＜１＞～＜７＞のいずれかに記載の防眩性積層体。
Figure JPOXMLDOC01-appb-C000010
 　（式中、Ｒ１は、炭素数８～３６のアルキル基、又は炭素数８～３６のアルケニル基を表し、Ｒ２～Ｒ５はそれぞれ独立して、水素原子、ハロゲン、又は置換基を有してもよい炭素数１～２０のアルキル基若しくは炭素数６～１２のアリール基を表し、前記置換基は、ハロゲン、炭素数１～２０のアルキル基、又は炭素数６～１２のアリール基である。）
＜９＞上記＜１＞～＜８＞のいずれかに記載の防眩性積層体を含む車載用表示装置。
＜１０＞上記＜１＞～＜８＞のいずれかに記載の防眩性積層体を含むタッチパネル前面保護板。
＜１１＞上記＜１＞～＜８＞のいずれかに記載の防眩性積層体を含むＯＡ機器用、携帯電子機器用、またはテレビ用の前面板。
＜１２＞上記＜１＞～＜８＞のいずれかに記載の防眩性積層体の製造方法であって、前記高硬度樹脂（Ｂ）を含む層上の光硬化性樹脂組成物に、柄目付きＰＥＴフィルムを圧着することにより、前記ハードコート層に凹凸形状を転写するステップを含む、前記防眩性積層体の製造方法。 <4> The antiglare laminate according to any one of <1> to <3>, wherein the hard coat layer having an uneven shape does not contain inorganic particles or organic particles.
<5> The hard coat layer having an uneven shape has at least one of antireflection performance, antifouling performance, antistatic performance, and weather resistance, according to any one of <1> to <4>. Anti-glare laminate.
<6> The antiglare laminate according to any one of <1> to <5>, which comprises a second hard coat layer on a surface opposite to the hard coat layer having the unevenness.
<7> The antiglare laminate according to <6>, wherein the second hard coat layer has at least one of antireflection performance, antifouling performance, antistatic performance, and weather resistance.
<8> The antiglare laminate according to any one of <1> to <7>, which comprises a component derived from a monohydric phenol represented by the following general formula (5) as the polycarbonate resin (a1).
Figure JPOXMLDOC01-appb-C000010
 (In the formula, R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R 2 to R 5 each independently have a hydrogen atom, a halogen, or a substituent. It represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the substituent may be a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. is there.)
<9> An in-vehicle display device including the antiglare laminate according to any one of <1> to <8> above.
<10> A touch panel front protective plate including the antiglare laminate according to any one of <1> to <8> above.
<11> A front plate for OA equipment, portable electronic equipment, or a television including the antiglare laminate according to any one of <1> to <8> above.
<12> The method for producing an antiglare laminate according to any one of <1> to <8>, wherein the photocurable resin composition on the layer containing the high hardness resin (B) has a handle. A method for producing the antiglare laminate, which comprises a step of transferring an uneven shape to the hard coat layer by crimping a grained PET film.
　本発明によれば、防眩性能を有しつつ、高い耐擦傷性を有し、形状安定性にも優れた、車載用液晶表示装置や携帯電話端末、パソコン、タブレットＰＣの前面板として用いられる防眩性積層体を提供することができる。 According to the present invention, it is used as a front plate of an in-vehicle liquid crystal display device, a mobile phone terminal, a personal computer, or a tablet PC, which has high scratch resistance and excellent shape stability while having antiglare performance. An antiglare laminate can be provided.
実施例１で得られた積層体について、映り込み防止と文字ボケを抑制した凹凸形状を示す白色顕微鏡で撮影した写真である。It is a photograph of the laminated body obtained in Example 1 taken with a white microscope showing an uneven shape that prevents reflection and suppresses character blurring. 比較例１で得られた積層体について、映り込み防止のみ優れた凹凸形状を示す白色顕微鏡で撮影した写真である。It is a photograph of the laminate obtained in Comparative Example 1 taken with a white microscope showing an uneven shape that is excellent only in preventing reflection. 比較例２で得られた積層体について、文字ボケの抑制のみ優れた凹凸形状を示す白色顕微鏡で撮影した写真である。It is a photograph of the laminate obtained in Comparative Example 2 taken with a white microscope showing an uneven shape excellent only in suppressing character blurring.
　以下、本発明について製造例や実施例等を例示して詳細に説明するが、本発明は例示される製造例や実施例等に限定されるものではなく、本発明の内容を大きく逸脱しない範囲であれば任意の方法に変更して行うこともできる。 Hereinafter, the present invention will be described in detail by exemplifying manufacturing examples and examples, but the present invention is not limited to the exemplified manufacturing examples and examples and does not deviate significantly from the contents of the present invention. If so, it can be changed to any method.
　本発明の防眩性積層体（以下、「樹脂シート」と呼ぶことがある）は、ポリカーボネート樹脂（ａｌ）を含む樹脂（Ａ）を含む層（以下、「基材層」と呼ぶことがある）の少なくとも一方の面に、高硬度樹脂（Ｂ）を含む層（以下、「高硬度樹脂層」、「高硬度層」と呼ぶことがある）および凹凸形状を有するハードコート層とが設けられている。前記基材層は、ポリカーボネート樹脂（ａｌ）を含む樹脂（Ａ）からなる層であってもよい。また、前記高硬度層は、高硬度樹脂（Ｂ）からなる層であってもよい。 The antiglare laminate of the present invention (hereinafter, may be referred to as "resin sheet") may be referred to as a layer containing a resin (A) containing a polycarbonate resin (al) (hereinafter, may be referred to as a "base material layer"). ), A layer containing the high-hardness resin (B) (hereinafter, may be referred to as a "high-hardness resin layer" or a "high-hardness layer") and a hard coat layer having an uneven shape are provided on at least one surface. ing. The base material layer may be a layer made of a resin (A) containing a polycarbonate resin (al). Further, the high hardness layer may be a layer made of a high hardness resin (B).
　積層の順番としては、高硬度樹脂層は基材層とハードコート層との間に存在し、最表層となるハードコート層の最表面に凹凸形状が付与されている。ポリカーボネート樹脂（ａｌ）を含む樹脂（Ａ）を含む層の他方の面は特に指定はないが、高硬度樹脂層およびハードコート層の両方、あるいはいずれか一つの層を設けてもよい。 As for the order of lamination, the high hardness resin layer exists between the base material layer and the hard coat layer, and the outermost surface of the hard coat layer, which is the outermost layer, is provided with an uneven shape. The other surface of the layer containing the resin (A) containing the polycarbonate resin (al) is not particularly specified, but both the high hardness resin layer and the hard coat layer, or any one of the layers may be provided.
　高硬度樹脂層としては、高硬度樹脂（Ｂ）から選択される樹脂を用いることが望ましく、また、高硬度樹脂層を基材層の両面に設ける場合には、両面で同一の高硬度樹脂（Ｂ）を用いることが形状安定性のためにもより望ましい。 As the high-hardness resin layer, it is desirable to use a resin selected from the high-hardness resin (B), and when the high-hardness resin layer is provided on both sides of the base material layer, the same high-hardness resin (on both sides). It is more desirable to use B) for shape stability.
　本発明の一実施形態において、ハードコート層は、凹凸形状を有する。両面にハードコート層を形成する場合、同様のハードコート層を設けることが、形状安定性が良くなることから、より望ましい。 In one embodiment of the present invention, the hard coat layer has an uneven shape. When forming the hard coat layer on both sides, it is more preferable to provide the same hard coat layer because the shape stability is improved.
　本発明の一実施形態において、防眩性積層体は、例えば、車載用表示装置としてカーナビゲーション、センターインフォメーションディスプレイ（CID）、リアシートエンターテインメント（RSE）、クラスターなど、タッチパネル全面保護板、ならびに、ＯＡ機器用、携帯電子機器用、またはテレビ用の前面板に用いることができる。また、例えば前面板は、単独で液晶表示装置の前面板として使用できるが、例えばタッチセンサーなどの別の基板とラミネートするなど、複合して前面板として使用してもよい。 In one embodiment of the present invention, the antiglare laminate is, for example, a car navigation system, a center information display (CID), a rear seat entertainment (RSE), a cluster, etc. as an in-vehicle display device, a touch panel full protection plate, and an OA device. It can be used as a front plate for a device, a portable electronic device, or a television. Further, for example, the front plate can be used alone as the front plate of the liquid crystal display device, but may be combined and used as the front plate, for example, by laminating with another substrate such as a touch sensor.
　以下に、本発明による防眩性積層体の各構成部材について説明する。 Hereinafter, each component of the antiglare laminate according to the present invention will be described.
（ポリカーボネート樹脂（ａ１）を含む樹脂（Ａ））
　本発明に使用されるポリカーボネート樹脂（ａ１）を含む樹脂（Ａ）とは、主にポリカーボネート樹脂（ａ１）を含む樹脂である。樹脂（Ａ）中のポリカーボネート樹脂（ａ１）の含有量としては７５質量％以上であるが、含有量を増やすことで耐衝撃性が向上することから、望ましくは９０質量％以上であり、より望ましくは１００質量％である。 (Resin (A) containing polycarbonate resin (a1))
The resin (A) containing the polycarbonate resin (a1) used in the present invention is a resin mainly containing the polycarbonate resin (a1). The content of the polycarbonate resin (a1) in the resin (A) is 75% by mass or more, but it is more preferably 90% by mass or more because the impact resistance is improved by increasing the content. Is 100% by mass.
　ポリカーボネート樹脂（ａｌ）としては、分子主鎖中に炭酸エステル結合、即ち、－［Ｏ－Ｒ－ＯＣＯ］－単位（Ｒが脂肪族基、芳香族基、又は脂肪族基と芳香族基の双方を含むもの、さらに直鎖構造あるいは分岐構造を有するもの）を含むものであれば特に限定されるものではないが、特に下記式（４）の構造単位を含むポリカーボネート樹脂を使用することが好ましい。このようなポリカーボネート樹脂を使用することで、耐衝撃性に優れた防眩性積層体を得ることができる。 The polycarbonate resin (al) has a carbonic acid ester bond in the main chain of the molecule, that is,-[OR-OCO] -unit (R is an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group. It is not particularly limited as long as it contains, and further has a linear structure or a branched structure), but it is particularly preferable to use a polycarbonate resin containing the structural unit of the following formula (4). By using such a polycarbonate resin, an antiglare laminate having excellent impact resistance can be obtained.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　具体的には、ポリカーボネート樹脂（ａ１）として、芳香族ポリカーボネート樹脂（例えば、三菱エンジニアリングプラスチックス社製、商品名：ユーピロンＳ－２０００、ユーピロンＳ－１０００、ユーピロンＥ－２０００）等が使用可能であるが、これらに限定されない。 Specifically, as the polycarbonate resin (a1), an aromatic polycarbonate resin (for example, manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade names: Iupiron S-2000, Iupiron S-1000, Iupilon E-2000) and the like can be used. However, it is not limited to these.
　また、近年、前面板にも曲げ加工を行うような要望が増えていることから、ポリカーボネート樹脂（ａｌ）として、下記一般式（５）で表される１価フェノールを末端停止剤として用いた樹脂が好ましい。 Further, in recent years, since there is an increasing demand for bending the front plate as well, a resin using monohydric phenol represented by the following general formula (5) as a terminal terminator as the polycarbonate resin (al). Is preferable.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　（式中、Ｒ１は、炭素数８～３６のアルキル基、又は炭素数８～３６のアルケニル基を表し、Ｒ２～Ｒ５はそれぞれ独立して、水素原子、ハロゲン、又は置換基を有してもよい炭素数１～２０のアルキル基若しくは炭素数６～１２のアリール基を表し、前記置換基は、ハロゲン、炭素数１～２０のアルキル基、又は炭素数６～１２のアリール基である。） (In the formula, R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R 2 to R 5 each independently have a hydrogen atom, a halogen, or a substituent. It represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the substituent may be a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. is there.)
　より好ましくは、一般式（５）で表わされる１価フェノールは、下記一般式（６）で表される。 More preferably, the monohydric phenol represented by the general formula (5) is represented by the following general formula (6).
Figure JPOXMLDOC01-appb-C000013
 　（式中、Ｒ１は、炭素数８～３６のアルキル基、又は、炭素数８～３６のアルケニル基を表す。）
Figure JPOXMLDOC01-appb-C000013
 (In the formula, R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.)
　一般式（５）又は一般式（６）におけるＲ１の炭素数は、特定の数値範囲内であることがより好ましい。具体的には、Ｒ１の炭素数の上限値として３６が好ましく、２２がより好ましく、１８が特に好ましい。また、Ｒ１の炭素数の下限値として、８が好ましく、１２がより好ましい。 It is more preferable that the carbon number of R 1 in the general formula (5) or the general formula (6) is within a specific numerical range. Specifically, as the upper limit of the number of carbon atoms of R 1 , 36 is preferable, 22 is more preferable, and 18 is particularly preferable. Further, as the lower limit of the number of carbon atoms of R 1 , 8 is preferable, and 12 is more preferable.
　一般式（５）又は一般式（６）で示される１価フェノール（末端停止剤）の中でも、パラヒドロキシ安息香酸ヘキサデシルエステル、パラヒドロキシ安息香酸２－ヘキシルデシルエステルのいずれかもしくは両方を末端停止剤として使用することが特に好ましい。 Among the monovalent phenols (terminal terminators) represented by the general formula (5) or the general formula (6), one or both of the parahydroxybenzoic acid hexadecyl ester and the parahydroxybenzoic acid 2-hexyldecyl ester are terminated. It is particularly preferable to use it as an agent.
　一般式（６）においてＲ１として、例えば、炭素数１６のアルキル基である１価フェノール（末端停止剤）を使用した場合、ガラス転移温度、溶融流動性、成形性、耐ドローダウン性、ポリカーボネート樹脂製造時の１価フェノールの溶剤溶解性が優れており、本発明におけるポリカーボネート樹脂に使用する末端停止剤として、特に好ましい。 As R 1 in the general formula (6), for example, when using a monohydric phenol which is alkyl group of 16 carbon atoms (terminating agent), a glass transition temperature, melt flowability, moldability, drawdown resistance, polycarbonate The monohydric phenol has excellent solvent solubility during resin production, and is particularly preferable as a terminal terminator used for the polycarbonate resin in the present invention.
　一方、一般式（５）又は一般式（６）におけるＲ１の炭素数が増加しすぎると、１価フェノール（末端停止剤）の有機溶剤溶解性が低下する傾向があり、ポリカーボネート樹脂製造時の生産性が低下することがある。 On the other hand, if the carbon number of R 1 in the general formula (5) or the general formula (6) is increased too much, the organic solvent solubility of the monohydric phenol (terminal terminator) tends to decrease, and the polycarbonate resin is manufactured. Productivity may decrease.
　一例として、Ｒ１の炭素数が３６以下であれば、ポリカーボネート樹脂を製造するにあたって生産性が高く、経済性も良い。Ｒ１の炭素数が２２以下であれば、１価フェノールは、特に有機溶剤溶解性に優れており、ポリカーボネート樹脂を製造するにあたって生産性を非常に高くすることができ、経済性も向上する。 As an example, when the carbon number of R 1 is 36 or less, the productivity is high and the economy is good in producing the polycarbonate resin. When the carbon number of R 1 is 22 or less, the monohydric phenol is particularly excellent in organic solvent solubility, and the productivity can be made very high in the production of the polycarbonate resin, and the economic efficiency is also improved.
　一般式（５）又は一般式（６）におけるＲ１の炭素数が小さすぎると、ポリカーボネー卜樹脂のガラス転移温度が十分に低い値とはならず、熱成形性が低下することがある。 If the carbon number of R 1 in the general formula (5) or the general formula (6) is too small, the glass transition temperature of the polycarbonate resin does not become a sufficiently low value, and the thermoformability may deteriorate.
　本発明において、ポリカーボネート樹脂（ａｌ）の重量平均分子量は、防眩性積層体の耐衝撃性および成形条件に影響する。つまり、重量平均分子量が小さすぎる場合は、防眩性積層体の耐衝撃性が低下するので好ましくない。重量平均分子量が高すぎる場合は、ポリカーボネート樹脂（ａｌ）を含む層を積層させる時に過剰な熱源を必要とする場合があり、好ましくない。また、成形法によっては高い温度が必要になるので、ポリカーボネート樹脂（ａｌ）が高温にさらされることになり、その熱安定性に悪影響を及ぼすことがある。ポリカーボネート樹脂（ａｌ）の重量平均分子量は、１５，０００～７５，０００が好ましく、２０，０００～７０，０００がより好ましい。さらに好ましくは２５，０００～６５，０００である。なお、重量平均分子量は、ゲル浸透クロマトグラフイー（ＧＰＣ）により測定される、標準ポリスチレン換算の重量平均分子量である。 In the present invention, the weight average molecular weight of the polycarbonate resin (al) affects the impact resistance and molding conditions of the antiglare laminate. That is, if the weight average molecular weight is too small, the impact resistance of the antiglare laminate is lowered, which is not preferable. If the weight average molecular weight is too high, an excessive heat source may be required when laminating the layer containing the polycarbonate resin (al), which is not preferable. In addition, since a high temperature is required depending on the molding method, the polycarbonate resin (al) is exposed to a high temperature, which may adversely affect its thermal stability. The weight average molecular weight of the polycarbonate resin (al) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000. More preferably, it is 25,000 to 65,000. The weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
　樹脂（Ａ）は、添加剤等をさらに含んでいてもよい。添加剤としては、樹脂シートにおいて通常使用されるものを使用することができる。添加剤としては、例えば、抗酸化剤、抗着色剤、抗帯電剤、離型剤、滑剤、染料、顔料、可塑剤、難燃剤、樹脂改質剤、相溶化剤、有機フィラーや無機フィラーのような強化材などが挙げられる。添加剤と樹脂とを混合する方法は特に限定されず、全量コンパウンドする方法、マスターバッチをドライブレンドする方法、全量ドライブレンドする方法などを用いることができる。添加剤の量は、基材層の全質量に対して０～１０質量％であることが好ましく、０～７質量％であることがより好ましく、０～５質量％であることが特に好ましい。 The resin (A) may further contain additives and the like. As the additive, those usually used in the resin sheet can be used. Additives include, for example, antioxidants, anticolorants, antichargers, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers and inorganic fillers. Such as reinforcing materials can be mentioned. The method of mixing the additive and the resin is not particularly limited, and a method of compounding the entire amount, a method of dry-blending the masterbatch, a method of dry-blending the entire amount, and the like can be used. 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 with respect to the total mass of the base material layer.
（高硬度樹脂（Ｂ））
　本発明に使用される高硬度樹脂（Ｂ）としては、高硬度樹脂（Ｂ１）、高硬度樹脂（Ｂ２）、高硬度樹脂（Ｂ３）、高硬度樹脂（Ｂ４）、および高硬度樹脂（Ｂ５）からなる群より選択される少なくとも一つを含む。 (High hardness resin (B))
The high-hardness resin (B) used in the present invention includes a high-hardness resin (B1), a high-hardness resin (B2), a high-hardness resin (B3), a high-hardness resin (B4), and a high-hardness resin (B5). Includes at least one selected from the group consisting of.
＜高硬度樹脂（Ｂ１）＞
　本発明に使用される高硬度樹脂（Ｂ１）とは、一般式（１）で表される（メタ）アクリル酸エステル構成単位（ａ）と、一般式（２）で表される脂肪族ビニル構成単位（ｂ）とを含む共重合樹脂であって、前記メタクリル酸エステル構成単位（ａ）と前記脂肪族ビニル構成単位（ｂ）との合計割合が前記共重合樹脂の全構成単位の９０～１００モル％であり、前記メタクリル酸エステル構成単位（ａ）の割合が前記共重合樹脂の全構成単位の６５～８０モル％である共重合樹脂である。 <High hardness resin (B1)>
The high-hardness resin (B1) used in the present invention includes a (meth) acrylic acid ester structural unit (a) represented by the general formula (1) and an aliphatic vinyl composition represented by the general formula (2). A copolymer resin containing the unit (b), wherein the total ratio of the methacrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is 90 to 100 of all the constituent units of the copolymer resin. It is a copolymer resin in which the proportion of the methacrylic acid ester structural unit (a) is 65 to 80 mol% of all the structural units of the copolymer resin.
Figure JPOXMLDOC01-appb-C000014
 　（式中、Ｒ１は水素原子またはメチル基であり、Ｒ２は炭素数１～１８のアルキル基である。）
Figure JPOXMLDOC01-appb-C000014
 (In the formula, R1 is a hydrogen atom or a methyl group, and R2 is an alkyl group having 1 to 18 carbon atoms.)
Figure JPOXMLDOC01-appb-C000015
 　（式中、Ｒ３は水素原子又はメチル基であり、Ｒ４は炭素数１～４の炭化水素基を有してもよいシクロヘキシル基である。）
Figure JPOXMLDOC01-appb-C000015
 (In the formula, R3 is a hydrogen atom or a methyl group, and R4 is a cyclohexyl group which may have a hydrocarbon group having 1 to 4 carbon atoms.)
　本明細書中において、「炭化水素基」は、直鎖状、分岐鎖状、環状のいずれであってもよく、置換基を有していてもよい。 In the present specification, the "hydrocarbon group" may be linear, branched or cyclic, or may have a substituent.
　一般式（１）で表される（メタ）アクリル酸エステル構成単位（ａ）において、Ｒ２は炭素数１～１８のアルキル基であり、炭素数１～１０のアルキル基であることが好ましく、炭素数１～６のアルキル基であることがより好ましい。具体的にはメチル基、エチル基、ブチル基、ラウリル基、ステアリル基、シクロヘキシル基、イソボルニル基などが挙げられる。 In the (meth) acrylic acid ester structural unit (a) represented by the general formula (1), R2 is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and carbon. More preferably, it is an alkyl group having the number 1 to 6. Specific examples thereof include a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group, and an isobornyl group.
　（メタ）アクリル酸エステル構成単位（ａ）のうち、好ましいのはＲ２がメチル基またはエチル基である（メタ）アクリル酸エステル構成単位であり、更に好ましいのはＲ１がメチル基であり、Ｒ２がメチル基であるメタクリル酸メチル構成単位である。 Of the (meth) acrylic acid ester structural units (a), R2 is a methyl group or an ethyl group (meth) acrylic acid ester structural unit, and more preferably R1 is a methyl group and R2 is It is a building block of methyl methacrylate, which is a methyl group.
　前記一般式（２）で表される脂肪族ビニル構成単位（ｂ）において、Ｒ３は水素原子又はメチル基であり、水素原子であることがより好ましい。Ｒ４はシクロヘキシル基又は炭素数１～４の炭化水素基を有するシクロヘキシル基である。前記脂肪族ビニル構成単位（ｂ）のうち、より好ましいのはＲ３が水素原子であり、Ｒ４がシクロヘキシル基である脂肪族ビニル構成単位である。 In the aliphatic vinyl structural unit (b) represented by the general formula (2), R3 is a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R4 is a cyclohexyl group having a cyclohexyl group or a hydrocarbon group having 1 to 4 carbon atoms. Of the aliphatic vinyl constituent units (b), more preferable is an aliphatic vinyl constituent unit in which R3 is a hydrogen atom and R4 is a cyclohexyl group.
　高硬度樹脂（Ｂ１）は、前記（メタ）アクリル酸ヱステル構成単位（ａ）を１種又は２種以上含有していてもよく、前記脂肪族ビニル構成単位（ｂ）を１種又は２種以上含有していてもよい。 The high-hardness resin (B1) may contain one or more of the (meth) acrylic acid easter constituent unit (a), and one or more of the aliphatic vinyl constituent unit (b). It may be contained.
　前記（メタ）アクリル酸エステル構成単位（ａ）と前記脂肪族ビニル構成単位（ｂ）との合計割合は、前記共重合樹脂の全構成単位の合計に対して９０～１００モル％であり、好ましくは９５～１００モル％であり、より好ましくは９８～１００モル％である。 The total ratio of the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is preferably 90 to 100 mol% with respect to the total of all the structural units of the copolymer resin. Is 95 to 100 mol%, more preferably 98 to 100 mol%.
　すなわち、高硬度樹脂（Ｂ１）は、（メタ）アクリル酸エステル構成単位（ａ）および脂肪族ビニル構成単位（ｂ）以外の構成単位を含有していてもよい。その量は、樹脂（Ｂ１）の全構成単位に対して１０モル％以下であることが好ましく、５モル％以下であることがより好ましく、２モル％以下であることが特に好ましい。 That is, the high hardness resin (B1) may contain a structural unit other than the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b). The amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less, based on all the constituent units of the resin (B1).
　（メタ）アクリル酸エステル構成単位（ａ）および脂肪族ビニル構成単位（ｂ）以外の構成単位としては、例えば、（メタ）アクリル酸エステルモノマーと芳香族ビニルモノマーとを重合した後に該芳香族ビニルモノマー由来の芳香族二重結合を水素化して樹脂（Ｂ１）を製造する過程において生じる、水素化されていない芳香族二重結合を含む芳香族ビニルモノマー由来の構成単位などが挙げられる。 Examples of the structural unit other than the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) include the aromatic vinyl after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer. Examples thereof include a structural unit derived from an aromatic vinyl monomer containing an unhydrogenated aromatic double bond, which is generated in the process of producing a resin (B1) by hydrogenating an aromatic double bond derived from the monomer.
　また、一般式（１）で表される（メタ）アクリル酸エステル構成単位（ａ）の含有量は、高硬度樹脂（Ｂ１）中の全構成単位に対して好ましくは６５～８０モル％であり、より好ましくは７０～８０モル％である。樹脂（Ｂ１）中の全構成単位に対する（メタ）アクリル酸エステル構成単位（ａ）の割合が６５モル％以上であると、基材層との密着性や表面硬度に優れた樹脂層を得ることができる。また、８０モル％以下であれば、樹脂シートの吸水による反りが発生しづらい。 The content of the (meth) acrylic acid ester structural unit (a) represented by the general formula (1) is preferably 65 to 80 mol% with respect to all the structural units in the high hardness resin (B1). , More preferably 70-80 mol%. When the ratio of the (meth) acrylic acid ester structural unit (a) to all the structural units in the resin (B1) is 65 mol% or more, a resin layer having excellent adhesion to the base material layer and surface hardness can be obtained. Can be done. Further, if it is 80 mol% or less, warpage due to water absorption of the resin sheet is unlikely to occur.
　また、一般式（２）で表される脂肪族ビニル構成単位（ｂ）の含有量は、高硬度樹脂（Ｂ１）中の全構成単位に対して好ましくは２０～３５モル％であり、より好ましくは２０～３０モル％である。脂肪族ビニル構成単位（ｂ）の含有量が２０モル％以上であれば、高温高湿下でのそりを防ぐことができ、また、３５モル％以下であれば、基材層との界面での剥離を防ぐことができる。 The content of the aliphatic vinyl constituent unit (b) represented by the general formula (2) is preferably 20 to 35 mol% with respect to all the constituent units in the high hardness resin (B1), more preferably. Is 20 to 30 mol%. If the content of the aliphatic vinyl constituent unit (b) is 20 mol% or more, warpage under high temperature and high humidity can be prevented, and if it is 35 mol% or less, at the interface with the base material layer. Can be prevented from peeling off.
　なお、本明細書において、「共重合体」は、ランダム、ブロック、および交互共重合体のいずれの構造であってもよい。 In the present specification, the "copolymer" may have any structure of random, block, and alternating copolymers.
　高硬度樹脂（Ｂ１）の製造方法は、特に限定されないが、少なくとも１種の（メタ）アクリル酸エステルモノマーと少なくとも１種の芳香族ビニルモノマーとを重合した後、該芳香族ビニルモノマー由来の芳香族二重結合を水素化して得られたものが好適である。なお、（メタ）アクリル酸とは、メタクリル酸及び／又はアクリル酸を示す。この際に使用される芳香族ビニルモノマーとしては、具体的にはスチレン、α－メチルスチレン、ｐ－ヒドロキシスチレン、アルコキシスチレン、クロロスチレン、及びそれらの誘導体などが挙げられる。これらの中で好ましいのはスチレンである。 The method for producing the high-hardness resin (B1) is not particularly limited, but after polymerizing at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer, the fragrance derived from the aromatic vinyl monomer is used. Those obtained by hydrogenating the group double bond are preferable. The (meth) acrylic acid means methacrylic acid and / or acrylic acid. Specific examples of the aromatic vinyl monomer used at this time include styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene is preferred.
　（メタ）アクリル酸エステルモノマーと芳香族ビニルモノマーの重合には、既知の方法を用いることができるが、例えば、塊状重合法や溶液重合法などにより製造することができる。塊状重合法は、上記モノマー、重合開始剤を含むモノマー組成物を完全混合槽に連続的に供給し、１００～１８０℃で連続重合する方法などにより行われる。上記モノマー組成物は、必要に応じて連鎖移動剤を含んでもよい。 A known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer, and for example, it can be produced by a massive polymerization method, a solution polymerization method, or the like. The massive polymerization method is carried out by a method in which a monomer composition containing the above-mentioned monomer and a polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ° C. The monomer composition may contain a chain transfer agent, if necessary.
　重合開始剤としては、特に限定されないが、ｔ－アミルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、過酸化ベンゾイル、１，１－ジ（ｔ－ヘキシルペルオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ジ（ｔ－ヘキシルペルオキシ）シクロヘキサン、１，１－ジ（ｔ－ブチルペルオキシ）シクロヘキサン、ｔ－ヘキシルプロポキシイソプロピルモノカーボネート、ｔ－アミルパーオキシノルマルオクトエート、ｔ－ブチルペルオキシイソプロピルモノカーボネート、ジ－ｔ－ブチルパーオキサイド等の有機過酸化物、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２－メチルブチロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）等のアゾ化合物が挙げられる。これらは単独でまたは２種以上を組み合わせて用いることができる。 The polymerization initiator is not particularly limited, but is t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di (t-hexyl). Peroxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, t-hexylpropoxyisopropyl monocarbonate, t-amylper Organic peroxides such as oxynormal octoate, t-butylperoxyisopropyl monocarbonate, di-t-butyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbuty) Examples of azo compounds include lonitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile). These can be used alone or in combination of two or more.
　連鎖移動剤は必要に応じて使用し、例えば、α－メチルスチレンダイマーが挙げられる。 The chain transfer agent is used as needed, and examples thereof include α-methylstyrene dimer.
　溶液重合法に用いられる溶媒としては、例えば、トルエン、キシレン、シクロヘキサン、メチルシクロヘキサンなどの炭化水素系溶媒、酢酸エチル、イソ酪酸メチルなどのエステル系溶媒、アセトン、メチルエチルケトンなどのケトン系溶媒、テトラヒドロフラン、ジオキサンなどのエーテル系溶媒、メタノール、イソプロパノールなどのアルコール系溶媒などが挙げられる。 Examples of the solvent used in the solution polymerization method 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, tetrahydrofuran, and the like. Examples thereof include ether solvents such as dioxane and alcohol solvents such as methanol and isopropanol.
　（メタ）アクリル酸エステルモノマーと芳香族ビニルモノマーを重合した後の水素化反応に用いられる溶媒は、前記の溶液重合法に用いられる溶媒と同じであっても異なっていてもよい。例えば、シクロヘキサン、メチルシクロヘキサンなどの炭化水素系溶媒、酢酸エチル、イソ酪酸メチルなどのエステル系溶媒、アセトン、メチルエチルケトンなどのケトン系溶媒、テトラヒドロフラン、ジオキサンなどのエーテル系溶媒、メタノール、イソプロパノールなどのアルコール系溶媒などが挙げられる。 The solvent used for the hydrogenation reaction after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer may be the same as or different from the solvent used in the above solution polymerization method. For example, 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, alcohol solvents such as methanol and isopropanol. Examples include solvents.
　上記のようにして（メタ）アクリル酸エステルモノマーと芳香族ビニルモノマーとを重合した後、該芳香族ビニルモノマー由来の芳香族二重結合を水素化することにより、本発明に用いられる高硬度樹脂（Ｂ１）が得られる。 The high hardness resin used in the present invention is obtained by polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer as described above, and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer. (B1) is obtained.
　水素化の方法は特に限定されず、既知の方法を用いることができる。例えば、水素圧力３～３０ＭＰａ、反応温度６０～２５０℃でバッチ式あるいは連続流通式で行うことができる。温度を６０℃以上とすることにより反応時間がかかり過ぎることがなく、また２５０℃以下とすることにより分子鎖の切断やエステル部位の水素化を起こすことが少ない。 The method of hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out in a batch system or a continuous flow system at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. When the temperature is 60 ° C. or higher, the reaction time does not take too long, and when the temperature is 250 ° C. or lower, the molecular chain is less likely to be cleaved or the ester site is hydrogenated.
　水素化反応に用いられる触媒としては、例えば、ニッケル、パラジウム、白金、コバル卜、ルテニウム、ロジウムなどの金属、又はそれら金属の酸化物もしくは塩もしくは錯体化合物を、カーボン、アルミナ、シリカ、シリカ．アルミナ、珪藻土などの多孔性担体に担持した固体触媒などが挙げられる。 Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobal, ruthenium, and rhodium, or oxides, salts, or complex compounds of these metals, and carbon, alumina, silica, and silica. Examples thereof include a solid catalyst supported on a porous carrier such as alumina and diatomaceous earth.
　前記高硬度樹脂（Ｂ１）は、芳香族ビニルモノマー由来の芳香族二重結合の７０％以上が水素化されたものであることが好ましい。即ち、芳香族ビニルモノマー由来の構成単位中の芳香族二重結合の未水素化部位の割合は３０％以下であることが好ましい。３０％を超える範囲であると高硬度樹脂（Ｂ１）の透明性が低下する場合がある。未水素化部位の割合は、より好ましくは１０％未満であり、さらに好ましくは５％未満の範囲である。 The high hardness resin (B1) is preferably one in which 70% or more of the aromatic double bonds derived from the aromatic vinyl monomer are hydrogenated. That is, the proportion of the unhydrogenated portion of the aromatic double bond in the structural unit derived from the aromatic vinyl monomer is preferably 30% or less. If it exceeds 30%, the transparency of the high hardness resin (B1) may decrease. The proportion of unhydrogenated sites is more preferably less than 10% and even more preferably less than 5%.
　高硬度樹脂（Ｂ１）の重量平均分子量は、特に制限はないが、強度及び成型性の観点から、５０，０００～４００，０００であることが好ましく、７０，０００～３００，０００であることがより好ましい。上記重量平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）により測定される、標準ポリスチレン換算の重量平均分子量である。 The weight average molecular weight of the high hardness resin (B1) is not particularly limited, but is preferably 50,000 to 400,000, preferably 70,000 to 300,000 from the viewpoint of strength and moldability. More preferred. The weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
　前記高硬度樹脂（Ｂ１）には、透明性を損なわない範囲で他の樹脂をブレンドすることができる。例えば、メタクリル酸メチル－スチレン共重合樹脂、ポリメタクリル酸メチル、ポリスチレン、ポリカーボネート、シクロオレフイン（コ）ポリマー樹脂、アクリロニトリル－スチレン共重合樹脂、アクリロニトリルーブタジエンースチレン共重合樹脂、各種エラストマーなどが挙げられる。 The high hardness resin (B1) can be blended with other resins as long as the transparency is not impaired. Examples thereof include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, polycarbonate, cycloolephine (co) polymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, and various elastomers. ..
　前記高硬度樹脂（Ｂ１）のガラス転移温度は、１１０～１４０℃の範囲であることが好ましい。ガラス転移温度が１１０℃以上であることにより本発明で提供される積層体が熱環境あるいは湿熱環境において変形や割れを生じることが少なく、また１４０℃以下であることにより鏡面ロールや賦形ロールによる連続式熱賦形、あるいは鏡面金型や賦形金型によるバッチ式熱賦形などの加工性に優れる。なお、本発明におけるガラス転移温度とは、示差走査熱量測定装置を用い、試料１０ｍｇ、昇温速度１０℃／分で測定し中点法で算出したときの温度である。 The glass transition temperature of the high hardness resin (B1) is preferably in the range of 110 to 140 ° C. When the glass transition temperature is 110 ° C. or higher, the laminate provided in the present invention is less likely to be deformed or cracked in a thermal environment or a moist heat environment, and when it is 140 ° C. or lower, it depends on a mirror surface roll or a shaping roll. It has excellent workability such as continuous heat shaping, or batch type heat shaping using a mirror surface mold or a shaping mold. The glass transition temperature in the present invention is a temperature calculated by the midpoint method when measured at a sample of 10 mg and a heating rate of 10 ° C./min using a differential scanning calorimetry device.
　高硬度樹脂（Ｂ１）として、例えば、オプティマス７５００，６０００（三菱ガス化学製）が挙げられるが、これらに限定されない。 Examples of the high hardness resin (B1) include, but are not limited to, Optimus 7500, 6000 (manufactured by Mitsubishi Gas Chemical Company).
＜高硬度樹脂（Ｂ２）＞
　本発明に使用される高硬度樹脂（Ｂ２）とは、高硬度樹脂（Ｂ１）を３５～６５質量％、およびスチレン－不飽和ジカルボン酸系共重合体（Ｃ）を３５～６５質量％を含む樹脂であって、前記スチレン－不飽和ジカルボン酸系共重合体（Ｃ）がスチレン系単量体単位（ｃ１）を６５～９０質量％、不飽和ジカルボン酸無水物単量体単位（ｃ２）を１０～３５質量％を含む樹脂である。 <High hardness resin (B2)>
The high hardness resin (B2) used in the present invention contains 35 to 65% by mass of the high hardness resin (B1) and 35 to 65% by mass of the styrene-unsaturated dicarboxylic acid-based copolymer (C). In the resin, the styrene-unsaturated dicarboxylic acid-based copolymer (C) contains 65 to 90% by mass of the styrene-based monomer unit (c1) and the unsaturated dicarboxylic acid anhydride monomer unit (c2). It is a resin containing 10 to 35% by mass.
　以下に、スチレン－不飽和ジカルボン酸系共重合体（Ｃ）について説明する。 The styrene-unsaturated dicarboxylic acid-based copolymer (C) will be described below.
＜スチレン－不飽和ジカルボン酸系共重合体（Ｃ）＞
　本発明で用いられるスチレン－不飽和ジカルボン酸系共重合体（Ｃ）は、スチレン系単量体単位（ｃ１）、不飽和ジカルボン酸無水物単量体単位（ｃ２）を含む。 <Styrene-unsaturated dicarboxylic acid copolymer (C)>
The styrene-unsaturated dicarboxylic acid-based copolymer (C) used in the present invention contains a styrene-based monomer unit (c1) and an unsaturated dicarboxylic acid anhydride monomer unit (c2).
＜スチレン系単量体単位（ｃ１）＞
　スチレン系単量体とは、特に限定せず、任意の既知のスチレン系単量体を用いることが出来るが、入手の容易性の観点からスチレン、ａ－メチルスチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ｔ－ブチルスチレン等が挙げられる。これらの中でも、相溶性の観点からスチレンが特に好ましい。これらのスチレン系単量体は２種以上を混合しても良い。 <Styrene-based monomer unit (c1)>
The styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used, but from the viewpoint of easy availability, styrene, a-methylstyrene, o-methylstyrene, m- Examples thereof include methyl styrene, p-methyl styrene and t-butyl styrene. Of these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these styrene-based monomers may be mixed.
＜不飽和ジカルボン酸無水物単量体単位（ｃ２）＞
　不飽和ジカルボン酸無水物単量体としては、例えばマレイン酸、イタコン酸、シトラコン酸、アコニット酸等の酸無水物が挙げられ、ビニル系単量体との相溶性の観点から無水マレイン酸が好ましい。これらの不飽和ジカルボン酸無水物単量体は２種以上を混合しても良い。 <Unsaturated dicarboxylic acid anhydride monomer unit (c2)>
Examples of the unsaturated dicarboxylic acid anhydride monomer include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferable from the viewpoint of compatibility with vinyl-based monomers. .. Two or more kinds of these unsaturated dicarboxylic acid anhydride monomers may be mixed.
＜スチレン－不飽和ジカルボン酸系共重合体（Ｃ）の組成比率＞
　スチレン－不飽和ジカルボン酸系共重合体（Ｃ）の組成比率は、スチレン系単量体単位（ｃ１）６５～９０質量％（好ましくは、７０～８５質量％）、不飽和ジカルボン酸無水物単量体単位（ｃ２）１０～３５質量％（好ましくは、１５～３０質量％）である。 <Composition ratio of styrene-unsaturated dicarboxylic acid copolymer (C)>
The composition ratio of the styrene-unsaturated dicarboxylic acid-based copolymer (C) was 65 to 90% by mass (preferably 70 to 85% by mass) of the styrene-based monomer unit (c1), and the unsaturated dicarboxylic acid anhydride alone. The unit of measure (c2) is 10 to 35% by mass (preferably 15 to 30% by mass).
　前記共重合体（Ｃ）として、具体的には、POLYSCOPE POLYMERS BV製ＸＩＢＯＮＤ１４０、ＸＩＢＯＮＤ１６０などが挙げられるが、これらに限定されない。 Specific examples of the copolymer (C) include, but are not limited to, POLYSCOPE POLYMERS BV XIBOND140 and XIBOND160.
＜高硬度樹脂（Ｂ３）＞
　本発明に使用される高硬度樹脂（Ｂ３）とは、ビニル系単量体を含有する樹脂（Ｄ）を５５～１０質量％（好ましくは、５０～２０質量％）、およびスチレン－不飽和ジカルボン酸系共重合体（Ｅ）を４５～９０質量％（好ましくは、５０～８０質量％）で含む樹脂であって、前記スチレン－不飽和ジカルボン酸系共重合体（Ｅ）が、スチレン系単量体単位（ｅ１）を５０～８０質量％、不飽和ジカルボン酸無水物単量体単位（ｅ２）を１０～３０質量％、およびビニル系単量体単位（ｅ３）を５～３０質量％で含む樹脂である。 <High hardness resin (B3)>
The high hardness resin (B3) used in the present invention includes 55 to 10% by mass (preferably 50 to 20% by mass) of the resin (D) containing a vinyl-based monomer, and styrene-unsaturated dicarboxylic. A resin containing the acid-based copolymer (E) in an amount of 45 to 90% by mass (preferably 50 to 80% by mass), wherein the styrene-unsaturated dicarboxylic acid-based copolymer (E) is a styrene-based simple resin. The weight unit (e1) is 50 to 80% by mass, the unsaturated dicarboxylic acid anhydride monomer unit (e2) is 10 to 30% by mass, and the vinyl-based monomer unit (e3) is 5 to 30% by mass. It is a resin containing.
　以下に、ビニル系単量体を含有する樹脂（Ｄ）とスチレン－不飽和ジカルボン酸系共重合体（Ｅ）について順次説明する。 The resin (D) containing the vinyl-based monomer and the styrene-unsaturated dicarboxylic acid-based copolymer (E) will be sequentially described below.
＜ビニル系単量体を含有する樹脂（Ｄ）＞
　本発明で用いられるビニル系単量体を含有する樹脂（Ｄ）としては、例えば、アクリロニトリル、メタアクリロニトリル、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－ブチル、アクリル酸２－エチルヘキシル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－ブチル、メタクリル酸２－エチルヘキシル等のビニル系単量体を単独重合したものが挙げられ、特に単量体単位として、メタクリル酸メチルが好ましい。また、前記単量体単位を２種類以上含んだ共重合体でも良い。ビニル茶単量体を含有する樹脂（Ｄ）の重量平均分子量は、１０，０００～５００，０００が好ましく、より好ましくは５０，０００～３００，０００である。 <Resin (D) containing vinyl-based monomer>
Examples of the resin (D) containing the vinyl-based monomer used in the present invention include acrylonitrile, methacrylic acid, acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like. Examples thereof include those obtained by homopolymerizing vinyl-based monomers such as methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate, and methyl methacrylate is particularly preferable as the monomer unit. .. Further, a copolymer containing two or more kinds of the monomer units may be used. The weight average molecular weight of the resin (D) containing the vinyl tea monomer is preferably 10,000 to 500,000, more preferably 50,000 to 300,000.
＜スチレン－不飽和ジカルボン酸系共重合体（Ｅ）＞
　本発明で用いられるスチレン－不飽和ジカルボン酸系共重合体（Ｅ）は、スチレン系単量体単位（e１）、不飽和ジカルボン酸無水物単量体単位（e２）、およびビニル系単量体単位（e３）を含む。 <Styrene-unsaturated dicarboxylic acid copolymer (E)>
The styrene-unsaturated dicarboxylic acid-based copolymer (E) used in the present invention includes a styrene-based monomer unit (e1), an unsaturated dicarboxylic acid anhydride monomer unit (e2), and a vinyl-based monomer. Includes unit (e3).
＜スチレン系単量体単位（e１）＞
　スチレン系単量体とは、特に限定せず、任意の既知のスチレン系単量体を用いることが出来るが、入手の容易性の観点からスチレン、ａ－メチルスチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ｔ－ブチルスチレン等が挙げられる。これらの中でも、相溶性の観点からスチレンが特に好ましい。これらのスチレン系単量体は２種以上を混合しても良い。 <Styrene-based monomer unit (e1)>
The styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used, but from the viewpoint of easy availability, styrene, a-methylstyrene, o-methylstyrene, m- Examples thereof include methyl styrene, p-methyl styrene and t-butyl styrene. Of these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these styrene-based monomers may be mixed.
＜不飽和ジカルボン酸無水物単量体単位（e２）＞
　不飽和ジカルボン酸無水物単量体としては、例えばマレイン酸、イタコン酸、シトラコン酸、アコニット酸等の酸無水物が挙げられ、ビニル系単量体との相溶性の観点から無水マレイン酸が好ましい。これらの不飽和ジカルボン酸無水物単量体は２種以上を混合しても良い。 <Unsaturated dicarboxylic acid anhydride monomer unit (e2)>
Examples of the unsaturated dicarboxylic acid anhydride monomer include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferable from the viewpoint of compatibility with vinyl-based monomers. .. Two or more kinds of these unsaturated dicarboxylic acid anhydride monomers may be mixed.
＜ビニル系単量体単位（e３）＞
　ビニル系単量体とは、例えばアクリロニトリル、メタアクリロニトリル、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－ブチル、アクリル酸２－エチルへキシル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－ブチル、メタクリル酸２－エチルヘキシル等のビニル系単量体が挙げられる。ビニル系単量体を含有する樹脂（Ｄ）との相溶性の観点からメタクリル酸メチル（ＭＭＡ）が好ましい。これらのビニル系単量体は２種以上を混合しても良い。 <Vinyl-based monomer unit (e3)>
The vinyl-based monomer includes, for example, acrylonitrile, metaacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, and the like. Examples thereof include vinyl-based monomers such as n-butyl methacrylate and 2-ethylhexyl methacrylate. Methyl methacrylate (MMA) is preferable from the viewpoint of compatibility with the resin (D) containing a vinyl-based monomer. Two or more kinds of these vinyl-based monomers may be mixed.
＜スチレン－不飽和ジカルボン酸系共重合体（Ｅ）の組成比率＞
　スチレン－不飽和ジカルボン酸系共重合体（Ｅ）の組成比率は、スチレン系単量体単位（e１）５０～８０質量％（好ましくは、５０～７５質量％）、不飽和ジカルボン酸無水物単量体単位（e２）１０～３０質量％（好ましくは、１０～２５質量％）、ビニル系単量体単位（e３）５～３０質量％（好ましくは、７～２７質量％）である。 <Composition ratio of styrene-unsaturated dicarboxylic acid copolymer (E)>
The composition ratio of the styrene-unsaturated dicarboxylic acid-based copolymer (E) was 50 to 80% by mass (preferably 50 to 75% by mass) of the styrene-based monomer unit (e1), and the unsaturated dicarboxylic acid anhydride alone. The unit of measure (e2) is 10 to 30% by mass (preferably 10 to 25% by mass), and the vinyl-based monomer unit (e3) is 5 to 30% by mass (preferably 7 to 27% by mass).
　スチレン－不飽和ジカルボン酸系共重合体（Ｅ）の重量平均分子量は、５０，０００～２００，０００が好ましく、８０，０００～２００，０００がより好ましい。重量平均分子量が５０，０００～２００，０００において、ビニル系単量体を含有する樹脂（Ｄ）との相溶性が良好であり、耐熱性の向上効果に優れる。上記樹脂（Ｄ）、共重合体（Ｅ）の重量平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）により測定される、標準ポリスチレン換算の重量平均分子量である。 The weight average molecular weight of the styrene-unsaturated dicarboxylic acid-based copolymer (E) is preferably 50,000 to 200,000, more preferably 80,000 to 200,000. When the weight average molecular weight is 50,000 to 200,000, the compatibility with the resin (D) containing a vinyl-based monomer is good, and the effect of improving heat resistance is excellent. The weight average molecular weight of the resin (D) and the copolymer (E) is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
　前記共重合体（Ｅ）として、具体的には、レジスファイ　Ｒ１００、Ｒ２００、Ｒ３１０（電気化学工業製）、デルペット９８０Ｎ（旭化成ケミカル製）などが挙げられるが、これらに限定されない。 Specific examples of the copolymer (E) include, but are not limited to, Regisphi R100, R200, R310 (manufactured by Denki Kagaku Kogyo), Delpet 980N (manufactured by Asahi Kasei Chemical Co., Ltd.), and the like.
＜高硬度樹脂（Ｂ４）＞
　本発明に使用される高硬度樹脂（Ｂ４）とは、スチレン構成単位を５～２０質量％、（メタ）アクリル酸エステル構成単位を６０～９０質量％、およびＮ－置換型マレイミド単量体を５～２０質量％含む樹脂共重合体（Ｇ）、または樹脂共重合体（Ｇ）と前記共重合体（Ｅ）とのアロイである。 <High hardness resin (B4)>
The high-hardness resin (B4) used in the present invention includes 5 to 20% by mass of a styrene constituent unit, 60 to 90% by mass of a (meth) acrylic acid ester constituent unit, and an N-substituted maleimide monomer. It is a resin copolymer (G) containing 5 to 20% by mass, or an alloy of the resin copolymer (G) and the copolymer (E).
　樹脂共重合体（Ｇ）におけるＮ－置換型マレイミド単量体としては、Ｎ―フェニルマレイミド、Ｎ―クロロフェニルマレイミド、Ｎ－メチルフェニルマレイミド、Ｎ－ナフチルマレイミド、Ｎ－ヒドロキシフェニルマレイミド、Ｎ－メトキシフェニルマレイミド、Ｎ－カルボキシフェニルマレイミド、Ｎ－ニトロフェニルマレイミド、Ｎ－トリブロモフェニルマレイミドなどのＮ－アリールマレイミド等が挙げられ、アクリル樹脂との相溶性の観点からＮ－フェニルマレイミドが好ましぃ。これらのＮ－置換型マレイミド単量体は２種以上を混合してもよい。Ｎ－置換型マレイミド単量体の含有量は、高硬度樹脂（Ｂ４）の全量に対して５～２０質量％であり、５～１５質量％であることが好ましく、５～１０質量％であることがより好ましい。 Examples of the N-substituted maleimide monomer in the resin copolymer (G) include N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, and N-methoxyphenyl. Examples thereof include N-arylmaleimide such as maleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide, and N-phenylmaleimide is preferable from the viewpoint of compatibility with acrylic resin. Two or more kinds of these N-substituted maleimide monomers may be mixed. The content of the N-substituted maleimide monomer is 5 to 20% by mass, preferably 5 to 15% by mass, and 5 to 10% by mass with respect to the total amount of the high hardness resin (B4). Is more preferable.
　スチレン構成単位とは、特に限定せず、任意の公知のスチレン系単量体を用いることができるが、入手の容易性の観点からスチレン、メチルスチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ｔ－ブチルスチレンなどが挙げられる。これらの中でも、相溶性の観点からスチレンが特に好ましい。これらのスチレン系単量体は２種以上を混合しても良い。スチレン構成単位の含有量は、高硬度樹脂（Ｂ４）の全質量に対して５～２０質量％であり、５～１５質量％であることが好ましく、５～１０質量％であることがより好ましい。 The styrene constituent unit is not particularly limited, and any known styrene-based monomer can be used, but from the viewpoint of easy availability, styrene, methylstyrene, o-methylstyrene, m-methylstyrene, p. -Methylstyrene, t-butylstyrene and the like can be mentioned. Of these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these styrene-based monomers may be mixed. The content of the styrene constituent unit is 5 to 20% by mass, preferably 5 to 15% by mass, and more preferably 5 to 10% by mass with respect to the total mass of the high hardness resin (B4). ..
　（メタ）アクリル酸エステル構成単位とは、例えば、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－ブチル、アクリル酸２－エチルヘキシル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－ブチル、メタクリル酸２－エチルヘキシル等が挙げられ、特に単量体単位として、メタクリル酸メチルが好ましい。また、前記単量体単位を２種類以上含んだ共重合体でも良い。 The (meth) acrylic acid ester constituent unit is, for example, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n methacrylate. -Butyl, 2-ethylhexyl methacrylate and the like can be mentioned, and methyl methacrylate is particularly preferable as the monomer unit. Further, a copolymer containing two or more kinds of the monomer units may be used.
　（メタ）アクリル酸エステル構成単位の含有量は、高硬度樹脂（Ｂ４）の全質量に対して６０～９０質量％であり、７０～９０質量％であることが好ましく、８０～９０質量％であることがより好ましい。 The content of the (meth) acrylic acid ester structural unit is 60 to 90% by mass, preferably 70 to 90% by mass, and 80 to 90% by mass with respect to the total mass of the high hardness resin (B4). More preferably.
　樹脂共重合体（Ｇ）の製造方法は、特に限定されないが、溶液重合、塊状重合などによって製造することができる。 The method for producing the resin copolymer (G) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, or the like.
　樹脂共重合体（Ｇ）は、例えば、デルペットＰＭ１２０Ｎ（旭化成ケミカル社製）が挙げられるが、これらに限定されない。 Examples of the resin copolymer (G) include, but are not limited to, Delpet PM120N (manufactured by Asahi Kasei Chemical Co., Ltd.).
　樹脂共重合体（Ｇ）の重量平均分子量は、５０，０００～２５０，０００であることが好ましく、１００，０００～２００，０００がより好ましい。 The weight average molecular weight of the resin copolymer (G) is preferably 50,000 to 250,000, more preferably 100,000 to 200,000.
＜高硬度樹脂（Ｂ５）＞
　高硬度樹脂（Ｂ５）は、下記式（３）で表される構成単位（Ｈ）と、任意に下記式（４）で表される構成単位（Ｊ）とを含む共重合体である。高硬度樹脂（Ｂ５）は、構成単位（Ｊ）を含んでいても含んでいなくてもよいが、含んでいることが好ましい。
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
 <High hardness resin (B5)>
The high hardness resin (B5) is a copolymer containing a structural unit (H) represented by the following formula (3) and optionally a structural unit (J) represented by the following formula (4). The high hardness resin (B5) may or may not contain the structural unit (J), but is preferably contained.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
　高硬度樹脂（Ｂ５）の全構成単位における構成単位（Ｈ）の割合は、５０～１００モル％であることが好ましく、６０～１００モル％であることがより好ましく、７０～１００モル％であることが特に好ましい。高硬度樹脂（Ｂ５）の全構成単位における構成単位（Ｊ）の割合は、０～５０モル％であることが好ましく、０～４０モル％であることがより好ましく、０～３０モル％であることが特に好ましい。 The ratio of the structural unit (H) to all the structural units of the high hardness resin (B5) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and 70 to 100 mol%. Is particularly preferred. The ratio of the structural unit (J) to all the structural units of the high hardness resin (B5) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and 0 to 30 mol%. Is particularly preferred.
　構成単位（Ｈ）と構成単位（Ｊ）の合計含有量は、高硬度樹脂（Ｂ５）に対して好ましくは９０～１００モル％であり、より好ましくは９５～１００モル％であり、特に好ましくは９８～１００モル％である。 The total content of the structural unit (H) and the structural unit (J) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 95 to 100 mol% with respect to the high hardness resin (B5). It is 98 to 100 mol%.
　高硬度樹脂（Ｂ５）は、構成単位（Ｈ）および構成単位（Ｊ）以外の構成単位を含んでいてもよい。その他の構成単位を含む場合、その量は、高硬度樹脂（Ｂ５）の全構成単位に対して１０モル％以下であることが好ましく、５モル％以下であることがより好ましく、２モル％以下であることが特に好ましい。 The high hardness resin (B5) may contain a structural unit other than the structural unit (H) and the structural unit (J). When other structural units are included, the amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and 2 mol% or less with respect to all the structural units of the high hardness resin (B5). Is particularly preferable.
　高硬度樹脂（Ｂ５）の製造方法は、特に限定されないが、モノマーとしてビスフェノールＣを使用することを除いて上述したポリカーボネート樹脂（ａ１）の製造方法と同様の方法で製造することができる。 The method for producing the high hardness resin (B5) is not particularly limited, but it can be produced by the same method as the above-mentioned method for producing the polycarbonate resin (a1) except that bisphenol C is used as the monomer.
　高硬度樹脂（Ｂ５）として、例えば、ユーピロン　ＫＨ３４１０ＵＲ、ＫＨ３５２０ＵＲ、ＫＳ３４１０ＵＲ（三菱エンジニアリングプラスチック社製）等が挙げられるが、これらに限定されない。 Examples of the high hardness resin (B5) include, but are not limited to, Iupiron KH3410UR, KH3520UR, KS3410UR (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and the like.
　高硬度樹脂（Ｂ５）の重量平均分子量は、１５，０００～７５，０００が好ましく、２０，０００～７０，０００がより好ましく、２５，０００～６５，０００が特に好ましい。 The weight average molecular weight of the high hardness resin (B5) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and particularly preferably 25,000 to 65,000.
　高硬度樹脂（Ｂ１）～（Ｂ５）は、添加剤等を含んでいてもよい。添加剤としては、樹脂シートにおいて通常使用されるものを使用することができ、そのような添加剤としては、例えば、抗酸化剤、抗着色剤、抗帯電剤、離型剤、滑剤、染料、顔料、可塑剤、難燃剤、樹脂改質剤、相溶化剤、有機フィラーや無機フィラーのような強化材などが挙げられる。添加剤と樹脂を混合する方法は特に限定されず、全量コンパウンドする方法、マスターバッチをドライブレンドする方法、全量ドライブレンドする方法などを用いることができる。添加剤の量は、高硬度樹脂層の全質量に対して０～１０質量％であることが好ましく、０～７質量％であることがより好ましく、０～５質量％であることが特に好ましい。 The high hardness resins (B1) to (B5) may contain additives and the like. As the additive, those usually used in a resin sheet can be used, and such an additive includes, for example, an antioxidant, an anticolorant, an anticharge agent, a release agent, a lubricant, a dye, and the like. Examples thereof include pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, and reinforcing materials such as organic fillers and inorganic fillers. The method of mixing the additive and the resin is not particularly limited, and a method of compounding the entire amount, a method of dry-blending the masterbatch, a method of dry-blending the entire amount, and the like can be used. 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 with respect to the total mass of the high hardness resin layer. ..
　高硬度樹脂層の厚さは、表面硬度や耐衝撃性に影響する。つまり、高硬度樹脂層が薄すぎると表面硬度が低くなり、厚すぎると耐衝撃性が低下する。高硬度樹脂層の厚みは、好ましくは１０～２５０μｍであり、より好ましくは３０～２００μｍであり、特に好ましくは６０～１５０μｍである。 The thickness of the high hardness resin layer affects the surface hardness and impact resistance. That is, if the high hardness resin layer is too thin, the surface hardness will be low, and if it is too thick, the impact resistance will be lowered. 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.
　ポリカーボネート層と高硬度樹脂層の間には更なる層が存在していても良いが、ここでは、基材層上に高硬度樹脂層を積層する場合について説明する。その積層方法は、特に限定されず、他の層が存在する場合にも同様に積層することができる。例えば、個別に形成した基材層と高硬度樹脂層とを重ね合わせて、両者を加熱圧着する方法；個別に形成した基材層と高硬度樹脂層とを重ね合わせて、両者を接着剤によって接着する方法；基材層と高硬度樹脂層とを共押出成形する方法；予め形成しておいた高硬度樹脂層に、基材層をインモールド成形して一体化する方法、などの各種方法がある。これらのうち、製造コストや生産性の観点から、共押出成形する方法が好ましい。 A further layer may exist between the polycarbonate layer and the high-hardness resin layer, but here, a case where the high-hardness resin layer is laminated on the base material layer will be described. The laminating method is not particularly limited, and laminating can be performed in the same manner when other layers are present. For example, a method in which an individually formed base material layer and a high hardness resin layer are superposed and heat-bonded to each other; a individually formed base material layer and a high hardness resin layer are superposed and both are bonded by an adhesive. Various methods such as a method of co-extruding a base material layer and a high-hardness resin layer; a method of in-molding a base material layer into a pre-formed high-hardness resin layer and integrating them. There is. Of these, the coextrusion molding method is preferable from the viewpoint of manufacturing cost and productivity.
　共押出成形の方法は特に限定されない。例えば、フィードブロック方式では、フィードブロックで基材層の片面上に高硬度樹脂層を配置し、Ｔダイでシート状に押し出した後、成形ロールを通過させながら冷却して所望の積層体を形成する。また、マルチマニホールド方式では、マルチマニホールドダイ内で基材層の片面上に高硬度樹脂層を配置し、シート状に押し出した後、成形ロールを通過させながら冷却して所望の積層体を形成する。 The coextrusion molding method is not particularly limited. For example, in the feed block method, a high-hardness resin layer is placed on one side of a base material layer with a feed block, extruded into a sheet shape with a T-die, and then cooled while passing through a molding roll to form a desired laminate. To do. Further, in the multi-manifold method, a high-hardness resin layer is arranged on one side of the base material layer in the multi-manifold die, extruded into a sheet shape, and then cooled while passing through a molding roll to form a desired laminated body. ..
　基材層と高硬度樹脂層の合計厚みは、好ましくは１００～３，０００μｍ、より好ましくは５００～３，０００μｍ、特に好ましくは１，０００～３，０００μｍである。合計厚みを１００μｍ以上とすることにより、シートの剛性を保つことができる。また、合計厚みを３，０００μｍ以下とすることにより、シートの下にタッチパネルを設置する場合等にタッチセンサーの感度が悪くなるのを防ぐことができる。基材層と高硬度樹脂層の合計厚みに占める基材層の厚みの割合は、好ましくは７５％～９９％であり、より好ましくは８０～９９％であり、特に好ましくは８５～９９％である。上記範囲とすることにより、硬度と耐衝撃性を両立できる。 The total thickness of the base material layer and the high hardness resin layer is preferably 100 to 3,000 μm, more preferably 500 to 3,000 μm, and particularly preferably 1,000 to 3,000 μm. By setting the total thickness to 100 μm or more, the rigidity of the sheet can be maintained. Further, by setting the total thickness to 3,000 μm or less, it is possible to prevent the sensitivity of the touch sensor from deteriorating when the touch panel is installed under the sheet. 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 preferably 75% to 99%, more preferably 80 to 99%, and particularly preferably 85 to 99%. is there. Within the above range, both hardness and impact resistance can be achieved.
（ハードコート層）
　本発明の防眩性積層体（樹脂シート）は、ハードコート層を具備する。ハードコート層と高硬度樹脂層との間にさらなる層が存在していてもよいが、好ましくは、ハードコート層は高硬度樹脂層上に積層される。ハードコート層は、アクリル系ハードコートであることが好ましい。本明細書において、「アクリル系ハードコート」とは、重合基として（メタ）アクリロイル基を含有するモノマーまたはオリゴマーまたはプレポリマーを重合して架橋構造を形成した塗膜を意味する。アクリル系ハードコートの組成としては、（メタ）アクリル系モノマー２～９８質量％、（メタ）アクリル系オリゴマー２～９８質量％および表面改質剤０～１５質量％を含むことが好ましく、さらに、（メタ）アクリル系モノマーと（メタ）アクリル系オリゴマーと表面改質剤との総和１００質量部に対して、０．００１～７質量部の光重合開始剤を含むことが好ましい。 (Hard coat layer)
The antiglare laminate (resin sheet) of the present invention includes a hard coat layer. An additional layer may be present between the hard coat layer and the high hardness resin layer, but preferably the hard coat layer is laminated on the high hardness resin layer. The hard coat layer is preferably an acrylic hard coat. As used herein, the term "acrylic hard coat" means a coating film formed by polymerizing a monomer or oligomer or prepolymer containing a (meth) acryloyl group as a polymerization group to form a crosslinked structure. The composition of the acrylic hard coat preferably contains 2 to 98% by mass of the (meth) acrylic monomer, 2 to 98% by mass of the (meth) acrylic oligomer, and 0 to 15% by mass of the surface modifier. It is preferable to contain 0.001 to 7 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer and the surface modifier.
　ハードコート層は、より好ましくは、（メタ）アクリル系モノマーを５～５０質量％、（メタ）アクリル系オリゴマーを５０～９５質量％および表面改質剤を１～１０質量％含み、特に好ましくは、（メタ）アクリル系モノマーを２０～４０質量％、（メタ）アクリル系オリゴマーを６０～８０質量％および表面改質剤を２～５質量％含む。 The hard coat layer more preferably contains 5 to 50% by mass of the (meth) acrylic monomer, 50 to 95% by mass of the (meth) acrylic oligomer, and 1 to 10% by mass of the surface modifier, and is particularly preferably. , 20-40% by mass of (meth) acrylic monomer, 60-80% by mass of (meth) acrylic oligomer, and 2-5% by mass of surface modifier.
　光重合開始剤の量は、（メタ）アクリル系モノマーと（メタ）アクリル系オリゴマーと表面改質剤との総和１００質量部に対して、０．０１～５質量部であることがより好ましく、０．１～３質量部であることが特に好ましい。 The amount of the photopolymerization initiator is more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer and the surface modifier. It is particularly preferably 0.1 to 3 parts by mass.
（１）（メタ）アクリル系モノマー
　（メタ）アクリル系モノマーとしては、分子内に（メタ）アクリロイル基が官能基として存在するものであれば使用でき、１官能モノマー、２官能モノマー、または３官能以上のモノマーであって良い。 (1) (Meta) Acrylic Monomer The (meth) acrylic monomer can be used as long as the (meth) acryloyl group is present as a functional group in the molecule, and is a monofunctional monomer, a bifunctional monomer, or a trifunctional monomer. It may be the above monomer.
　１官能モノマーとしては（メタ）アクリル酸、（メタ）アクリル酸エステルが例示でき、２官能および／または３官能以上の（メタ）アクリル系モノマーの具体例としては、ジエチレングリコールジ（メタ）アクリレート、ジプロピレングルコールジ（メタ）アクリレート、トリプロピレングルコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ビスフェノールＡジグリシジルエーテルジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，４－ブタンジオールジアクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、ポリエチレングリコールジアクリレート、１，４－ブタンジオールオリゴアクリレート、ネオペンチルグリコールオリゴアクリレート、１，６－ヘキサンジオールオリゴアクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエトキシトリ（メタ）アクリレート、トリメチロールプロパンプロポキシトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、グリセリルプロポキシトリ（メタ）アクリレート、トリメチロールプロパントリメタクリレート、トリメチロールプロパンエチレンオキシド付加物トリアクリレート、グリセリンプロピレンオキシド付加物トリアクリレート、ペンタエリスリトールテトラアクリレート等が例示できるが、これらに限定されない。 Examples of the monofunctional monomer include (meth) acrylic acid and (meth) acrylic acid ester. Specific examples of the bifunctional and / or trifunctional or higher (meth) acrylic monomer include diethylene glycol di (meth) acrylate and di. Propropylene 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 , Hydroxypivalate neopentyl glycol diacrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, Polyethylene glycol diacrylate, 1,4-butanediol oligo acrylate, neopentyl glycol oligo acrylate, 1,6-hexanediol oligo acrylate, trimethylol propanetri (meth) acrylate, trimethylol propaneethoxytri (meth) acrylate, trimethylol Propanepropoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, glyceryl propoxytri (meth) acrylate, trimethyl propoxytrimethacrylate, trimethylolpropaneethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, pentaerythritol tetra Examples include, but are not limited to, acrylates and the like.
　ハードコート層は、（メタ）アクリル系モノマーを１種類または２種類以上含んでいてよい。 The hard coat layer may contain one type or two or more types of (meth) acrylic monomers.
（２）（メタ）アクリル系オリゴマー
　（メタ）アクリル系オリゴマーとしては、２官能以上の多官能ウレタン（メタ）アクリレートオリゴマー（以下、「多官能ウレタン（メタ）アクリレートオリゴマー」ともいう）、２官能以上の多官能ポリエステル（メタ）アクリレートオリゴマー（以下、「多官能ポリエステル（メタ）アクリレートオリゴマー」ともいう）、２官能以上の多官能エポキシ（メタ）アクリレートオリゴマー（以下、「多官能エポキシ（メタ）アクリレートオリゴマー」ともいう）などが挙げられる。ハードコート層は、（メタ）アクリル系オリゴマーを１種類または２種類以上含んでいてよい。 (2) (Meta) Acrylic Oligomer The (meth) acrylic oligomer is a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer (hereinafter, also referred to as “polyfunctional urethane (meth) acrylate oligomer”), which is bifunctional or higher. Polyfunctional polyester (meth) acrylate oligomer (hereinafter, also referred to as "polyfunctional polyester (meth) acrylate oligomer"), bifunctional or higher polyfunctional epoxy (meth) acrylate oligomer (hereinafter, "polyfunctional epoxy (meth) acrylate oligomer") ”) And so on. The hard coat layer may contain one or more (meth) acrylic oligomers.
　多官能ウレタン（メタ）アクリレートオリゴマーとしては、１分子中に少なくとも１個の（メタ）アクリロイルオキシ基および水酸基を有する（メタ）アクリレートモノマーとポリイソシアネートとのウレタン化反応生成物；ポリオール類をポリイソシアネートと反応させて得られるイソシアネート化合物と１分子中に少なくとも１個以上の（メタ）アクリロイルオキシ基および水酸基を有する（メタ）アクリレートモノマーとのウレタン化反応生成物等が挙げられる。 As the polyfunctional urethane (meth) acrylate oligomer, a urethanization reaction product of a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule and polyisocyanate; polyols are polyisocyanates. Examples thereof include a urethanization reaction product of an isocyanate compound obtained by reacting with and a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule.
　ウレタン化反応に用いられる１分子中に少なくとも１個の（メタ）アクリロイルオキシ基および水酸基を有する（メタ）アクリレートモノマーとしては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、グリセリンジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートが挙げられる。 Examples of the (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule used in the urethanization reaction include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. 2-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerindi (meth) acrylate, trimethylpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta Examples include (meth) acrylate.
　ウレタン化反応に用いられるポリイソシアネートとしては、ヘキサメチレンジイソシアネート、リジンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、これらジイソシアネートのうち芳香族のイソシアネート類を水素添加して得られるジイソシアネート（例えば水素添加トリレンジイソシアネート、水素添加キシリレンジイソシアネートなどのジイソシアネート）、トリフェニルメタントリイソシアネート、ジメチレントリフェニルトリイソシアネートなどのジまたはトリのポリイソシアネート、あるいはジイソシアネートを多量化させて得られるポリイソシアネートが挙げられる。 The polyisocyanate used in the urethanization reaction includes hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diisocyanate obtained by hydrogenating aromatic isocyanates among these diisocyanates. (For example, diisocyanate such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate), di or tri polyisocyanate such as triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate, or polyisocyanate obtained by increasing the amount of diisocyanate. Can be mentioned.
　ウレタン化反応に用いられるポリオール類としては、一般的に芳香族、脂肪族および脂環式のポリオールのほか、ポリエステルポリオール、ポリエーテルポリオール等が使用される。通常、脂肪族および脂環式のポリオールとしては、１，４－ブタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、エチレングリコール、プロピレングリコール、トリメチロールエタン、トリメチロールプロパン、ジメチロールヘプタン、ジメチロールプロピオン酸、ジメチロールブチリオン酸、グリセリン、水添ビスフェノールＡなどが挙げられる。 As the polyols used in the urethanization reaction, in addition to aromatic, aliphatic and alicyclic polyols, polyester polyols, polyether polyols and the like are generally used. Usually, aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptan, and di. Examples thereof include methylolpropionic acid, dimethylolbutylionic acid, glycerin, and hydrogenated bisphenol A.
　ポリエステルポリオールとしては、上述したポリオール類とポリカルボン酸との脱水縮合反応により得られるものが挙げられる。ポリカルボン酸の具体的な化合物としては、コハク酸、アジピン酸、マレイン酸、トリメリット酸、ヘキサヒドロフタル酸、フタル酸、イソフタル酸、テレフタル酸などが挙げられる。これらのポリカルボン酸は、無水物であってもよい。また、ポリエーテルポリオールとしては、ポリアルキレングリコールのほか、上述したポリオール類またはフェノール類とアルキレンオキサイドとの反応により得られるポリオキシアルキレン変性ポリオールが挙げられる。 Examples of the polyester polyol include those obtained by a dehydration condensation reaction between the above-mentioned polyols and a polycarboxylic acid. Specific compounds of the polycarboxylic acid include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid and the like. These polycarboxylic acids may be anhydrides. In addition to the polyalkylene glycol, examples of the polyether polyol include the above-mentioned polyols or polyoxyalkylene-modified polyols obtained by reacting phenols with alkylene oxides.
　また、多官能ポリエステル（メタ）アクリレートオリゴマーは、（メタ）アクリル酸、ポリカルボン酸およびポリオールを使用した脱水縮合反応により得られる。脱水縮合反応に用いられるポリカルボン酸としては、コハク酸、アジピン酸、マレイン酸、イタコン酸、トリメリット酸、ピロメリット酸、ヘキサヒドロフタル酸、フタル酸、イソフタル酸、テレフタル酸などが挙げられる。これらのポリカルボン酸は、無水物であってもよい。また、脱水縮合反応に用いられるポリオールとしては、１，４－ブタンジオール、１，６－ヘキサンジオール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ネオペンチルグリコール、ジメチロールヘプタン、ジメチロールプロピオン酸、ジメチロールブチリオン酸、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトールなどが挙げられる。 Further, 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 the polycarboxylic acid 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 be anhydrides. The polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptan, dimethylolpropionic acid, and dimethylol. Examples thereof include butyric acid, trimethylolpropane, trimethylolpropane, pentaerythritol, and dipentaerythritol.
　多官能エポキシ（メタ）アクリレートオリゴマーは、ポリグリシジルエーテルと（メタ）アクリル酸との付加反応により得られる。ポリグリシジルエーテルとしては、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ビスフェノールＡジグリシジルエーテルなどが挙げられる。 The polyfunctional epoxy (meth) acrylate oligomer is obtained by an addition reaction between 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.
（３）改質剤
　本発明で使用される改質剤とは、レベリング剤、帯電防止剤、界面活性剤、撥水撥油剤、ＵＶ吸収剤などのハードコート層の性能を変えるものである。 (3) Modifier The modifier used in the present invention changes the performance of a hard coat layer such as a leveling agent, an antistatic agent, a surfactant, a water-repellent oil-repellent agent, and a UV absorber.
　レベリング剤としては、例えば、ポリエーテル変性ポリアルキルシロキサン、ポリエーテル変性シロキサン、ポリエステル変性水酸基含有ポリアルキルシロキサン、アルキル基を有するポリエーテル変性ポリジメチルシロキサン、変性ポリエーテル、シリコン変性アクリルなどが挙げられる。 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.
　帯電防止剤としては、例えば、グリセリン脂肪酸エステルモノグリセライド、グリセリン脂肪酸エステル有機酸モノグリセライド、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、陽イオン性界面活性剤、陰イオン性界面活性剤などが挙げられる。 Examples of the antistatic agent include glycerin fatty acid ester monoglyceride, glycerin fatty acid ester organic acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, cationic surfactant, and anionic surfactant.
　界面活性剤および撥水撥油剤としては、例えば、含フッ素基・親油性基含有オリゴマー、含フッ素基・親水性基・親油性基・ＵＶ反応性基含有オリゴマーなどのフッ素を含有した界面活性剤および撥水撥油剤が挙げられる。 Examples of the surfactant and the water- and oil-repellent agent include fluorine-containing surfactants such as fluorine-containing group / lipophilic group-containing oligomers, fluorine-containing groups / hydrophilic groups, lipophilic groups, and UV-reactive group-containing oligomers. And water and oil repellents.
　ＵＶ吸収剤としては、例えばヒドロキシフェニルトリアジン系やベンゾトリアゾール系、ベンゴフェノン系が挙げられる。 Examples of UV absorbers include hydroxyphenyltriazine-based, benzotriazole-based, and bengophenone-based.
　ハードコート層は、光重合開始剤を含んでいてよい。本明細書において、光重合開始剤とは光ラジカル発生剤を指す。 The hard coat layer may contain a photopolymerization initiator. In the present specification, the photopolymerization initiator refers to a photoradical generator.
　本発明で使用することができる単官能光重合開始剤としては、例えば、４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン［ダロキュアー２９５９：メルク社製］；α－ヒドロキシ－α，α’－ジメチルアセトフェノン［ダロキュアー１１７３：メルク社製］；メトキシアセトフェノン、２，２’－ジメトキシ－２－フェニルアセトフェノン［イルガキュア－６５１］、１－ヒドロキシ－シクロヘキシルフェニルケトンなどのアセトフェノン系開始剤；ベンゾインエチルエーテル、ベンゾインイソプロピルエーテルなどのベンゾインエーテル系開始剤；その他、ハロゲン化ケトン、アシルホスフィノキシド、アシルホスフォナートなどを例示することができる。 Examples of the monofunctional photopolymerization initiator that can be used in the present invention include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [Darocure 2959: manufactured by Merck]; α-hydroxy. -Α, α'-Dimethylacetophenone [DaroCure 1173: manufactured by Merck]; Acetphenone-based initiators such as methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651], 1-hydroxy-cyclohexylphenylketone Benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; other examples include halogenated ketones, acylphosphinoxides, and acylphosphonates.
　ハードコート層の形成方法は特に限定されないが、例えば、ハードコート層の下に位置する層（例えば高硬度樹脂層）上にハードコート液を塗布した後、光重合させることにより形成することができる。 The method for forming the hard coat layer is not particularly limited, but for example, it can be formed by applying a hard coat liquid on a layer (for example, a high hardness resin layer) located below the hard coat layer and then photopolymerizing the hard coat layer. ..
　本発明におけるハードコート塗料を塗布する方法は特に限定されず、既知の方法を用いることができる。例えば、スピンコート法、ディップ法、スプレー法、スライドコート法、バーコート法、ロールコート法、グラビアコート法、メニスカスコート法、フレキソ印刷法、スクリーン印刷法、ビートコート法、捌け法などが挙げられる。 The method of applying the hard coat paint in the present invention is not particularly limited, and a known method can be used. For example, spin coating method, dip method, spray method, slide coating method, bar coating method, roll coating method, gravure coating method, meniscus coating method, flexographic printing method, screen printing method, beat coating method, and handling method can be mentioned. ..
　光重合における光照射に用いられるランプとしては、光波長４２０ｎｍ以下に発光分布を有するものが用いられ、その例としては低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプなどが挙げられる。この中でも、高圧水銀灯またはメタルハライドランプは開始剤の活性波長領域の光を効率よく発光し、得られる高分子の粘弾性的性質を架橋により低下させるような短波長の光や、反応組成物を加熱蒸発させるような長波長の光を多く発光しないために好ましい。 As the lamp used for light irradiation in photopolymerization, a lamp having a light emission distribution with a light wavelength of 420 nm or less is used, and examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, and a black light lamp. , Microwave-excited mercury lamp, metal halide lamp, etc. Among these, high-pressure mercury lamps or metal halide lamps efficiently emit light in the active wavelength region of the initiator and heat short-wavelength light or reaction compositions that reduce the viscoelastic properties of the obtained polymer by cross-linking. This is preferable because it does not emit a large amount of long-wavelength light that causes evaporation.
　上記ランプの照射強度は、得られるポリマーの重合度を左右する因子であり、目的製品の性能毎に適宜制御される。通常のアセトフェノン基を有する開裂型の開始剤を配合した場合、照度は０．１～３００ｍＷ／ｃｍ２の範囲が好ましい。特に、メタルハライドランプを用いて、照度を１０～４０ｍＷ／ｃｍ２とすることが好ましい。 The irradiation intensity of the lamp is a factor that affects the degree of polymerization of the obtained polymer, and is appropriately controlled for each performance of the target product. When a cleavage-type initiator having a normal acetophenone group is blended, the illuminance is preferably in the range of 0.1 to 300 mW / cm 2. In particular, it is preferable to use a metal halide lamp and set the illuminance to 10 to 40 mW / cm 2.
　光重合反応は、空気中の酸素または反応性組成物中に溶解する酸素により阻害される。そのため、光照射は酸素による反応阻害を消去し得る手法を用いて実施することが望ましい。そのような手法の１つとして、反応性組成物をポリエチレンテレフタレートやテフロン製のフィルムによって覆って酸素との接触を断ち、フィルムを通して光を反応性組成物へ照射する方法がある。また、窒素ガスや炭酸ガスのような不活性ガスにより酸素を置換したイナート雰囲気下で、光透過性の窓を通して組成物に光を照射してもよい。 The photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to carry out light irradiation using a method that can eliminate the reaction inhibition due to oxygen. One such method is to cover the reactive composition with a film made of polyethylene terephthalate or Teflon to cut off contact with oxygen and irradiate the reactive composition with light through the film. Further, the composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen is replaced by an inert gas such as nitrogen gas or carbon dioxide gas.
　光照射をイナート雰囲気下で行う場合、その雰囲気酸素濃度を低レベルに保つために、常に一定量の不活性ガスが導入される。この不活性ガスの導入により、反応性組成物表面に気流が発生し、モノマー蒸発が起こる。モノマー蒸発のレベルを抑制するためには、不活性ガスの気流速度は、不活性ガス雰囲気下を移動するハードコート液が塗布された積層体に対する相対速度として１ｍ／ｓｅｃ以下であることが好ましく、０．１ｍ／ｓｅｃ以下であることがより好ましい。気流速度を上記範囲にすることにより、気流によるモノマー蒸発は実質的に抑えられる。 When light irradiation is performed in an inert atmosphere, a certain amount of inert gas is always introduced in order to keep the atmospheric oxygen concentration at a low level. Due to the introduction of this inert gas, an air flow is generated on the surface of the reactive composition, and monomer evaporation occurs. In order to suppress the level of monomer evaporation, the airflow velocity of the inert gas is preferably 1 m / sec or less as a relative velocity with respect to the laminate coated with the hard coat liquid moving under the atmosphere of the inert gas. More preferably, it is 0.1 m / sec or less. By setting the airflow velocity within the above range, monomer evaporation due to the airflow is substantially suppressed.
　ハードコート層の密着性を向上させる目的で、塗布面に前処理を行うことがある。処理例として、サンドブラスト法、溶剤処理法、コロナ放電処理法、クロム酸処理法、火炎処理法、熱風処理法、オゾン処理法、紫外線処理法、樹脂組成物によるプライマー処理法などの既知の方法が挙げられる。 The coated surface may be pretreated for the purpose of improving the adhesion of the hard coat layer. Known treatment examples include 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. Can be mentioned.
　ハードコート層は、ＵＶ光（２５４ｎｍ）の照射出力が２０ｍＷ／ｃｍ２のメタルハライドランプを用いて紫外線照射した場合に、鉛筆硬度が２Ｈ以上であることが好ましい。 The hard coat layer preferably has a pencil hardness of 2H or more when irradiated with ultraviolet rays using a metal halide lamp having an irradiation output of UV light (254 nm) of 20 mW / cm 2.
　ハードコート層の膜厚としては、１μｍ以上４０μｍ以下が望ましく、２μｍ以上１０μｍ以下がより望ましい。膜厚が１μｍ以上であることにより十分な硬度を得ることができる。また、膜厚が４０μｍ以下であることにより、曲げ加工時のクラックの発生を抑制することができる。なお、ハードコート層の膜厚は、断面を顕微鏡等で観察し、塗膜界面から表面までを実測することにより測定可能である。 The film thickness of the hard coat layer is preferably 1 μm or more and 40 μm or less, and more preferably 2 μm or more and 10 μm or less. Sufficient hardness can be obtained when the film thickness is 1 μm or more. Further, when the film thickness is 40 μm or less, the occurrence of cracks during bending can be suppressed. The film thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and actually measuring from the coating film interface to the surface.
　本発明の一実施形態において、凹凸形状を有するハードコート層は、反射防止性能、防汚性能、帯電防止性能、および耐候性のうち少なくとも１つの特性を有してよい。ハードコート層に、反射防止処理、防汚処理、帯電防止処理、耐候性処理などの処理を施す方法は特に限定されず、既知の方法を用いることができる。例えば、反射低減塗料を塗布する方法、誘電体薄膜を蒸着する方法、帯電防止塗料を塗布する方法などが挙げられる。 In one embodiment of the present invention, the hard coat layer having an uneven shape may have at least one of antireflection performance, antifouling performance, antistatic performance, and weather resistance. The method of applying the antireflection treatment, the antifouling treatment, the antistatic treatment, the weather resistance treatment and the like to the hard coat layer is not particularly limited, and a known method can be used. For example, a method of applying a reflection-reducing paint, a method of depositing a dielectric thin film, a method of applying an antistatic paint, and the like can be mentioned.
　ハードコート層への凹凸の形成方法としては、例えば、型による成形が挙げられる。型による成形は、凹凸面と相補的な形状からなる型を作製し、ハードコートを塗工した透明基材を密着させた状態で、紫外線硬化する方法により製造することができる。 As a method of forming unevenness on the hard coat layer, for example, molding by a mold can be mentioned. Molding by a mold can be produced by a method of producing a mold having a shape complementary to an uneven surface and curing it with ultraviolet rays in a state where a transparent base material coated with a hard coat is in close contact with the mold.
　文字ボケの評価方法として、ＪＩＳ　Ｋ７３７４に基づいた透過の像鮮明度(透過鮮明度)が挙げられる。光学くし幅は、０．１２５ｍｍ、０．２５ｍｍ、０．５ｍｍ、１．０ｍｍ、２．０ｍｍがあり、光学くし幅が狭いと値のバラツキが大きく、光学くし幅が広いと値のバラツキが小さくなることから、光学くし幅は２．０ｍｍが好ましい。 As a method for evaluating character blur, there is a transmission image sharpness (transmission sharpness) based on JIS K7374. The optical comb widths are 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm. When the optical comb width is narrow, the value variation is large, and when the optical comb width is wide, the value variation is small. Therefore, the optical comb width is preferably 2.0 mm.
　透過鮮明度は、値が大きいほど文字ボケが抑制されており、値が小さいほど文字ボケが発生していることを表している。なお、本発明において、透過鮮明度は後述する実施例に記載された方法で測定することができる。 For the transparency sharpness, the larger the value, the more the character blurring is suppressed, and the smaller the value, the more the character blurring occurs. In the present invention, the transmission sharpness can be measured by the method described in Examples described later.
　像の映り込みの評価方法として、ＪＩＳ　Ｋ７３７４に基づいた光の入射角４５°で測定される反射の像鮮明度（反射鮮明度）が挙げられる。光学くし幅は、０．１２５ｍｍ、０．２５ｍｍ、０．５ｍｍ、１．０ｍｍ、２．０ｍｍがあり、光学くし幅が狭いと値のバラツキが大きく、光学くし幅が広いと値のバラツキが小さくなることから、光学くし幅は２．０ｍｍが好ましい。 As a method for evaluating the reflection of an image, there is an image sharpness (reflection sharpness) of reflection measured at an incident angle of 45 ° of light based on JIS K7374. The optical comb widths are 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm. When the optical comb width is narrow, the value variation is large, and when the optical comb width is wide, the value variation is small. Therefore, the optical comb width is preferably 2.0 mm.
　光の入射角４５°で測定される反射鮮明度は、値が大きいほど像の映り込みがしやすく、値が小さいほど像の映り込みがしにくいことを表している。なお、本発明において、反射鮮明度は後述する実施例に記載された方法で測定することができる。 The reflection sharpness measured at an incident angle of light of 45 ° indicates that the larger the value, the easier the image is reflected, and the smaller the value, the less likely the image is reflected. In the present invention, the reflection sharpness can be measured by the method described in Examples described later.
　本発明における凹凸形状としては、文字ボケと像の映り込み性能を両立するために、２．０ｍｍ幅の光学くしを用いて光を透過させたときの透過鮮明度をＴ１、２．０ｍｍ幅の光学くしを用いて光の入射角４５°で測定される反射鮮明度をＴ２とした場合、Ｔ１/Ｔ２が２．０以上であることが好ましく、３．０以上であることがより好ましく、３．０～４．０であることが特に好ましい。また、反射鮮明度は、凹凸面の裏面に黒テープを貼りつけることにより裏面反射を抑制して測定することができる。 As the uneven shape in the present invention, in order to achieve both character blurring and image reflection performance, the transmission sharpness when light is transmitted using an optical comb having a width of 2.0 mm is T1, 2.0 mm width. When the reflection sharpness measured at an incident angle of light of 45 ° using an optical comb is T2, T1 / T2 is preferably 2.0 or more, more preferably 3.0 or more, 3 It is particularly preferable that it is 0.0 to 4.0. Further, the reflection sharpness can be measured by suppressing the back surface reflection by attaching a black tape to the back surface of the uneven surface.
　２．０ｍｍ幅の光学くしを用いて光を透過させたときの透過鮮明度Ｔ１が３０％≦Ｔ１≦５０％を満たすことが好ましく、４０％≦Ｔ１≦５０％を満たすことがより好ましく、２．０ｍｍ幅の光学くしを用いて光の入射角４５°で測定される反射鮮明度Ｔ２が１０％≦Ｔ２≦２０％を満たすことが好ましく、１０％≦Ｔ２≦１５％を満たすことがより好ましい。 It is preferable that the transmission sharpness T1 when light is transmitted using an optical comb having a width of 2.0 mm satisfies 30% ≤ T1 ≤ 50%, and more preferably 40% ≤ T1 ≤ 50%. The reflection sharpness T2 measured at an incident angle of light of 45 ° using a 0.0 mm wide optical comb preferably satisfies 10% ≦ T2 ≦ 20%, and more preferably 10% ≦ T2 ≦ 15%. ..
　本発明において、凹凸形状を有するハードコート層は、無機粒子または有機粒子を含まないことが好ましい。本発明における凹凸形状は、転写により設けられる。このように、ハードコート層に無機粒子または有機粒子を含まないことにより、耐擦傷性を向上させることができる。本発明において、凹凸を有するハードコート層とは反対の面に第２のハードコート層を備えてもよい。本発明好ましい態様では、第２のハードコート層が、反射防止性能、防汚性能、帯電防止性能、および耐候性のうち少なくとも１つの特性を有する。 In the present invention, the hard coat layer having an uneven shape preferably does not contain inorganic particles or organic particles. The uneven shape in the present invention is provided by transfer. As described above, the scratch resistance can be improved by not containing the inorganic particles or the organic particles in the hard coat layer. In the present invention, the second hard coat layer may be provided on the surface opposite to the uneven hard coat layer. In a preferred embodiment of the present invention, the second hard coat layer has at least one of antireflection performance, antifouling performance, antistatic performance, and weather resistance.
　本発明の別の実施形態は、高硬度樹脂（Ｂ）を含む層上の光硬化性樹脂組成物に、柄目付きＰＥＴフィルムを圧着することにより、前記ハードコート層に凹凸形状を転写するステップを含む、前記防眩性積層体の製造方法を提供する。柄目付きＰＥＴフィルムとしては、例えば、ユニチカ製エンブレットのＰＴＨやＰＴＨＡやＰＴＨＺ、ダイセル製低ギラツキＡＧフィルムのＰＦ１１やＰＦ２３などを用いることができる。 Another embodiment of the present invention comprises the step of transferring the uneven shape to the hard coat layer by pressing a patterned PET film onto the photocurable resin composition on the layer containing the high hardness resin (B). Provided is a method for producing the antiglare laminate including the above. As the patterned PET film, for example, PTH, PTHA, PTHZ of Unitika emblem, PF11 or PF23 of Daicel's low-glare AG film can be used.
　以下に本発明の実施例を示すが、本発明は実施例の様態に制限されるものではない。 Examples of the present invention are shown below, but the present invention is not limited to the modes of the examples.
＜透過鮮明度（Ｔ１）＞
　スガ試験機社製　「ＩＣＭ　１Ｔ」を用いて、ＪＩＳ　Ｋ７３７４に基づき、防眩性積層体の流れ方向と光学くしのくし歯の方向が平行になるように設置して測定を行った。光学くしのうち、２．０ｍｍ幅の光学くしを用いて、光源から透過した鮮明度を透過鮮明度とした。 <Transparency clarity (T1)>
Using "ICM 1T" manufactured by Suga Test Instruments Co., Ltd., measurement was performed by installing the antiglare laminate so that the flow direction and the direction of the optical comb teeth were parallel to each other based on JIS K7374. Of the optical combs, a 2.0 mm wide optical comb was used, and the sharpness transmitted from the light source was defined as the transmitted sharpness.
＜反射鮮明度（Ｔ２）＞
　スガ試験機社製　「ＩＣＭ　１Ｔ」を用いて、ＪＩＳ　Ｋ７３７４に基づき、防眩性積層体の流れ方向と光学くしのくし歯の方向が平行になるように設置して測定を行った。光学くしのうち、２．０ｍｍ幅の光学くしを用いて、光の入射角４５°で測定される反射の像鮮明度を反射鮮明度とした。凹凸面の裏面に黒テープ（３Ｍジャパン株式会社製　黒色ビニールテープ型番１１７ＢＬＡ）を貼りつけることで裏面反射を抑制して測定を実施した。 <Reflective sharpness (T2)>
Using "ICM 1T" manufactured by Suga Test Instruments Co., Ltd., measurement was performed by installing the antiglare laminate so that the flow direction and the direction of the optical comb teeth were parallel to each other based on JIS K7374. Among the optical combs, an optical comb having a width of 2.0 mm was used, and the image sharpness of reflection measured at an incident angle of light of 45 ° was defined as the reflection sharpness. The measurement was carried out by suppressing the reflection on the back surface by attaching a black tape (black vinyl tape model number 117BLA manufactured by 3M Japan Ltd.) to the back surface of the uneven surface.
＜ＳＷ硬度＞
　防眩性積層体に対し、日本スチールウール（株）製のスチールウール♯００００を使用して１００ｇ／ｃｍ２荷重で１５往復した際の傷の付き具合を目視観察で１０段階評価した。ＲＡＮＫ１～ＲＡＮＫ１０で記載した。
ＲＡＮＫ１　：傷なし（無機ガラスと同程度）
ＲＡＮＫ１０：傷多数（ポリカーボネートと同程度） <SW hardness>
The degree of scratches on the antiglare laminate when 15 reciprocations were made using steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd. under a load of 100 g / cm 2 was visually evaluated on a 10-point scale. It is described by RANK1 to RANK10.
RANK1: No scratches (similar to inorganic glass)
RANK10: Many scratches (similar to polycarbonate)
＜形状安定性＞
　試験片を１００ｍｍ×６０ｍｍに切り出した。切り出した試験片を２点支持型のホルダーにセットして温度２３％、相対湿度５０％に設定した環境試験機に２４時間以上投入して状態調整した後、反りを測定した（処理前）。次に試験片をホルダーにセットして温度８５℃、相対湿度８５％に設定した環境試験機の中に投入し、その状態で１２０時間保持した。更に温度２３％、相対湿度５０％に設定した環境試験機の中にホルダーごと移動し、その状態で４時間保持後に再度反りを測定した（処理後）。反りの測定は、電動ステージ具備の３次元形状測定機（ＫＥＹＥＮＣＥ製ＫＳ－１０００）を使用し、取り出した試験片を上に凸の状態で水平に設置し、１ミリ間隔でスキャンし中央部の盛り上がりをそりとして計測した。処理前後の反り量の差の絶対値、すなわち
　　　　　｜（処理後の反り量）－（処理前の反り量）｜
を形状安定性として評価した。 <Shape stability>
The test piece was cut out to a size of 100 mm × 60 mm. The cut out test piece was set in a two-point support type holder and put into an environmental tester set at a temperature of 23% and a relative humidity of 50% for 24 hours or more to adjust the state, and then the warp was measured (before treatment). Next, the test piece was set in a holder and placed in an environmental tester set at a temperature of 85 ° C. and a relative humidity of 85%, and held in that state for 120 hours. Further, the holder was moved into an environmental tester set at a temperature of 23% and a relative humidity of 50%, and the warp was measured again after holding for 4 hours in that state (after treatment). To measure the warp, use a three-dimensional shape measuring machine equipped with an electric stage (KS-1000 manufactured by KEYENCE), place the taken-out test piece horizontally in a convex state upward, scan at 1 mm intervals, and scan the central part. The excitement was measured as a sled. Absolute value of the difference in warpage amount before and after treatment, that is, | (warp amount after treatment)-(warp amount before treatment) |
Was evaluated as shape stability.
実施例１
＜積層体（Ｘ―１）＞
　軸径３５ｍｍの単軸押出機と、軸径６５ｍｍの単軸押出機と、全押出機に連結されたフィードブロックと、フィードブロックに連結されたＴダイとを有する多層押出装置を用いて合成樹脂積層体を成形した。軸径３５ｍｍの単軸押出機に高硬度樹脂（Ｂ１）として三菱ガス化学製Ｏｐｔｉｍａｓ７５００を連続的に導入し、シリンダー温度２４０℃、吐出速度２．６ｋｇ／ｈの条件で押し出した。また、軸径６５ｍｍの単軸押出機にポリカーボネート樹脂（三菱エンジニアリングプラスチックス社製、商品名：ユーピロンＳ－１０００）を連続的に導入し、シリンダー温度２８０℃、吐出速度５０．０ｋｇ／ｈで押し出した。全押出機に連結されたフィードブロックは２種２層の分配ピンを備え、温度２７０℃として高硬度樹脂（Ｂ１）とポリカーボネート樹脂を導入し積層した。その先に連結された温度２７０℃のＴダイでシート状に押し出し、上流側から温度１２０℃、１３０℃、１９０℃とした３本の鏡面仕上げロールで鏡面を転写しながら冷却し、高硬度樹脂（Ｂ１）層とポリカーボネート樹脂層との積層体（Ｘ－１）を得た。得られた積層体（Ｘ－１）の厚みは１．０ｍｍ、高硬度樹脂（Ｂ１）層の厚みは中央付近で６０μｍであった。
　なお、高硬度樹脂（Ｂ１）として用いた三菱ガス化学製Ｏｐｔｉｍａｓ７５００は、前記一般式（１）で表される（メタ）アクリル酸エステル構成単位（ａ）と、前記一般式（２）で表される脂肪族ビニル構成単位（ｂ）とを含む共重合樹脂であって、前記（メタ）アクリル酸エステル構成単位（ａ）と前記脂肪族ビニル構成単位（ｂ）との合計割合が前記共重合樹脂の全構成単位の９９モル％であり、前記（メタ）アクリル酸エステル構成単位（ａ）の割合が前記共重合樹脂の全構成単位の７５モル％である共重合樹脂である。 Example 1
<Laminated body (X-1)>
Synthetic resin using 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 all extruders, and a multi-layer extruder having a T-die connected to the feed block. The laminate was molded. Optimas 7500 manufactured by Mitsubishi Gas Chemical Company was continuously introduced as a high-hardness resin (B1) into a single-screw extruder having a shaft diameter of 35 mm, and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.6 kg / h. In addition, polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, trade name: Iupiron S-1000) is 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. It was. The feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a high hardness resin (B1) and a polycarbonate resin were introduced and laminated at a temperature of 270 ° C. It is extruded into a sheet with a T-die with a temperature of 270 ° C connected to the tip, and cooled while transferring the mirror surface with three mirror-finishing rolls with temperatures of 120 ° C, 130 ° C, and 190 ° C from the upstream side. A laminate (X-1) of the layer (B1) and the polycarbonate resin layer was obtained. The thickness of the obtained laminate (X-1) was 1.0 mm, and the thickness of the high hardness resin (B1) layer was 60 μm near the center.
The Optimas 7500 manufactured by Mitsubishi Gas Chemicals Co., Ltd. used as the high-hardness resin (B1) is represented by the (meth) acrylic acid ester structural unit (a) represented by the general formula (1) and the general formula (2). A copolymer resin containing the aliphatic vinyl constituent unit (b), wherein the total ratio of the (meth) acrylic acid ester constituent unit (a) and the aliphatic vinyl constituent unit (b) is the copolymer resin. The copolymer resin is 99 mol% of all the constituent units of the above, and the ratio of the (meth) acrylic acid ester constituent unit (a) is 75 mol% of all the constituent units of the copolymer resin.
＜光硬化性樹脂組成物（Ｙ－１）＞
　・Ｕ６ＨＡ：６官能ウレタンアクリレートオリゴマー（新中村化学工業（株）製）６０質量％、
　・＃２６０：１，９－ノナンジオールジアクリレート（大阪有機化学工業（株）製）３５質量％、
　・フッ素系レべリング剤５質量％の混合物を１００質量部として
　・光開始剤：Ｉ－１８４（ＢＡＳＦ（株）製〔化合物名：１－ヒドロキシ－シクロヘキシルフェニルケトン〕）を３質量部添加して、光硬化性樹脂組成物（Ｙ－１）を得た。 <Photocurable resin composition (Y-1)>
U6HA: 6-functional urethane acrylate oligomer (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) 60% by mass,
# 260: 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 35% by mass,
-A mixture of 5% by mass of a fluorine-based leveling agent is taken as 100 parts by mass.-Photoinitiator: I-184 (manufactured by BASF Co., Ltd. [Compound name: 1-hydroxy-cyclohexylphenyl ketone]) is added by 3 parts by mass. A photocurable resin composition (Y-1) was obtained.
＜柄目付きＰＥＴフィルム（Ｚ－１）＞
　凹凸形状を転写するためのＰＥＴフィルムとして、中島工業製Ｃ－５０　Ｇ－１００－１を使用した。 <PET film with pattern (Z-1)>
As a PET film for transferring the uneven shape, C-50 G-100-1 manufactured by Nakajima Kogyo was used.
　積層体（Ｘ－１）の高硬度樹脂（Ｂ１）層上に、光硬化樹脂組成物（Ｙ－１）を硬化後の塗膜厚さが５～１０μｍとなるようにバーコーターを用いて塗布し、柄目付きＰＥＴフィルム（Ｚ－１）の柄面が塗布液と接触するように覆って圧着した。その後、光源距離１２ｃｍ、メタルハライドランプ（２０ｍＷ／ｃｍ）を３０秒間照射し硬化させて、柄目付きＰＥＴフィルムを剥離し、高硬度樹脂（Ｂ１）層上に凹凸のあるハードコート層を備えた防眩性積層体を得た。 The photocurable resin composition (Y-1) is applied onto the high hardness resin (B1) layer of the laminate (X-1) using a bar coater so that the coating thickness after curing is 5 to 10 μm. Then, the handle surface of the patterned PET film (Z-1) was covered and crimped so as to come into contact with the coating liquid. After that, a metal halide lamp (20 mW / cm) with a light source distance of 12 cm was irradiated for 30 seconds to cure, the patterned PET film was peeled off, and an antiglare antiglare provided with an uneven hard coat layer on a high hardness resin (B1) layer. A sex laminate was obtained.
実施例２
　柄目付きＰＥＴフィルムに中島工業製Ｃ－５０　Ｇ－１００－２（Ｚ－２）を使用した以外は、実施例１と同様にして、防眩性積層体を得た。 Example 2
An antiglare laminate was obtained in the same manner as in Example 1 except that C-50 G-100-2 (Z-2) manufactured by Nakajima Kogyo Co., Ltd. was used for the patterned PET film.
実施例３
　柄目付きＰＥＴフィルムに中島工業製Ｃ－５０　Ｇ－１００－３（Ｚ－３）を使用した以外は、実施例１と同様にして、防眩性積層体を得た。 Example 3
An antiglare laminate was obtained in the same manner as in Example 1 except that C-50 G-100-3 (Z-3) manufactured by Nakajima Kogyo Co., Ltd. was used for the patterned PET film.
実施例４
＜高硬度樹脂（Ｂ２）の製造＞
　実施例１で使用した高硬度樹脂（Ｂ１）を４０質量％と、スチレン－不飽和ジカルボン酸系共重合体（Ｃ）としてPOLYSCOPE POLYMERS BV製ＸＩＢＯＮＤ１４０を６０質量％とを仕込み、ブレンダーで３０分混合後、スクリュー径２６ｍｍの押出機（東芝機械製、ＴＥＭ－２６ＳＳ、Ｌ／Ｄ≒４０）を用い、シリンダー温度２３０℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化し、高硬度樹脂（Ｂ２）を得た。ペレット化は安定して行われた。
　なお、スチレン－不飽和ジカルボン酸系共重合体（Ｃ）として使用したPOLYSCOPE POLYMERS BV製ＸＩＢＯＮＤ１４０は、スチレン系単量体単位（ｃ１）を８５質量％、不飽和ジカルボン酸無水物単量体単位（ｃ２）を１５質量％で含む樹脂である。 Example 4
<Manufacturing of high hardness resin (B2)>
40% by mass of the high hardness resin (B1) used in Example 1 and 60% by mass of XIBOND140 manufactured by POLYSCOPE POLYMERS BV as a styrene-unsaturated dicarboxylic acid-based copolymer (C) were charged and mixed in a blender for 30 minutes. After that, using an extruder with a screw diameter of 26 mm (manufactured by Toshiba Machine Co., Ltd., TEM-26SS, L / D≈40), it is melt-kneaded at a cylinder temperature of 230 ° C., extruded into strands, pelletized with a pelletizer, and made into a high-hardness resin. (B2) was obtained. Pelletization was stable.
The POLYSCOPE POLYMERS BV XIBOND140 used as the styrene-unsaturated dicarboxylic acid-based copolymer (C) contained 85% by mass of the styrene-based monomer unit (c1) and the unsaturated dicarboxylic acid anhydride monomer unit ( It is a resin containing c2) in an amount of 15% by mass.
＜積層体（Ｘ－２）＞
　軸径３５ｍｍの単軸押出機と、軸径６５ｍｍの単軸押出機と、全押出機に連結されたフィードブロックと、フィードブロックに連結されたＴダイとを有する多層押出装置を用いて合成樹脂積層体を成形した。軸径３５ｍｍの単軸押出機に高硬度樹脂（Ｂ２）を連続的に導入し、シリンダー温度２４０℃、吐出速度２．６ｋｇ／ｈの条件で押し出した。また、軸径６５ｍｍの単軸押出機にポリカーボネート樹脂（三菱エンジニアリングプラスチックス社製、商品名：ユーピロンＳ－１０００）を連続的に導入し、シリンダー温度２８０℃、吐出速度５０．０ｋｇ／ｈで押し出した。全押出機に連結されたフィードブロックは２種２層の分配ピンを備え、温度２７０℃として高硬度樹脂（Ｂ２）とポリカーボネート樹脂を導入し積層した。その先に連結された温度２７０℃のＴダイでシート状に押し出し、上流側から温度１２０℃、１３０℃、１９０℃とした３本の鏡面仕上げロールで鏡面を転写しながら冷却し、高硬度樹脂（Ｂ２）層とポリカーボネート樹脂層との積層体（Ｘ－２）を得た。得られた積層体（Ｘ－２）の厚みは１．０ｍｍ、高硬度樹脂（Ｂ２）層の厚みは中央付近で６０μｍであった。 <Laminated body (X-2)>
Synthetic resin using 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 all extruders, and a multi-layer extruder having a T-die connected to the feed block. The laminate was molded. A high-hardness resin (B2) was continuously introduced into a single-screw extruder having a shaft diameter of 35 mm, and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.6 kg / h. In addition, polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, trade name: Iupiron S-1000) is 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. It was. The feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a high hardness resin (B2) and a polycarbonate resin were introduced and laminated at a temperature of 270 ° C. It is extruded into a sheet with a T-die with a temperature of 270 ° C connected to the tip, and cooled while transferring the mirror surface with three mirror-finishing rolls with temperatures of 120 ° C, 130 ° C, and 190 ° C from the upstream side. A laminate (X-2) of the layer (B2) and the polycarbonate resin layer was obtained. The thickness of the obtained laminate (X-2) was 1.0 mm, and the thickness of the high hardness resin (B2) layer was 60 μm near the center.
　積層体（Ｘ－２）の高硬度樹脂（Ｂ２）層上に、光硬化樹脂組成物（Ｙ－１）を硬化後の塗膜厚さが５～１０μｍとなるようにバーコーターを用いて塗布し、柄目付きＰＥＴフィルム（Ｚ－１）の柄面が塗布液と接触するように覆って圧着した。その後、光源距離１２ｃｍ、メタルハライドランプ（２０ｍＷ／ｃｍ）を３０秒間照射し硬化させて、柄目付きＰＥＴフィルムを剥離し、高硬度樹脂（Ｂ２）層上に凹凸のあるハードコート層を備えた防眩性積層体を得た。 The photocurable resin composition (Y-1) is applied onto the high hardness resin (B2) layer of the laminate (X-2) using a bar coater so that the coating thickness after curing is 5 to 10 μm. Then, the handle surface of the patterned PET film (Z-1) was covered and crimped so as to come into contact with the coating liquid. After that, a metal halide lamp (20 mW / cm) with a light source distance of 12 cm was irradiated for 30 seconds to cure, the patterned PET film was peeled off, and an antiglare antiglare provided with an uneven hard coat layer on a high hardness resin (B2) layer. A sex laminate was obtained.
実施例５
＜高硬度樹脂（Ｂ３）の製造＞
　スチレン－不飽和ジカルボン酸系共重合体（Ｅ）としてレジスファイ　Ｒ１００（デンカ製）を７５質量％と、ビニル系単量体を含有する樹脂（Ｄ）としてメチルメタクリレート樹脂パラペットＨＲ－Ｌ（クラレ製、重量平均分子量：９０，０００）２５質量％とを仕込み、ブレンダーで３０分混合後、スクリュー径２６ｍｍの押出機（東芝機械製、ＴＥＭ－２６ＳＳ、Ｌ／Ｄ≒４０）を用い、シリンダー温度２３０℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化し、高硬度樹脂（Ｂ３）を得た。ペレット化は安定して行なわれた。
　なお、スチレン－不飽和ジカルボン酸系共重合体（Ｅ）として用いたレジスファイ　Ｒ１００（デンカ製）は、メタクリル酸メチル構成単位２１質量％、スチレン構成単位６４質量％、および無水マレイン酸構成単位１５質量％の共重合体である。 Example 5
<Manufacturing of high hardness resin (B3)>
Regisphi R100 (manufactured by Denka) as a styrene-unsaturated dicarboxylic acid-based copolymer (E) is 75% by mass, and methyl methacrylate resin parapet HR-L (manufactured by Kuraray) is used as a resin (D) containing a vinyl monomer. Weight average molecular weight: 90,000) 25% by mass, mixed with a blender for 30 minutes, and then using an extruder with a screw diameter of 26 mm (Toshiba Machine Co., Ltd., TEM-26SS, L / D ≈ 40), cylinder temperature 230 ° C. The resin was melt-kneaded in 1 and extruded into a strand to be pelletized with a pelletizer to obtain a high hardness resin (B3). Pelletization was stable.
The Regisphi R100 (manufactured by Denka) used as the styrene-unsaturated dicarboxylic acid-based copolymer (E) has 21% by mass of methyl methacrylate constituent unit, 64% by mass of styrene constituent unit, and 15 mass% of maleic anhydride constituent unit. % Is a copolymer.
＜積層体（Ｘ－３）＞
　軸径３５ｍｍの単軸押出機と、軸径６５ｍｍの単軸押出機と、全押出機に連結されたフィードブロックと、フィードブロックに連結されたＴダイとを有する多層押出装置を用いて合成樹脂積層体を成形した。軸径３５ｍｍの単軸押出機に高硬度樹脂（Ｂ３）を連続的に導入し、シリンダー温度２４０℃、吐出速度２．６ｋｇ／ｈの条件で押し出した。また、軸径６５ｍｍの単軸押出機にポリカーボネート樹脂（三菱エンジニアリングプラスチックス社製、商品名：ユーピロンＳ－１０００）を連続的に導入し、シリンダー温度２８０℃、吐出速度５０．０ｋｇ／ｈで押し出した。全押出機に連結されたフィードブロックは２種２層の分配ピンを備え、温度２７０℃として高硬度樹脂（Ｂ３）とポリカーボネート樹脂を導入し積層した。その先に連結された温度２７０℃のＴダイでシート状に押し出し、上流側から温度１２０℃、１３０℃、１９０℃とした３本の鏡面仕上げロールで鏡面を転写しながら冷却し、高硬度樹脂（Ｂ３）層とポリカーボネート樹脂層との積層体（Ｘ－３）を得た。得られた積層体（Ｘ－３）の厚みは１．０ｍｍ、高硬度樹脂（Ｂ３）層の厚みは中央付近で６０μｍであった。 <Laminated body (X-3)>
Synthetic resin using 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 all extruders, and a multi-layer extruder having a T-die connected to the feed block. The laminate was molded. A high-hardness resin (B3) was continuously introduced into a single-screw extruder having a shaft diameter of 35 mm, and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.6 kg / h. In addition, polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, trade name: Iupiron S-1000) is 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. It was. The feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a high hardness resin (B3) and a polycarbonate resin were introduced and laminated at a temperature of 270 ° C. It is extruded into a sheet with a T-die with a temperature of 270 ° C connected to the tip, and cooled while transferring the mirror surface with three mirror-finishing rolls with temperatures of 120 ° C, 130 ° C, and 190 ° C from the upstream side. A laminate (X-3) of the layer (B3) and the polycarbonate resin layer was obtained. The thickness of the obtained laminate (X-3) was 1.0 mm, and the thickness of the high hardness resin (B3) layer was 60 μm near the center.
　積層体（Ｘ－３）の高硬度樹脂（Ｂ３）層上に、光硬化樹脂組成物（Ｙ－１）を硬化後の塗膜厚さが５～１０μｍとなるようにバーコーターを用いて塗布し、柄目付きＰＥＴフィルム（Ｚ－１）の柄面が塗布液と接触するように覆って圧着した。その後、光源距離１２ｃｍ、メタルハライドランプ（２０ｍＷ／ｃｍ）を３０秒間照射し硬化させて、柄目付きＰＥＴフィルムを剥離し、高硬度樹脂（Ｂ３）層上に凹凸のあるハードコート層を備えた防眩性積層体を得た。 The photocurable resin composition (Y-1) is applied onto the high hardness resin (B3) layer of the laminate (X-3) using a bar coater so that the coating thickness after curing is 5 to 10 μm. Then, the handle surface of the patterned PET film (Z-1) was covered and crimped so as to come into contact with the coating liquid. After that, a metal halide lamp (20 mW / cm) with a light source distance of 12 cm was irradiated for 30 seconds to cure, the patterned PET film was peeled off, and an antiglare antiglare provided with an uneven hard coat layer on a high hardness resin (B3) layer. A sex laminate was obtained.
実施例６
＜高硬度樹脂（Ｂ４）の製造＞
　実施例５で使用したスチレン－不飽和ジカルボン酸系共重合体（Ｅ）を７５質量％と、樹脂共重合体（Ｇ）として、スチレン構成単位７質量％、メタクリル酸メチル構成単位８６質量％、およびＮ－フェニルマレイミド構成単位７質量％の共重合体であるデルペット　ＰＭ－１２０Ｎ（旭化成ケミカル製）２５質量％とを仕込み、ブレンダーで３０分間混合後、スクリュー径２６ｍｍの押出機（東芝機械製、ＴＥＭ－２６ＳＳ、Ｌ／Ｄ≒４０）を用い、シリンダー温度２３０℃で溶融混錬して、ストランド状に押出してペレタイザーでペレット化し、高硬度樹脂（Ｂ４）を得た。ペレット化は安定して行われた。 Example 6
<Manufacturing of high hardness resin (B4)>
The styrene-unsaturated dicarboxylic acid-based copolymer (E) used in Example 5 was 75% by mass, and the resin copolymer (G) was 7% by mass of the styrene constituent unit and 86% by mass of the methyl methacrylate constituent unit. And 25% by mass of Delpet PM-120N (manufactured by Asahi Kasei Chemical Co., Ltd.), which is a copolymer of 7% by mass of N-phenylmaleimide constituent unit, and mixed with a blender for 30 minutes, and then an extruder with a screw diameter of 26 mm (manufactured by Toshiba Machinery Co., Ltd.) , TEM-26SS, L / D≈40), melt-kneaded at a cylinder temperature of 230 ° C., extruded into strands and pelletized with a pelletizer to obtain a high hardness resin (B4). Pelletization was stable.
＜積層体（Ｘ－４）＞
　軸径３５ｍｍの単軸押出機と、軸径６５ｍｍの単軸押出機と、全押出機に連結されたフィードブロックと、フィードブロックに連結されたＴダイとを有する多層押出装置を用いて合成樹脂積層体を成形した。軸径３５ｍｍの単軸押出機に高硬度樹脂（Ｂ４）を連続的に導入し、シリンダー温度２４０℃、吐出速度２．６ｋｇ／ｈの条件で押し出した。また、軸径６５ｍｍの単軸押出機にポリカーボネート樹脂（三菱エンジニアリングプラスチックス社製、商品名：ユーピロンＳ－１０００）を連続的に導入し、シリンダー温度２８０℃、吐出速度５０．０ｋｇ／ｈで押し出した。全押出機に連結されたフィードブロックは２種２層の分配ピンを備え、温度２７０℃として高硬度樹脂（Ｂ４）とポリカーボネート樹脂を導入し積層した。その先に連結された温度２７０℃のＴダイでシート状に押し出し、上流側から温度１２０℃、１３０℃、１９０℃とした３本の鏡面仕上げロールで鏡面を転写しながら冷却し、高硬度樹脂（Ｂ４）層とポリカーボネート樹脂層との積層体（Ｘ－４）を得た。得られた積層体（Ｘ－４）の厚みは１．０ｍｍ、高硬度樹脂（Ｂ４）層の厚みは中央付近で６０μｍであった。 <Laminated body (X-4)>
Synthetic resin using 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 all extruders, and a multi-layer extruder having a T-die connected to the feed block. The laminate was molded. A high-hardness resin (B4) was continuously introduced into a single-screw extruder having a shaft diameter of 35 mm, and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.6 kg / h. In addition, polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, trade name: Iupiron S-1000) is 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. It was. The feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a high hardness resin (B4) and a polycarbonate resin were introduced and laminated at a temperature of 270 ° C. It is extruded into a sheet with a T-die with a temperature of 270 ° C connected to the tip, and cooled while transferring the mirror surface with three mirror-finishing rolls with temperatures of 120 ° C, 130 ° C, and 190 ° C from the upstream side. A laminate (X-4) of the layer (B4) and the polycarbonate resin layer was obtained. The thickness of the obtained laminate (X-4) was 1.0 mm, and the thickness of the high hardness resin (B4) layer was 60 μm near the center.
　積層体（Ｘ－４）の高硬度樹脂（Ｂ４）層上に、光硬化樹脂組成物（Ｙ－１）を硬化後の塗膜厚さが５～１０μｍとなるようにバーコーターを用いて塗布し、柄目付きＰＥＴフィルム（Ｚ－１）の柄面が塗布液と接触するように覆って圧着した。その後、光源距離１２ｃｍ、メタルハライドランプ（２０ｍＷ／ｃｍ）を３０秒間照射し硬化させて、柄目付きＰＥＴフィルムを剥離し、高硬度樹脂（Ｂ４）層上に凹凸のあるハードコート層を備えた防眩性積層体を得た。 The photocurable resin composition (Y-1) is applied onto the high hardness resin (B4) layer of the laminate (X-4) using a bar coater so that the coating thickness after curing is 5 to 10 μm. Then, the handle surface of the patterned PET film (Z-1) was covered and crimped so as to come into contact with the coating liquid. After that, a metal halide lamp (20 mW / cm) with a light source distance of 12 cm was irradiated for 30 seconds to cure, the patterned PET film was peeled off, and an antiglare antiglare provided with an uneven hard coat layer on a high hardness resin (B4) layer. A sex laminate was obtained.
実施例７
＜積層体（Ｘ－５）＞
　軸径３５ｍｍの単軸押出機と、軸径６５ｍｍの単軸押出機と、全押出機に連結されたフィードブロックと、フィードブロックに連結されたＴダイとを有する多層押出装置を用いて合成樹脂積層体を成形した。軸径３５ｍｍの単軸押出機に高硬度樹脂（Ｂ５）としてユーピロンＫＨ３４１０ＵＲ（三菱エンジニアプラスチックス製）を連続的に導入し、シリンダー温度２７０℃、吐出速度２．６ｋｇ／ｈの条件で押し出した。また、軸径６５ｍｍの単軸押出機にポリカーボネート樹脂（三菱エンジニアリングプラスチックス社製、商品名：ユーピロンＳ－１０００）を連続的に導入し、シリンダー温度２８０℃、吐出速度５０．０ｋｇ／ｈで押し出した。全押出機に連結されたフィードブロックは２種２層の分配ピンを備え、温度２７０℃として高硬度樹脂（Ｂ５）とポリカーボネート樹脂を導入し積層した。その先に連結された温度２７０℃のＴダイでシート状に押し出し、上流側から温度１２０℃、１３０℃、１９０℃とした３本の鏡面仕上げロールで鏡面を転写しながら冷却し、高硬度樹脂（Ｂ５）層とポリカーボネート樹脂層との積層体（Ｘ－５）を得た。得られた積層体（Ｘ－５）の厚みは１．０ｍｍ、高硬度樹脂（Ｂ５）層の厚みは中央付近で６０μｍであった。 Example 7
<Laminated body (X-5)>
Synthetic resin using 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 all extruders, and a multi-layer extruder having a T-die connected to the feed block. The laminate was molded. Iupiron KH3410UR (manufactured by Mitsubishi Engineering Plastics) was continuously introduced as a high hardness resin (B5) into a single-screw extruder having a shaft diameter of 35 mm, and extruded under the conditions of a cylinder temperature of 270 ° C. and a discharge rate of 2.6 kg / h. In addition, polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, trade name: Iupiron S-1000) is 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. It was. The feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a high hardness resin (B5) and a polycarbonate resin were introduced and laminated at a temperature of 270 ° C. It is extruded into a sheet with a T-die with a temperature of 270 ° C connected to the tip, and cooled while transferring the mirror surface with three mirror-finishing rolls with temperatures of 120 ° C, 130 ° C, and 190 ° C from the upstream side. A laminate (X-5) of the layer (B5) and the polycarbonate resin layer was obtained. The thickness of the obtained laminate (X-5) was 1.0 mm, and the thickness of the high hardness resin (B5) layer was 60 μm near the center.
　積層体（Ｘ－５）の高硬度樹脂（Ｂ５）層上に、光硬化樹脂組成物（Ｙ－１）を硬化後の塗膜厚さが５～１０μｍとなるようにバーコーターを用いて塗布し、柄目付きＰＥＴフィルム（Ｚ－１）の柄面が塗布液と接触するように覆って圧着した。その後、光源距離１２ｃｍ、メタルハライドランプ（２０ｍＷ／ｃｍ）を３０秒間照射し硬化させて、柄目付きＰＥＴフィルムを剥離し、高硬度樹脂（Ｂ５）層上に凹凸のあるハードコート層を備えた防眩性積層体を得た。 The photocurable resin composition (Y-1) is applied onto the high hardness resin (B5) layer of the laminate (X-5) using a bar coater so that the coating thickness after curing is 5 to 10 μm. Then, the handle surface of the patterned PET film (Z-1) was covered and crimped so as to come into contact with the coating liquid. After that, a metal halide lamp (20 mW / cm) with a light source distance of 12 cm was irradiated for 30 seconds to cure, the patterned PET film was peeled off, and an antiglare antiglare provided with an uneven hard coat layer on a high hardness resin (B5) layer. A sex laminate was obtained.
比較例１
　柄目付きＰＥＴフィルムにダイセル製ＰＳ－２７（Ｚ－４）を使用した以外は、実施例１と同様にして、防眩性積層体を得た。 Comparative Example 1
An antiglare laminate was obtained in the same manner as in Example 1 except that PS-27 (Z-4) manufactured by Daicel was used for the patterned PET film.
比較例２
　ＭＥＫ５０質量部に対し、アクリル系紫外線硬化型樹脂（固形分１００％　商品名：ライトアクリレートＤＰＥ－６Ａ共栄社化学株式会社製）５０質量部、シリカ微粒子（オクチルシラン処理フュームドシリカ、平均一次粒子径１２ｎｍ、日本アエロジル社製）０．５質量部、アクリルシラン処理シリカ（平均粒子径１．９μｍ、商品名：ＳＥ－６０５０－ＳＹＢ　アドマテックス株式会社製）１質量部、及び光開始剤（商品名Ｏｍｎｉｒａｄ１８４ＩＧＭ　Ｒｅｓｉｎｓ製）３質量部を混合し攪拌することでコーティング液（ｉ）を作製した。次に、コーティング液（ｉ）をＰＥＴ（ポリエチレンテレフタレート）フィルムにドライ膜厚２．５μｍとなるように塗布し、８０℃で２分間乾燥後、光源距離１２ｃｍ、出力８０Ｗ／ｃｍの高圧水銀灯を備えたコンベアでラインスピード１．５ｍ／分の条件で紫外線を照射し硬化させることで作製された柄目付きＰＥＴフィルム（Ｚ－５）を使用した以外は、実施例１と同様にして防眩性積層体を得た。 Comparative Example 2
50 parts by mass of acrylic ultraviolet curable resin (100% solid content: light acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), silica fine particles (octylsilane treated fumed silica, average primary particle diameter 12 nm) with respect to 50 parts by mass of MEK , Nippon Aerozil Co., Ltd.) 0.5 parts by mass, acrylic silane treated silica (average particle size 1.9 μm, trade name: SE-6050-SYB Admatex Co., Ltd.) 1 part by mass, and photoinitiator (trade name Omnirad184IGM) A coating liquid (i) was prepared by mixing and stirring 3 parts by mass (manufactured by Resins). Next, the coating liquid (i) is applied to a PET (polyethylene terephthalate) film so as to have a dry film thickness of 2.5 μm, dried at 80 ° C. for 2 minutes, and then equipped with a high-pressure mercury lamp having a light source distance of 12 cm and an output of 80 W / cm. Anti-glare lamination in the same manner as in Example 1 except that a patterned PET film (Z-5) produced by irradiating and curing ultraviolet rays at a line speed of 1.5 m / min on a conveyor was used. I got a body.
比較例３
　ＭＥＫ５０％質量部に対し、アクリル系紫外線硬化型樹脂（固形分１００％商品：ライトアクリレートＤＰＥ－６Ａ　共栄社化学社製）５０質量部、シリカ微粒子（オクチルシラン処理ヒュームドシリカ、平均一次粒子径１．９μｍ、商品名：ＳＥ６０５０－ＳＹＢ　アドマテックス株式会社製）１.５質量部、および光開始剤（商品名　イルガキュア１８４　豊通ケミプラス社製）３質量部を混合し攪拌することでコーティング液（Ｙ－２）を作製した。実施例１に記載の積層体（Ｘ－１）にドライ膜厚２．５μｍとなるようにコーティング液（Ｙ－２）を塗布し、８０℃で２分間乾燥後、窒素パージをしながらメタルハライドランプ（２０ｍＷ／ｃｍ）を３０秒間照射し硬化させることで、防眩性積層体を得た。 Comparative Example 3
50 parts by mass of acrylic ultraviolet curable resin (100% solid content product: light acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), silica fine particles (octylsilane treated fumed silica, average primary particle size 1.) With respect to 50% by mass of MEK. 9 μm, trade name: SE6050-SYB manufactured by Admatex Co., Ltd. 1.5 parts by mass and photoinitiator (brand name IrgaCure 184 manufactured by Toyotsu Chemiplas Co., Ltd.) 3 parts by mass are mixed and stirred to form a coating liquid (Y-). 2) was prepared. A coating liquid (Y-2) is applied to the laminate (X-1) according to Example 1 so as to have a dry film thickness of 2.5 μm, dried at 80 ° C. for 2 minutes, and then a metal halide lamp is purged with nitrogen. (20 mW / cm) was irradiated for 30 seconds and cured to obtain an antiglare laminate.
比較例４
　高硬度樹脂（Ｂ１）の代わりにメチルメタクリレート樹脂パラペットＨＲ－Ｌ（クラレ製、重量平均分子量：９０，０００）を用いて得られた積層体（Ｘ－６）を使用した以外は、実施例１と同等にハードコート層を形成し、防眩性積層体を得た。 Comparative Example 4
Example 1 except that a laminate (X-6) obtained by using a methyl methacrylate resin parapet HR-L (manufactured by Kuraray, weight average molecular weight: 90,000) was used instead of the high hardness resin (B1). A hard coat layer was formed in the same manner as in the above, and an antiglare laminate was obtained.
　実施例１～７、比較例１～４で得られた防眩性積層体について、透過鮮明度、４５°反射鮮明度、ＳＷ硬度、形状安定性を評価した。結果は下表に示す。
Figure JPOXMLDOC01-appb-T000018
 The antiglare laminates obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were evaluated for transmission sharpness, 45 ° reflection sharpness, SW hardness, and shape stability. The results are shown in the table below.
Figure JPOXMLDOC01-appb-T000018
　以上に示されているように、本発明により、像の映り込み防止性能と文字ボケの抑制を両立した防眩性を有しつつ、高い耐擦傷性を有し、形状安定性にも優れた防眩性積層体が得られることがわかった。
  As shown above, according to the present invention, the present invention has high scratch resistance and excellent shape stability while having antiglare properties that both prevent image reflection and suppress character blurring. It was found that an antiglare laminate was obtained.

Claims (12)

  1. 　ポリカーボネート樹脂（ａ１）を含む樹脂（Ａ）を含む層と、
    　ポリカーボネート樹脂（ａ１）を含む樹脂（Ａ）を含む層の少なくとも一方の面に設けられた、高硬度樹脂（Ｂ）を含む層と、
    　更に高硬度樹脂（Ｂ）を含む層上に設けられ、凹凸形状を有するハードコート層と、
    を備え、下記条件（ｉ）および（ｉｉ）を満たす防眩性積層体：
    　（ｉ）前記高硬度樹脂（Ｂ）を含む層の厚みが１０～２５０μｍであり、前記ポリカーボネー樹脂（ａ１）を含む樹脂（Ａ）を含む層と前記高硬度樹脂（Ｂ）を含む層との合計厚みが１００～３，０００μｍであり；
    　（ｉｉ）前記積層体は、２．０ｍｍ幅の光学くしを用いて光を透過させたときの透過鮮明度をＴ１、２．０ｍｍ幅の光学くしを用いて光の入射角４５°で測定される反射鮮明度をＴ２とした場合、Ｔ１/Ｔ２が２．０以上である、防眩性積層体。     A layer containing the resin (A) containing the polycarbonate resin (a1) and
    A layer containing the high hardness resin (B) provided on at least one surface of the layer containing the resin (A) containing the polycarbonate resin (a1), and a layer containing the high hardness resin (B).
    Further, a hard coat layer provided on a layer containing a high hardness resin (B) and having an uneven shape, and a hard coat layer.
    An antiglare laminate that satisfies the following conditions (i) and (ii):
    (I) The layer containing the high hardness resin (B) has a thickness of 10 to 250 μm, and the layer containing the resin (A) containing the polycarbonate resin (a1) and the layer containing the high hardness resin (B). The total thickness of is 100-3,000 μm;
    (Ii) In the laminated body, the transmission sharpness when light is transmitted using an optical comb having a width of 2.0 mm is measured at an incident angle of 45 ° using T1 and an optical comb having a width of 2.0 mm. An antiglare laminate having T1 / T2 of 2.0 or more, where T2 is the reflection sharpness.
  2. 　２．０ｍｍ幅の光学くしを用いて光を透過させたときの透過鮮明度Ｔ１が３０％≦Ｔ１≦５０％を満たし、２．０ｍｍ幅の光学くしを用いて光の入射角４５°で測定される反射鮮明度Ｔ２が１０％≦Ｔ２≦２０％を満たす、請求項１に記載の防眩性積層体。 The transmission sharpness T1 when light is transmitted using a 2.0 mm wide optical comb satisfies 30% ≤ T1 ≤ 50%, and is measured at an incident angle of 45 ° using a 2.0 mm wide optical comb. The antiglare laminate according to claim 1, wherein the reflected sharpness T2 is 10% ≤ T2 ≤ 20%.
  3. 　高硬度樹脂（Ｂ）が以下の樹脂（Ｂ１）から（Ｂ５）からなる群より選択される少なくとも一つを含む、
    　前記樹脂（Ｂ１）は、
    　下記一般式（１）で表される（メタ）アクリル酸エステル構成単位（ａ）と、下記一般式（２）で表される脂肪族ビニル構成単位（ｂ）とを含む共重合樹脂であって、前記（メタ）アクリル酸エステル構成単位（ａ）と前記脂肪族ビニル構成単位（ｂ）との合計割合が前記共重合樹脂の全構成単位の９０～１００モル％であり、前記（メタ）アクリル酸エステル構成単位（ａ）の割合が前記共重合樹脂の全構成単位の６５～８０モル％である、共重合樹脂：
    Figure JPOXMLDOC01-appb-C000001
     　（式中、Ｒ１は水素原子またはメチル基であり、Ｒ２は炭素数１～１８のアルキル基である。）
    Figure JPOXMLDOC01-appb-C000002
     　（式中、Ｒ３は水素原子またはメチル基であり、Ｒ４は炭素数１～４の炭化水素基を有しても良いシクロヘキシル基である。）
    であり、
    　前記樹脂（Ｂ２）は、
    　前記樹脂（Ｂ１）を３５～６５質量％、スチレン－不飽和ジカルボン酸系共重合体（Ｃ）を３５～６５質量％含み、前記スチレン－不飽和ジカルボン酸共重合体（Ｃ）が、スチレン系単量体単位（ｃ１）を６５～９０質量％、不飽和ジカルボン酸無水物単量体単位（ｃ２）を１０～３５質量％で含む樹脂であり、
    　前記樹脂（Ｂ３）は、
    　ビニル系単量体を含有する樹脂（Ｄ）を５５～１０質量％、スチレン－不飽和ジカルボン酸系共重合体（Ｅ）を４５～９０質量％含み、前記スチレン－不飽和ジカルボン酸系共重合体（Ｅ）が、スチレン系単量体単位（e１）を５０～８０質量％、不飽和ジカルボン酸単量体単位（e２）を１０～３０質量％、ビニル系単量体単位（e３）を５～３０質量％で含む樹脂であり、
    　前記樹脂（Ｂ４）は、
    　スチレン構成単位を５～２０質量％、（メタ）アクリル酸エステル構成単位を６０～９０質量％、Ｎ－置換型マレイミド単量体を５～２０質量％含む樹脂共重合体（Ｇ）、または樹脂共重合体（Ｇ）と前記共重合体（Ｅ）のアロイである樹脂であり、
    　前記樹脂（Ｂ５）は、
    　下記式（３）で表される構成単位（Ｈ）と、任意に下記式（４）で表される構成単位（Ｊ）とを含む共重合体である、
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
     請求項１または２に記載の防眩性積層体。     The high hardness resin (B) contains at least one selected from the group consisting of the following resins (B1) to (B5).
    The resin (B1) is
    A copolymer resin containing a (meth) acrylic acid ester structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (b) represented by the following general formula (2). The total ratio of the (meth) acrylic acid ester constituent unit (a) and the aliphatic vinyl constituent unit (b) is 90 to 100 mol% of the total constituent units of the copolymer resin, and the (meth) acrylic The copolymer resin: the ratio of the acid ester structural unit (a) is 65 to 80 mol% of the total structural units of the copolymer resin.
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R1 is a hydrogen atom or a methyl group, and R2 is an alkyl group having 1 to 18 carbon atoms.)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, R3 is a hydrogen atom or a methyl group, and R4 is a cyclohexyl group which may have a hydrocarbon group having 1 to 4 carbon atoms.)
    And
    The resin (B2) is
    The resin (B1) is 35 to 65% by mass, the styrene-unsaturated dicarboxylic acid copolymer (C) is 35 to 65% by mass, and the styrene-unsaturated dicarboxylic acid copolymer (C) is styrene-based. A resin containing 65 to 90% by mass of the monomer unit (c1) and 10 to 35% by mass of the unsaturated dicarboxylic acid anhydride monomer unit (c2).
    The resin (B3) is
    The resin (D) containing a vinyl monomer contains 55 to 10% by mass, the styrene-unsaturated dicarboxylic acid-based copolymer (E) contains 45 to 90% by mass, and the styrene-unsaturated dicarboxylic acid-based copolymer weight. The coalescence (E) contains 50 to 80% by mass of the styrene-based monomer unit (e1), 10 to 30% by mass of the unsaturated dicarboxylic acid monomer unit (e2), and a vinyl-based monomer unit (e3). It is a resin contained in an amount of 5 to 30% by mass.
    The resin (B4) is
    Resin copolymer (G) or resin containing 5 to 20% by mass of styrene constituent unit, 60 to 90% by mass of (meth) acrylic acid ester constituent unit, and 5 to 20% by mass of N-substituted maleimide monomer. A resin that is an alloy of the copolymer (G) and the copolymer (E).
    The resin (B5) is
    A copolymer containing a structural unit (H) represented by the following formula (3) and a structural unit (J) optionally represented by the following formula (4).
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
     The antiglare laminate according to claim 1 or 2.
  4. 　前記凹凸形状を有するハードコート層は、無機粒子または有機粒子を含まない、請求項１～３のいずれか１項に記載の防眩性積層体。 The antiglare laminate according to any one of claims 1 to 3, wherein the hard coat layer having an uneven shape does not contain inorganic particles or organic particles.
  5. 　前記凹凸形状を有するハードコート層は、反射防止性能、防汚性能、帯電防止性能、および耐候性のうち少なくとも１つの特性を有する、請求項１～４のいずれか１項に記載の防眩性積層体。 The antiglare property according to any one of claims 1 to 4, wherein the hard coat layer having an uneven shape has at least one property of antireflection performance, antifouling performance, antistatic performance, and weather resistance. Laminated body.
  6. 　前記凹凸を有するハードコート層とは反対の面に第２のハードコート層を備える、請求項１～５のいずれか１項に記載の防眩性積層体。 The antiglare laminate according to any one of claims 1 to 5, wherein a second hard coat layer is provided on a surface opposite to the hard coat layer having the unevenness.
  7. 　前記第２のハードコート層が、反射防止性能、防汚性能、帯電防止性能、および耐候性のうち少なくとも１つの特性を有する、請求項６に記載の防眩性積層体。 The antiglare laminate according to claim 6, wherein the second hard coat layer has at least one of antireflection performance, antifouling performance, antistatic performance, and weather resistance.
  8. 　ポリカーボネート樹脂（ａ１）として、下記一般式（５）で表される１価フェノール由来の成分を含む、請求項１～７のいずれか１項に記載の防眩性積層体。
    Figure JPOXMLDOC01-appb-C000005
     　（式中、Ｒ１は、炭素数８～３６のアルキル基、又は炭素数８～３６のアルケニル基を表し、Ｒ２～Ｒ５はそれぞれ独立して、水素原子、ハロゲン、又は置換基を有してもよい炭素数１～２０のアルキル基若しくは炭素数６～１２のアリール基を表し、前記置換基は、ハロゲン、炭素数１～２０のアルキル基、又は炭素数６～１２のアリール基である。）     The antiglare laminate according to any one of claims 1 to 7, which contains a component derived from a monohydric phenol represented by the following general formula (5) as the polycarbonate resin (a1).
    Figure JPOXMLDOC01-appb-C000005
     (In the formula, R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R 2 to R 5 each independently have a hydrogen atom, a halogen, or a substituent. It represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the substituent may be a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. is there.)
  9. 　請求項１～８のいずれか１項に記載の防眩性積層体を含む車載用表示装置。 An in-vehicle display device including the antiglare laminate according to any one of claims 1 to 8.
  10. 　請求項１～８のいずれか１項に記載の防眩性積層体を含むタッチパネル前面保護板。 A touch panel front protective plate containing the antiglare laminate according to any one of claims 1 to 8.
  11. 　請求項１～８のいずれか１項に記載の防眩性積層体を含むＯＡ機器用、携帯電子機器用、またはテレビ用の前面板。 A front plate for OA equipment, portable electronic equipment, or a television containing the antiglare laminate according to any one of claims 1 to 8.
  12. 　請求項１～８のいずれか１項に記載の防眩性積層体の製造方法であって、
    　前記高硬度樹脂（Ｂ）を含む層上の光硬化性樹脂組成物に、柄目付きＰＥＴフィルムを圧着することにより、前記ハードコート層に凹凸形状を転写するステップを含む、前記防眩性積層体の製造方法。
          The method for producing an antiglare laminate according to any one of claims 1 to 8.
    The antiglare laminate comprising a step of transferring an uneven shape to the hard coat layer by pressing a patterned PET film onto the photocurable resin composition on the layer containing the high hardness resin (B). Manufacturing method.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009122645A (en) * 2007-10-23 2009-06-04 Sumitomo Chemical Co Ltd Anti-glare film, anti-glare polarizing plate, and image display device
JP2009210592A (en) * 2008-02-29 2009-09-17 Sumitomo Chemical Co Ltd Antiglare polarizing plate and image display using the same
JP2010102072A (en) * 2008-10-23 2010-05-06 Sumitomo Chemical Co Ltd Anti-glare film, anti-glare polarizing sheet, and image display device
JP2010102186A (en) * 2008-10-24 2010-05-06 Sumitomo Chemical Co Ltd Anti-glare film, anti-glare polarizing sheet, and image display device
WO2017150646A1 (en) * 2016-03-04 2017-09-08 三菱瓦斯化学株式会社 Front plate for onboard lcd device
WO2019049704A1 (en) * 2017-09-06 2019-03-14 三菱瓦斯化学株式会社 High-hardness molding resin sheet and molded article using same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009122645A (en) * 2007-10-23 2009-06-04 Sumitomo Chemical Co Ltd Anti-glare film, anti-glare polarizing plate, and image display device
JP2009210592A (en) * 2008-02-29 2009-09-17 Sumitomo Chemical Co Ltd Antiglare polarizing plate and image display using the same
JP2010102072A (en) * 2008-10-23 2010-05-06 Sumitomo Chemical Co Ltd Anti-glare film, anti-glare polarizing sheet, and image display device
JP2010102186A (en) * 2008-10-24 2010-05-06 Sumitomo Chemical Co Ltd Anti-glare film, anti-glare polarizing sheet, and image display device
WO2017150646A1 (en) * 2016-03-04 2017-09-08 三菱瓦斯化学株式会社 Front plate for onboard lcd device
WO2019049704A1 (en) * 2017-09-06 2019-03-14 三菱瓦斯化学株式会社 High-hardness molding resin sheet and molded article using same

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