WO2021033483A1 - Corps stratifié anti-reflet - Google Patents

Corps stratifié anti-reflet Download PDF

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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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English (en)
Japanese (ja)
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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 CN202080057972.8A priority Critical patent/CN114270226A/zh
Priority to JP2021540683A priority patent/JPWO2021033483A1/ja
Publication of WO2021033483A1 publication Critical patent/WO2021033483A1/fr

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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 shape; Layered products comprising a layer 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 shape; Layered products comprising a layer 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 shape; Layered products comprising a layer 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.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un corps stratifié antireflet comprenant : une couche qui comprend une résine (A) contenant une résine de polycarbonate (a1) ; une couche qui comprend une résine de dureté élevée (B) et qui est disposée sur au moins un côté de la couche qui comprend la résine (A) contenant la résine de polycarbonate (a1) ; et une couche de revêtement dur qui a des renfoncements et des saillies et qui est disposée sur la couche comprenant la résine de dureté élevée (B). Le corps stratifié antireflet satisfait les conditions (i) et (ii) :　(I) l'épaisseur de la couche qui comporte une résine de dureté élevée (B) est de 10 à 250 µm et l'épaisseur combinée de la couche qui comporte la résine (A) comprenant la résine de polycarbonate (a1) et la couche comprenant une résine de dureté élevée (B) est de 100 à 3 000 µm ; (ii) dans un cas où T1 est la clarté de transmission obtenue lorsque la lumière est transmise à travers un peigne de fréquences optiques ayant une largeur de fente de 2,0 mm et T2 est la clarté de réflexion mesurée à l'aide d'un peigne de fréquences optiques ayant une largeur de fente de 2,0 mm à un angle d'incidence de lumière de 45°, T1/T2 est de 2,0 ou plus.
PCT/JP2020/028358 2019-08-20 2020-07-22 Corps stratifié anti-reflet WO2021033483A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009122645A (ja) * 2007-10-23 2009-06-04 Sumitomo Chemical Co Ltd 防眩フィルム、防眩性偏光板および画像表示装置
JP2009210592A (ja) * 2008-02-29 2009-09-17 Sumitomo Chemical Co Ltd 防眩性偏光板およびそれを用いた画像表示装置
JP2010102072A (ja) * 2008-10-23 2010-05-06 Sumitomo Chemical Co Ltd 防眩フィルム、防眩性偏光板および画像表示装置
JP2010102186A (ja) * 2008-10-24 2010-05-06 Sumitomo Chemical Co Ltd 防眩フィルム、防眩性偏光板および画像表示装置
WO2017150646A1 (fr) * 2016-03-04 2017-09-08 三菱瓦斯化学株式会社 Plaque avant pour dispositif lcd embarqué
WO2019049704A1 (fr) * 2017-09-06 2019-03-14 三菱瓦斯化学株式会社 Feuille de résine de moulage de haute dureté et article moulé l'utilisant

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009122645A (ja) * 2007-10-23 2009-06-04 Sumitomo Chemical Co Ltd 防眩フィルム、防眩性偏光板および画像表示装置
JP2009210592A (ja) * 2008-02-29 2009-09-17 Sumitomo Chemical Co Ltd 防眩性偏光板およびそれを用いた画像表示装置
JP2010102072A (ja) * 2008-10-23 2010-05-06 Sumitomo Chemical Co Ltd 防眩フィルム、防眩性偏光板および画像表示装置
JP2010102186A (ja) * 2008-10-24 2010-05-06 Sumitomo Chemical Co Ltd 防眩フィルム、防眩性偏光板および画像表示装置
WO2017150646A1 (fr) * 2016-03-04 2017-09-08 三菱瓦斯化学株式会社 Plaque avant pour dispositif lcd embarqué
WO2019049704A1 (fr) * 2017-09-06 2019-03-14 三菱瓦斯化学株式会社 Feuille de résine de moulage de haute dureté et article moulé l'utilisant

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