Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
  • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
• • 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
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • 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
  • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
• • 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
  • B32B38/00—Ancillary operations in connection with laminating processes
  • B32B38/14—Printing or colouring
  • B32B38/145—Printing
• • 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
• • 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
  • B32B7/027—Thermal properties
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/006—Anti-reflective 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
  • G02B1/11—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
  • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/26—Polymeric coating
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/28—Multiple coating on one surface
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/536—Hardness
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/538—Roughness
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/584—Scratch resistance
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—Thickness
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

• the present invention relates to an antiglare laminate and a manufacturing method thereof. More specifically, the present invention relates to an antiglare laminate that has antiglare performance, high scratch resistance, and excellent shape stability, and is used as a front protective plate for in-vehicle liquid crystal display devices, mobile phone terminals, personal computers, tablet PCs, etc., and a manufacturing method thereof.
• Liquid crystal display devices are provided with a front panel to protect the liquid crystal panel and other components.
• Materials used for the front panel of conventional liquid crystal display devices include (meth)acrylic resins, such as polymethyl methacrylate (PMMA).
• front panels In recent years, sheets made of polycarbonate resin have been used as front panels because of their high impact resistance, heat resistance, secondary processability, light weight, transparency, etc.
• front panels in which a hard coat is applied to a multilayer sheet in which an acrylic resin is laminated on the surface of a polycarbonate resin sheet have surface hardness and scratch resistance comparable to conventional acrylic resins with hard coats, while also having the excellent impact resistance, heat resistance, processability, and transparency of polycarbonate resin, and are therefore widely used as front panels.
• the front panel of a liquid crystal display device having the above-mentioned polycarbonate resin sheet is generally formed by melt extrusion together with an acrylic resin.
• an anti-reflection optical laminate is generally provided on the top surface.
• Such anti-reflection optical laminates suppress image reflections and reduce reflectance by scattering and interfering with light.
• An anti-glare film in which an anti-glare layer having an uneven surface is formed on the surface of a transparent substrate, is known as one type of anti-reflection optical laminate.
• This anti-glare film can prevent reduced visibility due to reflection of external light or glare of images by scattering external light due to the uneven surface.
• this optical laminate is usually placed on the outermost surface of a liquid crystal display device, it is also required to have hard coat properties to prevent scratches during handling.
• a mixture of fine particles and a binder resin or a curable resin is usually applied to a substrate, and a fine uneven surface is formed to prevent regular reflection and prevent image reflection.
• a fine uneven surface is formed to prevent regular reflection and prevent image reflection.
• the scattering of transmitted light that travels in a straight line increases, making the outlines of pixels unclear and causing blurred characters.
• fine particles to create surface irregularities is not preferred because the fine particles on the outermost surface fall off during the scratch resistance test and act as an abrasive, resulting in a significant decrease in scratch resistance compared to when fine particles are not added.
• Patent Document 2 also describes an antiglare laminate that has antiglare performance that prevents image reflection and suppresses character blurring, but claim 1 specifies that the haze specified in JIS K 7136 is 15% or more. If the haze exceeds 15%, it gives a whitish impression when used in an in-vehicle liquid crystal display device, which leads to reduced visibility.
• the present invention aims to solve at least one of the above-mentioned problems. Furthermore, the present invention aims to provide an antiglare laminate that has antiglare performance that combines the ability to prevent image reflection and the suppression of character blur, has high scratch resistance, and is also excellent in shape stability, and a method for manufacturing the same.
• the present invention is as follows. ⁇ 1> An antiglare laminate comprising a base layer containing at least a polycarbonate resin (a1), a high-hardness resin layer containing a high-hardness resin (B), and a hard coat layer arranged in this order, wherein the root-mean-square gradient (Sdq) and the root-mean-square height (Sq) of the hard coat layer are expressed by the following formulas (i) and (ii), respectively: 0.010 ⁇ Sdq ⁇ 0.10 (i) 0.040 ⁇ Sq ⁇ 0.40 (ii)
• the antiglare laminate satisfies the above requirements.
• the root mean square gradient (Sdq) and the root mean square height (Sq) of the hard coat layer are expressed by the following formulas (iii) and (iv), respectively: 0.035 ⁇ Sdq ⁇ 0.06 (iii) 0.20 ⁇ Sq ⁇ 0.35 (iv)
• the antiglare laminate according to the above item ⁇ 1>, ⁇ 3> The antiglare laminate according to ⁇ 1> or ⁇ 2> above, wherein the change in warpage of the antiglare laminate after being kept in an environment of a temperature of 85° C. and a relative humidity of 85% for 120 hours is 350 ⁇ m or less.
• ⁇ 4> The antiglare laminate according to any one of ⁇ 1> to ⁇ 3> above, wherein the high-hardness resin layer has a thickness of 10 to 250 ⁇ m.
• ⁇ 5> The antiglare laminate according to any one of ⁇ 1> to ⁇ 4> above, wherein a total thickness of the base layer and the high-hardness resin layer is 100 to 3,000 ⁇ m.
• ⁇ 6> The antiglare laminate according to any one of ⁇ 1> to ⁇ 5> above, wherein the hard coat layer does not contain organic particles and inorganic particles.
• the polycarbonate resin (a1) is represented by the following general formula (5): (wherein R 5 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms; each R 6 independently represents a hydrogen atom, a halogen, or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a substituent; and n is an integer from 0 to 4, and the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms).
• a touch panel front protection plate comprising the antiglare laminate according to any one of ⁇ 1> to ⁇ 7> above.
• a method for producing the antiglare laminate according to any one of ⁇ 1> to ⁇ 7> above A patterned PET film is pressure-bonded to the surface of the hard coat layer to transfer the uneven shape, and the hard coat layer after the transfer has a structure represented by the following formulas (i) and (ii): 0.010 ⁇ Sdq ⁇ 0.10 (i) 0.040 ⁇ Sq ⁇ 0.40 (ii)
• the present invention provides an antiglare laminate that has antiglare performance that combines the ability to prevent image reflections with the suppression of character blur, has high scratch resistance, and is also excellent in shape stability, as well as a method for producing the same.
• the antiglare laminate of the present invention comprises a substrate layer containing at least a polycarbonate resin (a1), a high-hardness resin layer containing a high-hardness resin (B), and a hard coat layer, arranged in this order.
• the order of lamination of the anti-glare laminate is preferably substrate layer-high hardness resin layer-hard coat layer.
• the other surface of the substrate layer is not particularly specified.
• a high hardness resin layer can be provided on the other surface of the substrate layer.
• the anti-glare laminate has a configuration of high hardness resin layer-substrate layer-high hardness resin layer-hard coat layer.
• a high hardness resin layer and a hard coat layer can be provided on the other surface of the substrate layer.
• the anti-glare laminate has a configuration of hard coat layer-high hardness resin layer-substrate layer-high hardness resin layer-hard coat layer.
• the base layer When high-hardness layers are provided on both sides of the base layer, it is more desirable to use the same high-hardness layers on both sides for shape stability. Also, when hard-coat layers are provided on both sides of the base, it is more desirable to provide similar hard-coat layers on both sides, as this improves shape stability.
• the base layer and high-hardness resin layer, and the high-hardness resin layer and hard-coat layer may be laminated directly or via another layer, but it is preferable that they are laminated directly.
• the antiglare laminate can be used, for example, as a touch panel front protection plate for in-vehicle display devices such as car navigation, center information displays (CID), rear seat entertainment (RSE), and clusters, and as a front panel for office automation devices, portable electronic devices, and televisions.
• the front panel can be used alone as the front panel for a liquid crystal display device, but it may also be used as a composite front panel, for example by laminating it with another substrate such as a touch sensor.
• the substrate layer contains a polycarbonate resin (a1).
• the substrate layer may further contain additives and the like.
• the polycarbonate resin (a1) is not particularly limited as long as it contains a carbonate bond, i.e., a -[O-R-OCO]- unit (wherein R may contain an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and may have a straight-chain structure or a branched structure), in the molecular main chain, but it is particularly preferable to use a polycarbonate resin containing a structural unit of the following formula (4). By using such a polycarbonate resin, a resin laminate having excellent impact resistance can be obtained.
• the polycarbonate resin (a1) may be an aromatic polycarbonate resin (for example, manufactured by Mitsubishi Engineering Plastics Corporation, product names: Iupilon S-2000, Iupilon S-1000, Iupilon E-2000), but is not limited thereto.
• R5 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms
• R6 each independently represents a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms
• n is an integer from 0 to 4, where the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• the "alkyl group” and the “alkenyl group” may be linear or branched, and may have a substituent.
• the monohydric phenol represented by general formula (5) is represented by the following general formula (6):
• R 5 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.
• the number of carbon atoms of R5 in general formula (5) or general formula (6) is more preferably within a specific numerical range.
• the upper limit of the number of carbon atoms of R5 is preferably 36, more preferably 22, and particularly preferably 18.
• the lower limit of the number of carbon atoms of R5 is preferably 8, and more preferably 12.
• the solubility of the monohydric phenol (terminal terminator) in an organic solvent tends to be high, and the productivity during the production of the polycarbonate resin is preferably high.
• the productivity is high and the economic efficiency is good in producing the polycarbonate resin.
• the carbon number of R5 is 22 or less, the monohydric phenol has particularly excellent solubility in organic solvents, and the productivity in producing the polycarbonate resin can be extremely high and the economic efficiency is improved.
• the glass transition point of the polycarbonate resin is not too high, and suitable thermoformability is obtained, which is preferable.
• terminal terminator which is an alkyl group having 16 carbon atoms
• the glass transition temperature, melt fluidity, moldability, drawdown resistance, and solvent solubility of the monohydric phenol during the production of the polycarbonate resin are excellent, and it is particularly preferable as the terminal terminator used for the polycarbonate resin in the present invention.
• the weight average molecular weight of the polycarbonate resin (a1) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and even more preferably 20,000 to 65,000.
• the weight average molecular weight of the polycarbonate resin (a1) is 15,000 or more, it is preferable because the impact resistance can be increased.
• the weight average molecular weight is 75,000 or less, it is preferable because the base layer can be formed with a small heat source and the thermal stability can be maintained even when the molding conditions become high temperature.
• the weight average molecular weight is the weight average molecular weight measured by gel permeation chromatography (GPC) and converted into standard polystyrene.
• the polycarbonate resin (a1) contained in the substrate layer may be one type or two or more types.
• the content of the polycarbonate resin (a1) in the base layer is preferably 75% by mass or more, based on the total mass of the base layer, and from the viewpoint of improving impact resistance, is more preferably 90% by mass or more, and even more preferably 100% by mass.
• the substrate layer may further contain an additive.
• the additives may be any additive that is commonly used in antiglare laminates, including, for example, antioxidants, anticoloring agents, antistatic agents, release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, and reinforcing materials such as organic fillers and inorganic fillers.
• the amount of additive is preferably 0 to 10% by mass, more preferably 0 to 7% by mass, and particularly preferably 0 to 5% by mass, relative to the total mass of the base layer.
• the method for mixing the additive and the resin is not particularly limited, and methods such as compounding the entire amount, dry blending the master batch, and dry blending the entire amount can be used.
• the thickness of the substrate layer is preferably from 0.1 to 3.5 mm, more preferably from 0.3 to 3 mm, and particularly preferably from 1.2 to 3 mm.
• the high-hardness resin layer includes a high-hardness resin.
• the high-hardness resin layer may further include additives, etc., as necessary.
• the high-hardness resin layer is provided between the substrate layer and the hard coat layer, so that an anti-glare laminate having high shape stability can be obtained.
• the high-hardness resin layer can have a function of increasing the hardness of the anti-glare laminate.
• the high-hardness resin means a resin having a higher hardness than the polycarbonate resin serving as the substrate, and a pencil hardness of HB or more, preferably HB to 3H, more preferably H to 3H, and even more preferably 2H to 3H.
• the pencil hardness of the high-hardness resin layer is a result of evaluation by a pencil scratch hardness test conforming to JIS K 5600-5-4:1999. Specifically, a pencil is pressed against the surface of the high-hardness resin layer at an angle of 45 degrees and a load of 750 g, with gradually increasing hardness, and the hardness of the hardest pencil that does not cause a scratch is evaluated as the pencil hardness.
• the high-hardness resin is not particularly limited, but preferably includes at least one selected from the group consisting of resins (B1) to (B6). Note that resins (B1) to (B6) may be referred to as resins (B1) to (B6) even in the case of a resin composition containing multiple types of resins.
• 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 resin (B1) (copolymer resin) may further have other structural units.
• the total ratio of the (meth)acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is 90 to 100 mol %, preferably 95 to 100 mol %, and more preferably 98 to 100 mol % of the total structural units of the copolymer resin.
• the ratio of the (meth)acrylic acid ester structural unit (a) is 65 to 80 mol % of the total structural units of the copolymer resin.
• (meth)acrylic refers to methacrylic and/or acrylic.
• R 1 is a hydrogen atom or a methyl group, and is preferably a methyl group.
• R2 is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group, and an isobornyl group. Of these, R2 is preferably a methyl group or an ethyl group, and more preferably a methyl group.
• the (meth)acrylic acid ester structural unit (a) represented by general formula (1) is a (meth)acrylic acid ester structural unit
• the (meth)acrylic acid ester structural unit (a) represented by general formula (1) is a methyl methacrylate structural unit
• the (meth)acrylic acid ester structural unit (a) represented by general formula (1) may be contained in the resin (B1) in one type or in two or more types.
• R3 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
• R4 is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms, and is preferably an unsubstituted cyclohexyl group.
• the "hydrocarbon group” may be linear, branched, or cyclic, and may have a substituent.
• the aliphatic vinyl structural unit (b) represented by general formula (2) is a vinylcyclohexane structural unit.
• the aliphatic vinyl structural unit (b) represented by general formula (2) may be contained in resin (B1) in one type or in two or more types.
• the other structural units are not particularly limited, but examples thereof include structural units derived from aromatic vinyl monomers containing unhydrogenated aromatic double bonds, which are generated in the process of producing resin (B1) by polymerizing a (meth)acrylic acid ester monomer and an aromatic vinyl monomer and then hydrogenating the aromatic double bonds derived from the aromatic vinyl monomer.
• a specific example of the other structural unit is a styrene structural unit.
• the other structural units may be contained in resin (B1) in one type or in two or more types.
• the content of the (meth)acrylic acid ester structural unit (a) represented by general formula (1) is 65 to 80 mol %, and preferably 70 to 80 mol %, based on the total structural units of the resin (B1) (copolymer resin).
• the content of the (meth)acrylic acid ester structural unit (a) is 65 mol % or more, a high-hardness resin layer having excellent adhesion to the base layer and surface hardness can be obtained.
• the content of the (meth)acrylic acid ester structural unit (a) is 80 mol % or less, warping due to water absorption of the antiglare laminate is less likely to occur, which is preferable.
• the content of the aliphatic vinyl structural unit (b) represented by general formula (2) is preferably 20 to 35 mol %, and more preferably 20 to 30 mol %, based on the total structural units of the resin (B1) (copolymer resin).
• a content of the aliphatic vinyl structural unit (b) of 20 mol % or more is preferable because it can prevent warping under high temperature and high humidity conditions.
• a content of the aliphatic vinyl structural unit (b) of 35 mol % or less is preferable because it can prevent peeling at the interface with the base layer.
• the content of the other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less, based on the total structural units of resin (B1) (copolymer).
• copolymer may be any of a random, block, and alternating copolymer structure.
• the weight average molecular weight of resin (B1) is not particularly limited, but from the viewpoint of strength and moldability, it is preferably 50,000 to 400,000, and more preferably 70,000 to 300,000.
• the glass transition temperature of resin (B1) is preferably 110 to 140°C, more preferably 110 to 135°C, and particularly preferably 110 to 130°C.
• a glass transition temperature of 110°C or higher is preferred because the resin sheet is less likely to deform or crack in a hot or humid heat environment.
• a glass transition temperature of 140°C or lower is preferred because it provides excellent processability when molded by continuous thermal shaping using a mirror roll or a shaping roll, or batch-type thermal shaping using a mirror mold or a shaping mold.
• the glass transition temperature in the present invention is the temperature measured using a differential scanning calorimeter with a 10 mg sample at a heating rate of 10°C/min and calculated by the midpoint method.
• resin (B1) examples include Optimus 7500 and 6000 (manufactured by Mitsubishi Gas Chemical).
• the above-mentioned resin (B1) may be used alone or in combination of two or more kinds.
• the method for producing resin (B1) is not particularly limited, but it is preferable to use a resin obtained by polymerizing at least one type of (meth)acrylic acid ester monomer and at least one type of aromatic vinyl monomer, and then hydrogenating the aromatic double bonds derived from the aromatic vinyl monomer.
• the aromatic vinyl monomer is not particularly limited, but examples include styrene, ⁇ -methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, it is preferable that the aromatic vinyl monomer is styrene.
• a known method can be used to polymerize the (meth)acrylic acid ester monomer and the aromatic vinyl monomer.
• it can be produced by a bulk polymerization method or a solution polymerization method.
• the bulk polymerization method is carried out by continuously supplying a monomer composition containing the above-mentioned monomers and a polymerization initiator to a complete mixing tank and polymerizing continuously at 100 to 180°C.
• the above-mentioned monomer composition may contain a chain transfer agent as necessary.
• the polymerization initiator is not particularly limited, but examples thereof include organic peroxides such as t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, t-hexylpropoxyisopropyl monocarbonate, t-amylperoxy normal octoate, t-butylperoxyisopropyl monocarbonate, and di-t-butyl peroxide, and azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2,4-dimethylval
• the chain transfer agent is not particularly limited, but may be ⁇ -methylstyrene dimer.
• Solvents used in solution polymerization include, for example, hydrocarbon solvents such as toluene, xylene, cyclohexane, and methylcyclohexane; ester solvents such as ethyl acetate and methyl isobutyrate; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; and alcohol solvents such as methanol and isopropanol. These solvents may be used alone or in combination of two or more.
• hydrocarbon solvents such as toluene, xylene, cyclohexane, and methylcyclohexane
• ester solvents such as ethyl acetate and methyl isobutyrate
• ketone solvents such as acetone and methyl ethyl ketone
• ether solvents such as tetrahydrofuran and dioxane
• the solvent used in the hydrogenation reaction after polymerization of the (meth)acrylic acid ester monomer and the aromatic vinyl monomer may be the same as or different from the polymerization solvent described above.
• Examples include hydrocarbon solvents such as cyclohexane and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran and dioxane, and alcohol solvents such as methanol and isopropanol.
• resin (B1) After polymerizing the (meth)acrylic acid ester monomer and the aromatic vinyl monomer as described above, the aromatic double bond derived from the aromatic vinyl monomer is hydrogenated to obtain resin (B1).
• the hydrogenation method is not particularly limited, and known methods can be used.
• the hydrogenation can be carried out in a batch or continuous flow manner at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250°C.
• a reaction temperature of 60°C or higher is preferred because the reaction time is not too long.
• a reaction temperature of 250°C or lower is preferred because side reactions such as scission of molecular chains and hydrogenation of ester moieties do not occur or occur very little.
• Catalysts used in hydrogenation reactions include, for example, solid catalysts in which metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium, or oxides, salts, or complex compounds of these metals are supported on porous carriers such as carbon, alumina, silica, silica-alumina, and diatomaceous earth.
• the unhydrogenated rate of the aromatic double bonds contained in the structural units derived from the aromatic vinyl monomer is preferably less than 30%, more preferably less than 10%, and even more preferably less than 5%. If the unhydrogenated rate is less than 30%, it is possible to obtain a resin with excellent transparency, which is preferable.
• the structural units of the unhydrogenated portion can be other structural units in the resin (B1).
• the resin (B1) can be blended with other resins as long as the transparency is not impaired.
• the resin (B1) is a resin composition containing the above-mentioned copolymer and other resins.
• the other resins include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co)polymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, various elastomers, etc.
• Resin (B2) contains 35 to 65 mass%, preferably 40 to 60 mass%, of resin (B1) and 35 to 65 mass%, preferably 40 to 60 mass%, of styrene-unsaturated dicarboxylic acid copolymer (C).
• the styrene-unsaturated dicarboxylic acid copolymer (C) contains 65 to 90 mass% of styrene structural unit (c1) and 10 to 35 mass% of unsaturated dicarboxylic anhydride structural unit (c2). That is, resin (B2) is a resin composition containing two or more resins.
• the resin (B1) may be any of the above-mentioned resins. In this case, the resin (B1) may be used alone or in combination of two or more kinds.
• the styrene-unsaturated dicarboxylic acid copolymer (C) contains a styrene structural unit (c1) and an unsaturated dicarboxylic acid anhydride structural unit (c2).
• the styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used. Specific examples of the styrene-based monomer include styrene, a-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and t-butylstyrene. Among these, styrene is particularly preferred from the viewpoint of compatibility. These styrene-based monomers may be used alone or in combination of two or more.
• the content of the styrene-based structural unit (c1) is 65 to 90% by mass, preferably 70 to 85% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid-based copolymer (C).
• Unsaturated dicarboxylic acid anhydride structural unit (c2) The unsaturated dicarboxylic anhydride monomer is not particularly limited, and examples thereof include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Among these, maleic anhydride is preferred from the viewpoint of compatibility with styrene-based monomers. These unsaturated dicarboxylic anhydride monomers may be used alone or in combination of two or more.
• the content of the unsaturated dicarboxylic anhydride structural unit (c2) is 10 to 35% by mass, preferably 15 to 30% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid copolymer (C).
• styrene-unsaturated dicarboxylic acid copolymers (C) include XIBOND140, XIBOND160, XIRAN SO23110, and XIRAN SO26080 (manufactured by Polyscope). These styrene-unsaturated dicarboxylic acid copolymers (C) may be used alone or in combination of two or more.
• Resin (B3) contains 55 to 10 mass% of resin (D) containing a vinyl monomer, and 45 to 90 mass% of styrene-unsaturated dicarboxylic acid copolymer (E).
• the styrene-unsaturated dicarboxylic acid copolymer (E) contains 50 to 80 mass% of styrene structural unit (e1), 10 to 30 mass% of unsaturated dicarboxylic acid structural unit (e2), and 5 to 30 mass% of vinyl structural unit (e3). That is, resin (B3) is a resin composition containing two or more resins.
• Resin containing vinyl monomer (D) The resin (D) containing a vinyl monomer is not particularly limited, and examples thereof include a homopolymer of a vinyl monomer such as acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate.
• the resin (D) containing a vinyl monomer preferably contains methyl methacrylate as a constituent unit.
• the resin (D) containing a vinyl monomer may be a polymer using one type of the constituent unit, or a copolymer using two or more types in combination.
• the weight average molecular weight of the resin (D) containing a vinyl monomer is preferably 10,000 to 500,000, and more preferably 50,000 to 300,000.
• the above-mentioned vinyl monomer-containing resin (D) may be used alone or in combination of two or more kinds.
• the styrene-unsaturated dicarboxylic acid copolymer (E) contains a styrene structural unit (e1), an unsaturated dicarboxylic anhydride structural unit (e2), and a vinyl structural unit (e3).
• the styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used. Specific examples of the styrene-based monomer include styrene, a-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and t-butylstyrene. Among these, styrene is particularly preferred from the viewpoint of compatibility. These styrene-based monomers may be used alone or in combination of two or more.
• the content of the styrene-based structural unit (e1) is 50 to 80% by mass, and preferably 50 to 75% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid-based copolymer (E).
• Unsaturated dicarboxylic acid anhydride structural unit (e2) The unsaturated dicarboxylic anhydride monomer is not particularly limited, and examples thereof include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Among these, maleic anhydride is preferred from the viewpoint of compatibility with vinyl monomers. These unsaturated dicarboxylic anhydride monomers may be used alone or in combination of two or more.
• the content of the unsaturated dicarboxylic anhydride structural unit (e2) is 10 to 30% by mass, preferably 10 to 25% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid copolymer (E).
• the vinyl monomer is not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate.
• methyl methacrylate (MMA) is preferred from the viewpoint of compatibility with the resin (D) containing the vinyl monomer.
• These vinyl monomers may be used alone or in combination of two or more.
• the content of the vinyl structural unit (e3) is 5 to 30% by mass, preferably 7 to 27% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid copolymer (E).
• the weight-average molecular weight of the styrene-unsaturated dicarboxylic acid copolymer (E) is preferably 50,000 to 200,000, and more preferably 80,000 to 200,000. If the weight-average molecular weight is within the above range, it is preferable because it has good compatibility with the resin (D) containing a vinyl monomer and is excellent in improving heat resistance.
• styrene-unsaturated dicarboxylic acid copolymers (E) include, but are not limited to, Resify R100, R200, and R310 (manufactured by Denki Kagaku Kogyo Co., Ltd.) and Delpet 980N (manufactured by Asahi Kasei Co., Ltd.).
• the above-mentioned styrene-unsaturated dicarboxylic acid copolymers (E) may be used alone or in combination of two or more kinds.
• the resin (B4) is a resin copolymer (G) containing 5 to 20 mass% of styrene constituent units, 60 to 90 mass% of (meth)acrylic acid ester constituent units, and 5 to 20 mass% of N-substituted maleimide constituent units, or an alloy of the resin copolymer (G) and a styrene-unsaturated dicarboxylic acid copolymer (E).
• Resin copolymer (G) contains a styrene structural unit, a (meth)acrylic acid ester structural unit, and an N-substituted maleimide structural unit.
• the styrene monomer is not particularly limited, and any known styrene monomer can be used. Specific examples of the styrene monomer include styrene, a-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and t-butylstyrene. Among these, styrene is particularly preferred from the viewpoint of compatibility. These styrene monomers may be used alone or in combination of two or more.
• the content of styrene structural units is 5 to 20 mass %, preferably 5 to 15 mass %, and more preferably 5 to 10 mass %, relative to the total mass of resin (B4) (resin copolymer (G)).
• the (meth)acrylic acid ester monomer is not particularly limited, and examples thereof include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, etc. Of these, methyl methacrylate is preferred.
• These (meth)acrylic acid ester monomers may be used alone or in combination of two or more.
• the content of the (meth)acrylic acid ester structural unit is 60 to 90 mass %, preferably 70 to 90 mass %, and more preferably 80 to 90 mass %, based on the total mass of the resin (B4) (resin copolymer (G)).
• N-Substituted Maleimide Structural Unit The N-substituted maleimide monomer is not particularly limited, and examples thereof include N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide.
• N-phenylmaleimide is preferred from the viewpoint of compatibility with the (meth)acrylic acid structural unit.
• These N-substituted maleimide monomers may be used alone or in combination of two or more.
• the content of the N-substituted maleimide structural units is 5 to 20% by mass, preferably 5 to 15% by mass, and more preferably 5 to 10% by mass, relative to the total mass of the resin (B4) (resin copolymer (G)).
• the weight average molecular weight of the resin copolymer (G) is preferably 50,000 to 250,000, and more preferably 100,000 to 200,000.
• resin copolymer (G) examples include, but are not limited to, Delpet PM120N (manufactured by Asahi Kasei Chemical Corporation).
• the method for producing the resin copolymer (G) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, etc.
• the alloy is an alloy of the resin copolymer (G) and the styrene-unsaturated dicarboxylic acid copolymer (E). In this case, it is preferable that the resin copolymer (G) and the styrene-unsaturated dicarboxylic acid copolymer (E) are alloyed together so as to have a high glass transition temperature.
• the method for producing the alloy is not particularly limited, but examples include a method in which the alloy is melt-kneaded at a cylinder temperature of 240°C using a twin-screw extruder with a screw diameter of 26 mm, extruded into strands, and pelletized using a pelletizer.
• Resin (B5) contains a structural unit (H) represented by the following formula (3).
• Resin (B5) is preferably a copolymer further containing a structural unit (J) represented by the following formula (4).
• the copolymer may further contain other structural units.
• the content of the structural unit (H) represented by formula (3) is preferably 50 to 100 mol %, more preferably 60 to 100 mol %, and even more preferably 70 to 100 mol %, relative to all structural units of the resin (B5).
• the content of the structural unit (J) represented by formula (4) is preferably 0 to 50 mol %, more preferably 0 to 40 mol %, and even more preferably 0 to 30 mol %, relative to all structural units of the resin (B5).
• the content of other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less, relative to the total structural units of resin (B5).
• the total content of the structural units (H) and (J) is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, and even more preferably 98 to 100 mol %, based on all structural units of the resin (B5).
• the weight average molecular weight of resin (B5) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and particularly preferably 25,000 to 65,000.
• resin (B5) examples include, but are not limited to, Iupilon KH3410UR, KH3520UR, and KS3410UR (manufactured by Mitsubishi Engineering Plastics Corporation).
• the above-mentioned resin (B5) may be used alone or in combination of two or more types.
• the method for producing resin (B5) is not particularly limited, but it can be produced in the same manner as the method for producing polycarbonate resin (a1) described above, except that bisphenol C is used as the monomer.
• Resin (B6) contains 35 to 65 mass% of resin (D) containing a vinyl monomer, and 35 to 65 mass% of styrene-unsaturated dicarboxylic acid copolymer (C).
• the styrene-unsaturated dicarboxylic acid copolymer (C) contains 65 to 90 mass% of styrene structural units (c1) and 10 to 35 mass% of unsaturated dicarboxylic anhydride structural units (c2). That is, resin (B6) is a resin composition containing two or more resins.
• Resin containing vinyl monomer (D) The vinyl monomer-containing resin (D) may be the same as that described for the resin (B3) above.
• the vinyl monomer-containing resin (D) may be used alone or in combination of two or more kinds.
• the styrene-unsaturated dicarboxylic acid copolymer (C) may be the same as that described for the resin (B2) above.
• the styrene-unsaturated dicarboxylic acid copolymer (C) may be used alone or in combination of two or more kinds.
• the high-hardness resin layer may contain an additive.
• the additives are not particularly limited, and may be those that are commonly used in antiglare laminates.Specific examples include antioxidants, anticoloring agents, antistatic agents, release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, and reinforcing materials such as organic fillers and inorganic fillers.
• the amount of additive is preferably 0 to 10% by mass, more preferably 0 to 7% by mass, and particularly preferably 0 to 5% by mass, relative to the total mass of the high-hardness resin layer.
• the method for mixing the additives and resin is not particularly limited, and methods such as compounding the entire amount, dry blending the master batch, and dry blending the entire amount can be used.
• 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.
• the thickness of the high-hardness resin layer is 10 ⁇ m or more, the surface hardness is increased, which is preferable.
• the thickness of the high-hardness resin layer is 250 ⁇ m or less, the impact resistance is increased, which is preferable.
• the total thickness of the base layer and the high-hardness resin layer is preferably 100 to 3500 ⁇ m, more preferably 100 to 3000 ⁇ m, even more preferably 500 to 3000 ⁇ m, and particularly preferably 1200 to 3000 ⁇ m.
• a total thickness of 100 ⁇ m or more is preferable because it allows the rigidity of the sheet to be maintained.
• a total thickness of 3500 ⁇ m or less is preferable because it prevents the sensitivity of the touch sensor from deteriorating when a touch panel is installed under the sheet, for example.
• the ratio of the thickness of the base layer to the total thickness of the base layer and the high-hardness resin layer is preferably 75% to 99%, more preferably 80% to 99%, and particularly preferably 85% to 99%. By keeping it in the above range, both hardness and impact resistance can be achieved.
• the method of laminating the high-hardness resin layer onto the base layer is not particularly limited, and examples thereof include a method of overlapping a base layer and a high-hardness resin layer that have been formed separately and heating and pressing them together; a method of overlapping a base layer and a high-hardness resin layer that have been formed separately and bonding them together with an adhesive; a method of co-extrusion molding the base layer and the high-hardness resin layer; and a method of in-mold molding the base layer into a previously formed high-hardness resin layer to integrate them.
• the co-extrusion molding method is preferred from the standpoint of manufacturing costs and productivity.
• the co-extrusion method is not particularly limited.
• a high-hardness resin layer is placed on one side of a base layer in a feed block, extruded into a sheet using a T-die, and then cooled while passing through a forming roll to form the desired laminate.
• a high-hardness resin layer is placed on one side of a base layer in a multi-manifold die, extruded into a sheet, and then cooled while passing through a forming roll to form the desired laminate.
• the hard coat layer is not particularly limited, but is preferably an acrylic hard coat.
• the term "acrylic hard coat” refers to a coating film formed by polymerizing a monomer, oligomer, or prepolymer containing a (meth)acryloyl group as a polymerizable group to form a crosslinked structure.
• the hard coat layer may further contain a UV absorber.
• the hard coat layer preferably does not contain organic particles or inorganic particles. By not containing organic particles or inorganic particles, scratch resistance can be improved. As described below, the anti-glare treatment of the hard coat layer can be performed by transfer using a mold, thereby forming a hard coat layer having an uneven shape without containing organic particles or inorganic particles.
• the content of the (meth)acrylic monomer is preferably 2 to 98% by mass, more preferably 5 to 50% by mass, and even more preferably 20 to 40% by mass, based on the total mass of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier.
• the content of the (meth)acrylic oligomer is preferably 2 to 98% by mass, more preferably 50 to 95% by mass, and even more preferably 60 to 80% by mass, based on the total mass of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier.
• the content of the surface modifier is preferably 0 to 15 mass % relative to the total mass of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier, more preferably 1 to 10 mass %, and even more preferably 2 to 5 mass %.
• the content of the photopolymerization initiator is preferably 0.001 to 7 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total of the (meth)acrylic monomer, (meth)acrylic oligomer, and surface modifier.
• the photopolymerization initiator refers to a photoradical generator.
• any monomer having a (meth)acryloyl group as a functional group in the molecule can be used, specifically, a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher functional monomer.
• monofunctional monomers include (meth)acrylic acid and (meth)acrylic acid esters.
• bifunctional and/or trifunctional or higher (meth)acrylic monomers include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, polyethylene glycol
• Examples include ethylene glycol diacrylate, 1,4-butanediol oligoacrylate, neopentyl glycol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane propoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glyceryl propoxy tri(meth)acrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, and pentaerythritol tetraacrylate.
• the hard coat layer may contain one or more types of (meth)acrylic monomers.
• Examples of the (meth)acrylic oligomer include difunctional or higher polyfunctional urethane (meth)acrylate oligomers (hereinafter also referred to as “polyfunctional urethane (meth)acrylate oligomers”), difunctional or higher polyfunctional polyester (meth)acrylate oligomers (hereinafter also referred to as “polyfunctional polyester (meth)acrylate oligomers”), difunctional or higher polyfunctional epoxy (meth)acrylate oligomers (hereinafter also referred to as "polyfunctional epoxy (meth)acrylate oligomers”).
• polyfunctional urethane (meth)acrylate oligomers difunctional or higher polyfunctional polyester (meth)acrylate oligomers
• polyfunctional polyester (meth)acrylate oligomers difunctional or higher polyfunctional epoxy (meth)acrylate oligomers
• the polyfunctional urethane (meth)acrylate oligomer may be a urethane reaction product of a (meth)acrylate monomer having at least one (meth)acryloyloxy group and hydroxyl group in one molecule with a polyisocyanate; a urethane reaction product of an isocyanate compound obtained by reacting a polyol with a polyisocyanate with a (meth)acrylate monomer having at least one (meth)acryloyloxy group and hydroxyl group in one molecule; etc.
• (Meth)acrylate monomers having at least one (meth)acryloyloxy group and one hydroxyl group per molecule that are used in the urethane reaction include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.
• Polyisocyanates used in the urethane reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these isocyanates (e.g., diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate), di- or tri-polyisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, and polyisocyanates obtained by polymerizing diisocyanates.
• diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate
• di- or tri-polyisocyanates such as triphenylmethane triisocyanate and dim
• Polyols used in urethane reactions generally include aromatic, aliphatic and alicyclic polyols, as well as polyester polyols and polyether polyols.
• Typical aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerin, and hydrogenated bisphenol A.
• Polyester polyols include those obtained by a dehydration condensation reaction between the above-mentioned polyols and polycarboxylic acid.
• polycarboxylic acid compounds include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides.
• Polyether polyols include polyalkylene glycols, as well as polyoxyalkylene-modified polyols obtained by reacting the above-mentioned polyols or 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.
• polycarboxylic acids used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides.
• polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.
• the polyfunctional epoxy (meth)acrylate oligomer is obtained by an addition reaction between a polyglycidyl ether and (meth)acrylic acid.
• polyglycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.
• the hard coat layer may contain one or more types of (meth)acrylic oligomers.
• the surface modifier is an agent that changes the surface performance of the hard coat layer, such as a leveling agent, an antistatic agent, a surfactant, a water- and oil-repellent agent, inorganic particles, or organic particles.
• leveling agent examples include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyester-modified hydroxyl-containing polyalkylsiloxane, polyether-modified polydimethylsiloxane with alkyl groups, 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 surfactants, and anionic surfactants.
• the surfactants and water/oil repellents include, for example, fluorine-containing surfactants and water/oil repellents, such as oligomers containing fluorine-containing groups and lipophilic groups, and oligomers containing fluorine-containing groups, hydrophilic groups, lipophilic groups, and UV-reactive groups.
• fluorine-containing surfactants and water/oil repellents such as oligomers containing fluorine-containing groups and lipophilic groups, and oligomers containing fluorine-containing groups, hydrophilic groups, lipophilic groups, and UV-reactive groups.
• examples of the inorganic particles include silica particles, alumina particles, zirconia particles, silver particles, and glass particles.
• organic particles examples include acrylic particles and silicone particles.
• the hard coat layer may contain one or more types of surface modifiers.
• photopolymerization initiator examples include monofunctional photopolymerization initiators. Specific examples include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone [Darocure 2959: manufactured by Merck]; ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone [Darocure 1173: manufactured by Merck]; acetophenone-based initiators such as methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651], and 1-hydroxy-cyclohexylphenyl ketone; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; and other halogenated ketones, acylphosphinoxides, and acylphosphonates. These photopolymerization initiators may be used alone or in combination of two or more.
• UV absorbent examples include hydroxyphenyltriazines, benzotriazoles, and benzophenones.
• the UV absorbents may be used alone or in combination of two or more.
• the thickness of the hard coat layer is preferably 1 to 40 ⁇ m, and more preferably 2 to 10 ⁇ m.
• a hard coat layer having a thickness of 1 ⁇ m or more is preferable because sufficient hardness can be obtained.
• a hard coat layer having a thickness of 40 ⁇ m or less is preferable because the occurrence of cracks during bending can be suppressed.
• the thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and measuring from the coating interface to the surface.
• the pencil hardness of the hard coat layer surface is preferably HB or higher, more preferably H or higher, even more preferably 2H or higher, and particularly preferably 2H to 3H.
• the pencil hardness of the hard coat layer is the result of evaluation in a pencil scratch hardness test conforming to JIS K 5600-5-4:1999. Specifically, pencils of gradually increasing hardness were pressed against the surface of the hard coat layer at an angle of 45 degrees and with a load of 750 g, and the hardness of the hardest pencil that did not leave a scratch was evaluated as the pencil hardness.
• the hard coat layer has an uneven shape, which makes it possible to obtain an antiglare laminate that has excellent antiglare properties and a pleasant feel to the touch.
• the hard coat layer has a root-mean-square gradient (Sdq) and a root-mean-square height (Sq) that satisfy the following formulas (i) and (ii), respectively.
• the root-mean-square gradient (Sdq) and the root-mean-square height (Sq) are measured in accordance with ISO 25178-2:2012, as described in the examples described later.
• the root mean square gradient (Sdq) is an index of antiglare properties and is correlated with haze. If Sdq exceeds 0.10, excessive light scattering will cause whitening and a poor texture. It is more preferable that formula (i) satisfies 0.020 ⁇ Sdq ⁇ 0.08, even more preferable that it satisfies 0.030 ⁇ Sdq ⁇ 0.07, and particularly preferable that it satisfies 0.035 ⁇ Sdq ⁇ 0.06.
• the root mean square height (Sq) is an index of antiglare properties and is correlated with image clarity. If Sq exceeds 0.40, excessive light scattering will cause whitening and a deterioration in texture. It is more preferable that formula (ii) satisfies 0.050 ⁇ Sq ⁇ 0.38, even more preferable that it satisfies 0.10 ⁇ Sq ⁇ 0.37, and particularly preferable that it satisfies 0.20 ⁇ Sq ⁇ 0.35.
• the haze of the hard coat layer of the antiglare laminate of the present invention is preferably 30% or less, more preferably 25% or less, even more preferably 22% or less, and particularly preferably 21%.
• the haze is a value measured in accordance with JIS K 7136:2000 using HR-100 type (manufactured by Murakami Color Research Laboratory).
• ⁇ Image clarity> As an evaluation method for image reflection, there is the image clarity of reflection measured at a light incidence angle of 60° based on JIS K 7374.
• the optical comb widths are 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm. A narrower optical comb width results in a larger variation in values, whereas a wider optical comb width results in a smaller variation in values. Therefore, the optical comb width is preferably 2.0 mm.
• the reflection clarity measured at a light incidence angle of 60° indicates that the larger the value, the easier it is for an image to be reflected, and the smaller the value, the less likely it is for an image to be reflected. In the present invention, the reflection clarity can be measured by the method described in the examples below.
• the uneven shape of the present invention preferably has a reflection clarity of 15% or more, more preferably 40% or more, and particularly preferably 50% or more, measured at a light incidence angle of 60° using a 2.0 mm wide optical comb.
• the method for forming the hard coat layer is not particularly limited.
• the hard coat layer can be formed by applying a hard coat liquid onto a layer (e.g., a high-hardness resin layer) located below the hard coat layer, and then photopolymerizing the hard coat liquid.
• the method for applying the hard coat liquid is not particularly limited, and any known method can be used. Examples include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, beat coating, and the like.
• the lamps used for light irradiation in photopolymerization have an emission distribution with a light wavelength of 420 nm or less.
• Examples include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, extra high pressure mercury lamps, chemical lamps, black light lamps, microwave excited mercury lamps, and metal halide lamps.
• high pressure mercury lamps and metal halide lamps are preferred because they efficiently emit light in the active wavelength range of the photopolymerization initiator and do not emit much short wavelength light that reduces the viscoelastic properties of the resulting polymer through crosslinking, or long wavelength light that heats and evaporates the reaction composition.
• the irradiation intensity of the lamp is a factor that determines the degree of polymerization of the resulting 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/ cm2 .
• the photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to perform light irradiation using a method that can eliminate reaction inhibition caused by oxygen.
• One such method is to cover the reactive composition with a film made of polyethylene terephthalate or Teflon to prevent contact with oxygen, and irradiate the reactive composition with light through the film.
• the reactive composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen has been replaced with an inert gas such as nitrogen gas or carbon dioxide gas.
• the airflow velocity of the inert gas is preferably 1 m/sec or less, and more preferably 0.1 m/sec or less, relative to the laminate coated with the hard coat liquid moving under the inert gas atmosphere.
• the coating surface may be pretreated.
• treatments include known methods such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment using a resin composition.
• a method using a mold is preferred.
• a high-hardness resin layer, a coating film obtained by applying a reactive composition, and a mold are first laminated in that order.
• the reactive composition is then photopolymerized, and the mold is removed.
• the photopolymer of the reactive composition (hard coat layer) will have a shape that reflects the rough surface of the mold at the surface that comes into contact with the mold.
• this method involves performing anti-glare treatment of the hard coat layer by transfer using a mold.
• the mold is not particularly limited as long as it transmits UV light, and glass, transparent resin, etc. are used.
• the mold is a mold in which a transparent film and a transparent resin having a rough surface are laminated.
• the transparent film is PET film.
• the transparent resin having a rough surface is acrylic resin, etc.
• the rough surface of the transparent resin is not particularly limited, and may be formed by adding particles (organic particles, inorganic particles, etc.) to the transparent resin, may be formed by etching the transparent resin, or may be formed by printing and curing the transparent resin.
• the shape of the rough surface is not particularly limited, but from the viewpoint of use in applications such as liquid crystal panels, it is preferable that it is a pattern.
• the surface (uneven shape) of the hard coat layer can be controlled by controlling the type of mold used (material, surface haze, thickness, shape, etc.), the amount of particles added, etc., and the like. This makes it possible to form a hard coat layer that satisfies the above-mentioned formulas (i) to (ii). In addition, it is preferable to form a hard coat layer that further satisfies the above-mentioned formulas (iii) to (iv).
• the manufacturing method includes a step of pressing a patterned PET film onto the surface of the hard coat layer to transfer the uneven shape.
• the patterned PET film for example, PF11 or PF23, a low glare AG film manufactured by Daicel, can be used.
• a patterned PET film can be produced by applying a coating liquid to a PET (polyethylene terephthalate) film so that the dry film thickness is 1.0 to 4.0 ⁇ m, drying at 70 to 90° C. for 1 to 3 minutes, and then curing by irradiating with ultraviolet light at a line speed of 1.0 to 3.0 m/min using a conveyor equipped with a high-pressure mercury lamp having a light source distance of 12 cm and an output of 80 W/cm.
• a coating liquid to a PET (polyethylene terephthalate) film so that the dry film thickness is 1.0 to 4.0 ⁇ m, drying at 70 to 90° C. for 1 to 3 minutes, and then curing by irradiating with ultraviolet light at a line speed of 1.0 to 3.0 m/min using a conveyor equipped with a high-pressure mercury lamp having a light source distance of 12 cm and an output of 80 W/cm.
• the coating liquid preferably contains an organic solvent such as methyl ethyl ketone (MEK), an acrylic ultraviolet-curable resin, silica fine particles, and a photoinitiator.
• the content of these components is preferably 70 to 80 parts by mass of the organic solvent such as methyl ethyl ketone (MEK), 19 to 29 parts by mass of the acrylic ultraviolet-curable resin, 0.2 to 1.0 parts by mass of silica fine particles (average particle size 3.5 to 5.0 ⁇ m), and 2.0 to 4.0 parts by mass of the photoinitiator.
• MEK methyl ethyl ketone
• silica fine particles average particle size 3.5 to 5.0 ⁇ m
• the antiglare laminate preferably has high shape stability.
• the change in warp after 120 hours of storage in an environment of 85° C. and 85% relative humidity is preferably 350 ⁇ m or less, more preferably 250 ⁇ m or less, even more preferably 175 ⁇ m or less, and particularly preferably 75 ⁇ m or less. If the change in warp is 350 ⁇ m or less, it is preferable because it can be used suitably even in a high-temperature and high-humidity environment.
• High shape stability can be obtained by using a high-hardness resin layer.
• Shape stability can also be controlled by appropriately changing the material of the substrate layer and the hard coat layer, the difference in glass transition temperature (Tg) between the substrate layer and the high-hardness resin layer, the difference in hardness, the difference in glass transition temperature (Tg) between the high-hardness resin layer and the hard coat layer, the difference in hardness, etc.
• the antiglare laminate of the present invention is excellent in antiglare properties and tactile feel, and is therefore used as a protective plate or front panel for a liquid crystal surface, as described above.
• an in-vehicle display device including the antiglare laminate is provided.
• a touch panel front protective plate including the antiglare laminate is provided.
• a front panel for an office automation device, a portable electronic device, or a television is provided.
• ⁇ HAZE> The haze was calculated using "HM-150N” manufactured by Murakami Color Research Laboratory according to the method defined in JIS K 7136:2000.
• ⁇ SW hardness> The hard coat layer having a concave-convex shape of the antiglare laminate was subjected to 15 round trips of steel wool #0000 manufactured by Japan Steel Wool Co., Ltd. at a load of 100 g/ cm2 , and the degree of damage was visually observed and evaluated on a 10-point scale. The results were ranked from RANK 1 to RANK 10. The measurement was performed twice, and if the results differed, the range was used as the measurement result.
• Rank 1 No scratches (same as inorganic glass)
• RANK 2 1-5 scratches
• RANK 3 6-10 scratches
• RANK 4 11-15 scratches
• RANK 5 16-20 scratches
• RANK 6 21-25 scratches
• RANK 7 26-30 scratches
• RANK 8 31-40 scratches
• RANK 9 41-50 scratches (equivalent to polymethacrylic acid)
• Rank 10 51 or more scratches (same as polycarbonate)
• a test piece (antiglare laminate) was cut to 100 mm x 60 mm.
• the cut test piece was set on a two-point support holder and placed in an environmental tester set at a temperature of 23% and a relative humidity of 50% for 24 hours or more to condition it, and then the warpage was measured (before treatment).
• the test piece was set on 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.
• the holder was moved into an environmental tester set at a temperature of 23% and a relative humidity of 50%, and after holding in that state for 4 hours, the warpage was measured again (after treatment).
• the warpage was measured using a three-dimensional shape measuring machine (KS-1000 manufactured by KEYENCE) equipped with an electric stage, and the taken-out test piece was placed horizontally in a convex state, scanned at 1 mm intervals, and the swelling in the center was measured as the warpage.
• Example 1 A synthetic resin laminate was formed using a multi-layer extrusion apparatus having a single screw extruder with a shaft diameter of 35 mm, a single screw extruder with a shaft diameter of 65 mm, a feed block connected to all the extruders, and a T-die connected to the feed block.
• Mitsubishi Gas Chemical's Optimas 7500 was continuously introduced as the high hardness resin (B1) into the single screw extruder with 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 Corporation, trade name: Iupilon S-1000
• Iupilon S-1000 polycarbonate resin
• the feed block connected to all the extruders was equipped with a two-type two-layer distribution pin, and the high hardness resin (B1) and polycarbonate resin were introduced and laminated at a temperature of 270 ° C.
• the sheet was extruded into a sheet shape using a T-die connected to the upstream side at a temperature of 270° C., and cooled while transferring a mirror surface using three mirror-finished rolls at temperatures of 120° C., 130° C., and 190° C. from the upstream side, to obtain a laminate of a high-hardness resin (B1) layer (high-hardness resin layer) and a polycarbonate resin layer (substrate layer).
• the thickness of the obtained laminate 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 Chemical Company, used as the high hardness resin (B1), is a copolymer resin containing the (meth)acrylic acid ester structural unit (a) represented by the general formula (1) and the aliphatic vinyl structural unit (b) represented by the general formula (2).
• the total ratio of the (meth)acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is 99 mol% of the total structural units of the copolymer resin
• the ratio of the (meth)acrylic acid ester structural unit (a) is 75 mol% of the total structural units of the copolymer resin.
• U6HA hexafunctional urethane acrylate oligomer, manufactured by Shin-Nakamura Chemical Co., Ltd.
• #260 (1,9-nonanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.
• Coating liquid (i) was prepared by mixing and stirring 18.8 parts by mass of acrylic ultraviolet-curable resin (solid content 100%, product name: Light Acrylate DPE-6A; manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 parts by mass of silica fine particles (NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of photoinitiator (product name Omnirad 184; manufactured by IGM Resins) with external addition, relative to 81 parts by mass of MEK.
• acrylic ultraviolet-curable resin solid content 100%, product name: Light Acrylate DPE-6A; manufactured by Kyoeisha Chemical Co., Ltd.
• silica fine particles NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.
• photoinitiator product name Omnirad 184; manufactured by IGM Resins
• coating liquid (i) was applied to a PET (polyethylene terephthalate) film so as to have a dry film thickness of 1.4 ⁇ m, and after drying at 80 ° C. for 2 minutes, the film was irradiated with ultraviolet light at a line speed of 1.5 m / min on a conveyor equipped with a high-pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm to cure the film, thereby preparing a patterned PET film (Z-1).
• a photocurable resin composition (Y-1) was applied using a bar coater onto the high-hardness resin (B1) layer of a laminate of a high-hardness resin (B1) layer (high-hardness resin layer) and a polycarbonate resin layer (substrate layer) so that the coating thickness after curing would be 5 to 10 ⁇ m, and the patterned PET film (Z-1) was covered and pressed so that the patterned surface of the film was in contact with the coating liquid.
• the film was then cured for 30 seconds by irradiating the film with a metal halide lamp (20 mW/cm) from a light source distance of 12 cm, and the patterned PET film was peeled off to obtain an anti-glare laminate with an uneven hard coat layer on the high-hardness resin layer (B1).
• a metal halide lamp (20 mW/cm) from a light source distance of 12 cm
• Example 2 An antiglare laminate was produced in the same manner as in Example 1, except that the high hardness resin (B3) below was used instead of the high hardness resin (B1).
• the high-hardness resin (B3) was prepared as follows. That is, 75% by mass of Resify R100 (manufactured by Denki Kagaku Kogyo Co., Ltd.) was used as the styrene-unsaturated dicarboxylic acid copolymer (E) and 25% by mass of Parapet HR-L (manufactured by Kuraray Co., Ltd.), a methyl methacrylate resin, was used as the resin (D) containing a vinyl monomer, and mixed in a blender for 30 minutes.
• Resify R100 manufactured by Denki Kagaku Kogyo Co., Ltd.
• Parapet HR-L manufactured by Kuraray Co., Ltd.
• the mixture was melt-kneaded at a cylinder temperature of 230°C, extruded into a strand shape, and pelletized with a pelletizer to obtain the high-hardness resin (B3).
• the pelletization was performed stably.
• Example 3 An antiglare laminate was produced in the same manner as in Example 1, except that the high hardness resin (B6) below was used instead of the high hardness resin (B1).
• the high-hardness resin (B6) was prepared as follows. That is, 50% by mass of XIBOND160 (manufactured by Polyscope) as a styrene-unsaturated dicarboxylic acid copolymer (C) and 50% by mass of Parapet HR-L (manufactured by Kuraray), a methyl methacrylate resin, as a resin (D) containing a vinyl monomer were charged and mixed in a blender for 30 minutes.
• XIBOND160 manufactured by Polyscope
• Parapet HR-L manufactured by Kuraray
• the mixture was melt-kneaded at a cylinder temperature of 230°C, extruded into a strand shape, and pelletized with a pelletizer to obtain a high-hardness resin (B6).
• the pelletization was performed stably.
• Example 4 An antiglare laminate was produced in the same manner as in Example 1, except that the following patterned PET film (Z-2) was used instead of the patterned PET film (Z-1). ⁇ Patterned PET film (Z-2)> A patterned PET film (Z-2) was produced by using the following coating liquid (ii) instead of the coating liquid (i).
• the coating liquid (ii) was prepared by mixing and stirring 85 parts by mass of MEK with 14.9 parts by mass of an acrylic ultraviolet-curable resin (solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.1 parts by mass of silica fine particles (NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad 184; manufactured by IGM Resins) added externally.
• an acrylic ultraviolet-curable resin solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.
• silica fine particles NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.
• 3 parts by mass of a photoinitiator product name Omnirad 184; manufactured by IGM Resins
• Example 5 An antiglare laminate was produced in the same manner as in Example 1, except that the patterned PET film (Z-3) below was used instead of the patterned PET film (Z-1). ⁇ Patterned PET film (Z-3)> A patterned PET film (Z-3) was produced by using the following coating liquid (iii) instead of the coating liquid (i).
• the coating liquid (iii) was prepared by mixing and stirring 76 parts by mass of MEK with 23.8 parts by mass of an acrylic ultraviolet-curable resin (solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 parts by mass of silica fine particles (NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad 184; manufactured by IGM Resins) added externally.
• an acrylic ultraviolet-curable resin solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.
• silica fine particles NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.
• a photoinitiator product name Omnirad 184; manufactured by IGM Resins
• Example 6 An antiglare laminate was produced in the same manner as in Example 1, except that the patterned PET film (Z-4) shown below was used instead of the patterned PET film (Z-1). ⁇ Patterned PET film (Z-4)> A patterned PET film (Z-4) was produced by using the following coating liquid (iv) instead of the coating liquid (i).
• the coating liquid (iv) was prepared by mixing and stirring 71.5 parts by mass of MEK, 27.7 parts by mass of an acrylic ultraviolet-curable resin (solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.8 parts by mass of silica fine particles (NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad 184; manufactured by IGM Resins) added externally.
• an acrylic ultraviolet-curable resin solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.
• silica fine particles NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.
• 3 parts by mass of a photoinitiator product name Omnirad 184; manufactured by IGM Resins
• Example 7 An antiglare laminate was produced in the same manner as in Example 1, except that the patterned PET film (Z-5) shown below was used instead of the patterned PET film (Z-1). ⁇ Patterned PET film (Z-5)> A patterned PET film (Z-5) was produced by using the following coating liquid (v) instead of the coating liquid (i).
• the coating liquid (v) was prepared by mixing and stirring 80 parts by mass of MEK with 19.9 parts by mass of an acrylic ultraviolet-curable resin (solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.1 parts by mass of silica fine particles (NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad 184; manufactured by IGM Resins) added externally.
• an acrylic ultraviolet-curable resin solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.
• silica fine particles NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.
• 3 parts by mass of a photoinitiator product name Omnirad 184; manufactured by IGM Resins
• Example 8 An antiglare laminate was produced in the same manner as in Example 1, except that a methyl methacrylate resin, Parapet HR-L (manufactured by Kuraray, weight average molecular weight: 90,000, pencil hardness: 2H), which is a high hardness resin, was used instead of the high hardness resin (B1).
• a methyl methacrylate resin Parapet HR-L (manufactured by Kuraray, weight average molecular weight: 90,000, pencil hardness: 2H), which is a high hardness resin, was used instead of the high hardness resin (B1).
• Example 1 An antiglare laminate was produced in the same manner as in Example 1, except that the following patterned PET film (Z-6) was used instead of the patterned PET film (Z-1). ⁇ Patterned PET film (Z-6)> A patterned PET film (Z-6) was produced by using the following coating liquid (vi) instead of the coating liquid (i).
• the coating liquid (vi) was prepared by mixing and stirring 90 parts by mass of MEK with 9.5 parts by mass of an acrylic ultraviolet-curable resin (solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.5 parts by mass of silica fine particles (NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad 184; manufactured by IGM Resins) added externally.
• an acrylic ultraviolet-curable resin solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.
• silica fine particles NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.
• a photoinitiator product name Omnirad 184; manufactured by IGM Resins
• Example 2 An antiglare laminate was produced in the same manner as in Example 1, except that the patterned PET film (Z-7) below was used instead of the patterned PET film (Z-1). ⁇ Patterned PET film (Z-7)> A patterned PET film (Z-7) was produced by using the following coating liquid (vii) instead of the coating liquid (i).
• the coating liquid (vii) was prepared by mixing and stirring 90 parts by mass of MEK with 9.8 parts by mass of an acrylic ultraviolet-curable resin (solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 parts by mass of silica fine particles (NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad 184; manufactured by IGM Resins) added externally.
• an acrylic ultraviolet-curable resin solid content 100%, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.
• silica fine particles NP-30, average particle size 4 ⁇ m, manufactured by AGC Si-Tech Co., Ltd.
• 3 parts by mass of a photoinitiator product name Omnirad 184; manufactured by IGM Resins
• Example 3 An antiglare laminate was produced in the same manner as in Example 1, except that the patterned PET film (Z-1) was replaced with Cosmoshine A4295 (Z-8) manufactured by Toyobo Co., Ltd.
• Example 4 An antiglare laminate was produced in the same manner as in Example 1, except that the hard coat layer was formed as follows. That is, 85 parts by mass of MEK was mixed and stirred with 15.7 parts by mass of an acrylic ultraviolet curable resin (100% solids product: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.3 parts by mass of silica fine particles (octylsilane-treated fumed silica, average primary particle size 1.9 ⁇ m, product name: SE6050-SYB, manufactured by Admatechs Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Irgacure 184, manufactured by Toyota Tsusho Chemiplas Co., Ltd.) to prepare a photocurable composition (Y-2).
• an acrylic ultraviolet curable resin (100% solids product: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.
• silica fine particles octylsilane-
• the photocurable composition (Y-2) was applied onto the high-hardness resin layer using a bar coater so that the coating thickness after curing was 1.4 ⁇ m, and then dried for 2 minutes at 80° C.
• the coating was cured by irradiating with a metal halide lamp (20 mW/cm) for 30 seconds at a light source distance of 12 cm while purging with nitrogen, to obtain an antiglare laminate.

Landscapes

• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• General Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Theoretical Computer Science (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Organic Chemistry (AREA)
• Thermal Sciences (AREA)
• Mechanical Engineering (AREA)
• Laminated Bodies (AREA)
• Devices For Indicating Variable Information By Combining Individual Elements (AREA)
• Optical Elements Other Than Lenses (AREA)
• Electroluminescent Light Sources (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=92590619

Family Applications (1)

Country Status (5)

Citations (7)

• 2023
  • 2023-02-27 JP JP2023028588A patent/JP2024121464A/ja active Pending
• 2024
  • 2024-02-22 KR KR1020257013839A patent/KR20250156078A/ko active Pending
  • 2024-02-22 CN CN202480010245.4A patent/CN120615174A/zh active Pending
  • 2024-02-22 EP EP24763771.3A patent/EP4675319A1/en active Pending
  • 2024-02-22 WO PCT/JP2024/006477 patent/WO2024181290A1/ja not_active Ceased

Patent Citations (7)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events