WO2022185815A1 - 積層体およびその製造方法 - Google Patents

積層体およびその製造方法 Download PDF

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Publication number
WO2022185815A1
WO2022185815A1 PCT/JP2022/003844 JP2022003844W WO2022185815A1 WO 2022185815 A1 WO2022185815 A1 WO 2022185815A1 JP 2022003844 W JP2022003844 W JP 2022003844W WO 2022185815 A1 WO2022185815 A1 WO 2022185815A1
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Prior art keywords
laminate
particles
hard coat
layer
resin
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Ceased
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PCT/JP2022/003844
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English (en)
French (fr)
Japanese (ja)
Inventor
花子 長谷部
治規 小山
幸展 嶋本
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Kaneka Corp
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Kaneka Corp
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Publication date
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Priority to CN202280018541.XA priority Critical patent/CN116963907A/zh
Priority to EP22762873.2A priority patent/EP4302996A4/en
Priority to JP2023503644A priority patent/JPWO2022185815A1/ja
Publication of WO2022185815A1 publication Critical patent/WO2022185815A1/ja
Priority to US18/241,465 priority patent/US20230416556A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/18—Homopolymers or copolymers of nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/04—Laminate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2502/00—Acrylic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds

Definitions

  • the present invention relates to a laminate containing an acrylic resin film as a base material and a method for producing the same.
  • Acrylic resin films which are made by processing and molding acrylic resin compositions containing elastic bodies, are used and developed in various applications by taking advantage of their excellent properties such as transparency, hardness, weather resistance, and secondary moldability. It is Applications of acrylic resin films include, for example, automobile interior and exterior parts that are used by laminating films on the three-dimensional surface of a molded body by methods such as thermal lamination, adhesion, in-mold molding, insert molding, and three-dimensional lamination molding. Applications include decoration, protection, and display as an alternative to painting and printing, decoration and protection of the exterior of products such as mobile electronic devices, personal computers, and home appliances, and use as a building material. In addition, taking advantage of the transparency and low inherent retardation characteristics of acrylic resin films, acrylic resin films are also being used as optical film members for various display devices such as liquid crystal panels and organic EL panels.
  • a method for further imparting functionality such as surface hardness, scratch resistance, anti-reflection properties, and anti-glare properties to decorative/protective films including such acrylic resin films, coatings, etc.
  • the method of forming a functional layer is performed by the technique of.
  • an ionizing radiation-curable resin having a pencil hardness of B or higher and an elongation rate indicating moldability of 100% or higher, a fluorine-based leveling agent or a fluorine-based siloxane-based leveling agent, and inorganic oxide fine particles are contained.
  • a molding hard coat film or the like is described which is characterized by providing a hard coat layer formed by coating a coating composition on a film substrate and curing the coating composition.
  • Patent Document 2 discloses a translucent resin base sheet, a base layer formed on the base sheet, a hard coat layer formed on the base layer, and a medium refractive index layer formed on the hard coat layer.
  • a transparent resin substrate comprising a low refractive index layer and a low refractive index layer formed on the medium refractive index layer is disclosed.
  • Patent Document 3 discloses an antireflection film for insert molding in which four layers of a hard coat layer, a medium refractive index layer, a high refractive index layer, and a low refractive index layer are provided in this order on a thermoplastic transparent substrate film. is described.
  • JP 2016-040105 A WO2018/117018 JP 2016-071307 A JP 2015-152691 A JP 2012-189978 A
  • Patent Documents 1 to 3 have sufficient performance from the viewpoint of compatibility between the moldability of the laminate and the functionality of the laminate such as pencil hardness and scratch resistance of the surface of the laminate. That said, there is room for further improvement.
  • an object of one embodiment of the present invention is to provide a laminate containing an acrylic resin film, which has functionality such as surface hardness and antireflection properties and is excellent in formability, and a method for producing the same. be.
  • the present inventors have found that a hard coat layer having specific physical properties can be used in a laminate composed of an acrylic resin film, a hard coat layer, a low refractive index layer, and the like.
  • the present inventors have found for the first time that a laminate having excellent moldability can be obtained by this method, and completed an embodiment of the present invention.
  • a resin layer containing a urethane acrylate resin applied to at least one surface of an acrylic resin film is irradiated with an active energy ray to cure the resin layer containing the urethane acrylate resin.
  • the acrylic resin film has a tensile elongation at break of 170% or more at 120°C
  • the hard coat layer contains a urethane acrylate resin
  • the laminate has a crack elongation of 80 at 120°C. % or more.
  • a resin layer containing a urethane acrylate resin applied to at least one surface of an acrylic resin film is irradiated with an active energy ray to cure the resin layer containing the urethane acrylate resin.
  • forming a hard coat layer wherein the acrylic resin film has a tensile elongation at break of 170% or more at 120° C., and the hard coat layer is made of urethane acrylate resin. and wherein the laminate has a crack elongation of 80% or more at 120°C.
  • one aspect of the present invention is a laminate including an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, wherein the acrylic resin film is heated at 120°C.
  • the tensile elongation at break is 170% or more
  • the hard coat layer contains a urethane acrylate resin
  • the laminate has a pencil hardness of H or more
  • a laminate containing an acrylic resin film which has functionality such as surface hardness and antireflection properties, and which has excellent formability, and a method for producing the same.
  • FIG. 2 is a diagram showing a TEM image after a tensile test of a laminate obtained by laminating an acrylic resin film, a hard coat layer and a low refractive index layer according to one embodiment of the present invention.
  • first method for producing a laminate includes (A1) a urethane acrylate resin applied to at least one side of an acrylic resin film.
  • the acrylic resin film has a tensile elongation at break of 170% or more at 120 ° C.
  • the coat layer contains a urethane acrylate resin, and the laminate has a crack elongation of 80% or more at 120°C.
  • the laminate obtained by the above-described first laminate manufacturing method has surface hardness and is excellent in surface hardness.
  • the surface hardness of the laminate is evaluated by the "pencil hardness” of the laminate.
  • a method for measuring the "pencil hardness” of the laminate will be described in detail later.
  • the laminate obtained by the first method for producing a laminate has antireflection properties and is excellent in antireflection properties.
  • the antireflection property of the laminate is evaluated by the "luminous reflectance" of the laminate.
  • a method for measuring the "luminous reflectance” of the laminate will be described in detail later.
  • the laminate obtained by the first method for producing a laminate has excellent moldability.
  • the moldability of the laminate is evaluated by the "crack elongation at 120°C" of the laminate.
  • a method for measuring the "crack elongation at 120°C” of the laminate will be described in detail later.
  • the laminate obtained by the first method for producing the laminate described above also has excellent scratch resistance. Further, when the laminate obtained by the first method for producing a laminate described above contains particles in the hard coat layer as described later, the laminate has antiglare properties and is excellent in antiglare properties. , can also be said.
  • the method for manufacturing a laminate includes (A1) irradiating a resin layer containing a urethane acrylate resin applied to at least one side of an acrylic resin film with an active energy ray. and curing the resin layer containing the urethane acrylate resin to form a hard coat layer, wherein the acrylic resin film has a tensile elongation at break of 170 at 120°C. % or more, the hard coat layer contains a urethane acrylate resin, and the laminate has a crack elongation of 80% or more at 120°C.
  • This manufacturing method is also a manufacturing method of the first laminate.
  • first laminate includes an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film. and, wherein the acrylic resin film has a tensile elongation at break of 170% or more at 120 ° C., the hard coat layer contains a urethane acrylate resin, and the laminate has a pencil hardness is H or higher, and the crack elongation at 120° C. is 80% or higher.
  • first laminate both the laminate obtained by the method for manufacturing the laminate according to the first embodiment and the laminate according to the first embodiment may be referred to as "first laminate".
  • Patent Literatures 1 and 2 have low surface hardness and, for example, when used to protect the surface of a display device having a touch panel function, there is a possibility that problems such as scratches on the display portion may occur. be.
  • the techniques described in Patent Documents 2 and 3 for example, when laminating a decorative and protective film on a three-dimensional surface of a large molded body such as an automobile interior part integrated with the information display part as described above, in addition, as the film is stretched and shaped along the shape of the molded product, partial whitening of the stretched part of the film, cracking, peeling from the surface of the molded product, cracking and peeling of the functional layer, etc. It turned out that there was a problem.
  • the prior art has (1) a problem of moldability of the laminate, (2) a problem of antireflection of the laminate provided with a low refractive index layer, and (3) a problem of whitening of the laminate. rice field. Therefore, no decorative or protective film has been found that satisfies the requirements when used for the above purposes, and there is room for further improvement.
  • the inventors of the present invention have mainly studied the improvement of the moldability of the laminate, and have made a large-sized molded article by giving specific physical properties to the hard coat layer, the refractive index adjustment layer, etc. in the laminate. It was found for the first time that even when laminated on a three-dimensional surface, peeling and cracking of the functional layer do not occur, and it is possible to obtain a laminate having excellent formability. Moreover, the present inventors have found that the laminate obtained by the above method can solve the problem of antireflection and the problem of whitening of the stretched portion in addition to the moldability.
  • the present inventors found that with regard to the whitening of the stretched portion, on the surface of the low refractive index layer located on the outermost surface of the laminate, during stretching, there was a minute crack that did not reach a visually identifiable size. It has been found that the occurrence of microcracks is one of the causes of whitening. Whitening is caused by microcracks in the low refractive index layer. It is surprising that the resulting whitening of the stretch can be ameliorated.
  • a laminate having various functions and having excellent moldability which is composed of an acrylic resin film and a hard coat layer, or an acrylic resin film, a hard coat layer and a low refractive index layer, No report has been made so far, and the first method for manufacturing a laminate is an extremely excellent technique.
  • the present inventor believes that the mechanism for suppressing whitening is that the hard coat layer before forming the low refractive index layer has uncured residual functional groups by adjusting the configuration of the hard coat layer and the curing conditions using active energy rays. and the crosslink density is lower than that in the completely cured state, the adhesion between the hard coat layer and the low refractive index layer is increased, and as a result, the shape of the microcracks in the low refractive index layer is caused It is speculated that bleaching is suppressed. It should be noted that the present invention is by no means limited to such speculation. The method for manufacturing the first laminate will be described in detail below.
  • the "laminate” intends a product (laminate) containing a hard coat layer, and a product (laminate) that does not contain a hard coat layer is described as a "laminate film". More specifically, in the first embodiment, for example, the “laminate” is a laminate composed of (1) an acrylic resin film and a hard coat layer, or (2) an acrylic resin film and a hard coat layer. A laminate consisting of a coat layer and a low refractive index layer is intended, and the "laminated film” intends a laminate consisting of (3) an acrylic resin film and a low refractive index layer.
  • the surface hardness of the hard coat layer is improved, and the crack elongation is high.
  • the film should not break or become significantly whitened upon stretching.
  • the cured product of the curable resin composition is highly crosslinked and/or contains a filler with high hardness to suppress deformation of the surface of the cured product against external stress. , surface hardness and scratch resistance. Therefore, conventionally, surface hardness and scratch resistance and deformability and extensibility are contradictory properties, and it was not easy to achieve both.
  • Examples of methods for imparting high stretchability during secondary molding to such hard coat curable resins while maintaining hardness include the following methods.
  • the glass transition temperature of the curable resin is designed between room temperature and the secondary molding temperature so that it is hard at room temperature and softens and deforms at the secondary molding temperature. As a result, while exhibiting high surface hardness at room temperature, it exhibits high stretchability during secondary molding.
  • the crosslinked structure after curing of the curable resin is not uniform, and has portions with high crosslink density and portions with low crosslink density. , is designed to be non-uniform in terms of microstructure.
  • the high crosslink density portion in the cured product exhibits high surface hardness, and the low crosslink density portion deforms during secondary molding to exhibit high stretchability.
  • Examples of such resin components having a low cross-linking degree, uncross-linked or low elastic modulus include (a) methacrylic resins, styrene acrylonitrile resins, aliphatic or aromatic polycarbonate resins, polyester resins, phenoxy resins, cellulose acylate resins, and the like.
  • a crosslinked or non-crosslinked soft resin such as acrylic rubber, silicone rubber, hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene rubber, olefin rubber, which may optionally have a reactive functional group;
  • core-shell type rubber particles in which a thermoplastic resin is graft-polymerized on the surface of crosslinked rubber particles For the hard coat layer in the first laminate, these methods (1) to (3) may be used alone or in combination as appropriate.
  • the first laminate manufacturing method includes the following steps (A1) and (B1).
  • Step (A1) A resin layer containing a urethane acrylate resin applied to at least one side of an acrylic resin film is irradiated with an active energy ray to cure the resin layer containing the urethane acrylate resin to form a hard coat layer.
  • the acrylic resin film has a tensile elongation at break of 170% or more at 120° C.
  • the hard coat layer contains a urethane acrylate resin
  • the laminate is , the crack elongation at 120° C. is 80% or more.
  • a resin layer containing a urethane acrylate resin applied to at least one surface of an acrylic resin film is irradiated with active energy rays to cure the resin layer containing the urethane acrylate resin to form a hard coat layer.
  • a resin layer containing an acrylate-based resin is applied in a solution state on the hard coat layer containing the cured urethane acrylate resin formed in the step (A1), dried, and dried.
  • a low refractive index layer is formed by irradiating the resin layer with an active energy ray to cure the resin layer.
  • the hard coat layer and the low refractive index layer is preferably well adhered.
  • the low refractive index layer often contains a hard filler such as hollow silica, and often has a lower crack elongation than the hard coat layer. For this reason, there is a possibility that microcracks that cause whitening may occur at a drawing ratio lower than the crack elongation of the hard coat layer alone.
  • the opening width of microcracks generated in the low refractive index layer by stretching becomes extremely fine, for example, 1 ⁇ m or less, and whitening occurs due to stretching. less likely to occur.
  • the following (a) and (b) are preferable: (a) a resin layer that becomes the low refractive index layer in step (B1) is applied in a solution state, the applied resin layer (low refractive index layer) is hardened to a certain extent within the range that the final interface between the two layers does not become unclear and the antireflection properties are not impaired. (b) the acrylate groups remaining after curing of the hard coat layer are impregnated into the resin layer ( Reactive curing with the low refractive index layer) to form a chemical bond at the interface between the finally obtained hard coat layer and the low refractive index layer.
  • the resin layer containing the urethane acrylate resin forming the hard coat layer is not completely cured, the crosslink density is slightly lowered, and the unreacted acrylate groups are partially removed. It is preferable to leave it.
  • a resin layer containing an acrylate-based resin that forms a low refractive index layer is applied in a solution state and optionally dried. In order to impregnate the layer surface, (a) the coating conditions and drying conditions of the solvent are appropriately adjusted, and/or (b) a fixed amount of a slow-drying, high-boiling solvent is used as the solvent used in the solution. and the like are preferred.
  • the tensile elongation at break at 120° C. of the acrylic resin film in the laminate is 170% or more, preferably 180% or more, and 190% or more. is more preferred.
  • the tensile elongation at break at 120° C. of the acrylic resin film is 170% or more, there is an advantage that the shape followability of molding is excellent.
  • the upper limit of the tensile elongation at break is not particularly limited, but from the viewpoint of improving the tensile strength and elastic modulus, it is, for example, 350% or less, and 300% or less. is preferred.
  • tensile elongation at break at 120°C means the elongation at which the film breaks after a tensile test is performed in a constant temperature bath at 120°C.
  • the tensile elongation at break at 120°C of the acrylic resin film is measured by the method described in Examples.
  • the crack elongation of the laminate at 120° C. is, for example, 80% or more, preferably 100% or more, more preferably 110% or more, and 120 % or more is particularly preferable.
  • the crack elongation at 120° C. of the laminate is 80% or more, it has the advantages of being excellent in shape followability during molding and suppressing whitening of the stretched portion during molding.
  • the upper limit of the crack elongation is not particularly limited, but from the viewpoint of improving surface hardness and wear resistance, it is, for example, 200% or less and 180% or less. is preferred.
  • the "crack elongation of the laminate at 120°C” means the elongation at which cracks occur in the coating layer when the laminate is subjected to a tensile test in a constant temperature bath at 120°C.
  • the crack elongation of the laminate at 120°C is measured by the method described in Examples.
  • the crack elongation of the laminate at 120 ° C. is 80%. It is preferably 100% or more, more preferably 120% or more, and most preferably 130% or more.
  • the "crack elongation of the laminate at 120 ° C.” means "a laminate composed of an acrylic resin film, a hard coat layer, and a low refractive index layer. , crack elongation at 120° C.”.
  • the acrylic resin film is preferably composed of an acrylic resin composition containing graft copolymer particles containing an acrylic resin and a rubber component.
  • the acrylic resin film preferably contains graft copolymer particles (A) having an average particle diameter of 20 nm or more and 200 nm or less as the rubber component-containing graft copolymer particles.
  • graft copolymer particles (B) having a larger average particle size than the graft copolymer particles (A) may be included.
  • the graft copolymer particles (A) are dispersed in the acrylic resin or the matrix containing the acrylic resin and other components, or the It is preferred that the copolymer particles (A) and the graft copolymer particles (B) are dispersed.
  • acrylic resins can be used as the acrylic resin used for the acrylic resin film.
  • the acrylic resin contains 50% by mass or more and 100% by mass or less of methyl methacrylate units, and 0% by mass or more and 50% by mass of other structural units. It preferably contains 20% by mass or more and 100% by mass or less of the thermoplastic acrylic polymer composed of 20% by mass or less.
  • the total amount of methyl methacrylate units and other structural units in the thermoplastic acrylic polymer is 100% by mass.
  • Examples of other structural units include structural units derived from acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, aromatic vinyl derivatives, vinyl cyanide derivatives, and the like.
  • the other structural units contained in the acrylic resin may be of one type or a combination of two or more types.
  • acrylic acid derivatives include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-phenoxyethyl acrylate, and acrylic acid.
  • acrylicates such as benzyl and glycidyl acrylate.
  • methacrylic acid derivatives examples include ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-phenoxyethyl methacrylate, and isobornyl methacrylate.
  • a methacrylic acid ester and the like can be mentioned.
  • Styrene, vinyltoluene, and ⁇ -methylstyrene are examples of aromatic vinyl derivatives.
  • vinyl cyanide derivatives examples include acrylonitrile and methacrylonitrile.
  • a structural unit having a specific structure may be introduced into the acrylic resin by copolymerization, functional group modification, modification, or the like.
  • specific structures include, for example, glutarimide structures as disclosed in JP-A-62-89705, JP-A-02-178310, and WO2005/54311, JP-A-2004-168882, and Lactone ring structures as shown in JP-A-2006-171464, etc., glutaric acid obtained by thermally condensing (meth)acrylic acid units as shown in JP-A-2004-307834, etc.
  • Anhydride structures maleic anhydride structures as disclosed in JP-A-5-119217, N-substituted maleimide structures and unsubstituted maleimide structures as disclosed in WO2009/84541, and the like.
  • introducing these structures into an acrylic resin makes the molecular chain rigid.
  • effects such as improved heat resistance, improved surface hardness, reduced heat shrinkage, and improved chemical resistance can be expected.
  • the method for producing the acrylic resin is not particularly limited, and for example, known polymerization methods such as suspension polymerization method, bulk polymerization method, solution polymerization method and emulsion polymerization method can be applied. Also, any of known radical polymerization methods, living radical polymerization methods, anionic polymerization methods, and cationic polymerization methods can be applied.
  • the acrylic resin film is preferably formed by molding an acrylic resin composition containing a thermoplastic acrylic polymer and polymer particles containing a crosslinked elastomer.
  • a crosslinked elastomer is a rubber component. Therefore, the polymer particles can be said to be polymer particles containing a rubber component.
  • the polymer particles preferably have a core-shell structure (multilayer structure) comprising a crosslinked elastomer that is a rubber component and a graft polymer layer positioned closer to the surface than the crosslinked elastomer.
  • a polymer particle having a core-shell structure comprising a crosslinked elastomer and a graft polymer layer is sometimes referred to as a graft copolymer particle.
  • the crosslinked elastomer preferably contains 50% by mass or more of acrylic acid ester units in 100% by mass of the crosslinked elastomer.
  • the crosslinked elastomer is preferably a crosslinked elastomer (A1) and/or a crosslinked elastomer (B1) described below.
  • the polymer particles are preferably graft copolymer particles containing a crosslinked elastomer and a graft polymer layer located closer to the surface than the crosslinked elastomer.
  • the graft copolymer particles are preferably graft copolymer particles (A) and/or graft copolymer particles (B) which will be described later.
  • the acrylic resin film preferably contains the graft copolymer particles (A) as the rubber component-containing graft copolymer particles. It may further contain graft copolymer particles (B).
  • the graft copolymer particles (A) have a core-shell structure (multilayer structure) comprising a crosslinked elastomer (A1) as a rubber component and a graft polymer layer (A2) positioned closer to the surface than the crosslinked elastomer (A1). is preferred.
  • the crosslinked elastomer (A1) may be a known crosslinked elastomer.
  • the crosslinked elastomer (A1) is an acrylic ester-based crosslinked elastomer (a crosslinked elastomer composed of a polymer containing an acrylic ester as a main component).
  • the particles of the acrylate-based crosslinked elastomer (A1) may have a concentric spherical multilayer structure in which a hard or semi-hard crosslinked resin layer is provided inside the crosslinked elastomer layer.
  • a hard or semi-hard crosslinked resin layer examples include hard crosslinked methacrylic resin particles as shown in JP-B-55-27576, methyl methacrylate-acrylic acid as shown in JP-A-4-270751 and the like.
  • Examples include semi-rigid crosslinked particles made of ester-styrene, crosslinked rubber particles with a high degree of crosslinking, and the like.
  • the graft copolymer particles (A) are formed by graft-polymerizing a monomer mixture forming the graft polymer layer (A2) in the presence of the particles of the above-mentioned acrylic acid ester-based crosslinked elastomer (A1). , preferably have a core-shell structure.
  • the average particle size of the graft copolymer particles (A) is preferably 20 nm or more and 200 nm or less, more preferably 50 nm or more and 150 nm or less, and particularly preferably 50 nm or more and 120 nm or less.
  • the average particle size of the graft copolymer particles (A) When the average particle size of the graft copolymer particles (A) is too small, the impact resistance and bending crack resistance of the acrylic resin film tend to decrease. If the average particle size of the graft copolymer particles (A) is excessively large, the transparency of the acrylic resin film tends to deteriorate, and whitening tends to occur easily due to bending.
  • the acrylic acid ester-based crosslinked elastomer (A1) is a multifunctional polyfunctional polymer that is copolymerizable with (a) an acrylic acid ester and (b) an acrylic acid ester and has two or more non-conjugated double bonds per molecule.
  • crosslinked elastomer particles obtained by polymerizing a monomer mixture (a-1) containing a vinyl monomer and (c) optionally another vinyl monomer copolymerizable with an acrylic acid ester. Available.
  • the acrylic acid ester, other vinyl-based monomers, and polyfunctional monomers may all be mixed and polymerized in one step.
  • the composition of the acrylic acid ester, other vinyl monomers, and polyfunctional monomers may be appropriately changed or the same.
  • the acrylic acid ester, the other vinyl-based monomer, and the polyfunctional monomer may be polymerized in two or more stages without changing the composition.
  • acrylate ester aliphatic esters of acrylic acid are preferable, alkyl acrylate esters are more preferable, and the number of carbon atoms in the alkyl group is preferable, because they are excellent in polymerizability, are inexpensive, and give a polymer having a low Tg. is 1 or more and 22 or less can be particularly preferably used.
  • alkyl acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and isobornyl acrylate. , cyclohexyl acrylate, dodecyl acrylate, stearyl acrylate, heptadecyl acrylate, octadecyl acrylate, and the like. These may be used individually by 1 type, and may use 2 or more types together.
  • the amount of acrylic acid ester is preferably 50% by mass or more, more preferably 70% by mass or more, most preferably 80% by mass or more in 100% by mass of the monomer mixture (a-1). preferable.
  • the acrylic acid ester content is 50% by mass or more, the acrylic resin film has good impact resistance and elongation at breakage, and cracks are less likely to occur during secondary molding.
  • vinyl monomers include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid.
  • methacrylic acid esters such as cyclohexyl, phenoxyethyl methacrylate, isobornyl methacrylate, and dicyclopentenyl methacrylate; vinyl cyanide derivatives such as acrylonitrile and methacrylonitrile; aromatics such as styrene, vinyltoluene, and ⁇ -methylstyrene Vinyl derivatives; acrylic acid; acrylic acid derivatives such as ⁇ -hydroxyethyl acrylate, phenoxyethyl acrylate, benzyl acrylate, glycidyl acrylate; methacrylic acid; ⁇ -hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, and methacrylic acid methacrylic acid derivatives such as glycidyl acid; maleic anhydride; maleic acid derivatives such as N-alkylmaleimide and N-phenylmaleimide; These may be used individually by 1 type, and 2 or more
  • the amount of the other vinyl monomer is preferably 0% by mass or more and 49.9% by mass or less, and 0% by mass or more and 30% by mass or less in 100% by mass of the monomer mixture (a-1). is more preferable, and it is most preferably 0% by mass or more and 20% by mass or less. If the amount of the other vinyl monomer exceeds 49.9% by mass, the impact resistance of the acrylic resin film tends to decrease, the elongation at tensile breakage decreases, and cracks tend to occur during secondary molding. Sometimes.
  • polyfunctional monomer a monomer that is commonly used as a cross-linking agent and/or a graft crossing agent can be suitably used.
  • polyfunctional monomers include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl maleate, divinyl adipate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, and the like can be used.
  • One of these polyfunctional monomers may be used alone, or two or more thereof may be used in combination.
  • those having a function as a graft crossing agent improve the number of graft bonds in the later-described graft polymer layer (A2) with respect to the crosslinked elastomer (A1). It is more preferable because it brings about good dispersibility of the polymer (A) in the acrylic resin, improves crack resistance against tensile and bending deformation, and reduces stress whitening.
  • a polyfunctional monomer having the function of a graft crossing agent those having an allyl group such as allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, and diallyl maleate are preferred. , allyl methacrylate, allyl acrylate and the like are particularly preferred.
  • the amount of the polyfunctional monomer is preferably 0.1% by mass or more and 10% by mass or less in 100% by mass of the monomer mixture (a-1), and 1.0% by mass or more and 4% by mass or less. It is more preferable to have If the blending amount of the polyfunctional monomer is within such a range, it is preferable from the viewpoint of bending crack resistance and bending whitening resistance of the acrylic resin film and fluidity of the resin during molding.
  • the amount of the polyfunctional monomer is adjusted to the inside and surface of the crosslinked elastomer (A1). It may be changed in the vicinity. Specifically, as shown in Japanese Patent No. 1460364 and Japanese Patent No.
  • a polyfunctional monomer having a function as a graft crossing agent By increasing the content from the inside, the coating of the graft copolymer particles (A) with the graft polymer layer is improved, the dispersibility in the acrylic resin is improved, and the graft copolymer particles (A) and the acrylic It is possible to suppress deterioration of cracking resistance due to exfoliation of resin interfaces.
  • the graft copolymer particles (A ) can be reduced, and therefore the melt viscosity of the acrylic resin composition can be reduced, and the melt processability of the acrylic resin film, the improvement of the film processing accuracy, the improvement of the surface hardness, etc. can be expected.
  • the monomer mixture (a-1) contains the double bonds of the polymer for the purpose of controlling the molecular weight and crosslink density of the acrylic ester-based crosslinked elastomer (A1) and the disproportionation termination reaction during polymerization.
  • a chain transfer agent may be added for the purpose of controlling thermal stability and the like by reducing the number of terminals.
  • the chain transfer agent can be selected and used from those commonly used in radical polymerization.
  • chain transfer agents examples include monofunctional or polyfunctional mercaptan compounds having 2 to 20 carbon atoms such as n-octylmercaptan, n-dodecylmercaptan, and t-dodecylmercaptan, mercapto acids, thiophenol, and tetrachloride. Carbon or mixtures thereof and the like are preferred.
  • the amount of the chain transfer agent added is preferably 0 parts by mass or more and 1.0 parts by mass or less, more preferably 0 parts by mass or more and 0 .2 parts by mass or less.
  • the particles of the crosslinked elastomer (A1) may be a single layer composed of the acrylic ester-based crosslinked elastomer (A1), or two or more layers composed of the acrylic ester-based crosslinked elastomer (A1). It may be a multilayer structure containing a hard or semi-hard crosslinked resin layer, and may have an acrylic ester-based crosslinked elastomer (A1) in at least one layer of the multilayer particles.
  • Examples of monomers constituting the hard or semi-hard crosslinked resin layer include methacrylate esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate and phenoxyethyl methacrylate, methyl acrylate and ethyl acrylate.
  • methacrylate esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate and phenoxyethyl methacrylate, methyl acrylate and ethyl acrylate.
  • alkyl acrylates such as propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate; fragrances such as styrene and ⁇ -methyl styrene group vinyl derivatives, vinyl cyanide derivatives such as acrylonitrile, maleic acid derivatives such as maleic anhydride and maleimides, and polyfunctional monomers having two or more nonconjugated double bonds per molecule.
  • fragrances such as styrene and ⁇ -methyl styrene group vinyl derivatives, vinyl cyanide derivatives such as acrylonitrile, maleic acid derivatives such as maleic anhydride and maleimides, and polyfunctional monomers having two or more nonconjugated double bonds per molecule.
  • one or more selected from the group consisting of methyl methacrylate, butyl methacrylate, butyl acrylate, ethyl acrylate, styrene, acrylonitrile and the like is particularly preferable.
  • the polyfunctional monomer the same monomers as those used for the polymerization of the acrylic acid ester-based crosslinked elastomer (A1) layer can be used.
  • chain A transfer agent may be used in combination.
  • the chain transfer agent the same chain transfer agent as used in the polymerization of the acrylate-based crosslinked elastomer (A1) layer can be used.
  • the amount of the chain transfer agent added is preferably 0 parts by mass or more and 2 parts by mass or less, more preferably 0 parts by mass or more and 0.5 parts by mass with respect to 100 parts by mass of the total amount of the rigid or semi-rigid crosslinked resin layer. It is below the department.
  • the graft copolymer particle (A) When the graft copolymer particle (A) has a two-layer structure of a crosslinked elastomer particle (A1) as a core particle and a graft polymer layer (A2), the graft copolymer particle (A) is typically contains 50% by mass or more and 100% by mass or less of a methacrylic acid ester and 0% by mass or more and 50% by mass or less of another vinyl monomer copolymerizable with the methacrylic acid ester in the presence of the crosslinked elastomer particles (A1). by graft-copolymerizing a monomer mixture (a-2) containing (provided that the total of methacrylic acid ester and other vinyl monomers is 100% by mass) to form a graft polymer layer (A2) Obtainable.
  • the amount of methacrylic acid ester in 100% by mass of the monomer mixture (a-2) is (a) to ensure compatibility with the matrix acrylic resin, and (b) to be a solvent during coating on the acrylic resin film. It is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more from the viewpoint of suppressing deterioration of toughness of the coating film due to impregnation of the coating film, whitening and cracking due to stretching during molding. It is even more preferable to have
  • the graft polymer layer (A2) preferably contains 70% by mass or more and 99% by mass or less of an alkyl methacrylate in the presence of 5 parts by mass or more and 90 parts by mass or less of the crosslinked elastomer particles (A1), and the number of carbon atoms in the alkyl group is 2 or more acrylic acid alkyl esters of 0.5% by mass or more and 30% by mass or less, and other vinyl monomers of 0% by mass or more and 19% by mass or less (however, methacrylic acid alkyl esters, acrylic acid alkyl esters and other 100 mass % of the vinyl-based monomer in total) monomer mixture (a-2) 10 parts by mass or more and 95 parts by mass or less is graft-copolymerized in at least one step or more. .
  • the total amount of the crosslinked elastomer particles (A1) and the monomer mixture (a-2) should satisfy 100 parts by mass.
  • methacrylates in the graft polymer layer (A2) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, and methacrylic acid. and methacrylic acid alkyl esters such as cyclohexyl, 2-ethylhexyl methacrylate, octyl methacrylate, phenyl methacrylate, and benzyl methacrylate. Among them, methacrylic acid alkyl esters in which the alkyl group has 1 to 4 carbon atoms are preferred.
  • an acrylic acid alkyl ester having an alkyl group having 2 or more carbon atoms can be used as another vinyl-based monomer.
  • alkyl acrylates having 2 or more carbon atoms in the alkyl group include ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, and acrylic.
  • One or more selected from the group consisting of octyl acid, dodecyl acrylate, stearyl acrylate, and the like is preferable, and selected from the group consisting of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate.
  • One or more are more preferred, and n-butyl acrylate is particularly preferred.
  • vinyl monomers that can be used in the monomer mixture (a-2) include aromatic vinyl derivatives such as styrene and its nucleus-substituted derivatives, vinyl cyanide derivatives such as acrylonitrile, methacrylic acid and its derivatives, Acrylic acid and its derivatives, N-substituted maleimides, maleic anhydride, methacrylamide, acrylamide and the like.
  • the monomer mixture (a-2) preferably contains a reactive UV absorber as another vinyl-based monomer. That is, the graft polymer layer (A2) preferably contains structural units derived from the reactive ultraviolet absorber. When the monomer mixture (a-2) contains a reactive ultraviolet absorber, it is easy to obtain an acrylic resin film with good weather resistance and chemical resistance.
  • a known reactive UV absorber can be used as the reactive UV absorber, and is not particularly limited.
  • Compounds represented by the following general formula (1) are preferable as the reactive ultraviolet absorber from the standpoint of moldability and weather resistance of the acrylic resin film.
  • X is a hydrogen atom or a halogen atom
  • R 1 is a hydrogen atom, a methyl group, or a t-alkyl group having 4 to 6 carbon atoms
  • R 2 is linear, or a branched alkylene group having 2 to 10 carbon atoms
  • R 3 is a hydrogen atom or a methyl group
  • the reactive ultraviolet absorber represented by the general formula (1) include 2-(2′-hydroxy-5′-(meth)acryloyloxyethylphenyl)-2H-benzotriazoles. , more specifically 2-(2′-hydroxy-5′-acryloyloxyethylphenyl)-2H-benzotriazole, 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl-2H-benzotriazole, 2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-5-chloro-2H-benzotriazole, 2-(2′-hydroxy-5′-methacryloyloxypropylphenyl)-2H-benzotriazole, 2- (2'-Hydroxy-5'-methacryloyloxyethyl-3'-t-butylphenyl)-2H-benzotriazole, etc.
  • the content of the structural unit derived from the reactive ultraviolet absorber in 100% by mass of the graft polymer layer (A2) is preferably 0.01% by mass or more and 5% by mass or less, and 0.1% by mass or more and 3 % or less is more preferable.
  • graft copolymer particles (A) especially in the graft copolymerization of the monomer mixture (a-2) in the presence of the crosslinked elastomer particles (A1), for example, the acrylic acid ester-based crosslinked elastomer particles (A1)
  • a polymer component (free polymer) that is not graft-bonded to the acrylic acid ester-based crosslinked elastomer particles (A1) may occur.
  • a free polymer can be used as one that constitutes part or all of the acrylic resin that constitutes the matrix phase of the acrylic resin composition and the acrylic resin film.
  • the rate of grafting to the crosslinked elastomer (A1) and the amount of free polymer not bonded to the crosslinked elastomer (A1) are controlled.
  • a chain transfer agent may be added for the purpose of controlling the thermal stability and the like by reducing the double bond ends of the polymer due to the disproportionation termination reaction during polymerization.
  • the same chain transfer agents as those usable for polymerization of the crosslinked elastomer (A1) can be used.
  • the amount of the chain transfer agent used is 0 to 2 parts by mass, preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total amount of the monomer mixture (a-2).
  • the graft ratio of the monomer mixture (a-2) to the crosslinked elastomer particles (A1) is preferably 5% or more and 250% or less, more preferably 10% or more and 200% or less, and even more preferably 20% or more and 150% or less. If the graft ratio is less than 5%, the acrylic resin film may have reduced resistance to whitening on bending, reduced transparency, or reduced elongation at tensile break, which may cause cracks during secondary molding. tend to become If the graft ratio exceeds 250%, the melt viscosity of the acrylic resin composition tends to increase during film formation, and the formability of the acrylic resin film tends to deteriorate.
  • the average particle diameter d (nm) of the crosslinked elastomer particles (A1) in the acrylic resin film and the amount w (% by mass) of the polyfunctional monomer used in the acrylic acid ester-based crosslinked elastomer are represented by the relational expression: It is preferable to satisfy 0.015d ⁇ w ⁇ 0.06d, more preferably 0.02d ⁇ w ⁇ 0.05d. If the amount of the polyfunctional monomer is within the range of the above relational expression, the elongation during secondary molding of the acrylic resin film is less likely to decrease, cracks are less likely to occur during molding and cutting, and transparency is improved.
  • the graft copolymer particles (B) used as necessary also include the crosslinked elastomer (B1), which is a rubber component, like the graft copolymer particles (A).
  • the graft copolymer particles (B) typically have a graft polymer layer (B2) located closer to the surface than the crosslinked elastomer (B1), like the graft copolymer particles (A). That is, the graft copolymer particles (B) preferably comprise a crosslinked elastomer (B1) and a graft polymer layer (B2).
  • the graft copolymer particles (B) are generally the same as the graft copolymer particles (A) in raw materials, production method, etc., except that the average particle size thereof is larger than that of the graft copolymer particles (A). good too.
  • the particles of the acrylate-based crosslinked elastomer (B1) have a concentric spherical multi-layered structure comprising a hard or semi-hard crosslinked resin layer inside the crosslinked elastomer layer. Examples of such a hard or semi-hard crosslinked resin layer include hard crosslinked methacrylic resin particles as shown in JP-B-55-27576, etc., and as shown in JP-A-4-270751 and WO2014/41803.
  • the graft copolymer particles (B) having a larger particle diameter than the graft copolymer particles (A) can be improved in transparency, bending whitening resistance, and folding resistance. Flexural crack resistance and the like can be improved.
  • the average particle size of the graft copolymer particles (B) is preferably 150 nm or more and 400 nm or less, more preferably 200 nm or more and 350 nm or less.
  • the average particle size of the graft copolymer particles (B) is larger than the average particle size of the graft copolymer particles (A).
  • Graft copolymer particles (B) having a large average particle size more effectively induce plastic deformation (craze) in the acrylic resin phase surrounding the graft copolymer particles against the action of external force on the acrylic resin material. do. Therefore, the graft copolymer particles (B) are extremely effective in imparting impact resistance and crack resistance to the acrylic resin material.
  • the graft copolymer particles (B) are inferior to the graft copolymer particles (A) in bending whitening resistance and/or solvent whitening resistance.
  • the graft copolymer particles (B) for example, by adding a small amount of the graft copolymer particles (B) to the acrylic resin composition containing the acrylic resin and the graft copolymer particles (A), (a) the acrylic resin film (b) when external stress is applied to the acrylic resin film, when a coating liquid containing an organic solvent is applied, and / Alternatively, the whitening property during molding is hardly deteriorated, and (c) the effect of efficiently improving the crack resistance, secondary moldability, etc. of the functional film can be expected.
  • the average particle size of the graft copolymer particles (A) and the graft copolymer particles (B) is determined by a laser diffraction method such as Microtrac particle size distribution analyzer MT3000 manufactured by Nikkiso Co., Ltd. It can be measured using a particle size distribution analyzer and a light scattering method in a latex state.
  • the method for producing the graft copolymer particles (A) and the graft copolymer particles (B) is not particularly limited, and known emulsion polymerization methods, miniemulsion polymerization methods, suspension polymerization methods, solution polymerization methods, etc. are applicable. It is possible.
  • the emulsion polymerization method is particularly preferred because it has a wide adjustment range for the resin structure.
  • initiators used in the emulsion polymerization of the graft copolymer particles (A) and/or the graft copolymer particles (B) known organic peroxides, inorganic peroxides, azo compounds and the like can be used. of initiators can be used.
  • t-butyl hydroperoxide 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, alkylperoxycarbonates, alkylperoxide, Organic peroxides such as oxyesters; inorganic peroxides such as potassium persulfate, sodium persulfate and ammonium persulfate; and azo compounds such as azobisisobutyronitrile can be used. These may be used individually by 1 type, and may use 2 or more types together.
  • initiators may be used (a) as thermal decomposition radical polymerization initiators, or (b) in combination with these initiators sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic It may be used as a redox type polymerization initiator system in combination with reducing agents such as acids, hydroxyacetone acid and ferrous sulfate. Ferrous sulfate may be used in combination with a complex such as ethylenediaminetetraacetate-2-sodium.
  • inorganic peroxides such as potassium persulfate, sodium persulfate and ammonium persulfate are used, or t-butyl hydroperoxide, cumene hydroperoxide and the like are used.
  • an inorganic reducing agent such as divalent iron salt and/or an organic reducing agent such as sodium formaldehyde sulfoxylate, reducing sugar and ascorbic acid. more preferred.
  • the above inorganic peroxide or organic peroxide is added by a known method such as a method of adding as it is to the polymerization system, a method of adding by mixing with a monomer, or a method of adding by dispersing in an aqueous emulsifier solution.
  • a method of adding by mixing with a monomer and a method of adding by dispersing in an aqueous emulsifier solution are preferable.
  • the surfactant (also referred to as an emulsifier) used for emulsion polymerization of the graft copolymer particles (A) and/or the graft copolymer particles (B) is not particularly limited. A wide range of known surfactants can be used for emulsion polymerization.
  • Preferred surfactants include, for example, (a) alkylsulfonic acid, alkylbenzenesulfonic acid, dioctylsulfosuccinic acid, alkylsulfuric acid, fatty acid sodium, polyoxyethylene alkyl ether acetic acid, alkyl phosphoric acid, alkyl ether phosphate, alkylphenyl Anionic surfactants such as ether phosphoric acid, sodium salts such as surfactin, potassium salts and ammonium salts, and (b) reaction products of alkylphenols, aliphatic alcohols and propylene oxide and/or ethylene oxide, etc. nonionic surfactants, and the like. These surfactants may be used alone or in combination of two or more.
  • Graft copolymer particles (A) or graft copolymer particles ( B) can be separated and recovered. For example, after coagulating the graft copolymer particles by adding a water-soluble electrolyte such as calcium chloride, magnesium sulfate, magnesium chloride, calcium acetate, sodium chloride, hydrochloric acid, acetic acid, and sulfuric acid to the latex, or by freezing the latex. After the graft copolymer particles are coagulated, the graft copolymer particles (A) or graft copolymer particles (B) can be separated and recovered by filtration, washing and drying of the solid content. Alternatively, the graft copolymer particles (A) or the graft copolymer particles (B) can be separated and recovered by treating the latex with spray drying, freeze drying, or the like.
  • a water-soluble electrolyte such as calcium chloride, magnesium sulfate, magnesium chloride, calcium acetate, sodium chloride, hydrochloric
  • graft copolymerization is carried out in advance.
  • a filter and/or a mesh By filtering the latex of the coalesced particles (A) or the latex of the graft copolymer particles (B) with a filter and/or a mesh, substances causing foreign matter defects such as environmental foreign matter and polymerization scale are removed.
  • filter and mesh known filters and meshes used for filtering liquid media can be used.
  • the type of filter and mesh, the mesh size of the filter and mesh, filtration accuracy, filtration capacity, etc. are appropriately selected according to the target application, the type, size and amount of foreign matter to be removed.
  • the opening and filtering accuracy of the filter and mesh are preferably, for example, at least twice the average particle size of the graft copolymer particles (A) or graft copolymer particles (B).
  • the content of the graft copolymer particles (A) in 100% by mass of the acrylic resin film is not particularly limited, but is preferably 1% by mass or more and 70% by mass or less, and 5% by mass or more and 65% by mass or less. more preferably 10% by mass or more and 60% by mass or less.
  • the content of the graft copolymer particles (B) in 100% by mass of the acrylic resin film is not particularly limited, but is preferably 20% by mass or less, more preferably 10% by mass or less, and 5% by mass. % or less.
  • the acrylic resin film may optionally contain a thermoplastic resin at least partially compatible with the acrylic resin within a range that does not impair the object of the present invention. may contain.
  • thermoplastic resins include styrene resins, polycarbonate resins, amorphous saturated polyester resins, polyamide resins, phenoxy resins, polyarylate resins, olefin-methacrylic acid derivative resins, olefin-acrylic acid derivative resins, Cellulose derivatives (cellulose acylate, etc.), vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polylactic acid resins, and PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)) resins.
  • Styrene-based resins include, for example, styrene-acrylonitrile resin, styrene-(meth)acrylic acid resin, styrene-maleic anhydride resin, styrene-N-substituted or unsubstituted maleimide resin, styrene-acrylonitrile-butadiene resin, and styrene- Acrylonitrile-acrylic acid ester resins, etc.
  • thermoplastic resins selected from the group consisting of styrene resins, polycarbonate resins, and cellulose acylate resins have excellent compatibility with acrylic resins, and acrylic It is preferable because it is possible to improve the bending crack resistance, solvent resistance, low hygroscopicity of the resin film, and the glass scattering prevention performance of the laminate.
  • the acrylic resin film (acrylic resin composition that constitutes the acrylic resin film) may also be used in conventional acrylic resin films, if necessary, to the extent that the object of one embodiment of the present invention is not impaired. It may contain known additives. Such additives include antioxidants, ultraviolet absorbers, light stabilizers, light diffusing agents, matting agents, lubricants, colorants such as pigments and dyes, fibrous fillers, organic particles and/or inorganic particles. Antiblocking agents consisting of, infrared reflecting agents consisting of metals and / or metal oxides, plasticizers, antistatic agents, and the like. Additives are not limited to these. These additives can be used in an arbitrary amount depending on the type of additive within a range that does not hinder the purpose of one embodiment of the present invention or to enhance the effects of one embodiment of the present invention.
  • the glass transition temperature (Tg) of the acrylic resin film is preferably 140° C. or lower, more preferably 135° C. or lower, and even more preferably 130° C. or lower.
  • Tg glass transition temperature
  • the lower limit of the glass transition temperature of the acrylic resin film is not particularly limited, it is preferably 100° C. or higher from the viewpoints of preventing printing misalignment during drying of printing and improving reliability.
  • the glass transition temperature of the acrylic resin film is measured by the method described in Examples.
  • the thickness of the acrylic resin film is not particularly limited, it is, for example, 75 to 500 ⁇ m, more preferably 75 to 300 ⁇ m, and more preferably 100 to 250 ⁇ m.
  • the film thickness of the acrylic resin film is 75 to 500 ⁇ m, it has the advantage that the film has elasticity and is excellent in handleability.
  • the film thickness of the acrylic resin film is measured by the method described in Examples.
  • the pencil hardness of the acrylic resin film measured according to JIS K 5600-5-4 is preferably 2B or higher, more preferably B or higher, and particularly preferably HB or higher.
  • the acrylic resin film can be produced by a known processing method.
  • known processing methods include melt processing, calendar molding, press molding, and solvent casting.
  • the melt processing method include an inflation method and a T-die extrusion method.
  • the solvent casting method after the acrylic resin composition is dissolved and dispersed in a solvent, the resulting dispersion (dope) is poured onto a belt-like substrate in the form of a film. Next, an acrylic resin film is obtained by volatilizing the solvent from the drooled film-like dope.
  • the melt processing method that does not use a solvent is preferred, and the T-die extrusion method is particularly preferred. According to the melt processing method, there are few restrictions on the thickness of the film to be manufactured, it is possible to manufacture a film with excellent surface properties with high productivity, and the load on the natural environment and working environment due to the solvent and the manufacturing cost are reduced. be able to.
  • the acrylic resin composition When the acrylic resin composition is formed into a film by a melt processing method or a solvent casting method, from the viewpoint of improving the appearance quality of the acrylic resin film, filtration using a filter or mesh is used to remove appearance defects of the acrylic resin film. It is preferable to remove environmental foreign matter, polymerization scale, degraded resin, etc. in the acrylic resin composition, which cause internal foreign matter and the like.
  • the acrylic resin When producing a film by melt processing, the acrylic resin is added at any one or more times during the preparation of the acrylic resin composition by melt mixing, during pelletization of the molten acrylic resin composition, and during the film formation process using a T-die. Filtration of the composition can be performed. In the solvent casting method, after the acrylic resin, the graft copolymer particles (A), (B) and other components are mixed with a solvent, the acrylic resin composition may be filtered before cast film formation.
  • filters and meshes known filters and meshes can be used without particular limitations, as long as the filters and meshes have heat resistance and durability according to melt processing conditions, and resistance to casting solvents, dopes, etc. can.
  • the film thickness distribution in the TD direction (perpendicular to the extrusion direction) of the extruded film is measured online.
  • An automatic die device can be used that measures and automatically adjusts the T-die lip clearance during film extrusion based on this. Applying an automatic die with an appropriate control method may improve the thickness accuracy of the acrylic resin film.
  • both sides of the molten film are brought into contact with (sandwiched between) cooling rolls or cooling belts at the same time to produce a film with better surface properties.
  • the molten film is simultaneously brought into contact with a roll or cooling belt maintained at a temperature of ⁇ 80° C. or higher, preferably ⁇ 70° C. or higher, of the glass transition temperature of the acrylic resin composition.
  • At least one of the rolls for such sandwiching use a roll having an elastic metal sleeve as disclosed in JP-A-2000-153547 and JP-A-11-235747, Low pinch pressure is used to transfer roll mirrors or specific surface topography.
  • a film with less residual strain and excellent smoothness, and / or (b) an internal strain with moderate surface roughness and excellent film surface slipperiness and blocking between films is suppressed. can be obtained.
  • uniaxial stretching or biaxial stretching subsequent to film molding can be carried out using a known stretching device.
  • Biaxial stretching can be carried out in a known manner, such as successive biaxial stretching, simultaneous biaxial stretching, and longitudinal stretching followed by transverse stretching while relaxing the longitudinal direction to reduce bowing of the film. be.
  • one side or both sides of the acrylic resin film can be coated with hairlines, prisms, uneven shapes, three-dimensional decorations, matte surfaces, rough surfaces with a certain degree of surface roughness, knurling on the edges of the film, etc.
  • Any surface shape may be given.
  • Such a surface profile can be imparted by a known method. For example, by sandwiching both sides of a molten film immediately after extrusion or a molded film fed out from a feeding device between two rolls or belts having a surface shape on at least one surface, the surface shape of the roll is changed.
  • a method of transcription can be mentioned.
  • the hard coat layer in the first method for producing a laminate is a functional layer laminated on at least one side of the acrylic resin film and contains a urethane acrylate resin.
  • the hard coat layer may be laminated on one side or both sides of the acrylic resin film.
  • various hard coat layers containing urethane acrylate resin which are conventionally provided in various functional films, resin molded products, etc., can be employed without particular limitation.
  • a urethane acrylate resin can be obtained, for example, by mixing a polyhydric alcohol, a polyvalent isocyanate, and a hydroxyl group-containing (meth)acrylate to form a urethane bond through a reaction between the isocyanate group and the hydroxyl group.
  • urethane acrylate resins include urethane acrylate resins commercially available as UV-curable hard coating agents.
  • the hard coat layer of the laminate may contain other components in addition to the urethane acrylate resin.
  • Components other than the urethane acrylate resin include, for example, monofunctional or polyfunctional (meth)acrylates, epoxy acrylate monomers, polyester acrylates, silicon acrylates, polycarbonate acrylates, polyacrylic acrylates, and the like, which have radically reactive functional groups. Monomers, oligomers, resins, or mixtures thereof can be used in combination.
  • a urethane acrylate resin and, for example, (a) a hydrolytic condensate of a difunctional to tetrafunctional silane compound, and/or (b) a cationically curable and/or anionically curable functional group such as an epoxy group and an oxetane group may be used in combination with a composition containing a monomer, oligomer, resin, or mixture thereof having As a component used for forming the hard coat layer, the urethane acrylate resin may be used alone, or in addition to the urethane acrylate resin, one or more of the other components may be added in combination. .
  • the (meth)acrylate is not particularly limited as long as it has at least one (meth)acryloyl group. Specifically, (a) alicyclic (meth)acrylates such as alkyl (meth)acrylates, aryl (meth)acrylates, phenoxyethyl (meth)acrylates and isobornyl (meth)acrylates, (b) polyalkylene glycol di( meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol multifunctional (meth)acrylates such as tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane
  • (meth)acrylates include those commercially available as UV-curable hard coating agents.
  • (meth)acrylate is meant to include methacrylate and acrylate.
  • the (meth)acryloyl group is intended to include methacryloyl and acryloyl groups.
  • epoxy acrylate monomer there are no particular restrictions on the epoxy acrylate monomer. Specifically, glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and vinylcyclohexene monoxide (i.e., 1,2-epoxy-4-vinylcyclohexane ) and the like.
  • the hydroxyl group-containing (meth)acrylates are not particularly limited, and hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, and optionally (a) at least one Compounds with an ethylenically unsaturated bond having a hydroxyl group such as 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylpropane mono (meth) acrylate, trimethylolpropane di(meth) acrylate, allyl alcohol, ethylene glycol allyl ether, glycerin (mono, di) allyl ether, N-methylol (meth) acrylamide, etc. (b) or a mixture thereof is added It is possible.
  • the polyvalent isocyanate is not particularly limited.
  • Polyvalent isocyanate compounds that are compounds containing two or more isocyanate groups include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate isocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane triisocyanate , 3,3′-dimethylphenylene diisocyanate, 4,4′-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohe
  • polyhydric alcohols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,8-octanediol, 1,4-cyclohexanediol Examples include methanol and polytetramethylene glycol. These polyhydric alcohols may be used singly or in combination of two or more.
  • An organic tin-based urethanization catalyst is used to promote the reaction of the isocyanate component with the isocyanate group.
  • the organic tin-based urethanization catalyst may be any one generally used in urethanization reactions, and examples thereof include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dialkylmalate, tin stearate, and tin octylate. be done.
  • a composition comprising a hydrolytic condensate of a silane compound preferably has the following general formula (2): R 4 —(SiR 5 a (OR 6 ) 3-a ) (2)
  • R 4 is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and carbon a monovalent hydrocarbon group selected from the group consisting of aralkyl groups having 7 to 12
  • the weight average molecular weight of the condensate (A) is preferably 30,000 or less.
  • the proportion of the silane compound having a reactive substituent is preferably 10% by mass or more of the total amount of the silane compound (Z) used.
  • the reactive substituent in the general formula (2) is an epoxy group or an oxetane group from the viewpoints of less curing shrinkage during the formation of the hard coat layer and the ease of obtaining a functional film with excellent durability and suppressed curling. is preferred.
  • a neutral salt catalyst is more preferably used as the catalyst for the hydrolytic condensation reaction of the silane compound (Z). This is because when the reactive substituent is an epoxy group and/or an oxetane group, decomposition of the reactive substituent during hydrolytic condensation is easily suppressed.
  • a method for curing the resin layer (resin composition) when forming the hard coat layer a known method can be applied.
  • a method of irradiating active energy rays represented by ultraviolet rays is preferable.
  • a photopolymerization initiator is used when curing is performed by irradiation with an active energy ray.
  • a hydrolytic condensate of the above silane compound and/or (b) a monomer, oligomer, or resin having a cationically curable and/or anionically curable functional group such as an epoxy group and an oxetane group, or these
  • a composition containing a mixture of is used in combination with a urethane acrylate resin, a photoanion generator, photocation generator, or the like is also used as appropriate.
  • photopolymerization initiators include acetophenone, benzophenone, benzoylmethyl ether, benzoylethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy- 2-phenylacetophenone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 1-one compounds and the like.
  • 1-hydroxy-cyclohexyl-phenyl-ketone is preferred because of its excellent compatibility with the resin.
  • the photocation generator include, for example, CPI-100P, CPI-101A, CPI-200K, and CPI-200S manufactured by San-Apro; Wako Pure Chemical Industries, Ltd. WPI-124, WPI-113, WPI- 116, WPI-169, WPI-170, and WPI-124; and Rhodia 2074 manufactured by Rhodia.
  • photoanion generator examples include acetophenone o-benzoyloxium, nifedipine, 2-(9-oxoxanthen-2-yl)-1,5,7-triazabicyclopropionic acid [4.4.0].
  • Dec-5-ene 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3-[bis(dimeramino)methylene]guanidinium 2-(3-benzoylphenyl)propionate, 1, 2-dicyclohexyl-4,4,5,5-tetramethylpiguanidinium, n-butyltriphenylbalate and the like.
  • the curable composition is used for the purpose of improving coating properties, scratch resistance after curing, and antifouling properties.
  • various known leveling agents may be added.
  • leveling agents fluorine-based leveling agents, acrylic leveling agents, silicone-based leveling agents, and adducts or mixtures thereof can be used.
  • the amount of the leveling agent to be added is not particularly limited, it is, for example, an amount within the range of 0.03 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the curable composition.
  • the curable composition When forming a hard coat layer by applying a curable composition, the curable composition contains an ultraviolet absorber, a light stabilizer, an antifoaming agent, an antioxidant, a light diffusing agent, a matting agent, and an anti-oxidant.
  • Various additives such as staining agents, lubricants, colorants such as pigments and dyes, organic particles, inorganic particles, and antistatic agents can be added as required. Additives are not limited to these.
  • An organic solvent is usually blended in order to give the curable composition appropriate applicability.
  • the organic solvent is not particularly limited as long as it can impart desired coatability to the curable composition and can form a hard coat layer with desired film thickness and performance.
  • the boiling point of the organic solvent is preferably 50° C. or higher and 150° C. or lower from the viewpoint of coatability and drying property of the formed resin layer (coating film).
  • organic solvents include saturated hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and methylene chloride; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol.
  • Esters such as methyl acetate, ethyl acetate, and butyl acetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ethers such as tetrahydrofuran, dioxane, propylene glycol monoethyl ether, methyl cellosolve, and ethyl cellosolve. and amides such as N-methylpyrrolidone and dimethylformamide.
  • An organic solvent can be used individually by 1 type or in combination of 2 or more types.
  • any method can be employed without particular limitation as the application method.
  • coating methods include reverse coating, gravure coating, bar coating, die coating, spray coating, kiss coating, wire bar coating, and curtain coating. These coating methods may be carried out singly or in combination.
  • the organic solvent is removed from the coating film by drying, and ultraviolet irradiation or the like is performed.
  • a hard coat layer is formed by curing the obtained resin layer with light.
  • the drying temperature for removing the organic solvent from the coated resin layer is preferably 60°C or higher and 120°C or lower, more preferably 70°C or higher and 100°C or lower. If the drying temperature is too low, the organic solvent may remain in the resin layer (coating film). On the other hand, if the drying temperature is too high, thermal deformation of the base film may impair the flatness of the functional film (hard coat layer).
  • the wavelength of the ultraviolet rays irradiated when curing the resin layer (coating film) is preferably in the range of 200 nm or more and 400 nm or less.
  • the ultraviolet (UV) integrated light quantity is described later in [4. Laminate manufacturing method] is preferably used.
  • Examples of irradiation devices for ultraviolet exposure light include (a) lamp light sources such as high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, electrodeless lamps, and excimer lamps, and/or (b) argon ion lasers and helium neon. Irradiation devices comprising pulsed or continuous laser sources, such as lasers, etc., can be used.
  • compositions for forming a hard coat layer include, for example, the product name "Z-607-27L” manufactured by Aica Kogyo Co., Ltd., the product name "ENS102” manufactured by DIC Corporation, and the product name manufactured by Arakawa Chemical Industries, Ltd.
  • the thickness of the hard coat layer is not particularly limited, but is, for example, 0.6 ⁇ m to 10.0 ⁇ m, preferably 0.7 ⁇ m to 7.0 ⁇ m, more preferably 0.8 ⁇ m to 5.0 ⁇ m. preferable.
  • the film thickness of the hard coat layer is 0.6 ⁇ m to 10.0 ⁇ m, there is an advantage that both wear resistance and moldability can be achieved.
  • the thickness of the hard coat layer is measured by the method described in Examples.
  • inorganic particles and/or metal particles may be added in order to improve the hardness, wear resistance, antistatic properties, etc. of the hard coat layer.
  • inorganic particles and metal particles include, but are not limited to, silica, alumina, titanium oxide, zinc oxide, zirconia, graphene, nanocarbon, carbon black, nanodiamond, mica, barium titanate, boron nitride, metallic silver, metal copper etc. are mentioned. These particles may be used without surface treatment, or may be surface-treated in advance by a known method to control the dispersed state, and the affinity with the hard coat layer may be appropriately controlled. .
  • the hard coat layer in the first laminate manufacturing method may further contain particles in addition to the urethane acrylate resin.
  • the hard coat layer contains particles, it is possible to obtain a laminate containing an acrylic resin film having excellent antiglare properties.
  • Particles to be blended in the hard coat layer for the purpose of imparting antiglare properties are desired antiglare properties, sharpness of transmitted images, glare, jet-blackness of the surface, surface hardness, slipperiness, antistatic properties, and the like.
  • the material of the particles, the number of parts to be blended, the type of dispersion solvent for the particles, the particle diameter, the dispersed particle diameter, the film thickness of the hard coat layer, and the relative refractive index difference with the hard coat base material can be appropriately adjusted within a known technical range that does not impair the effects of the present invention.
  • the material of the particles to be compounded in the hard coat layer is not particularly limited as long as the effects of the present invention are achieved.
  • Examples include (a) silica, alumina, glass beads or flakes, mica, clay, titanium oxide, and zinc oxide. , zirconia, metal particles, and/or (b) crosslinked organic resin particles based on alkyl (meth)acrylate units, aromatic vinyl units, siloxane units, etc., and (c) core-shell type multilayer structure resin particles, and the like.
  • the particles are inorganic oxide particles (for example, silica, alumina, titanium oxide, zinc oxide, zirconia, etc.) and/or crosslinked organic Resin particles are preferable, and at least one selected from the group consisting of silica, alumina, zirconia, crosslinked silicone resins, crosslinked acrylic resins and crosslinked aromatic vinyl resins is more preferable.
  • Silica particles, alumina particles, and crosslinked organic resin particles are particularly preferred from the viewpoint of the balance of physical properties such as antiglare properties, dispersibility, and surface hardness.
  • these particles are formed by known methods such as using a silane coupling agent or reactive monomer that may have a reactive substituent, plasma treatment, corona treatment, etc.
  • Reactive functional groups having reactivity with urethane acrylate resins include (a) radical reactive functional groups such as vinyl groups and (meth)acryloyl groups, (b) epoxy groups, oxetane groups, hydroxyl groups, carboxyl groups, mercapto ionic functional groups such as groups, isocyanyl groups, hydroxyl groups and amino groups; and (c) moisture-curable functional groups such as silyl groups and alkoxysilyl groups.
  • particles may be dispersed in the state of primary particles, or may be dispersed in an aggregated state of multiple particles, depending on the size of the primary particles.
  • the size of a region (dispersed domain) in which these particles or aggregates thereof are distributed is defined as "average dispersed particle size".
  • average dispersed particle size When the size of the primary particles is large, the average dispersed particle size and the primary (basic) particle size may be the same.
  • the average dispersed particle diameter of the particles is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 0.1 ⁇ m to 50.0 ⁇ m, 0.2 ⁇ m to 25.0 ⁇ m, 0.5 ⁇ m to It may be 10 ⁇ m or the like.
  • the average dispersed particle size of particles is measured by the method described in Examples.
  • the content of the particles in the hard coat layer is not particularly limited as long as the effect of one embodiment of the present invention is exhibited, but for example, 0.1% by weight to 30.0% by weight. %, and may be 0.5 wt % to 20.0 wt %, 1.0 wt % to 15.0 wt %, and the like.
  • Low refractive index layer In the method for manufacturing the first laminate, it is preferable that a low refractive index layer containing an acrylate resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm is further provided on the hard coat layer.
  • the low refractive index layer constitutes an antireflection layer.
  • the low refractive index layer is typically formed by curing a composition for forming a low refractive index layer (curable composition).
  • the low refractive index layer is a layer for exhibiting an antireflection effect due to a significant refractive index difference with the hard coat layer described above and/or a significant refractive index difference with the high refractive index layer described later.
  • the low refractive index layer may be, for example, a layer containing an acrylate-based resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm. can.
  • As the composition for forming a low refractive index layer a composition obtained by adding hollow silica fine particles as a material for adjusting the refractive index to an acrylate-based resin as the base organic material can be used.
  • the acrylate resin contained in the low refractive index layer contains hollow silica fine particles.
  • the particle diameter of the hollow silica fine particles is less than 100 nm, preferably 80 nm or less, more preferably 60 nm or less. When the particle diameter of the hollow silica fine particles is less than 100 nm, there is an advantage that the transparency is excellent.
  • the lower limit of the particle size of the hollow silica fine particles is not particularly limited, it is, for example, 10 nm or more, preferably 20 nm or more, from the viewpoint of improving antireflection performance.
  • the particle diameter of the hollow silica fine particles is measured by the method described in Examples.
  • the content of hollow silica fine particles in the acrylate resin is 40% or more, preferably 45% or more, more preferably 50% or more.
  • the content of the hollow silica fine particles in the acrylate resin is 50% or more, there is an advantage that antireflection properties are excellent.
  • the upper limit of the content of the hollow silica fine particles in the acrylate resin is not particularly limited, but from the viewpoint of improving surface hardness and wear resistance, it is, for example, 80% or less, preferably 70% or less.
  • the composition for forming a low refractive index layer may contain a resin similar to the resin contained in the hard coat layer as an organic material other than the acrylate resin. Further, in the first embodiment of the present invention, the composition for forming a low refractive index layer may contain silica fine particles, fluoride fine particles, etc. as a refractive index adjusting material other than the hollow silica fine particles. Magnesium fluoride, lithium fluoride, aluminum fluoride, calcium fluoride, and the like are examples of fluorides constituting the fluoride fine particles.
  • part of the organic material may be replaced with a water-repellent material or an oil-repellent material.
  • Water-repellent materials or oil-repellent materials include, for example, (a) compounds containing long-chain hydrocarbon skeletons, fluorocarbon skeletons, fluoropolyether skeletons, polysiloxane skeletons, etc., and (b) each skeleton described above. and resins having These may have, for example, reactive functional groups with urethane acrylate resins, and may contain two or more of these skeletons in one molecule. Also, a plurality of these may be used in combination.
  • additives can be added to the low refractive index layer as other components within a range that does not impair the effects of one embodiment of the present invention.
  • additives include photopolymerization initiators, dispersants, surfactants, ultraviolet absorbers, antioxidants, light stabilizers, antistatic agents, leveling agents, antifouling agents, anti-fingerprint agents, lubricants.
  • Additives such as a property-imparting agent may be used.
  • composition for forming a low refractive index layer examples include, for example, the product name “Z-824” manufactured by Aica Kogyo Co., Ltd., the product name “TU-2359” manufactured by Arakawa Chemical Industries, Ltd., and the product name manufactured by JGC Catalysts and Chemicals Co., Ltd. “ A commercially available product such as ELCOM P-5062 may also be used. Since these commercially available products have elongation even after curing, the 120° C. crack elongation of the first laminate can be further increased by using these commercially available products.
  • the first laminate may have functional layers other than those described above.
  • Other functional layers are not particularly limited, and for example, conventionally known various functional layers can be employed.
  • Specific examples of other functional layers include an antiglare layer, an antifouling layer, an anti-fingerprint layer, an anti-scratch layer, an antistatic layer, an ultraviolet shielding layer, an infrared shielding layer, an uneven surface layer, a light diffusion layer, a matte layer, A polarizing layer, a colored layer, a design layer, an embossed layer, a conductive layer, a gas barrier layer, a gas absorbing layer, a high refractive index layer, and the like. Two or more of these functional layers may be combined. Also, one functional layer may have two or more functions.
  • the active energy rays include ultraviolet rays (UV).
  • the integrated light amount of active energy ray irradiation is, for example, 150 mJ/cm 2 to 500 mJ/cm 2 , and 180 mJ/cm 2 to 450 mJ/cm 2 . and more preferably 200 mJ/cm 2 to 400 mJ/cm 2 .
  • the cumulative light quantity of the UV irradiation is 150 mJ/cm 2 to 500 mJ/cm 2 , it is possible to obtain an appropriate hardness of the hard coat layer while ensuring moldability.
  • the cumulative amount of UV irradiation is 150 mJ/cm 2 or more, the degree of cross-linking of the hard coat layer is improved, and surface hardness and scratch resistance can be improved.
  • the integrated amount of UV irradiation is 500 mJ/m 2 or less, impregnation of the composition for forming a low refractive index layer into the hard coat layer becomes moderate during coating of the composition for forming a low refractive index layer. , the amount of residual acrylate groups in the hard coat layer becomes moderate.
  • the adhesion between the hard coat layer and the low refractive index layer is maintained, and the obtained laminate is whitened when stretched 80% at 120°C. can be suppressed.
  • the chill roll temperature is, for example, 20°C to 70°C, preferably 25°C to 60°C, and more preferably 30°C to 55°C.
  • the resin layer hard coat layer
  • the resin layer can be cured while suppressing the temperature rise of the resin layer of the composition for forming a hard coat layer during ultraviolet irradiation. can be performed to produce a laminate with desired physical properties.
  • step (A1) For conditions other than the above in step (A1), those described in the above (hard coat layer) are incorporated.
  • step (B1) an acrylate-based resin (composition for forming a low refractive index layer) containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm is applied on the hard coat layer obtained in step (A1).
  • the resin layer containing the acrylate resin (composition for forming a low refractive index layer) thus obtained is irradiated with an active energy ray to cure the resin layer containing the acrylate resin to form a low refractive index layer.
  • the active energy ray includes ultraviolet (UV).
  • the same conditions as in the step (A1) can be adopted for the integrated light amount of active energy ray irradiation (for example, the integrated light amount of ultraviolet (UV) irradiation).
  • the chill roll temperature is, for example, 20°C to 70°C, preferably 25°C to 60°C, and more preferably 30°C to 55°C.
  • the cooling roll temperature in the step (B1) is 20° C. to 70° C.
  • the resin layer (low refractive index layer) is formed while suppressing the temperature rise of the resin layer of the composition for forming a low refractive index layer during ultraviolet irradiation. can be performed to produce laminates with desired physical properties.
  • a solvent is added to the acrylate resin that is the material of the low refractive index layer, and the particle diameter is less than 100 nm.
  • a laminate comprising a step of preparing an acrylate resin containing 40% or more of hollow silica fine particles, wherein the solvent contains at least one solvent, and the solvent having the highest boiling point has a boiling point of 115°C to 180°C.
  • the "acrylate-based resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm" can also be said to be a "composition for forming a low refractive index layer.”
  • the boiling point of the solvent with the highest boiling point is, for example, 115°C to 180°C, preferably 120°C to 170°C, and more preferably 125°C to 160°C.
  • the boiling point of the solvent with the highest boiling point is 115° C. to 180° C., the adhesion between the hard coat layer and the low refractive index layer is improved, and a laminate with less whitening (lower degree of whitening) is produced during stretching. Obtainable.
  • the solvent used in step (B1') is not particularly limited as long as it contains a solvent having the above boiling point.
  • the solvent having a boiling point of 115° C. to 180° C. is not particularly limited, and examples thereof include propylene glycol monomethyl ether (PGM), cyclohexanone, butyl acetate, propylene glycol monomethyl ether acetate (PGMA) and the like.
  • PGM is preferable from the viewpoint of compatibility with resin and drying efficiency. These may be used alone or in combination of two or more.
  • the method of adding a solvent to the acrylate resin to prepare the acrylate resin containing 40% or more of the hollow silica fine particles having a particle diameter of less than 100 nm is not particularly limited, and a known method is used. can do.
  • the acrylate resin containing the hollow silica fine particles is prepared by the method described in Examples.
  • the first laminate includes an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film. More specifically, the first laminate is a laminate including an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, and the acrylic resin film comprises: The tensile elongation at break at 120° C. is 170% or more, the hard coat layer contains a urethane acrylate resin, the laminate has a pencil hardness of H or more, and a crack elongation at 120° C. 80% or more. Moreover, in a preferred aspect of the first embodiment of the present invention, the first laminate further includes a low refractive index layer on the hard coat layer.
  • the first laminate is composed of at least a specific acrylic resin film and a specific hard coat layer, as described above. Moreover, in a preferred aspect of the first embodiment of the present invention, the first laminate is composed of a specific acrylic resin film, a specific hard coat layer, and a specific low refractive index layer.
  • the first laminate is composed of the acrylic resin film described above (acrylic resin film) and the hard coat layer described above (hard coat layer).
  • the first laminate comprises the acrylic resin film described above (acrylic resin film) and the hard coat layer described above (hard coat layer). and the low refractive index layer described above (low refractive index layer).
  • the first laminate is preferably the above [1-2. First Laminate Manufacturing Method].
  • the pencil hardness of the first laminate is H or higher, preferably 2H or higher, and more preferably 3H or higher. If the pencil hardness of the first laminate is H or higher, it has the advantage of being less likely to be scratched.
  • pencil hardness is an index of abrasion resistance, and abrasion resistance is evaluated by the degree of scratches formed when scratched. In this specification, the pencil hardness of the laminate is measured by the method described in Examples.
  • the "tensile elongation at break at 120°C” and the “crack elongation at 120°C” of the first laminate are the same as in [1-2. Laminate manufacturing method] is used.
  • the haze of the first laminate is, for example, 1.0% or less, preferably 0.8% or less, and more preferably 0.5% or less.
  • the haze of the first laminate is 1.0% or less, there is an advantage that the transparency is excellent.
  • the haze of the laminate is measured by the method described in Examples.
  • the ⁇ haze after 80% stretching at 120° C. of the first laminate is, for example, 3.0% or less, preferably 2.5% or less, and more preferably 2.0% or less. preferable.
  • the ⁇ haze after 80% stretching at 120° C. of the first laminate is 3.0% or less, there is an advantage that whitening during molding can be suppressed.
  • the ⁇ haze of the first laminate after being stretched by 80% at 120° C. is measured by the method described in Examples.
  • ⁇ haze after 20% stretching at 120 ° C. is preferably 30% or less, more preferably 20% or less.
  • the low refractive index layer in the first laminate improves the crack elongation of the first laminate at 120 ° C. and / or suppresses whitening during stretching at 120 ° C., so whitening during stretching is suppressed. Less is preferred.
  • the laminated film obtained by laminating the low refractive index layer on the acrylic resin film if the ⁇ haze after 20% stretching at 120 ° C.
  • the first laminate at 120 ° C. is 30% or less
  • the first laminate at 120 ° C. is 80% Whitening after stretching is reduced, and a laminate having excellent moldability can be obtained.
  • ⁇ haze after 20% stretching at 120° C. is measured by the method described in Examples, with a laminated film obtained by laminating a low refractive index layer on an acrylic resin film. be.
  • the luminous reflectance of the first laminate is, for example, 2.0% or less, preferably 1.8% or less, and more preferably 1.6% or less.
  • the luminous reflectance of the first laminate is 2.0% or less, there are advantages of excellent antireflection performance and excellent visibility when laminated on the display surface.
  • the luminous reflectance of the first laminate is measured by the method described in Examples.
  • the in-plane retardation (Re) of the first laminate is, for example, 10 nm or less, preferably 9 nm or less, more preferably 8 nm or less, more preferably 7 nm or less, and 6 nm or less. is particularly preferred.
  • the in-plane retardation (Re) is 10 nm or less, a decrease in contrast can be suppressed in a liquid crystal display device.
  • the in-plane retardation (Re) is measured by the method described in Examples.
  • the absolute value of the thickness direction retardation (Rth) of the first laminate is, for example, 30 nm or less, preferably 25 nm or less, and more preferably 20 nm or less.
  • the absolute value of the thickness direction retardation (Rth) is 30 nm or less, a decrease in contrast can be suppressed in a liquid crystal display device.
  • the thickness direction retardation (Rth) is measured by the method described in Examples.
  • microcrack width of the first laminate is For example, it is 2.0 ⁇ m or less, preferably 1.5 ⁇ m or less, more preferably 1.0 ⁇ m or less.
  • microcrack width of the first laminate is measured by the method described in Examples. Further, in this specification, “at the time of 80% stretching at 120°C” can also be described as “80% stretching at 120°C”. In this case, the "stretch ratio" simply indicates elongation.
  • the depth of the groove of the microcrack from the surface of the low refractive index layer side of the laminate at the microcrack portion in the direction parallel to the tensile stress when the first laminate is stretched 80% at 120 ° C. (hereinafter , sometimes simply referred to as “the depth of the microcrack grooves in the first laminate”) is, for example, 1.0 ⁇ m or less, preferably 0.8 ⁇ m or less, and 0.5 ⁇ m or less. is more preferable. If the depth of the grooves of the microcracks in the first laminate is 1.0 ⁇ m or less, there is an advantage that changes in appearance during molding can be suppressed. The depth of the grooves of the microcracks in the first laminate is measured by the method described in Examples.
  • FIG. 1 is a diagram showing a TEM image of the laminate according to the first embodiment of the present invention after a tensile test.
  • a laminate 4 in FIG. 1 is composed of an acrylic resin film 1 , a hard coat layer 2 and a low refractive index layer 3 .
  • microcracks 5 are generated on the surface of the laminate 4 according to the tensile stress.
  • the crack width in the direction parallel to the tensile stress of the generated microcracks 5 is called a microcrack width 6, and the crack width in the stacking direction is called a groove depth 7 of the microcracks.
  • the first laminate may have a primer layer on the surface opposite to the surface provided with the hard coat layer.
  • the composition of the primer layer includes (a) ink used for printing in the post-processing step, (b) injection resin used for injection molding, and (c) adhesiveness to metals used for metal deposition.
  • a good resin, etc. is used.
  • urethane-based resins, acrylic-based resins, polyester-based resins, polycarbonates, epoxy-based resins, melamine-based resins, copolymers of vinyl acetate and vinyl chloride, and vinyl acetate resins are used as resin components.
  • These resin components may appropriately contain functional groups such as acid groups, amino groups, epoxy groups, oxetane groups, vinyl groups, hydroxyl groups, mercapto groups, isocyanyl groups, silyl groups and salts.
  • a resin component and a compound having these functional groups may be used in combination.
  • the thickness of the primer layer is preferably 0.5-10 ⁇ m, more preferably 0.5-5 ⁇ m, most preferably 0.5-3 ⁇ m.
  • the thickness of the primer layer is 0.5 ⁇ m or more, the adhesion between the injection resin, ink, etc. and the acrylic resin of the first laminate can be ensured, and when the thickness is 10 ⁇ m or less, productivity is better.
  • a molded article (hereinafter referred to as "first molded article") comprising a first laminate is provided. Further, in the first embodiment of the present invention, the first molded body is obtained by laminating the first laminate on at least part of the surface of the molded body having a non-planar shape at least in part.
  • applications of the first molded body include automotive interior applications such as instrument panels, in-vehicle display front panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, and dashboards; a) Weatherstrips, bumpers, bumper guards, side mudguards, body panels, spoilers, front rills, strut mounts, hubcaps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, etc., and (b) windows and heads Automobile exterior applications such as lamp covers, tail lamp covers, windshield parts; housings, display windows, buttons, etc.
  • the first laminate When the first laminate is used, (a) it has a complicated three-dimensional shape, and (b) surface hardness, scratch resistance, chemical resistance, antifouling property, reflective property, antiglare property, etc. are controlled. In addition, it is possible to easily produce a molded product with excellent appearance. For this reason, the first molded body is preferably used for, among the above uses, for example, an in-vehicle display front panel having a planar shape, a curved surface shape and/or a three-dimensional shape. Accordingly, in a first embodiment of the present invention, there is provided an in-vehicle display front panel comprising a first molded body.
  • 2nd Embodiment of this invention is related with the laminated body which contains an acrylic resin film as a base material, and its manufacturing method.
  • a method of forming a functional layer on a film substrate by a technique such as coating is used as a method of further imparting functionality to a decorative/protective film containing an acrylic resin film.
  • an antiglare hard coat layer is provided on a thermoplastic transparent substrate film, and a specific component is added as the outermost layer on the antiglare hard coat layer side of the thermoplastic transparent substrate film.
  • An insert-molding antiglare antireflection film and the like having a low refractive index layer containing a specific concentration are disclosed.
  • Patent Document 5 discloses a support, an easy-adhesion layer provided on one surface of the support, and a transparent layer made of a translucent resin provided on the other surface of the support.
  • the layer contains light-transmitting particles, the volume-average particle diameter r of the light-transmitting particles satisfies 0.4 ⁇ m ⁇ r ⁇ 3.0 ⁇ m, and the total sum S of the light-transmitting particles is 30 mg/m 2 . It describes an optical laminated film or the like that satisfies ⁇ S ⁇ 500 mg/m 2 and the average film thickness t of the transparent layer satisfies r/4 ⁇ t ⁇ r.
  • Patent Documents 4 and 5 have sufficient performance from the viewpoint of compatibility between the moldability of the laminate and the functionality of the laminate such as surface hardness and antiglare properties of the surface of the laminate. That said, there is room for further improvement.
  • an object of one embodiment (second embodiment) of the present invention is to provide a laminate containing an acrylic resin film, which is excellent in formability, surface hardness and antiglare properties, and a method for producing the same.
  • the present inventors have made intensive studies to solve the above problems, and found that a hard coat containing specific particles and having specific physical properties in a laminate composed of an acrylic resin film, a hard coat layer, etc. It was found for the first time that a layered product having excellent formability, surface hardness and antiglare properties can be obtained by using a layer, and one embodiment (second embodiment) of the present invention was completed.
  • (A2) a resin layer containing a urethane acrylate resin and particles, which is coated on at least one side of an acrylic resin film, is irradiated with an active energy ray, and the urethane acrylate a step of curing a resin layer containing a resin and particles to form a hard coat layer, wherein the acrylic resin film has a tensile elongation at break of 170% or more at 120°C.
  • the content of the particles is 2.0 to 5.0% by weight with respect to the hard coat layer after curing, the average dispersed particle diameter of the particles is r ( ⁇ m), and the hard coat layer
  • the laminate has a pencil hardness of H or higher, a haze of 3% or higher, and a crack elongation of 170 at 120° C., where d ( ⁇ m) is the film thickness. % or more, and the crack elongation at 120° C. of the laminated film obtained by laminating the resin layer containing no particles on the acrylic resin film is 80% or more.
  • one aspect of the second embodiment of the present invention is a laminate including an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, wherein the acrylic resin film is , a tensile elongation at break at 120° C. of 170% or more, the hard coat layer contains a urethane acrylate resin and particles, the average dispersed particle diameter of the particles is r ( ⁇ m), and the hard coat layer
  • the laminate has a pencil hardness of H or more and a haze of 3% or more, and the particles are formed on the acrylic resin film
  • the second embodiment of the present invention it is possible to provide a laminate containing an acrylic resin film, which is excellent in moldability, surface hardness and antiglare properties, and a method for producing the same.
  • a method for manufacturing a laminate according to a second embodiment of the present invention comprises (A2) a urethane acrylate resin applied to at least one side of an acrylic resin film; and a step of irradiating the resin layer containing the urethane acrylate resin and the particles with an active energy ray to cure the resin layer containing the urethane acrylate resin and the particles to form a hard coat layer.
  • the acrylic resin film has a tensile elongation at break of 170% or more at 120° C., and the content of the particles is 2.0 to 5.0% by weight with respect to the hard coat layer after curing,
  • d ⁇ r is satisfied
  • the laminate has a pencil hardness of H or more
  • a laminate according to a second embodiment of the present invention (hereinafter referred to as a "second laminate”) includes an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film. and, wherein the acrylic resin film has a tensile elongation at break of 170% or more at 120 ° C., the hard coat layer includes a urethane acrylate resin and particles, and the average of the particles When the dispersed particle diameter is r ( ⁇ m) and the film thickness of the hard coat layer is d ( ⁇ m), d ⁇ r is satisfied, and the laminate has a pencil hardness of H or more and a haze of 3% or more, and the crack elongation at 120° C. of a laminated film obtained by laminating a resin layer containing no particles on the acrylic resin film is 80% or more.
  • both the laminate obtained by the method for manufacturing the laminate according to the second embodiment and the laminate according to the second embodiment may be referred to as "second laminate".
  • the laminate obtained by the above-described second laminate manufacturing method has surface hardness and is excellent in surface hardness. Moreover, it can be said that the laminate obtained by the second laminate manufacturing method has antiglare properties and is excellent in antiglare properties.
  • the method for evaluating the antiglare property of the laminate in this specification will be described in detail in later examples. Moreover, the laminate obtained by the second method for producing a laminate has excellent moldability.
  • Patent Document 4 only discloses a large-sized and flat-shaped film, and does not disclose a technique for solving "formability", which is one of the problems of the second embodiment.
  • Patent Document 5 discloses a constituent element in which the dispersed particle diameter of the antiglare particles is larger than the thickness of the antiglare particle-containing layer, the technical requirement is that the crack elongation of the resin layer is large.
  • configurations such as "moldability” and "small whitening during stretching”.
  • no laminate that satisfies requirements such as formability, surface hardness and antiglare property has been found in the prior art, and there is room for further improvement.
  • the present inventors have mainly studied the improvement of the moldability and surface hardness of the laminate and the antiglare property, and have found (i) a hard coat layer and a refractive index adjustment layer (for example, (low refractive index layer) and the like, and (ii) by controlling the dispersion state of particles in the hard coat layer, the functional It was found for the first time that a laminate excellent in formability, surface hardness and antiglare property can be obtained without causing peeling and cracking of the layers. Moreover, the present inventors have found that the laminate obtained by the above method can solve the problem of whitening of the stretched portion in addition to the moldability.
  • a hard coat layer and a refractive index adjustment layer for example, (low refractive index layer) and the like
  • laminates for molding having functional layers with surface hardness, anti-glare properties and anti-reflection properties have problems such as peeling and cracking of the coating layer at the stretched portion during molding and breakage of the film.
  • problems such as peeling and cracking of the coating layer at the stretched portion during molding and breakage of the film.
  • there was the following problem regarding whitening of the stretched portion (1) In the hard coat layer containing antiglare particles in the laminate, the hard coat layer sometimes undergoes significant whitening when the laminate is stretched during molding. (2) The low refractive index layer located on the outermost surface of the laminate sometimes whitened during stretching.
  • the inventors succeeded in obtaining the following knowledge in the process of earnestly examining these issues.
  • the resin used for the hard coat layer in the laminate should have a high crack elongation when stretched, and the film thickness of the hard coat layer and the content and dispersion state of the particles should be controlled. As a result, it has been found that, during the process of stretching the laminate, minute cleavage of the hard coat layer surface around the particles dispersed in the hard coat layer can be suppressed, and significant whitening of the hard coat layer during stretching can be prevented. .
  • the resin used in the hard coat layer in the laminate should have a high crack elongation during stretching
  • a laminate having excellent moldability, surface hardness and antiglare properties which is composed of an acrylic resin film and a hard coat layer, or an acrylic resin film, a hard coat layer and a low refractive index layer, has not been developed so far. There is no report, and the manufacturing method of the second laminate is an extremely excellent technique. The method for manufacturing the laminate will be described in detail below.
  • “laminate” intends a product (laminate) containing a hard coat layer containing particles, and a product (laminate) that does not contain a hard coat layer or a hard coat layer that contains particles.
  • the surface hardness of the hard coat layer is improved, and the crack elongation is high. Originally, it may be required not to cause breakage or significant whitening upon stretching. However, as described above, conventionally, surface hardness and scratch resistance and deformability and extensibility are contradictory properties, and it was not easy to achieve both.
  • Methods for imparting high stretchability during secondary molding while maintaining hardness to such a curable resin for hard coating include, for example, the methods (1) to (3) described above. . These methods (1) to (3) may be used alone or in combination as appropriate for the hard coat layer in the second laminate. may
  • the second laminate manufacturing method includes the following step (A2). - Step (A2): A resin layer containing a urethane acrylate resin and particles applied to at least one side of an acrylic resin film is irradiated with an active energy ray to cure the resin layer containing the urethane acrylate resin and particles. forming a hard coat layer.
  • the method for manufacturing the second laminate further includes the following step (B2). - Step (B2): A coating liquid containing an acrylate resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm is applied onto the hard coat layer obtained in the step (A2), and dried. A step of irradiating the obtained resin layer containing the acrylate-based resin with an active energy ray to cure the resin layer containing the acrylate-based resin to form a low refractive index layer.
  • step (A2) the resin layer containing the urethane acrylate resin and the particles applied to at least one side of the acrylic resin film is irradiated with active energy rays to cure the resin layer containing the urethane acrylate resin and the particles. to form a hard coat layer.
  • step (B2) a resin layer containing an acrylate-based resin is applied in a solution state on the hard coat layer containing the cured urethane acrylate resin formed in step (A2), and the resin layer is coated with The resin layer is cured by irradiation with active energy rays to form a low refractive index layer.
  • the second laminate manufacturing method further includes the following configuration in addition to the step (A2) and optional step (B2).
  • the acrylic resin film has a tensile elongation at break of 170% or more at 120°C.
  • the content of the particles is 2.0 to 5.0% by weight with respect to the hard coat layer after curing, and the average dispersed particle diameter of the particles is r ( ⁇ m), and the thickness of the hard coat layer is is d ( ⁇ m), d ⁇ r is satisfied.
  • the laminate has a pencil hardness of H or higher, a haze of 3% or higher, and a crack elongation at 120°C of 170% or higher.
  • the crack elongation at 120°C of the laminated film obtained by laminating the resin layer containing no particles on the acrylic resin film is 80% or more.
  • the hard coat layer and the low refractive index layer is preferably well adhered.
  • the low refractive index layer often contains a hard filler such as hollow silica, and often has a lower crack elongation than the hard coat layer. Therefore, cracks and microcracks may occur at a drawing ratio lower than the crack elongation of the hard coat layer alone.
  • the opening width of microcracks generated in the low refractive index layer will be fine, for example, 1 ⁇ m or less, and whitening will not easily occur due to stretching. .
  • the following (a) and/or (b) are preferable: (a) the low refractive index layer is formed in the step (B2) When the resin layer is applied in a solution state, the applied resin layer (low refractive index layer) to a certain extent within a range where the final interface between the two layers does not become unclear and the antireflection properties are not impaired. is impregnated into the hard coat layer; (b) the acrylate groups remaining after curing of the hard coat layer cause the resin layer Reactive curing with (low refractive index layer) to form a chemical bond at the interface between the finally obtained hard coat layer and the low refractive index layer.
  • the resin layer containing the urethane acrylate resin forming the hard coat layer is not completely cured, the crosslink density is slightly lowered, and the unreacted acrylate groups are partially removed. It is preferable to leave it.
  • a resin layer containing an acrylate-based resin that forms a low refractive index layer is applied in a solution state and optionally dried. In order to impregnate the layer, (a) appropriately adjusting the coating conditions and drying conditions, and/or (b) using a fixed amount of a slow-drying, high-boiling solvent as the solvent used in the solution, etc. is preferred.
  • the tensile elongation at break at 120°C of the acrylic resin film in the laminate is 170% or more, preferably 180% or more, and 190% or more. is more preferred.
  • the tensile elongation at break at 120° C. of the acrylic resin film is 170% or more, there is an advantage that the shape followability of molding is excellent.
  • the upper limit of the tensile elongation at break is not particularly limited, but from the viewpoint of improving the tensile strength, it is, for example, 350% or less, preferably 300% or less.
  • the pencil hardness of the laminate is H or higher, preferably 2H or higher, and more preferably 3H or higher.
  • H or higher it has the advantage of being less likely to be scratched.
  • the laminate has a haze of 3.0% or more, preferably 3.5% or more, more preferably 4.0% or more, and 4.5%. % or more is more preferable.
  • the haze of the laminate is 3.0% or more, there is an advantage that the antiglare property is excellent.
  • the haze of the laminate is measured by the method described in Examples.
  • the crack elongation of the laminate at 120°C is 80% or more, preferably 90% or more, and more preferably 100% or more.
  • the crack elongation at 120° C. of the laminate is 80% or more, there is an advantage that the shape followability during molding is excellent.
  • the upper limit of the crack elongation is not particularly limited, but from the viewpoint of improving surface hardness and wear resistance, it is, for example, 350% or less, and 300% or less. is preferred.
  • the "crack elongation of the laminate at 120°C” means the elongation at which cracks occur in the coating layer when the laminate is subjected to a tensile test in a constant temperature bath at 120°C.
  • the crack elongation of the laminate at 120°C is measured by the method described in Examples.
  • the crack elongation at 120 ° C. in the laminated film (hereinafter also referred to as "particle-free laminated film") in which the resin layer not containing the particles is laminated on the acrylic resin film
  • the degree is 80% or more, preferably 90% or more, and more preferably 100% or more.
  • the crack elongation at 120° C. of the particle-free laminated film is 80% or more, the advantage is that the laminated body is excellent in shape followability during molding, and whitening of the stretched portion during molding is suppressed. have The upper limit of the crack elongation at 120° C.
  • the particle-free laminated film is not particularly limited, but from the viewpoint of improving surface hardness and/or wear resistance, it is, for example, 200% or less and 180% or less. is preferred.
  • the crack elongation at 120° C. of the particle-free laminated film is measured by the method described in Examples.
  • the hard coat layer in the second laminate manufacturing method is a functional layer laminated on at least one side of the acrylic resin film, and contains a urethane acrylate resin and particles.
  • the hard coat layer may be laminated on one side or both sides of the acrylic resin film.
  • the content of the particles is 2.0 to 5.0% by weight with respect to the hard coat layer after curing, and the average dispersed particles of the particles When the diameter is r ( ⁇ m) and the thickness of the hard coat layer is d ( ⁇ m), d ⁇ r is satisfied.
  • various hard coat layers containing urethane acrylate resin which are conventionally provided in various functional films, resin molded products, etc., can be employed without particular limitation.
  • Particles to be blended in the hard coat layer for the purpose of imparting antiglare properties are desired antiglare properties, sharpness of transmitted images, glare, jet-blackness of the surface, surface hardness, slipperiness, antistatic properties, and the like.
  • the material of the particles, the number of parts to be blended, the type of dispersion solvent for the particles, the particle diameter, the dispersed particle diameter, the film thickness of the hard coat layer, and the relative refractive index difference with the hard coat base material can be appropriately adjusted within a known technical range that does not impair the effects of the present invention.
  • the material of the particles to be compounded in the hard coat layer is not particularly limited as long as the effects of the present invention are achieved.
  • Examples include (a) silica, alumina, glass beads or flakes, mica, clay, titanium oxide, and zinc oxide. , zirconia, metal particles, and/or (b) crosslinked organic resin particles based on alkyl (meth)acrylate units, aromatic vinyl units, siloxane units, etc., and (c) core-shell type multilayer structure resin particles, and the like.
  • the particles are inorganic oxide particles (for example, silica, alumina, titanium oxide, zinc oxide, zirconia, etc.) and/or crosslinked organic Resin particles are preferable, and at least one selected from the group consisting of silica, alumina, zirconia, crosslinked silicone resins, crosslinked acrylic resins and crosslinked aromatic vinyl resins is more preferable.
  • Silica particles, alumina particles, and crosslinked organic resin particles are particularly preferred from the viewpoint of the balance of physical properties such as antiglare properties, dispersibility, and surface hardness.
  • these particles are formed by known methods such as using a silane coupling agent or reactive monomer that may have a reactive substituent, plasma treatment, corona treatment, etc.
  • Reactive functional groups having reactivity with urethane acrylate resins include (a) radical reactive functional groups such as vinyl groups and (meth)acryloyl groups, (b) epoxy groups, oxetane groups, hydroxyl groups, carboxyl groups, mercapto ionic functional groups such as groups, isocyanyl groups, hydroxyl groups and amino groups; and (c) moisture-curable functional groups such as silyl groups and alkoxysilyl groups.
  • the particles contained in the hard coat layer satisfy d ⁇ r, where r ( ⁇ m) is the average dispersed particle diameter of the particles and d ( ⁇ m) is the film thickness of the hard coat layer. That is, the particles contained in the hard coat layer have an average dispersed particle size equal to or larger than the thickness of the hard coat layer.
  • the average dispersed particle diameter of the particles contained in the hard coat layer is smaller than the film thickness of the hard coat layer, local cleavage of the hard coat layer occurs at the peripheral portion of the dispersed particles in the thin hard coat layer during stretching. / Or cracks may occur and the dispersed particles may be exposed on the surface of the hard coat layer.
  • the state of the hard coat surface changes (color difference, haze, smoothness, etc.) before and after stretching becomes large, and this is thought to be observed as whitening of the stretched portion.
  • the average dispersed particle size of the particles contained in the hard coat layer is approximately the same as the thickness of the hard coat layer or larger than the thickness of the hard coat layer, at least Since some particles are exposed on the hard coat layer surface, there is a tendency for changes in the state of the hard coat surface before and after stretching (color difference, haze, gloss, smoothness, etc.) to be small, and whitening after stretching is reduced. It is considered to have the advantage of
  • particles may be dispersed in the state of primary particles, or may be dispersed in an aggregated state of multiple particles, depending on the size of the primary particles.
  • the size of a region (dispersed domain) in which these particles or aggregates thereof are distributed is defined as "average dispersed particle size".
  • average dispersed particle size When the size of the primary particles is large, the average dispersed particle size and the primary (basic) particle size may be the same.
  • the average dispersed particle diameter of the particles is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 0.1 ⁇ m to 50.0 ⁇ m, 0.2 ⁇ m to 25.0 ⁇ m, 0.5 ⁇ m to It may be 10 ⁇ m, 1.0 ⁇ m to 4.0 ⁇ m, 1.2 ⁇ m to 3.8 ⁇ m, 1.4 ⁇ m to 3.6 ⁇ m, and the like.
  • the average dispersed particle size of particles is measured by the method described in Examples.
  • the content of the particles in the hard coat layer is not particularly limited as long as the effect of one embodiment of the present invention is exhibited. Yes, 0.5 to 20.0 wt%, 1.0 to 15.0 wt%, 2.0 to 5.0 wt%, 2.2 to 4.8 wt%, 2.4 to It may be 4.6% by weight or the like.
  • the thickness of the hard coat layer is not particularly limited as long as the effects of the present invention can be achieved. It may be 0.4 to 2.8 ⁇ m or the like. The thickness of the hard coat layer is measured by the method described in Examples.
  • urethane acrylate resin in addition to the urethane acrylate resin, other components may be used in combination in the hard coat layer of the laminate in the second method for producing the laminate.
  • Components other than the urethane acrylate resin include, for example, monofunctional or polyfunctional (meth)acrylates, epoxy acrylate monomers, polyester acrylates, silicon acrylates, polycarbonate acrylates, polyacrylic acrylates, and the like, which have radically reactive functional groups. Monomers, oligomers, resins, or mixtures thereof can be used in combination.
  • a urethane acrylate resin and, for example, (a) a hydrolytic condensate of a difunctional to tetrafunctional silane compound, and/or (b) a cationically curable and/or anionically curable functional group such as an epoxy group and an oxetane group may be used in combination with a composition containing a monomer, oligomer, resin, or mixture thereof having As a component used for forming the hard coat layer, the urethane acrylate resin may be used alone, or in addition to the urethane acrylate resin, one or more of the other components may be added in combination. .
  • composition comprising (meth)acrylate, epoxy acrylate monomer, hydroxyl group-containing (meth)acrylate, polyisocyanate, polyhydric alcohol, organotin-based urethanization catalyst and hydrolytic condensate of silane compound, Since the contents are the same as those described in the ⁇ Others> section of the first embodiment, the description is used and the description is omitted here.
  • the curable composition When a resin layer (coating film) made of a curable composition is cured to form a hard coat layer, the curable composition is used for the purpose of improving coating properties, scratch resistance after curing, and antifouling properties.
  • various known leveling agents may be added. The content of the leveling agent is the same as that described in the ⁇ Others> section of the first embodiment, so the description is incorporated and the description thereof is omitted here.
  • the curable composition When forming a hard coat layer by applying a curable composition, the curable composition contains an ultraviolet absorber, a light stabilizer, an antifoaming agent, an antioxidant, a light diffusing agent, a matting agent, and an anti-oxidant.
  • Various additives such as staining agents, lubricants, colorants such as pigments and dyes, organic particles, inorganic particles, and antistatic agents can be added as required. Additives are not limited to these.
  • An organic solvent is usually blended in order to give the curable composition appropriate applicability. Since the content of the organic solvent is the same as that described in the ⁇ Others> section of the first embodiment, the description is incorporated and the description thereof is omitted here.
  • the method of applying the curable composition to the main surface of the above-mentioned acrylic resin film, which is the base film, is the same as the content described in the ⁇ Others> section of the first embodiment. , the description is used, and the description is omitted here.
  • the hard coat is formed by curing the resin layer obtained by light such as ultraviolet irradiation. A layer is formed.
  • the organic solvent may optionally be removed from the resin layer (coating film) by drying.
  • the drying temperature of the resin layer (coating film) when removing the organic solvent by drying is the same as the content described in the ⁇ Others> section of the first embodiment, so that description is used and described here. is omitted.
  • a commercially available product may be used as the composition for forming the hard coat layer. Since the content of the marketing is the same as that described in the ⁇ Others> section of the first embodiment, the description is used and the description is omitted here.
  • inorganic particles and/or metal particles may be further added.
  • examples of such inorganic particles and metal particles include, but are not limited to, silica, alumina, titanium oxide, zinc oxide, zirconia, graphene, nanocarbon, carbon black, nanodiamond, mica, barium titanate, boron nitride, Examples thereof include metallic silver and metallic copper.
  • These particles may be added for the purpose of improving the abrasion resistance of the hard coat layer, or may be added for further imparting antiglare properties.
  • inorganic particles and/or metal particles having a function of improving wear resistance and inorganic particles and/or metal particles having a function of imparting antiglare properties may be used in combination. These particles may be used without surface treatment, or may be surface-treated in advance by a known method to control the dispersed state, and the affinity with the hard coat layer may be appropriately controlled. .
  • a low refractive index layer containing an acrylate resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm is further provided on the hard coat layer.
  • the low refractive index layer constitutes an antireflection layer. Since each aspect of the low refractive index layer is the same as the content described in the section (low refractive index layer) of the first embodiment, the description is used and the description is omitted here.
  • the second laminate may have functional layers other than those described above.
  • the other functional layers are the same as those described in the ⁇ Other functional layers> section of the first embodiment, so the description is used and the description is omitted here.
  • each aspect of (a) the integrated amount of ultraviolet (UV) light in the step (A2) and (b) the chill roll temperature in the step (A2) will be described in the (Others) section of the first embodiment.
  • the conditions described in the above (hard coat layer) section of the second embodiment are used for conditions other than those described above in the step (A2).
  • the hard coat layer obtained in the step (A2) is coated with an acrylate resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm. Then, the resin layer containing the acrylate-based resin is irradiated with an active energy ray to cure the resin layer containing the acrylate-based resin, thereby forming a low refractive index layer.
  • each aspect of (a) the integrated amount of ultraviolet (UV) light in the step (B2) and (b) the cooling roll temperature in the step (B2) will be described in the (Others) section of the first embodiment.
  • the conditions described in the above (hard coat layer) section of the second embodiment are used for conditions other than those described above in the step (B2).
  • a solvent is added to the acrylate resin that is the material of the low refractive index layer, and the particle diameter is less than 100 nm.
  • a laminate comprising a step of preparing an acrylate resin containing 40% or more of hollow silica fine particles, wherein the solvent contains at least one solvent, and the solvent having the highest boiling point has a boiling point of 115°C to 180°C.
  • the "acrylate-based resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm" can also be said to be a "composition for forming a low refractive index layer.”
  • step (a) the boiling point of the highest boiling solvent in step (B2′), (b) the solvent used in step (B2′), and (c) in step (B2′), the acrylate-based
  • the acrylate-based Each aspect of the method of adding a solvent to the resin to prepare the acrylate-based resin containing 40% or more of the hollow silica fine particles having a particle diameter of less than 100 nm was described in the (Others) section of the first embodiment.
  • step (12′) (a) the boiling point of the solvent with the highest boiling point in step (B1′), (b) the solvent used in step (B1′), and (c) the solvent added to the acrylate resin in step (12′) and the method for preparing an acrylate-based resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm.
  • the second laminate includes an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film. More specifically, the second laminate is a laminate including an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, and the acrylic resin film is The hard coat layer has a tensile elongation at break of 170% or more at 120° C., contains a urethane acrylate resin and particles, and has an average dispersed particle diameter of r ( ⁇ m) of the particles. When the thickness is d ( ⁇ m), d ⁇ r is satisfied, the laminate has a pencil hardness of H or more and a haze of 3% or more, and the particles are formed on the acrylic resin film.
  • the crack elongation at 120° C. of the laminated film laminated with the resin layer not containing the resin layer is 80% or more.
  • the second laminate further includes a low refractive index layer on the hard coat layer.
  • the second laminate is composed of at least a specific acrylic resin film and a specific hard coat layer, as described above. Moreover, in a preferred aspect of the second embodiment of the present invention, the second laminate is composed of a specific acrylic resin film, a specific hard coat layer, and a specific low refractive index layer.
  • the second laminate is composed of the acrylic resin film described above (acrylic resin film) and the hard coat layer described above (hard coat layer).
  • the second laminate comprises the acrylic resin film described above (acrylic resin film) and the hard coat layer described above (hard coat layer). and the low refractive index layer described above (low refractive index layer).
  • the second laminate is preferably the above [2-2. Second Laminate Manufacturing Method].
  • the ⁇ haze after 80% stretching at 120° C. of the second laminate is, for example, 8.0% or less. , preferably 7.5% or less, more preferably 7.0% or less.
  • the ⁇ haze of the second laminate after 80% stretching at 120° C. is 8.0% or less, it has the advantage of suppressing whitening during molding.
  • the ⁇ haze of the second laminate after being stretched by 80% at 120° C. is measured by the method described in Examples.
  • the ⁇ haze after 80% stretching at 120° C. of the second laminate is, for example, , 10% or less, preferably 9.5% or less, more preferably 9.0% or less, and even more preferably 8.5% or less. If the ⁇ haze of the second laminate after 80% stretching at 120° C. is 10% or less, it has the advantage of suppressing whitening during molding.
  • the ⁇ haze of the second laminate after being stretched by 80% at 120° C. is measured by the method described in Examples.
  • the luminous reflectance of the second laminate is, for example, 3.0% or less, preferably 2.8% or less, and more preferably 2.6% or less.
  • the second laminate has a luminous reflectance of 3.0% or less, it has the advantage of excellent antireflection performance and excellent visibility when laminated on the display surface.
  • the luminous reflectance of the second laminate is measured by the method described in Examples.
  • each aspect of the absolute value of the thickness direction retardation (Rth) is, for each aspect, in the first laminate described in the section (Laminate) of the first embodiment, (a) In the laminated film obtained by laminating the low refractive index layer on the acrylic resin film, ⁇ haze after 20% stretching at 120 ° C., (b) in-plane retardation (Re) and (c) thickness direction retardation ( Rth), the description is incorporated, and the description is omitted here.
  • the second laminate may have a primer layer on the surface (two surfaces) of the acrylic resin film opposite to the surface provided with the hard coat layer.
  • the aspect of the primer layer in the second laminate is the same as the aspect of the primer layer in the first laminate described in the section (Laminate) of the first embodiment, so the description is omitted. The description is omitted here.
  • a molded body (hereinafter referred to as "second molded body") comprising a second laminate is provided.
  • the second molded body is obtained by laminating the second laminate on at least part of the surface of the molded body having at least a non-planar shape.
  • the second laminate When the second laminate is used, (a) it has a complicated three-dimensional shape, and (b) surface hardness, scratch resistance, chemical resistance, antifouling property, reflective property, antiglare property, etc. are controlled. In addition, it is possible to easily produce a molded product with excellent appearance. For this reason, the second molded body is the same as [1-4. Molded article], for example, it is preferably used for applications such as a front plate of an in-vehicle display having a planar shape, a curved shape and/or a three-dimensional shape. Accordingly, in a second embodiment of the present invention, there is provided an in-vehicle display front panel comprising a second molded body.
  • An embodiment of the present invention may have the following configuration. ⁇ X1> (A1) A resin layer containing a urethane acrylate resin applied to at least one surface of an acrylic resin film is irradiated with an active energy ray to cure the resin layer containing the urethane acrylate resin to form a hard coat layer. process and (B1) An acrylate-based resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm is coated on the hard coat layer obtained in the step (A1) to obtain a resin containing the acrylate-based resin.
  • a method for producing a laminate comprising a step of irradiating the layer with an active energy ray to cure the resin layer containing the acrylate resin to form a low refractive index layer,
  • the acrylic resin film has a tensile elongation at break of 170% or more at 120°C
  • the hard coat layer contains a urethane acrylate resin
  • the method for producing a laminate wherein the laminate has a crack elongation of 80% or more at 120°C.
  • ⁇ X2> The method for producing a laminate according to ⁇ X1>, wherein the integrated amount of active energy ray irradiation in the step (A1) is 150 to 500 mJ/cm 2 .
  • a solvent is added to the acrylate resin that is the material of the low refractive index layer to contain 40% or more of the hollow silica fine particles having a particle diameter of less than 100 nm.
  • ⁇ X4> Any of ⁇ X1> to ⁇ X3>, wherein the laminated film obtained by laminating the low refractive index layer on the acrylic resin film has a ⁇ haze of 30% or less after 20% stretching at 120°C. 2.
  • ⁇ X5> (A1) A resin layer containing a urethane acrylate resin applied to at least one side of an acrylic resin film is irradiated with an active energy ray to cure the resin layer containing the urethane acrylate resin to form a hard coat layer.
  • a method for manufacturing a laminate comprising: The acrylic resin film has a tensile elongation at break of 170% or more at 120° C., and the hard coat layer contains a urethane acrylate resin, The method for producing a laminate, wherein the laminate has a crack elongation of 80% or more at 120°C.
  • ⁇ X6> A laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, The acrylic resin film has a tensile elongation at break of 170% or more at 120°C, The hard coat layer contains a urethane acrylate resin, The laminate has a pencil hardness of H or more and a crack elongation at 120° C. of 80% or more.
  • a low refractive index layer is further provided on the hard coat layer,
  • ⁇ X8> The laminate according to ⁇ X7>, wherein the laminate has a luminous reflectance of 2.0% or less.
  • ⁇ X9> The laminate according to ⁇ X7> or ⁇ X8>, wherein the laminate has an in-plane retardation (Re) of 10 nm or less and an absolute value of a thickness direction retardation (Rth) of 30 nm or less.
  • ⁇ X10> The laminate according to any one of ⁇ X6> to ⁇ X9>, having a ⁇ haze of 3.0% or less when the stretching rate at 120° C. is 80%.
  • ⁇ X11> Any one of ⁇ X7> to ⁇ X10>, wherein the microcrack width in the direction parallel to the tensile stress of the low refractive index layer is 2.0 ⁇ m or less when the stretching ratio at 120° C. is 80%.
  • the laminate according to . ⁇ X12> When the stretching ratio at 120° C. is 80%, microcracks from the surface of the laminate on the low refractive index layer side at the microcrack sites in the direction parallel to the tensile stress of the low refractive index layer.
  • ⁇ X13> A molded article comprising the laminate according to any one of ⁇ X6> to ⁇ X12>.
  • ⁇ X14> A product obtained by laminating the laminate according to any one of ⁇ X6> to ⁇ X12> on at least part of the surface of a molded article having a non-planar shape at least in part. , ⁇ X13>.
  • one embodiment of the present invention may have the following configuration.
  • ⁇ Y1> A resin layer containing a urethane acrylate resin and particles coated on at least one side of an acrylic resin film is irradiated with an active energy ray to cure the resin layer containing the urethane acrylate resin and particles.
  • a method for manufacturing a laminate comprising a step of forming a hard coat layer by The acrylic resin film has a tensile elongation at break of 170% or more at 120°C,
  • the content of the particles is 2.0 to 5.0% by weight with respect to the hard coat layer after curing, where r ( ⁇ m) is the average dispersed particle diameter of the particles and d ( ⁇ m) is the film thickness of the hard coat layer, satisfying d ⁇ r
  • the laminate has a pencil hardness of H or higher, a haze of 3% or higher, and a crack elongation at 120° C. of 170% or higher,
  • a method for producing a laminate wherein a crack elongation at 120° C.
  • step (B) A coating liquid containing an acrylate-based resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm is applied onto the hard coat layer obtained in the step (A), and the obtained acrylate-based A step of irradiating a resin layer containing a resin with an active energy ray to cure the resin layer containing the acrylate resin to form a low refractive index layer.
  • ⁇ Y3> The method for producing a laminate according to ⁇ Y1> or ⁇ Y2>, wherein the integrated amount of active energy ray irradiation in the step (A) is 150 to 500 mJ/cm 2 .
  • step (B) Before the step (B), (B′) a solvent is added to the acrylate resin that is the material of the low refractive index layer, and the hollow silica fine particles having a particle diameter of less than 100 nm are contained in an amount of 40% or more.
  • a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film,
  • the acrylic resin film has a tensile elongation at break of 170% or more at 120°C
  • the hard coat layer contains a urethane acrylate resin and particles, where r ( ⁇ m) is the average dispersed particle diameter of the particles and d ( ⁇ m) is the film thickness of the hard coat layer, satisfying d ⁇ r
  • the laminate has a pencil hardness of H or more and a haze of 3% or more,
  • ⁇ Y7> The laminate according to ⁇ Y6>, wherein the particles are silica particles.
  • the hard coat layer contains 2.0 to 5.0% by weight of the silica particles, The laminate according to ⁇ Y7>, wherein the silica particles have an average dispersed particle size of 1.0 to 4.0 ⁇ m.
  • ⁇ Y9> The laminate according to any one of ⁇ Y6> to ⁇ Y8>, wherein the hard coat layer has a thickness of 0.2 to 3.0 ⁇ m.
  • ⁇ Y10> The laminate according to any one of ⁇ Y6> to ⁇ Y9>, having a ⁇ haze of 8.0% or less when the stretching rate at 120° C. is 80%.
  • a low refractive index layer is further provided on the hard coat layer,
  • ⁇ Y12> The laminate according to ⁇ Y11>, wherein the laminate has a luminous reflectance of 3.0% or less.
  • ⁇ Y13> The laminate according to ⁇ Y11> or ⁇ Y12>, which has a crack elongation of 170% or more at 120°C.
  • ⁇ Y14> The laminate according to any one of ⁇ Y11> to ⁇ Y13>, which has a ⁇ haze of 10% or less when the stretching rate at 120° C. is 80%.
  • ⁇ Y15> A molded article comprising the laminate according to any one of ⁇ Y6> to ⁇ Y14>.
  • one embodiment of the present invention may have the following configuration.
  • ⁇ Z1> A method for manufacturing a laminate, (A1) A step of irradiating a resin layer containing a urethane acrylate resin applied to at least one surface of an acrylic resin film with an active energy ray to cure the resin layer containing the urethane acrylate resin to form a hard coat layer; (B1) An acrylate-based resin containing 40% or more of hollow silica fine particles having a particle diameter of less than 100 nm is coated on the hard coat layer obtained in the step (A1) to obtain a resin containing the acrylate-based resin.
  • a step of irradiating the layer with an active energy ray to cure the resin layer containing the acrylate resin to form a low refractive index layer The acrylic resin film has a tensile elongation at break of 170% or more at 120°C, The method for producing a laminate, wherein the laminate has a crack elongation of 80% or more at 120°C.
  • the acrylic resin film is formed by molding an acrylic resin composition containing a thermoplastic acrylic polymer and polymer particles containing a crosslinked elastomer, and the thermoplastic acrylic polymer is methyl methacrylate.
  • Consisting of 50% by mass to 100% by mass of units and 0% by mass to 50% by mass of other structural units, the total amount of the methyl methacrylate unit and the other structural units in the thermoplastic acrylic polymer is The method for producing a laminate according to ⁇ Z1>, which is 100% by mass.
  • the crosslinked elastomer contains 50% by mass or more of an acrylic acid ester unit in 100% by mass of the crosslinked elastomer, and the polymer particles are a graft polymer positioned on the surface layer side of the crosslinked elastomer and the crosslinked elastomer.
  • the method for producing a laminate according to ⁇ Z2> which is a graft copolymer particle containing a layer.
  • ⁇ Z4> The method for producing a laminate according to any one of ⁇ Z1> to ⁇ Z3>, wherein the resin layer containing the urethane acrylate resin further contains particles.
  • ⁇ Z5> The method for producing a laminate according to ⁇ Z4>, wherein the particles are inorganic oxide particles and/or crosslinked organic resin particles.
  • ⁇ Z6> The particles are one or more selected from the group consisting of silica, alumina, zirconia, crosslinked silicone resins, crosslinked acrylic resins and crosslinked aromatic vinyl resins, ⁇ Z4> or ⁇ Z5>.
  • ⁇ Z7> Any one of ⁇ Z4> to ⁇ Z6>, wherein at least some of the particles contain a reactive functional group having reactivity with the urethane acrylate resin on the surface of the particles A method for manufacturing the described laminate.
  • ⁇ Z8> The content of the particles is 2.0 to 5.0% by weight with respect to the hard coat layer after curing, where r ( ⁇ m) is the average dispersed particle diameter of the particles and d ( ⁇ m) is the film thickness of the hard coat layer, satisfying d ⁇ r,
  • the laminate has a pencil hardness of H or higher, a haze of 3% or higher, and a crack elongation at 120° C.
  • a solvent is added to the acrylate resin that is the material of the low refractive index layer to contain 40% or more of the hollow silica fine particles having a particle diameter of less than 100 nm.
  • the solvent contains at least one or more solvents, and the boiling point of the solvent with the highest boiling point among the solvents is 115 to 180 ° C. body manufacturing method.
  • ⁇ Z11> Any of ⁇ Z1> to ⁇ Z10>, wherein the laminated film obtained by laminating the low refractive index layer on the acrylic resin film has a ⁇ haze of 30% or less after 20% stretching at 120°C. or a method for producing a laminate according to any one of the above.
  • a method for manufacturing a laminate (A1) irradiating a resin layer containing a urethane acrylate resin applied to at least one side of an acrylic resin film with an active energy ray to cure the resin layer containing the urethane acrylate resin to form a hard coat layer; including
  • the acrylic resin film has a tensile elongation at break of 170% or more at 120° C., and the hard coat layer contains a urethane acrylate resin,
  • ⁇ Z13> The method for producing a laminate according to ⁇ Z12>, wherein the laminate has a ⁇ haze of less than 8.0% when the stretch ratio at 120°C is 80%.
  • the acrylic resin film is formed by molding an acrylic resin composition containing a thermoplastic acrylic polymer and polymer particles containing a crosslinked elastomer, and the thermoplastic acrylic polymer is methyl methacrylate. Consisting of 50% by mass to 100% by mass of units and 0% by mass to 50% by mass of other structural units, the total amount of the methyl methacrylate unit and the other structural units in the thermoplastic acrylic polymer is The method for producing a laminate according to ⁇ Z12> or ⁇ Z13>, which is 100% by mass.
  • the crosslinked elastomer contains 50% by mass or more of an acrylic acid ester unit in 100% by mass of the crosslinked elastomer, and the polymer particles are a graft polymer positioned on the surface layer side of the crosslinked elastomer and the crosslinked elastomer.
  • ⁇ Z16> A laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film,
  • the acrylic resin film has a tensile elongation at break of 170% or more at 120°C
  • the hard coat layer contains a urethane acrylate resin
  • the laminate has a pencil hardness of H or more and a crack elongation at 120° C. of 80% or more.
  • ⁇ Z17> The laminate according to ⁇ Z16>, wherein the hard coat layer further contains particles.
  • ⁇ Z18> The laminate according to ⁇ Z17>, wherein the particles are inorganic oxide particles and/or crosslinked organic resin particles.
  • the particles are one or more selected from the group consisting of silica, alumina, zirconia, crosslinked silicone resins, crosslinked acrylic resins and crosslinked aromatic vinyl resins, ⁇ Z17> or ⁇ Z18>.
  • a low refractive index layer is further provided on the hard coat layer,
  • ⁇ Z22> The laminate according to ⁇ Z21>, wherein the laminate has a luminous reflectance of 2.0% or less.
  • ⁇ Z23> The laminate according to ⁇ Z21> or ⁇ Z22>, wherein the laminate has an in-plane retardation (Re) of 10 nm or less and an absolute value of a thickness direction retardation (Rth) of 30 nm or less.
  • ⁇ Z24> The laminate according to any one of ⁇ Z16> to ⁇ Z23>, which has a ⁇ haze of less than 8.0% when the stretching rate at 120° C. is 80%.
  • ⁇ Z25> The laminate according to any one of ⁇ Z16> to ⁇ Z24>, which has a ⁇ haze of 3.0% or less when the stretching rate at 120° C. is 80%.
  • ⁇ Z26> Any one of ⁇ Z21> to ⁇ Z25>, wherein the microcrack width in the direction parallel to the tensile stress of the low refractive index layer is 2.0 ⁇ m or less when the stretching ratio at 120° C. is 80%. 1. Laminate according to one. ⁇ Z27> When the stretching ratio at 120° C.
  • ⁇ Z28> A molded article comprising the laminate according to any one of ⁇ Z16> to ⁇ Z27>.
  • ⁇ Z29> ⁇ Z28> obtained by laminating the laminate according to any one of ⁇ Z16> to ⁇ Z27> on at least part of the surface of the molded body having a non-planar shape at least in part >.
  • a method for manufacturing a laminate (A2) A resin layer containing a urethane acrylate resin and particles coated on at least one side of an acrylic resin film is irradiated with an active energy ray to cure the resin layer containing the urethane acrylate resin and particles for hard coating.
  • the acrylic resin film has a tensile elongation at break of 170% or more at 120°C,
  • the content of the particles is 2.0 to 5.0% by weight with respect to the hard coat layer after curing, where r ( ⁇ m) is the average dispersed particle diameter of the particles and d ( ⁇ m) is the film thickness of the hard coat layer, satisfying d ⁇ r,
  • the laminate has a pencil hardness of H or higher, a haze of 3% or higher, and a crack elongation at 120° C. of 170% or higher,
  • a method for producing a laminate wherein a crack elongation at 120° C. in a laminated film obtained by laminating a resin layer containing no particles on the acrylic resin film is 80% or more.
  • ⁇ Z31> The method for producing a laminate according to ⁇ Z30>, wherein the laminate has a ⁇ haze of less than 8.0% when the stretch ratio at 120°C is 80%.
  • ⁇ Z32> A laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, The acrylic resin film has a tensile elongation at break of 170% or more at 120°C, The hard coat layer contains a urethane acrylate resin and particles, where r ( ⁇ m) is the average dispersed particle diameter of the particles and d ( ⁇ m) is the film thickness of the hard coat layer, satisfying d ⁇ r, The laminate has a pencil hardness of H or more and a haze of 3% or more, A laminate having a crack elongation at 120° C.
  • Example A Hereinafter, the first embodiment of the present invention will be described in more detail based on Example A, but the present invention is not limited to these Examples A.
  • Parts and “%” in Example A and Comparative Example A below mean parts by mass or % by mass.
  • the average particle size of the crosslinked elastomer or graft copolymer particles dispersed in the aqueous latex was measured using a laser diffraction particle size distribution analyzer (Microtrac particle size distribution analyzer MT3000 manufactured by Nikkiso Co., Ltd.).
  • Glass transition temperature (Tg) A differential scanning calorimeter (DSC) SSC-5200 manufactured by Seiko Instruments was used. The sample (acrylic resin film) was once heated to 200°C at a rate of 25°C/min, held at 200°C for 10 minutes, and then lowered to 50°C at a rate of 25°C/min (preliminary adjustment). . Thereafter, the sample was heated to 200° C. at a heating rate of 10° C./min, during which DSC measurement was performed. A differential value (SSDC) was obtained from the obtained DSC curve, and the glass transition temperature of the acrylic resin film was obtained from the maximum point thereof.
  • SSDC differential value
  • Test breaking elongation A piece of 10 mm (width) ⁇ 100 mm (length) was cut from the acrylic resin film to obtain a test piece.
  • the test piece using a Tensilon tensile tester (Shimadzu Corporation, AG-2000D) equipped with a high temperature bath set at 120 ° C., the preheating time is 2 minutes, the distance between chucks is 40 mm, and the tensile speed is 200 mm / min. Measurement was performed under the conditions of The elongation at break of the acrylic resin film was taken as the tensile elongation at break.
  • the value of the tensile elongation at break is the arithmetic mean of the three values excluding the highest and lowest values among the measurement results obtained using five test pieces.
  • the crack elongation was measured for a laminate in which a hard coat layer or a hard coat layer and a low refractive index layer were formed on one side of an acrylic resin film. Specifically, the laminate was cut into a size of 10 mm (width) ⁇ 100 mm (length) to obtain a sample. For the sample, using a Tensilon tensile tester (Shimadzu Corporation, AG-2000D) equipped with a high temperature bath set at 120 ° C., preheating time 2 minutes, distance between chucks 40 mm, tensile speed 200 mm / min. Measurements were made under the following conditions. The crack elongation at 120° C. was defined as the elongation when cracks occurred in the hard coat layer. The value of crack elongation is the arithmetic mean value of the test results (three) obtained by measuring three samples. The results are shown in Table 5.
  • the measurement of whitening after 80% stretching at 120° C. was performed on a laminate having a hard coat layer and a low refractive index layer formed on one side of an acrylic resin film. Specifically, the laminate was cut into a size of 10 mm (width) ⁇ 100 mm (length) to obtain a sample.
  • a Tensilon tensile tester (Shimadzu Corporation, AG-2000D) equipped with a high temperature bath set at 120 ° C. was used for a preheating time of 2 minutes, a distance between chucks of 40 mm, and a tensile speed of 200 mm / min.
  • the film was stretched by 80% under these conditions, and the degree of whitening was visually observed.
  • the evaluation criteria are ⁇ (excellent): no whitening in both reflection and transmission, ⁇ (good): no whitening in reflection, slight whitening in transmission, ⁇ (acceptable): slight whitening in both reflection and transmission, ⁇ (poor): Whitening is assumed to occur in both reflection and transmission.
  • the film thickness of the acrylic resin film was measured with a PEACOCK dial gauge No. 25 (manufactured by Ozaki Manufacturing Co., Ltd.).
  • the film thickness of the hard coat layer was measured with an F20 film thickness measurement system (manufactured by Filmetrics Co., Ltd.).
  • the opposite side of the hard coat layer was painted black with a felt-tip pen, and the refractive index of the acrylic resin film was set at 1.49 and the refractive index of the hard coat layer at 1.50.
  • the haze of the laminate was measured according to ISO14782 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
  • ⁇ haze after 80% stretch at 120°C The measurement of ⁇ haze after stretching the laminate by 80% at 120° C. was performed on a laminate having a hard coat layer and a low refractive index layer formed on one side of an acrylic resin film. Specifically, the laminate was cut into a size of 10 mm (width) ⁇ 100 mm (length) to obtain a sample.
  • a Tensilon tensile tester (Shimadzu Corporation, AG-2000D) equipped with a high temperature bath set at 120 ° C. was used for a preheating time of 2 minutes, a distance between chucks of 40 mm, and a tensile speed of 200 mm / min.
  • the haze of the laminated body after stretching was measured according to ISO14782 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the difference between the haze of the laminate before stretching and the haze of the laminate after 80% stretching was defined as " ⁇ haze after 80% stretching at 120°C”.
  • ⁇ haze after 20% stretching at 120°C Measurement of ⁇ haze after 20% stretching at 120° C. of the laminate was performed on a laminate in which a low refractive index layer was formed directly on one side of the acrylic resin film without forming a hard coat layer on one side of the acrylic resin film. done for film. Specifically, the laminate film was cut into a piece of 10 mm (width) ⁇ 100 mm (length) to obtain a sample. For the sample, a Tensilon tensile tester (Shimadzu Corporation, AG-2000D) equipped with a high temperature bath set at 120 ° C.
  • the haze of the laminated body after stretching was measured according to ISO14782 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The difference between the haze of the laminate before stretching and the haze of the laminate after 20% stretching was defined as " ⁇ haze after 20% stretching at 120°C”.
  • the luminous reflectance of the laminate was measured for a laminate having a hard coat layer and a low refractive index layer formed on one side of an acrylic resin film.
  • the surface opposite to the surface on which the hard coat layer and the low refractive index layer are formed is painted black with a black oil-based marking pen (Magic Ink (registered trademark), manufactured by Teranishi Kagaku Kogyo), and then A black vinyl tape was pasted together to form a sample.
  • the luminous reflectance of the sample was measured according to JIS Z 8722 using a colorimeter SC-P (manufactured by Suga Test Instruments Co., Ltd.).
  • the pencil hardness of the laminate was measured according to JIS K5600-5-4.
  • the width of the microcracks and the depth of the grooves of the microcracks were measured for a laminate in which a hard coat layer and a low refractive index layer were formed on one side of an acrylic resin film. Specifically, the laminate was cut into a size of 10 mm (width) ⁇ 100 mm (length) to obtain a sample.
  • a Tensilon tensile tester (Shimadzu Corporation, AG-2000D) equipped with a high temperature bath set at 120 ° C. was used for a preheating time of 2 minutes, a distance between chucks of 40 mm, and a tensile speed of 200 mm / min. Stretched 80% under conditions. The stretched sample was observed with a transmission microscope to measure the width of the microcracks and the depth of the grooves of the microcracks.
  • the particle diameter of the hollow silica fine particles was obtained by observing a cross-sectional photograph of the laminate of 1200 nm ⁇ 800 nm at a magnification of 200,000 times measured with an electron microscope (Hitachi High-Technologies Corporation, H7650). An arithmetic mean value of the particle diameters of 10 hollow silica fine particles was calculated, and the obtained value was taken as the particle diameter of the hollow silica fine particles.
  • the average dispersed particle diameter of the particles in the hard coat was obtained by observing a cross-sectional photograph of the laminate of 1200 nm ⁇ 800 nm at a magnification of 200,000 using an electron microscope (Hitachi High-Technologies Corporation, H7650). An arithmetic mean value of the particle sizes of 10 dispersed domains of the particles in the hard coat was calculated, and the obtained value was defined as the average dispersed particle size of the particles in the hard coat.
  • the in-plane retardation was measured for a laminate in which a hard coat layer and a low refractive index layer were formed on one side of an acrylic resin film. Specifically, the laminate was cut into a size of 40 mm ⁇ 40 mm and used as a sample. The sample was measured using an automatic birefringence meter (KOBRA-WR manufactured by Oji Keisoku Co., Ltd.) at a temperature of 23 ⁇ 2° C. and a humidity of 50 ⁇ 5% at a wavelength of 590 nm and an incident angle of 0°.
  • KOBRA-WR automatic birefringence meter
  • Thickness direction retardation The thickness direction retardation was measured for a laminate in which a hard coat layer and a low refractive index layer were formed on one side of an acrylic resin film. Specifically, the laminate was cut into a size of 40 mm ⁇ 40 mm and used as a sample. The sample was measured using an automatic birefringence meter (KOBRA-WR manufactured by Oji Keisoku Co., Ltd.) at a temperature of 23 ⁇ 2° C. and a humidity of 50 ⁇ 5% at a wavelength of 590 nm and an incident angle of 0°.
  • KOBRA-WR automatic birefringence meter
  • the average dispersed particle diameter of the particles was obtained by observing a cross-sectional photograph of 48 ⁇ m ⁇ 32 ⁇ m at a magnification of 10,000 times measured with an electron microscope (Hitachi High-Technologies Co., Ltd., H7650). The average value of dispersed particles was calculated.
  • the antiglare properties were measured on laminates having a hard coat layer or a hard coat layer and a low refractive index layer formed on one side. Specifically, a black adhesive PET film was adhered to the surface of the laminate opposite to the side on which the hard coat layer was formed, and reflection of a fluorescent lamp was visually observed in a bright room environment. ⁇ : The outline of the fluorescent lamp was blurred and could not be confirmed, ⁇ : The outline of the fluorescent lamp could be clearly confirmed.
  • gloss The glossiness of the laminate was measured for a laminate having a hard coat layer and a low refractive index layer formed on one side of an acrylic resin film.
  • specular gloss of the sample at 60° was measured according to JIS Z 8741 using a gloss meter VG7000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the following monomer mixture was continuously added into the polymerization apparatus at a rate (rate) of 10 parts by mass/hour. After the completion of the addition of the monomer mixture, the polymerization was continued for 0.5 hour to obtain particles of crosslinked elastomer (A1) (average particle size: 90 nm). The polymerization conversion rate was 99.5%.
  • Monomer mixture - Vinyl monomer mixture (90% n-butyl acrylate (BA) and 10% methyl methacrylate (MMA)) 30 parts - Allyl methacrylate (AlMA) 1 part - Cumene hydroperoxide (CHP) 0.2 parts.
  • BA n-butyl acrylate
  • MMA methyl methacrylate
  • AlMA Allyl methacrylate
  • CHP Cumene hydroperoxide
  • 0.05 part by mass of sodium dioctyl sulfosuccinate was charged into the polymerization apparatus containing the particles of the crosslinked elastomer (A1).
  • the internal temperature of the polymerization apparatus was set to 60° C., and 70 parts of a vinyl monomer mixture (MMA 98%, BA 1%, and RUVA 1%) for forming the graft polymer layer (A2), tertiary dodecyl mercaptan (t-DM) 0.
  • a monomer mixture consisting of .5 parts and 0.5 parts of CHP was continuously added into the polymerization apparatus at a rate of 10 parts/hour.
  • RUVA is a reactive ultraviolet absorber (2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2-H-benzotriazole (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.)).
  • graft copolymer particles (B1) consisting of a two-layer core (crosslinked elastomer (B1)) and shell (graft polymer layer (B2)) was obtained.
  • the polymerization conversion rate was 100.0%.
  • the coagulated solid content was washed with water and dried to obtain white powdery graft copolymer particles (B).
  • the average particle size of the graft copolymer particles (B) was 250 nm. Table 2 shows the blending amount of each component.
  • melt-kneaded product was taken out from the extruder in the form of a strand, cooled in a water tank, and then cut using a pelletizer to obtain pellets.
  • a die with ⁇ 4.5 ⁇ 15 holes was used, and a leaf disk filter (manufactured by Nagase & Co., Ltd., filtration system 10 ⁇ m, size 7 inches, number of sheets 33) was installed as a polymer filter between the die and the head of the extruder.
  • the obtained pellets are melt-kneaded at a discharge rate of 150 kg/hr at a cylinder setting temperature of 180° C. to 240° C. using a 90 mm ⁇ single screw extruder with a T die, and discharged from a T die at a die temperature of 240° C. , Both sides are brought into contact with a touch roll equipped with a metal cast roll temperature-controlled to 90 ° C. and an elastic metal sleeve temperature-controlled to 60 ° C. While cooling and solidifying, a film is formed and wound up, and an acrylic film with a thickness of 175 ⁇ m ( An acrylic resin film) was obtained.
  • Example A1 On the acrylic film (acrylic resin film) obtained in Production Example 3, Paint 1 shown in Table 4 was applied using a bar coater to form a resin layer on the acrylic film. After coating, the resin layer was dried at 80° C. for 1 minute to volatilize the solvent from the resin layer. Then, the resin layer was irradiated with ultraviolet rays (active energy rays) at the UV integrated light quantity shown in Table 5 to cure the resin layer and form a hard coat layer. The temperature of the cooling roll when forming the hard coat layer was 50°C. Various properties of the obtained laminate were evaluated. Table 5 shows the results. In addition, in Example 1, a laminate composed of an acrylic film and a hard coat layer was produced.
  • ultraviolet rays active energy rays
  • Example 1 the obtained laminate was measured and evaluated for various physical properties described in the column of "Laminate (hard coat layer, low refractive index layer formation)" in Table 5, and the results are shown in Table 5.
  • 5 “Laminate (formation of hard coat layer and low refractive index layer)”.
  • the coating material 1 shown in Table 4 is a curable composition for forming a hard coat layer, and can be said to be a composition for forming a hard coat layer.
  • Examples A2 to A12, Comparative Examples A1 to A2 On the acrylic film (acrylic resin film) obtained in Production Example 3, the paints 1 to 5 shown in Table 4 are applied in the combinations shown in Table 5 using a bar coater, and the resin layer is formed on the acrylic film. formed. After coating, the resin layer was dried at 80° C. for 1 minute to volatilize the solvent from the resin layer. Then, the resin layer was irradiated with ultraviolet rays (active energy rays) at the UV integrated light quantity shown in Table 5 to cure the resin layer and form a hard coat layer. The temperature of the cooling roll when forming the hard coat layer was 50°C.
  • the paints 6 to 9 shown in Table 4 were applied on the resulting hard coat layer in the combinations shown in Table 5 using a bar coater to form a resin layer on the hard coat layer.
  • the particle diameter of the hollow silica fine particles in the paints 6 to 9 was all about 50 nm.
  • the resin layer was dried at 80° C. for 1 minute to volatilize the solvent from the resin layer.
  • the resin layer was irradiated with ultraviolet rays (activation energy rays) at the integrated UV light amount and nitrogen atmosphere shown in Table 5 to cure the resin layer and form a low refractive index layer on the hard coat layer.
  • ultraviolet rays activation energy rays
  • Coatings 1 to 5 listed in Table 4 are curable compositions for forming a hard coat layer, and can also be said to be compositions for forming a hard coat layer.
  • Coatings 6 to 9 listed in Table 4 are curable compositions for forming a low refractive index layer, and can also be said to be compositions for forming a low refractive index layer.
  • paints 6 to 9 shown in Table 4 were separately applied onto the acrylic film (acrylic resin film) obtained in Production Example 3. It was applied using a bar coater to form a resin layer on the acrylic film. After coating, it was dried at 80° C. for 1 minute to volatilize the solvent from the resin layer. Then, the resin layer was irradiated with ultraviolet rays (active energy rays) at the UV integrated light amount and nitrogen atmosphere shown in Table 5, and the resin layer was cured to prepare a laminated film in which only the low refractive index layer was formed on the acrylic film. did. Table 5 shows the results of evaluation of ⁇ haze after 20% stretching at 120°C for the obtained laminated film.
  • ultraviolet rays active energy rays
  • Example A was excellent in formability. It was also found that the laminates of Examples A1 to A7, A10 and A11 had good whitening (low whitening) after 80% stretching at 120° C. in addition to moldability. Furthermore, it was found that the laminates of Examples A2 to A12 are excellent in antireflection effect. On the other hand, the laminate of Comparative Example A was found to be inferior in formability.
  • Examples A13 to A21 First, particles 1 to 12 shown in Table 6 were mixed with methyl ethyl ketone (MEK) and thoroughly stirred to prepare a 20 mass % particle dispersion. Next, 20% by mass of the particle dispersion and the coating material 1 were mixed in a predetermined amount (in the finally obtained laminate, the amount of particles contained in the hard coat layer was the amount shown in Table 7). The particles were mixed and sufficiently stirred to prepare a hard coat layer-forming composition containing particles. Next, on the acrylic film (acrylic resin film) obtained in Production Example 3, the composition for forming a hard coat layer containing the particles prepared as described above was applied using a bar coater so as to have the combinations shown in Table 7. to form a resin layer on the acrylic film.
  • MEK methyl ethyl ketone
  • the resin layer was dried at 80° C. for 1 minute to volatilize the solvent from the resin layer.
  • the resin layer was irradiated with ultraviolet rays (active energy rays) at the UV integrated light amount shown in Table 7 to cure the resin layer and form a hard coat layer containing particles.
  • the temperature of the cooling roll when forming the hard coat layer was 50°C.
  • paint 6 shown in Table 4 was applied using a bar coater to form a resin layer on the hard coat layer. After coating, the resin layer was dried at 80° C. for 1 minute to volatilize the solvent from the resin layer.
  • the resin layer was irradiated with ultraviolet rays (activation energy rays) at the cumulative UV light amount shown in Table 7 and in a nitrogen atmosphere to cure the resin layer and form a low refractive index layer on the hard coat layer.
  • ultraviolet rays activation energy rays
  • Table 7 shows the results.
  • the numerical values of these items are obtained by forming a hard coat layer composed of paint 1 containing no particles on the acrylic film (acrylic resin film) obtained in Production Example 3 by the method described above. It is a value obtained by measuring the crack elongation at 120° C. as a sample.
  • Example B The second embodiment of the present invention will be described below in more detail based on Example B, but the present invention is not limited to these Examples B.
  • FIG. In addition, “parts” and “%” in Example B and Comparative Example B below mean parts by mass or % by mass.
  • the crack elongation at 120°C in laminated film containing no particles was measured for the laminated film having a particle-free hard coat layer formed on one side of the acrylic resin film. Specifically, the laminated film is cut into 10 mm (width) ⁇ 100 mm (length), and a Tensilon tensile tester (Shimadzu Corporation, AG-2000D) equipped with a high temperature chamber set at 120 ° C. is used. , preheating time of 2 minutes, distance between chucks of 40 mm, and tensile speed of 200 mm/min. The crack elongation at 120° C. of the particle-free laminated film was defined as the elongation when cracks occurred in the hard coat layer.
  • Example A Since the contents described in the section [Example A] are the same as those described in the above [Example A] section except that the laminate in which the coat layer and the low refractive index layer are formed is used, the description is used and the description is omitted here. omitted.
  • Example B In Example B, graft copolymer particles (A) and graft copolymer particles (B) obtained by the same methods as in [Production Example 1] and [Production Example 2] of [Example A] were used. used. Moreover, in Example B, a film obtained by producing in the same manner as in [Example 3] of [Example A] was used as the acrylic film.
  • Comparative Example B7 a laminate film of a PMMA resin layer and a PC resin layer (manufactured by AW-10U Shine Techno, thickness 200 ⁇ m) was used as the base film instead of the acrylic film.
  • Examples B1 to B10, Comparative Examples B1 to B7 First, particles 1 to 12 shown in Table 6 were mixed with MEK and thoroughly stirred to prepare a 20% by mass particle dispersion. Next, 20% by mass of the particle dispersion and the paints 1 to 5 shown in Table 4 are mixed in predetermined amounts (in the finally obtained laminate, the amount of particles contained in the hard coat layer is shown in Tables 8 and 9). The ingredients were mixed so as to achieve the stated amount) and sufficiently stirred to prepare a hard coat layer-forming composition containing particles. Next, the composition for forming a hard coat layer containing the particles prepared as described above is applied on the acrylic film (acrylic resin film) obtained in Production Example 3 or the laminated film of the PMMA resin layer and the PC resin layer.
  • Examples B11 to B15, Comparative Examples B8 to B9 In the same manner as in [Examples B1 to B10, Comparative Examples B1 to B7], a hard coat layer-forming composition containing particles was used to obtain an acrylic film (acrylic resin film) in Production Example 3. A hard coat layer was formed thereon. Next, on the resulting hard coat layer, paints 6, 8 or 9 listed in Table 4 are applied in the combinations listed in Tables 8 and 9 using a bar coater to form a resin layer on the hard coat layer. did. After coating, the resin layer was dried at 80° C. for 1 minute to volatilize the solvent from the resin layer.
  • the resin layer was irradiated with ultraviolet rays (active energy rays) at the integrated UV light amount shown in Tables 8 and 9 in a nitrogen atmosphere to cure the resin layer and form a low refractive index layer on the hard coat layer.
  • ultraviolet rays active energy rays
  • the first method for manufacturing a laminate can obtain a laminate with excellent moldability and low whitening.
  • the second method for producing a laminate can provide a laminate excellent in moldability, surface hardness, and antiglare properties. Therefore, one embodiment of the present invention can be suitably used in various fields including automotive interior applications such as in-vehicle displays.

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