WO2024203401A1 - 積層体及びそれを含む樹脂成形体 - Google Patents

積層体及びそれを含む樹脂成形体 Download PDF

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Publication number
WO2024203401A1
WO2024203401A1 PCT/JP2024/010061 JP2024010061W WO2024203401A1 WO 2024203401 A1 WO2024203401 A1 WO 2024203401A1 JP 2024010061 W JP2024010061 W JP 2024010061W WO 2024203401 A1 WO2024203401 A1 WO 2024203401A1
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Prior art keywords
laminate
acrylic resin
hard coat
coat layer
acrylate
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Ceased
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PCT/JP2024/010061
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English (en)
French (fr)
Japanese (ja)
Inventor
石丸富士雄
長谷部花子
小山治規
嶋本幸展
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Kaneka Corp
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Kaneka Corp
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Priority to CN202480020857.1A priority Critical patent/CN120936661A/zh
Priority to JP2025510474A priority patent/JPWO2024203401A1/ja
Publication of WO2024203401A1 publication Critical patent/WO2024203401A1/ja
Priority to US19/341,306 priority patent/US20260022221A1/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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
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    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
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    • B32B2307/71—Resistive to light or to UV
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08J2433/06—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
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Definitions

  • the present invention relates to a laminate containing an acrylic resin film and a resin molded body containing the same.
  • Acrylic resin films have excellent transparency, weather resistance, high formability that allows lamination following the surface of a substrate with a planar and/or three-dimensional shape, adhesion, adhesiveness, and printability to other substrates, and are therefore widely used in various applications such as surface protection and/or coloring, decoration, etc. for automobile interior materials, automobile exterior materials, optical components, home appliance components, architectural exterior materials, retroreflective materials, etc.
  • a hard coat layer is provided for the purpose of further improving surface hardness, scratch resistance, and chemical resistance against various solvents and drugs.
  • Patent Document 1 describes a hard coat film having a substrate made of an acrylic resin film and a hard coat layer made of an electron beam cured product of an electron beam cured resin composition containing an electron beam cured resin and a triazine ultraviolet absorber.
  • Patent Document 2 describes a laminate that includes an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, the hard coat layer including a urethane acrylate resin, and has a crack elongation of 80% or more at 120°C.
  • the present invention has been made in consideration of the above problems, and provides a laminate that has good transparency, surface hardness, and chemical resistance, high secondary formability, and excellent long-term weather resistance, and can be used to protect the surface of a resin molded body having a flat and/or three-dimensional surface, and a resin molded body containing the laminate.
  • One or more embodiments of the present invention relate to a laminate including an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, the acrylic resin film having a tensile break elongation of 200% or more at 120°C, the hard coat layer being formed of a cured product of a curable resin composition including a urethane acrylate resin and a hindered amine light stabilizer having a reactive functional group, and the laminate having a tensile crack elongation of 100% or more at 120°C.
  • One or more embodiments of the present invention relate to a resin molded article that includes the laminate and a thermoplastic resin substrate, and at least a portion of the thermoplastic resin substrate is covered with the laminate arranged so that the acrylic resin film faces the thermoplastic resin substrate.
  • the present invention provides a laminate that has good transparency, surface hardness, and chemical resistance, high secondary moldability, and excellent long-term weather resistance, and can be used to protect the surface of a resin molded product having a flat and/or three-dimensional surface, and a resin molded product containing the laminate.
  • FIG. 1 is a schematic cross-sectional view of a laminate according to one embodiment of the present invention.
  • the inventors of the present invention have conducted intensive research to solve the above problems. As a result, they have surprisingly found that, in a laminate including an acrylic resin film and a hard coat layer, by using an acrylic resin film having specific physical properties and forming the hard coat layer from a cured product of a specific curable resin composition including a urethane acrylate resin and a hindered amine light stabilizer having a reactive functional group, the laminate has good transparency, surface hardness, and chemical resistance, and has improved secondary moldability and long-term weather resistance. Specifically, the laminate according to one or more embodiments of the present invention has a tensile crack elongation of 100% or more at 120° C.
  • the laminate according to one or more embodiments of the present invention has improved long-term weather resistance by forming the hard coat layer from a cured product of a specific curable resin composition containing a urethane acrylate resin and a hindered amine-based light stabilizer having a reactive functional group.
  • accelerated weathering test in which the laminate is placed with the hard coat layer side facing the light source, a xenon lamp is used as the light source, and an irradiance of 180 W/ m2 (300 to 400 nm) is applied under conditions of a total of 120 minutes, consisting of step 1 with an exposure time of 102 minutes, a black panel temperature of 60 ⁇ 3°C, a relative humidity of 65 ⁇ 5%, and no rainfall, and step 2 with an exposure time of 18 minutes, a chamber temperature of 38 ⁇ 3°C, a relative humidity of 95 ⁇ 5%, and rainfall, for 1000 cycles (total of 2000 hours) (hereinafter also referred to simply as "accelerated weathering test").
  • a numerical range when a numerical range is indicated with “ ⁇ ”, the numerical range includes both end values (upper and lower limits).
  • a numerical range of "X to Y” is a range that includes both end values X and Y, and is the same range as "X or more and Y or less”. Any number within that range and any range contained within that range are specifically disclosed.
  • multiple numerical ranges are described in this specification, they are considered to include numerical ranges that appropriately combine the upper and lower limits of different numerical ranges.
  • the acrylic resin film has a tensile elongation at break of 200% or more at 120° C. This increases the tensile crack elongation at 120° C. of the laminate with the hard coat layer, and the secondary formability of the laminate tends to be good.
  • the upper limit of the tensile elongation at break of the acrylic resin film at 120° C. is not particularly limited.
  • the acrylic resin film may have a tensile elongation at break of 200% or more at 120°C, and although there are no particular limitations on its composition, it is preferably formed from an acrylic resin composition that contains graft copolymer particles that contain an acrylic resin and a rubber component (also called a cross-linked elastomer).
  • acrylic resin a conventionally known one can be appropriately used.
  • an acrylic resin also called a thermoplastic acrylic polymer
  • an acrylic resin composed of 50 to 100% by mass of methyl methacrylate units and 0 to 50% by mass of other structural units, assuming that the total amount of the structural units of the acrylic resin is 100% by mass.
  • the total amount of the methyl methacrylate units and other structural units in the thermoplastic acrylic polymer is 100% by mass.
  • Other structural units include, for example, structural units derived from acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, aromatic vinyl derivatives, and vinyl cyanide derivatives.
  • the other structural units may be glutarimide structures, lactone ring structures, N-substituted maleimide structures, and unsubstituted maleimide structures, which will be described later.
  • the other structural units contained in the acrylic resin may be one type, or a combination of two or more types.
  • Acrylic acid derivatives include, but are not limited to, acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-phenoxyethyl acrylate, benzyl acrylate, and glycidyl acrylate.
  • acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-phenoxyethyl acrylate, benzyl acrylate, and glycidyl acrylate.
  • Methacrylic acid derivatives include, but are not limited to, methacrylic acid esters such as ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-phenoxyethyl methacrylate, and isobornyl methacrylate, as well as reactive ultraviolet absorbers described below.
  • methacrylic acid esters such as ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-phenoxyethyl methacrylate, and isobornyl methacrylate, as well as reactive ultraviolet absorbers described below.
  • aromatic vinyl derivatives include, but are not limited to, styrene, vinyltoluene, and ⁇ -methylstyrene.
  • Vinyl cyanide derivatives include, but are not limited to, acrylonitrile and methacrylonitrile.
  • a structural unit having a specific structure may be introduced into the acrylic resin by copolymerization, functional group modification, modification, etc.
  • specific structures include glutarimide structures as shown in JP-A-62-89705, JP-A-02-178310, and WO2005/54311, lactone ring structures as shown in JP-A-2004-168882 and JP-A-2006-171464, glutaric anhydride structures obtained by thermal condensation cyclization of (meth)acrylic acid units as shown in JP-A-2004-307834, maleic anhydride structures as shown in JP-A-5-119217, and N-substituted maleimide structures and unsubstituted maleimide structures as shown in WO2009/84541.
  • the molecular chain becomes rigid.
  • the method for producing the acrylic resin is not particularly limited, and for example, known polymerization methods such as suspension polymerization, bulk polymerization, solution polymerization, and emulsion polymerization can be applied. It is also possible to apply any of known radical polymerization, living radical polymerization, anionic polymerization, and cationic polymerization methods.
  • the acrylic resin content may be 20-100% by mass, preferably 20-99% by mass, more preferably 25-95% by mass, and even more preferably 30-90% by mass.
  • the acrylic resin film preferably contains graft copolymer particles (A) having an average particle size of 20 to 200 nm as the graft copolymer particles containing a rubber component.
  • the acrylic resin film preferably contains the graft copolymer particles (A) dispersed in a matrix containing an acrylic resin or an acrylic resin and other components.
  • the acrylic resin film may contain, as the graft copolymer particles containing a rubber component, graft copolymer particles (B) having an average particle size larger than that of the graft copolymer particles (A) in addition to the graft copolymer particles (A), if necessary.
  • the acrylic resin film preferably contains the graft copolymer particles (A) and the graft copolymer particles (B) dispersed in a matrix containing an acrylic resin or an acrylic resin and other components.
  • the graft copolymer particles (A) preferably have a core-shell structure (multilayer structure) that includes a crosslinked elastomer (A1) that is a rubber component and a graft polymer layer (A2) that is located on the surface side of the crosslinked elastomer (A1).
  • the crosslinked elastomer (A1) may be a known crosslinked elastomer.
  • the crosslinked elastomer (A1) is an acrylic acid ester-based crosslinked elastomer (a crosslinked elastomer made of a polymer whose main component is an acrylic acid ester).
  • the term "main component" refers to a component whose content is 50% by mass or more.
  • the particles of the acrylic acid ester-based crosslinked elastomer (A1) may have a concentric spherical multilayer structure with a hard or semi-hard crosslinked resin layer inside the crosslinked elastomer layer.
  • hard or semi-hard crosslinked resin layers include hard crosslinked methacrylic resin particles as shown in JP-B-55-27576, semi-hard crosslinked particles made of methyl methacrylate-acrylic acid ester-styrene as shown in JP-A-4-270751, and crosslinked rubber particles with a high degree of crosslinking.
  • the graft copolymer particles (A) preferably have a core-shell structure formed by graft polymerizing a monomer mixture that forms the graft polymer layer (A2) in the presence of particles of the aforementioned acrylic acid ester-based crosslinked elastomer (A1).
  • the average particle size of the graft copolymer particles (A) may be 20 to 200 nm, preferably 50 to 150 nm, and particularly preferably 50 to 120 nm. If the average particle size of the graft copolymer particles (A) is too small, the impact resistance and resistance to cracking due to bending of the acrylic resin film tend to decrease. If the average particle size of the graft copolymer particles (A) is too large, the transparency of the acrylic resin film tends to decrease and whitening due to bending tends to occur easily.
  • acrylic acid ester-based crosslinked elastomer (A1) crosslinked elastomer particles obtained by polymerizing a monomer mixture (a-1) containing (a) an acrylic acid ester, (b) a multifunctional monomer that is copolymerizable with the acrylic acid ester and has two or more non-conjugated double bonds per molecule, and (c) any other vinyl monomer that is copolymerizable with the acrylic acid ester can be preferably used.
  • the acrylic acid ester, other vinyl monomers, and polyfunctional monomers may all be mixed together and polymerized in one step.
  • the acrylic acid ester, other vinyl monomers, and polyfunctional monomers may be polymerized in two or more stages by changing the composition of the acrylic acid ester, other vinyl monomers, and polyfunctional monomers as appropriate, or by keeping the composition the same.
  • alkyl acrylate esters are more preferred, and alkyl acrylate esters in which the alkyl group has 1 to 22 carbon atoms are particularly preferred, because they have excellent polymerizability, are inexpensive, and give polymers with low Tg.
  • the alkyl group may have any of a linear, branched, and cyclic (also called alicyclic) structure.
  • alkyl acrylate esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dodecyl acrylate, stearyl acrylate, heptadecyl acrylate, and octadecyl acrylate. These may be used alone or in combination of two or more.
  • the amount of acrylic acid ester (preferably an alkyl acrylic acid ester, more preferably an alkyl acrylic acid ester having an alkyl group with 1 to 22 carbon atoms) is preferably 50 to 99.9% by mass, more preferably 70 to 99% by mass, and most preferably 80 to 99% by mass, in 100% by mass of monomer mixture (a-1). If the amount of acrylic acid ester is 50% by mass or more, the acrylic resin film has good impact resistance and elongation at tensile break, and is less likely to crack during secondary molding.
  • vinyl monomers include, for example, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, and dicyclopentenyl methacrylate; cyanide vinyl derivatives such as acrylonitrile and methacrylonitrile; aromatic vinyl derivatives such as styrene, vinyl toluene, and ⁇ -methylstyrene; acrylic acid; acrylic acid derivatives such as ⁇ -hydroxyethyl acrylate, phenoxyethyl acrylate, benzyl acrylate, and glycidyl acrylate; methacrylic acid; methacrylic acid derivatives
  • the amount of the other vinyl monomer is preferably 0 to 49.9% by mass, more preferably 0 to 30% by mass, and even more preferably 0 to 20% by mass, in 100% by mass of the monomer mixture (a-1). If the amount of the other vinyl monomer exceeds 49.9% by mass, the impact resistance of the acrylic resin film is likely to decrease, the elongation at tensile break is reduced, and cracks may easily occur during secondary molding.
  • polyfunctional monomer monomers that are normally used as crosslinking agents and/or graft crosslinking agents can be suitably used.
  • the polyfunctional monomer for example, allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl maleate, divinyl adipate, divinyl benzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, and dipropylene glycol dimethacrylate can be used.
  • These polyfunctional monomers may be used alone or in combination of two or more.
  • those that function as a graft crosslinking agent are more preferred because they increase the number of graft bonds of the graft polymer layer (A2) described below to the crosslinked elastomer (A1), resulting in good dispersibility of the graft copolymer particles (A) in the acrylic resin, improving the crack resistance of the acrylic resin film against tensile and bending deformation, and reducing stress whitening.
  • polyfunctional monomers that function as such graft crosslinking agents those having an allyl group such as allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, and diallyl maleate are preferred, with allyl methacrylate and allyl acrylate being particularly preferred.
  • the amount of the polyfunctional monomer is preferably 0.1 to 10 mass %, and more preferably 1.0 to 4 mass %, in 100 mass % of the monomer mixture (a-1). If the amount of the polyfunctional monomer is within this range, it is preferable from the viewpoints of the resistance to cracking and whitening due to folding of the acrylic resin film, and the fluidity of the resin during molding.
  • the amount of polyfunctional monomer may be changed between the inside and the surface vicinity of the crosslinked elastomer (A1) for the purpose of increasing the graft coating efficiency of the graft polymer layer (A2) described later.
  • the content of the polyfunctional monomer functioning as a graft crosslinking agent is made higher in the surface vicinity of the crosslinked elastomer (A1) than in the inside, thereby improving the coating of the graft copolymer particles (A) with the graft polymer layer, improving the dispersibility in the acrylic resin, and suppressing the decrease in crack resistance due to peeling at the interface between the graft copolymer particles (A) and the acrylic resin.
  • the amount of graft copolymer particles (A) required to introduce a predetermined amount of crosslinked elastomer (A1) into the acrylic resin composition can be reduced, which is expected to reduce the melt viscosity of the acrylic resin composition and improve the melt processability and film processing accuracy of the acrylic resin film, as well as the surface hardness.
  • a chain transfer agent may be used in addition to the monomer mixture (a-1).
  • the chain transfer agent may be selected from those usually used in radical polymerization.
  • the chain transfer agent include monofunctional or polyfunctional mercaptan compounds having 2 to 20 carbon atoms, such as n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan; mercapto acids; thiophenol; carbon tetrachloride; or mixtures thereof.
  • the amount of the chain transfer agent added is preferably 0 to 1.0 parts by mass, more preferably 0 to 0.2 parts by mass, based on 100 parts by mass of the total amount of the monomer mixture (a-1).
  • the particles of crosslinked elastomer (A1) may be a single layer made of the above-mentioned acrylic ester-based crosslinked elastomer (A1), or may have a multilayer structure including two or more layers made of the above-mentioned acrylic ester-based crosslinked elastomer (A1).
  • the particles of the crosslinked elastomer (A1) may also be multi-layer particles containing a hard or semi-hard crosslinked resin layer, and at least one layer of the particles may contain the acrylic ester-based crosslinked elastomer (A1).
  • monomers constituting the hard or semi-hard crosslinked resin layer include methacrylic esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, and phenoxyethyl methacrylate; acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate; aromatic vinyl derivatives such as styren
  • the same one as that used in the polymerization of the acrylic acid ester-based crosslinked elastomer (A1) layer can be used.
  • one or more selected from the group consisting of methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, styrene, acrylonitrile, etc. are particularly preferred.
  • a chain transfer agent may be used in the polymerization of the hard or semi-hard crosslinked resin layer for the purpose of controlling the crosslink density and controlling the thermal stability by reducing the double bond terminals of the polymer.
  • the chain transfer agent the same chain transfer agent as that used in the polymerization of the acrylic acid ester-based crosslinked elastomer (A1) layer can be used.
  • the amount of the chain transfer agent added is preferably 0 to 2 parts by mass, more preferably 0 to 0.5 parts by mass, based on 100 parts by mass of the total amount of the monomer mixture constituting the hard or semi-hard crosslinked resin layer.
  • the graft copolymer particle (A) When the graft copolymer particle (A) has a two-layer structure consisting of a particle of crosslinked elastomer (A1) as a core particle and a graft polymer layer (A2), the graft copolymer particle (A) can typically be obtained by graft copolymerizing a monomer mixture (a-2) containing 50 to 100 mass% of a methacrylic acid ester and 0 to 50 mass% of another vinyl monomer copolymerizable with the methacrylic acid ester (however, the total of the methacrylic acid ester and the other vinyl monomer is 100 mass%) in the presence of the particle of crosslinked elastomer (A1) to form the graft polymer layer (A2).
  • the amount of methacrylic acid ester in 100% by mass of monomer mixture (a-2) is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 97% by mass or more, from the viewpoints of (a) ensuring compatibility with the acrylic resin matrix, and (b) preventing a decrease in toughness of the film due to solvent impregnation during coating of the acrylic resin film, and preventing whitening and cracking due to stretching during molding.
  • examples of the methacrylic acid ester include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, phenyl methacrylate, and benzyl methacrylate.
  • alkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms are preferred.
  • the other vinyl monomer may be an alkyl acrylate ester having an alkyl group with 2 or more carbon atoms.
  • the alkyl acrylate ester having an alkyl group with 2 or more carbon atoms for example, one or more selected from the group consisting of ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, dodecyl acrylate, and stearyl acrylate are preferred, one or more selected from the group consisting of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate are more preferred, and n-butyl acrylate is particularly preferred.
  • vinyl monomers that can be used 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, and acrylamide.
  • 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, and acrylamide.
  • the monomer mixture (a-2) preferably contains a reactive UV absorber as another vinyl monomer.
  • the graft polymer layer (A2) preferably contains a structural unit derived from a reactive UV absorber.
  • the reactive UV absorber may be any known reactive UV absorber, and is not particularly limited. From the viewpoint of the moldability and weather resistance of the acrylic resin film, the reactive UV absorber is preferably a compound represented by the following general formula (1).
  • 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 a linear or branched alkylene group having 2 to 10 carbon atoms
  • R 3 is a hydrogen atom or a methyl group.
  • reactive UV absorbers represented by 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, and 2-(2'-hydroxy-5'-methacryloyloxyethyl-3'-t-butylphenyl)-2H-benzotriazole.
  • (meth)acryloyl is a general term for acryloyl and methacryloyl.
  • the content of the structural units derived from the reactive UV absorber in 100% by mass of the graft polymer layer (A2) is preferably 0.01 to 5% by mass, and more preferably 0.1 to 3% by mass.
  • the graft polymer layer (A2) is preferably obtained by graft copolymerizing, in at least one stage, 10 to 95 parts by mass of a monomer mixture (a-2) containing 70 to 99.5% by mass of an alkyl methacrylate ester, 0.5 to 30% by mass of an alkyl acrylate ester having an alkyl group with 2 or more carbon atoms, and 0 to 19% by mass of other vinyl monomers (provided that the total of the alkyl methacrylate ester, alkyl acrylate ester, and other vinyl monomers is 100% by mass) in the presence of 5 to 90 parts by mass of crosslinked elastomer particles (A1). However, the total amount of the particles of the crosslinked elastomer (A1) and the monomer mixture (a-2) must be 100 parts by mass.
  • graft copolymer particles (A) particularly during graft copolymerization of monomer mixture (a-2) in the presence of particles of crosslinked elastomer (A1), for example particles of acrylic acid ester-based crosslinked elastomer (A1), polymer components (free polymers) that are not graft-bonded to the particles of acrylic acid ester-based crosslinked elastomer (A1) may be generated.
  • free polymers can be used to constitute part or all of the acrylic resin that constitutes the matrix phase of acrylic resin compositions and acrylic resin films.
  • a chain transfer agent may be added to the monomer mixture (a-2) for the purposes of controlling the molecular weight of the polymer, controlling the graft rate to the crosslinked elastomer (A1) and the amount of free polymer generated that is not bonded to the crosslinked elastomer (A1), and controlling thermal stability, etc., by reducing the double bond terminals of the polymer accompanying the disproportionation termination reaction during polymerization.
  • a chain transfer agent the same chain transfer agent as that usable in the polymerization of the crosslinked elastomer (A1) can be used.
  • the amount of the chain transfer agent used is preferably 0 to 2 parts by mass or less, more 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 particles of the crosslinked elastomer (A1) i.e., the graft ratio of the graft copolymer particles (A)
  • the graft ratio of the monomer mixture (a-2) to the particles of the crosslinked elastomer (A1) is preferably 5 to 250%, more preferably 10 to 200%, and even more preferably 20 to 150%. If the graft ratio is less than 5%, the acrylic resin film tends to have a lowered resistance to whitening upon folding, a lowered transparency, or a lowered elongation at tensile break, which tends to make it easier for cracks to occur during secondary molding.
  • the average particle diameter d (nm) of the acrylic acid ester-based crosslinked elastomer (A1) in the acrylic resin film and the amount w (mass%) of the polyfunctional monomer used in the acrylic acid ester-based crosslinked elastomer (A1) preferably satisfy the relational expression: 0.015d ⁇ w ⁇ 0.06d, and more preferably 0.02d ⁇ w ⁇ 0.05d.
  • the acrylic resin film has the advantages of being less likely to have a decrease in elongation during secondary molding, being less likely to crack during molding and cutting, having excellent transparency, and being less likely to cause stress whitening during bending or tensile deformation at room temperature (about 25°C), at high temperatures above the softening temperature of the acrylic resin film, or in the temperature range between room temperature and the Tg of the crosslinked elastomer (A1), and being less likely to cause moisture-induced clouding or whitening of the film due to moisture penetrating into the acrylic resin film due to contact between the acrylic resin film and moisture.
  • the graft copolymer particles (B) also comprise a crosslinked elastomer (B1) which is a rubber component.
  • the graft copolymer particles (B) typically comprise a graft polymer layer (B2) located on the surface side of the crosslinked elastomer (B1).
  • the graft copolymer particles (B) comprise a crosslinked elastomer (B1) and a graft polymer layer (B2).
  • the graft copolymer particles (B) may be generally similar to the graft copolymer particles (A) in terms of raw materials and manufacturing method, etc., except that the average particle size of the graft copolymer particles (B) is larger than that of the graft copolymer particles (A).
  • the particles of the acrylic acid ester-based crosslinked elastomer (B1) have a concentric spherical multilayer structure with a hard or semi-hard crosslinked resin layer inside the crosslinked elastomer layer.
  • hard or semi-hard crosslinked resin layers examples include hard crosslinked methacrylic resin particles as shown in JP-B-55-27576 and crosslinked particles having a semi-hard layer made of a methyl methacrylate-acrylic acid ester-styrene copolymer as shown in JP-A-4-270751 and WO2014/41803.
  • a hard or semi-hard crosslinked resin layer it is possible to improve the transparency, resistance to whitening when folded, and resistance to cracking when folded of the graft copolymer particles (B) having a larger particle size than the graft copolymer particles (A).
  • the average particle size of the graft copolymer particles (B) is preferably 150 to 400 nm, and more preferably 200 to 350 nm. Graft copolymer particles (B) with a large average particle size more effectively induce plastic deformation (craze) in the acrylic resin phase surrounding the graft copolymer particles in response to the action of an external force on the acrylic resin material. For this reason, the graft copolymer particles (B) are extremely effective in imparting impact resistance and crack resistance to the acrylic resin material. On the other hand, the graft copolymer particles (B) are inferior to the graft copolymer particles (A) in bending whitening resistance and/or solvent whitening resistance, etc.
  • graft copolymer particles (B) for example, by adding a small amount of graft copolymer particles (B) to an acrylic resin composition containing an acrylic resin and graft copolymer particles (A), (a) the total content of soft components in the acrylic resin film is lowered, so that the surface hardness of the acrylic resin film and laminate is not reduced, (b) the whitening property is less likely to deteriorate when an external stress is applied to the acrylic resin film, when a coating liquid containing an organic solvent is applied, and/or during molding processing, and (c) the crack resistance and secondary moldability of the acrylic resin film and laminate are efficiently improved.
  • the average particle size of the graft copolymer particles (A) and the graft copolymer particles (B) is the average particle size on a volume basis (also called a mass basis if the density is uniform), and can be measured in the latex state using a laser diffraction type particle size distribution measuring device such as the Microtrac particle size distribution measuring device MT3000 manufactured by Nikkiso Co., Ltd., using a dynamic light scattering method.
  • the method for producing the graft copolymer particles (A) and the graft copolymer particles (B) is not particularly limited, and known methods such as emulsion polymerization, mini-emulsion polymerization, suspension polymerization, and solution polymerization can be used.
  • the emulsion polymerization method is particularly preferred because it allows for a wide range of adjustment of the resin structure.
  • the initiator used in the emulsion polymerization of the graft copolymer particles (A) and/or the graft copolymer particles (B) may be a known initiator such as an organic peroxide, an inorganic peroxide, or an azo compound.
  • organic peroxides such as t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, alkyl peroxycarbonates, and alkyl peroxy esters
  • inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate
  • azo compounds such as azobisisobutyronitrile.
  • These initiators may be used (a) as thermal decomposition type radical polymerization initiators, or (b) as redox type polymerization initiator systems in which these initiators are combined with a catalyst such as ferrous sulfate and a reducing agent such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, or hydroxyacetone.
  • a catalyst such as ferrous sulfate and a reducing agent such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, or hydroxyacetone.
  • the catalyst may be used as a complex with 2-sodium ethylenediaminetetraacetate or the like to ensure water solubility.
  • the surfactant (also called emulsifier) used in the emulsion polymerization of the graft copolymer particles (A) and/or the graft copolymer particles (B) is not particularly limited.
  • a wide variety of known surfactants can be used in the emulsion polymerization.
  • Preferred surfactants include, for example, (a) anionic surfactants such as sodium salts, potassium salts, and ammonium salts of alkylsulfonic acid, alkylbenzenesulfonic acid, dialkylsulfosuccinic acid (dioctyl sulfosuccinic acid, etc.), alkylsulfuric acid, fatty acid sodium salts, polyoxyethylene alkyl ether acetic acid, polyoxyethylene alkyl ether phosphate, alkyl phosphate, alkyl ether phosphate, alkylphenyl ether phosphate, and surfactin, and (b) nonionic surfactants such as reaction products of alkylphenols, aliphatic alcohols, and propylene oxide and/or ethylene oxide. These surfactants may be used alone or in combination of two or more.
  • anionic surfactants such as sodium salts, potassium salts, and ammonium salts of alkylsulfonic acid, al
  • graft copolymer particles (A) or the latex of graft copolymer particles (B) obtained by emulsion polymerization From the latex of graft copolymer particles (A) or the latex of graft copolymer particles (B) obtained by emulsion polymerization, graft copolymer particles (A) or graft copolymer particles (B) can be separated and recovered by a known method.
  • the graft copolymer particles (A) or graft copolymer particles (B) can be separated and recovered by filtering, washing, and drying the solids.
  • the graft copolymer particles (A) or graft copolymer particles (B) can be separated and recovered by spray drying, freeze drying, or other treatments on the latex.
  • the latex of the graft copolymer particles (A) or the latex of the graft copolymer particles (B) is filtered with a filter and/or mesh in advance to remove environmental foreign matter and substances that may cause foreign matter defects, such as polymerization scale.
  • the filter and mesh may be any known filter and mesh material used for filtering liquid media.
  • the type of filter and mesh, the aperture of the filter and mesh, the filtering accuracy, and the filtering capacity are appropriately selected according to the intended use and the type, size, and amount of foreign matter to be removed.
  • the aperture and filtering accuracy of the filter and mesh are preferably at least twice as large as the average particle size of the graft copolymer particles (A) or the graft copolymer particles (B), respectively.
  • 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 to 80% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass.
  • the content of graft copolymer particles (B) in 100% by mass of acrylic resin film is not particularly limited, and can be adjusted appropriately within a preferred range depending on the application without impairing the quality of the laminate of the present invention. However, from the viewpoint of suppressing stress whitening during stretching or bending processing of the acrylic resin film and clouding of the film after contact with moisture, it is desirable not to use an excessive amount, and 0 to 20% by mass is preferable, 0 to 10% by mass is more preferable, and 0 to 5% by mass is most preferable.
  • the acrylic resin film may not contain any graft copolymer particles (B).
  • the acrylic resin film may contain a thermoplastic resin having at least partial compatibility with the acrylic resin, if necessary, within a range that does not impair the object of the present invention.
  • thermoplastic resins include styrene resins, polycarbonate resins, amorphous saturated polyester resins, olefin-methacrylic acid derivative resins, olefin-acrylic acid derivative resins, polyimide resins, polylactic acid resins, and PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)) resins.
  • styrene resins include styrene-acrylonitrile resins, styrene-(meth)acrylic acid resins, styrene-maleic anhydride resins, styrene-N-substituted or unsubstituted maleimide resins, styrene-acrylonitrile-butadiene resins, and styrene-acrylonitrile-acrylic acid ester resins.
  • thermoplastic resins selected from the group consisting of styrene resins, polycarbonate resins, and polyimide resins are preferred because they have excellent compatibility with acrylic resins and may be able to improve the bending crack resistance, solvent resistance, chemical resistance, low moisture absorption, etc. of the acrylic resin film.
  • (meth)acrylic acid is a general term for acrylic acid and methacrylic acid.
  • the acrylic resin film may also contain, as necessary, additives that are conventionally known and used in acrylic resin films, as long as they do not impair the purpose of one embodiment of the present invention.
  • additives include antioxidants, ultraviolet absorbers (hereinafter also referred to as UVA), light stabilizers, light diffusing agents, matting agents, lubricants, colorants such as pigments and dyes, fibrous fillers, antiblocking agents made of organic particles and/or inorganic particles, infrared reflectors made of metals and/or metal oxides, plasticizers, and antistatic agents.
  • UVA ultraviolet absorbers
  • light stabilizers light diffusing agents
  • matting agents lubricants
  • colorants such as pigments and dyes
  • fibrous fillers such as fibrous fillers
  • antiblocking agents made of organic particles and/or inorganic particles
  • infrared reflectors made of metals and/or metal oxides
  • plasticizers plasticizers
  • antistatic agents antistatic agents.
  • the additives are not limited to
  • the glass transition temperature (Tg) of the acrylic resin film is preferably 145°C or less, more preferably 140°C or less, even more preferably 135°C or less, and particularly preferably 130°C or less.
  • Tg glass transition temperature
  • the lower limit of the glass transition temperature of the acrylic resin film is not particularly limited, but from the viewpoint of preventing printing misalignment during drying of the print and improving reliability, it is preferable that it is, for example, 100°C or more.
  • the glass transition temperature of the acrylic resin film may be 100 to 145°C, 100 to 140°C, 100 to 135°C, or 100 to 130°C.
  • the glass transition temperature of the acrylic resin film is measured by the method described in the examples.
  • the thickness of the acrylic resin film is not particularly limited, but is preferably 50 to 500 ⁇ m, more preferably 75 to 350 ⁇ m, even more preferably 80 to 300 ⁇ m, and particularly preferably 100 to 300 ⁇ m.
  • the thickness of the acrylic resin film is within the above-mentioned range, the film has sufficient stretchability and excellent handleability, and has the advantage of excellent appearance after lamination onto a resin substrate during production of a molded product.
  • the thickness of the acrylic resin film is measured by the method described in the examples.
  • the pencil hardness of the acrylic resin film measured in accordance with JIS K 5600-5-4 is preferably 2B or more under a load of 500 g, more preferably B or more, and particularly preferably HB or more, from the viewpoint of excellent scratch resistance.
  • 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.
  • melt processing methods include inflation and T-die extrusion.
  • solvent casting method for example, an acrylic resin composition is dissolved and dispersed in a solvent, and then the resulting dispersion (dope) is cast in a film on a belt-shaped substrate. Next, the solvent is evaporated from the cast film-shaped dope to obtain an acrylic resin film.
  • melt processing methods which does not use solvents, is preferred, and the T-die extrusion method and calendar molding method are particularly preferred.
  • Melt processing methods have fewer limitations on the thickness of the film to be produced, and can produce films with excellent surface properties with high productivity, while also reducing the burden on the natural and working environments caused by solvents, as well as production costs.
  • the acrylic resin composition When the acrylic resin composition is formed into a film by melt processing or solvent casting, in order to improve the appearance quality of the acrylic resin film, it is preferable to use filtration using a filter or mesh to remove environmental foreign matter, polymerization scale, deteriorated resin, etc. in the acrylic resin composition that may cause appearance defects or internal foreign matter in the acrylic resin film.
  • the acrylic resin composition can be filtered at any one or more of the following times: when melt-kneading the acrylic resin composition after blending the raw materials such as acrylic resin and graft copolymer particles, and during the molten film production process using a T-die.
  • the acrylic resin composition can be filtered before film casting.
  • any known filters and meshes can be used without particular restrictions, so long as the filters and meshes have heat resistance and durability according to the melt processing conditions, and resistance to the casting solvent and dope, etc.
  • a filter that has a large filtration capacity and reduces retention of molten resin, which can cause resin deterioration and cross-linking that impair the quality of the film.
  • a leaf disc type filter or a pleated type filter from the standpoint of filtration efficiency and productivity.
  • an automatic die device can be used that measures the film thickness distribution in the TD direction (direction perpendicular to the extrusion direction) of the extruded film online and automatically adjusts the lip clearance of the T-die while the film is being extruded based on this.
  • an automatic die By applying an automatic die with an appropriate control method, it is possible to improve the thickness accuracy of the acrylic resin film.
  • both sides of the molten film are simultaneously brought into contact (sandwiched) with a cooling roll or cooling belt to obtain a film with better surface properties.
  • a cooling roll or cooling belt it is preferable to simultaneously bring the molten film into contact with a roll or cooling belt maintained at a temperature equal to or higher than the glass transition temperature of the acrylic resin composition minus 80°C, preferably equal to or higher than the glass transition temperature minus 70°C.
  • a roll having an elastic metal sleeve as disclosed in, for example, JP-A-2000-153547 and JP-A-11-235747 is used, and a roll mirror surface or a specific surface shape is transferred using a low sandwiching pressure.
  • Uniaxial or biaxial stretching can be performed using a known stretching device.
  • Biaxial stretching can be performed in a known manner, such as sequential biaxial stretching, simultaneous biaxial stretching, or a method in which transverse stretching is performed while relaxing the longitudinal direction after longitudinal stretching to suppress the bowing phenomenon of the film.
  • one or both sides of the acrylic resin film may be given any surface shape, such as hairlines, prisms, uneven shapes, three-dimensional decoration, matte surfaces, rough surfaces with a certain degree of surface roughness, and knurling on the film edges.
  • Such surface shapes can be given by known methods. For example, a method can be used in which a molten film immediately after extrusion, or both sides of a molded film unwound from a winding device are sandwiched between two rolls or belts with a surface shape on at least one surface, thereby transferring the surface shape of the roll.
  • the hard coat layer is formed of a cured product of a curable resin composition containing a urethane acrylate resin and a hindered amine-based light stabilizer having a reactive functional group. Specifically, the hard coat layer is formed by laminating a curable resin composition containing a urethane acrylate resin and a hindered amine-based light stabilizer having a reactive functional group on the surface of an acrylic resin film and then curing the composition. The hard coat layer may be laminated on one side or both sides of the acrylic resin film.
  • the curable resin composition for the hard coat layer preferably has active energy curability, and more preferably the urethane acrylate resin has active energy curability, from the viewpoints of not requiring a large-scale device such as heating, being cured quickly, and being cost-effective.
  • the hard coat layer is required to have high crack elongation as well as improved surface hardness. This prevents breakage or significant whitening during stretching, bending, or the like during secondary molding of the laminate into the shape of a resin molded product.
  • the cured product of the curable resin composition containing the curable resin is highly crosslinked and/or contains a filler with high hardness, thereby suppressing deformation of the cured product surface due to external stress, thereby exhibiting surface hardness and scratch resistance.
  • Surface hardness and scratch resistance are contradictory properties to deformability and extensibility, and it has not been easy to achieve both of these properties in the hard coat layer.
  • the curable resin used in the hard coat layer may be improved, for example, by the following methods (1) to (3).
  • any of the methods (1) to (3) may be used alone or in appropriate combination.
  • a commercially available curable resin composition containing a urethane acrylate resin that can impart high extensibility during secondary molding while maintaining the surface hardness of the hard coat layer may be appropriately used.
  • the glass transition temperature of the curable resin (specifically, urethane acrylate resin) is designed to be between room temperature (20 ⁇ 5°C) and the secondary molding temperature (e.g., about 110 to 140°C), and the resin is designed to be hard at room temperature but soften and deformable at the secondary molding temperature.
  • the cured product (hard coat layer) of the curable resin exhibits high surface hardness at room temperature and high extensibility during secondary molding.
  • the crosslinked structure after curing of the curable resin is designed to be not uniform but to have a high crosslink density part and a low crosslink density part with large plastic deformation, and to be non-uniform in microstructure.
  • the high crosslink density part in the cured product of the curable resin exhibits high surface hardness, and the low crosslink density part deforms during secondary molding, showing high extensibility.
  • a resin component with a low degree of crosslinking or non-crosslinking and/or a resin component with a low modulus of elasticity is blended into the curable resin, whereby after the curable resin is cured, a structure is formed in which fine regions (domains) with a low degree of crosslinking or non-crosslinking and/or low modulus of elasticity are dispersed in the curable resin phase with a high crosslinking density, thereby imparting deformability and extensibility to the cured product of the curable resin (hard coat layer) while maintaining a certain degree of surface hardness.
  • thermoplastic resins such as thermoplastic methacrylic resins, styrene acrylonitrile resins, aliphatic polycarbonate resins, aromatic polycarbonate resins, polyester resins, phenoxy resins, cellulose acylate resins, fluororesins, and polyurethane resins
  • crosslinked or non-crosslinked soft resins such as acrylic rubber, silicone rubber, hydrogenated styrene butadiene rubber, acrylonitrile butadiene rubber, olefin rubber, and urethane rubber, which may have a reactive functional group as necessary, as well as thermoplastic elastomer materials such as polyester-based, polyurethane-based, acrylic-based, olefin-based, styrene-based, silicone-based, and fluororesin-based materials; and (c) core-shell type rubber particles in which a thermoplastic resins such as thermoplastic methacrylic resins, styrene acrylonitrile resins, aliphatic polycarbon
  • the urethane acrylate resin can be obtained, for example, by mixing a polyhydric alcohol, a polyisocyanate, and a hydroxyl group-containing (meth)acrylate, and generating a urethane bond by a reaction between the isocyanate group and the hydroxyl group.
  • (meth)acrylate is a general term for acrylate and methacrylate.
  • a urethane acrylate resin can be obtained by reacting a polyhydric alcohol with a polyhydric isocyanate to form an isocyanate group at the end or side chain of a polyurethane compound, which is obtained by reacting the isocyanate group with a hydroxyl group-containing (meth)acrylate to form a (meth)acryloyl group at the end or side chain.
  • the term (meth)acryloyl group includes both methacryloyl and acryloyl groups.
  • Further examples of the urethane acrylate resin include urethane acrylate resins commercially available as ultraviolet-curable hard coating agents.
  • the polyisocyanate is not particularly limited as long as it is a compound containing two or more isocyanate groups.
  • polyisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 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, methylene bis(4-cyclohexyl isocyan
  • polyisocyanate compounds that do not contain an aromatic skeleton and have a saturated aliphatic skeleton or an alicyclic skeleton are preferred because they provide a structure with better weather resistance.
  • polyisocyanate compounds include 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 2,5-bis(isocyanate methyl)-bicyclo[2.2.1]heptane, and 2,6-bis(isocyanate methyl)-bicyclo[2.2.1]heptane.
  • These polyisocyanates can be used alone or in combination of two or more.
  • polyhydric alcohols include ethylene glycol, 1,3-propanediol, 1,3-butanediol, 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, cyclohexanediol, 1,4-cyclohexanedimethanol, glycerol, pentaerythritol, dipentaerythritol, polycaprolactone diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyester diol, polycarbonate diol, polyurethan
  • polyhydric alcohols that do not contain an aromatic skeleton and have a saturated aliphatic skeleton or an alicyclic skeleton are preferred because they provide a structure with better weather resistance.
  • These polyhydric alcohols may be used alone or in combination of two or more.
  • Hydroxyl group-containing (meth)acrylates are not particularly limited, and examples thereof include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, as well as (a) compounds having an ethylenically unsaturated bond with at least one 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, and (b) mixtures thereof, which can be added as necessary.
  • 2-hydroxypropyl (meth)acrylate 4-hydroxybutyl acrylate
  • polyethylene glycol mono(meth)acrylate polypropylene glycol mono(meth)acryl
  • an organotin urethane catalyst is used.
  • the organotin urethane catalyst may be any catalyst commonly used in urethane reactions, such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dialkyl malate, tin stearate, and tin octoate.
  • the curable resin composition for the hard coat layer may be a commercially available curable resin composition containing a urethane acrylate resin.
  • commercially available products include "Z-607-27L” manufactured by Aica Kogyo Co., Ltd., "Beamset 1200W” manufactured by Arakawa Chemical Industries Co., Ltd., "Acrit 8UX-116A” manufactured by Taisei Fine Chemical Co., Ltd., "NXD-004AP” manufactured by Nippon Kako Toryo Co., Ltd., "P-5820TAH-1" and “P-5820TA-20J” manufactured by Daido Kasei Kogyo Co., Ltd., and "Lioduras MOL7200” manufactured by Toyochem Co., Ltd.
  • These commercially available curable resin compositions containing a urethane acrylate resin have high elongation even after curing, so by using them, the crack elongation
  • the curable resin composition for a hard coat layer contains a light stabilizer.
  • the stability of the hard coat layer against ultraviolet degradation and light degradation is improved, and weathering degradation such as surface cracking and peeling is suppressed in a site or application exposed to sunlight outdoors or indoors of a resin molded article covered with a laminate including the hard coat layer.
  • the curable resin composition for the hard coat layer contains a hindered amine light stabilizer (hereinafter also referred to as "reactive HALS") having at least a reactive functional group as a light stabilizer.
  • the reactive functional group may be any one that is reactive with the urethane acrylate resin, for example, a functional group having an ethylenic double bond, and more specifically, it is preferable that the reactive functional group contains one or more selected from the group consisting of methacryloyl groups, acryloyl groups, vinyl groups, and allyl groups, and more preferably contains one or more selected from the group consisting of methacryloyl groups and acryloyl groups.
  • the substituent on the nitrogen atom of the amine functional group may be hydrogen, or may be a substituent such as an alkyl group such as a methyl group, an ethyl group, or a propyl group, a phenyl group, a benzyl group, an alkyloxy group, an acyl group, or an acyloxy group.
  • the hindered amine light stabilizer has a reactive functional group, when the urethane acrylate resin is cured, the hindered amine light stabilizer molecules react with the urethane acrylate resin and are introduced in a chemically bonded state into the cured product that forms the hard coat layer. This prevents the hindered amine light stabilizer from migrating or flowing out from the surface of the hard coat layer even in environments such as outdoor exposure, making it possible to suppress weathering deterioration of the hard coat layer for a longer period of time.
  • Reactive HALS include, for example, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy
  • Examples of reactive HALS include, but are not limited to, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, and 1-crotonoyl-4-crotoyloxy-2,2,6,
  • Reactive HALS may be, for example, commercially available products such as 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (manufactured by ADEKA Corporation under the trade name "ADEKA STAB LA-82", or manufactured by Hitachi Chemical Co., Ltd. under the trade name "FA-711MM”), 2,2,6,6-tetramethyl-piperidinyl methacrylate (also known as 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, manufactured by ADEKA Corporation under the trade name "ADEKA STAB LA-87", or manufactured by Hitachi Chemical Co., Ltd. under the trade name "FA-712HM”).
  • 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate manufactured by ADEKA Corporation under the trade name "ADEKA STAB LA-82", or manufactured by Hitachi Chemical Co., Ltd. under the trade name "FA-711MM
  • 2,2,6,6-tetramethyl-piperidinyl methacrylate also known
  • the curable resin composition for the hard coat layer preferably contains 1 to 10 parts by mass of reactive HALS per 100 parts by mass of urethane acrylate resin, more preferably 1.5 to 6 parts by mass, and even more preferably 2 to 4 parts by mass.
  • 1 part by mass or more of reactive HALS long-term weather resistance is improved.
  • the reactive HALS is 10 parts by mass or less, weather resistance can be improved without impairing the quality of the hard coat layer.
  • the curable resin composition for the hard coat layer may contain other light stabilizers such as hindered amine light stabilizers (hereinafter also referred to as HALS) that do not have reactive functional groups, as necessary.
  • HALS include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine.
  • the curable resin composition for the hard coat layer may contain a total of 1 to 10 parts by mass, 1.5 to 6 parts by mass, or 2 to 4 parts by mass of the light stabilizer per 100 parts by mass of the urethane acrylate resin.
  • the hard coat layer curable resin composition may contain other components in addition to the urethane acrylate resin and the light stabilizer.
  • the other components for example, (meth)acrylate compounds, epoxy acrylate monomers, polyester acrylates, polyacryl acrylates, and other radical reactive functional group-containing monomers, oligomers, resins, or mixtures thereof may be used in combination.
  • the urethane acrylate resin may be used in combination with, for example, (a) a hydrolysis condensate of a di- to tetrafunctional silane compound, and/or (b) a monomer, oligomer, resin, or mixture thereof having a cationic curable and/or anionic curable functional group such as an epoxy group and an oxetane group.
  • a hydrolysis condensate of a di- to tetrafunctional silane compound and/or
  • a monomer, oligomer, resin, or mixture thereof having a cationic curable and/or anionic curable functional group such as an epoxy group and an oxetane group.
  • the (meth)acrylate compound is not particularly limited as long as it has at least one (meth)acryloyl group.
  • Specific examples include alicyclic (meth)acrylates such as alkyl (meth)acrylate, aryl (meth)acrylate, phenoxyethyl (meth)acrylate, and isobornyl (meth)acrylate; and polyfunctional (meth)acrylates such as 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 tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri
  • epoxy acrylate monomer there are no particular limitations on the epoxy acrylate monomer. Specific examples include glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and vinylcyclohexene monoxide (i.e., 1,2-epoxy-4-vinylcyclohexane).
  • a known method can be used to cure the resin layer (curable resin composition) when forming the hard coat layer.
  • a preferred curing method is to irradiate with active energy rays such as ultraviolet rays or electron beam rays.
  • active energy rays such as ultraviolet rays or electron beam rays.
  • a photopolymerization initiator is used.
  • photopolymerization initiators include acetophenone, benzophenone, benzoyl methyl ether, benzoyl ethyl 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-morpholinopropan-1-one compounds.
  • 1-hydroxy-cyclohexyl-phenyl-ketone is preferred from the viewpoint of excellent compatibility with urethane acrylate resins.
  • a hard coat layer can be formed by applying a curable composition to one or both sides of an acrylic resin film and curing a resin layer (coating film) made of the curable composition.
  • various known leveling agents and antifouling agents may be blended into the curable composition for the purpose of improving the coatability, scratch resistance after curing, antifouling properties, smoothness, etc.
  • the leveling agent or antifouling agent various compounds such as fluorine-based, acrylic-based, and silicone-based compounds, and their adducts or mixtures can be used. These leveling agents and antifouling agents may contain a functional group that is reactive with the urethane acrylate resin.
  • the amount of the leveling agent or antifouling agent to be blended is not particularly limited, but may be, for example, 0.03 to 3.0 parts by mass per 100 parts by mass of the curable composition.
  • a hard coat layer is formed by applying a curable composition to one or both sides of an acrylic resin film and curing the coating
  • various additives such as ultraviolet absorbers, defoamers, antioxidants, light diffusing agents, matting agents, antifouling agents, lubricants, colorants such as pigments and dyes, organic particles, inorganic particles, and antistatic agents can be added to the curable composition as necessary.
  • the additives are not limited to these.
  • the curable resin composition for the hard coat layer may contain inorganic particles.
  • the inorganic particles are not particularly limited, but examples thereof include silica, alumina, titanium oxide, zinc oxide, zirconia, graphene, nanocarbon, carbon black, nanodiamond, mica, barium titanate, boron nitride, metallic silver, and metallic copper. These particles may be used without surface treatment, or may be surface-treated in advance by a known method to control the dispersion state and maintain good extensibility, and the affinity with the hard coat layer may be appropriately controlled.
  • the curable resin composition for the hard coat layer may contain particles from the viewpoint of enhancing the antiglare properties of the laminate.
  • the particles to be blended in the hard coat layer for the purpose of imparting antiglare properties, etc. in order to obtain a balance of various properties such as the desired antiglare properties, clarity of transmitted images, glare, jet black surface, surface hardness, slipperiness, and antistatic properties, the particle material, blending number, type of particle dispersion solvent, particle diameter, dispersed particle diameter, hard coat layer thickness, relative refractive index difference with the hard coat substrate, affinity and reactivity of the particle surface with the hard coat substrate or solvent, etc. can be appropriately adjusted within the scope of known techniques that do not impair the effects of the present invention.
  • the material of the particles to be incorporated into the hard coat layer is not particularly limited as long as it can enhance the antiglare properties of the laminate within a range that does not impede the object of the present invention, and for example, inorganic particles and/or organic particles can be used.
  • inorganic particles include silica, alumina, glass beads, glass flakes, mica, clay, titanium oxide, zinc oxide, zirconia, and metal particles.
  • organic particles include crosslinked organic resin particles mainly composed of one or more selected from the group consisting of alkyl (meth)acrylate units, aromatic vinyl units, and organic functional group-substituted siloxane units, as well as core-shell type multilayer structure resin particles.
  • the particles are preferably one or more selected from the group consisting of inorganic oxide particles (e.g., silica, alumina, titanium oxide, zinc oxide, zirconia, etc.) and crosslinked organic resin particles (e.g., crosslinked silicone resin, crosslinked acrylic resin, crosslinked aromatic vinyl resin, etc.), and more preferably one or more selected from the group consisting of silica, alumina, zirconia, and crosslinked organic resin particles.
  • inorganic oxide particles e.g., silica, alumina, titanium oxide, zinc oxide, zirconia, etc.
  • crosslinked organic resin particles e.g., crosslinked silicone resin, crosslinked acrylic resin, crosslinked aromatic vinyl resin, etc.
  • the particles are one or more selected from the group consisting of silica, alumina, and crosslinked organic resin particles.
  • these particles may be subjected to surface treatment and/or graft polymerization treatment using a known method such as the use of a silane coupling agent or reactive monomer that may have a reactive substituent, plasma treatment, corona treatment, etc.
  • the particles contain reactive functional groups that are reactive with urethane acrylate resins on the surface of the particles.
  • the “particles” may be dispersed as primary particles or multiple particles may be dispersed in an aggregated state, depending on the size of the primary particles.
  • the size of the area (dispersion domain) in which these particles or their aggregates are distributed is defined as the "average dispersed particle size.”
  • the average dispersed particle size When the primary particles are large, the average dispersed particle size may be the same as the primary (basic) particle size.
  • the average dispersed particle diameter of the particles is not particularly limited as long as the effects of the present invention are achieved, but may be, for example, 0.1 to 50.0 ⁇ m, 0.2 to 25.0 ⁇ m, or 0.5 to 10 ⁇ m.
  • a cross-sectional photograph of the laminate, 1200 nm x 800 nm, measured at a magnification of 200,000 times using an electron microscope (Hitachi High-Technologies Corporation, H7650) is observed, the arithmetic mean value of the particle diameters of 10 dispersed domains of particles in the hard coat layer is calculated, and the obtained value is regarded as the average dispersed particle diameter of the particles in the hard coat layer.
  • the content of the particles in the hard coat layer is not particularly limited as long as it can increase the antiglare properties of the laminate within a range that does not impede the object of the present invention, but may be, for example, 0.1 to 30.0 mass %, 0.5 to 20.0 mass %, or 1.0 to 15.0 mass %, etc.
  • an organic solvent is usually blended.
  • the organic solvent there are no particular limitations on the organic solvent, so long as it can impart the desired coatability to the curable composition and form a hard coat layer with the desired thickness and performance. From the standpoint of coatability and drying properties of the resin layer (coating film) formed, it is preferable for the boiling point of the organic solvent to be 50 to 150°C.
  • 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.
  • the organic solvents can be used alone or in combination of two or more.
  • any method can be used as the application method without any particular restrictions.
  • application methods include reverse coating, gravure coating, bar coating, die coating, spray coating, kiss coating, wire bar coating, and curtain coating. These application methods may be used alone or in combination.
  • the above-described hard coat layer curable composition is applied to one or both sides of an acrylic resin film to form a resin layer (coating film), and then the organic solvent is removed from the coating film by drying, and the resin layer is cured by exposure to active energy rays such as ultraviolet light, thereby forming a hard coat layer.
  • the drying temperature for removing the organic solvent from the resin layer after coating is preferably 60 to 120°C, and more preferably 70 to 100°C. If the drying temperature is too low, the organic solvent may remain in the resin layer (coating film). If the drying temperature is too high, the flatness of the laminate (hard coat layer) may be impaired due to thermal deformation of the acrylic resin film.
  • the wavelength of the ultraviolet light irradiated when curing the resin layer (coating film) is preferably in the range of 200 to 400 nm.
  • the ultraviolet (UV) integrated light amount is, for example, preferably 150 to 700 mJ/cm 2 , more preferably 180 to 500 mJ/cm 2 , and even more preferably 200 to 400 mJ/cm 2.
  • the integrated light amount of the UV irradiation is within the above-mentioned range, it is possible to obtain an appropriate hardness of the hard coat layer while ensuring moldability.
  • an irradiation device for ultraviolet exposure light for example, an irradiation device equipped with either (a) a lamp light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an electrodeless lamp, and an excimer lamp, and/or (b) a pulsed or continuous laser light source such as an argon ion laser and a helium-neon laser can be used.
  • a lamp light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an electrodeless lamp, and an excimer lamp
  • a pulsed or continuous laser light source such as an argon ion laser and a helium-neon laser
  • an operation of irradiating active energy rays such as ultraviolet rays may be performed after secondary molding by vacuum and/or pressure molding of the laminate, or on at least a part of the resin molded article having the laminate disposed on its surface.
  • a laminate 1 in one or more embodiments of the present invention, as shown in FIG. 1, includes an acrylic resin film 2 and a hard coat layer 3 laminated on one side of the acrylic resin film 2. Although not shown, a hard coat layer may be laminated on both sides of the acrylic resin film.
  • the laminate may also include another functional layer laminated between the acrylic resin film and the hard coat layer and/or on the hard coat layer, as necessary, within a range that does not impair the effects of the present invention.
  • the laminate may also have another functional layer laminated on the opposite side to the hard coat layer.
  • the other functional layers are not particularly limited, and a wide variety of layers that are conventionally known can be used. Examples include a low refractive index layer, a primer layer, a high refractive index layer, an adhesive layer, an anti-glare layer, an anti-fouling layer, a fingerprint resistant layer, a scratch resistant layer, an antistatic layer, an ultraviolet shielding layer, an infrared shielding layer, a surface irregularity layer, a light diffusion layer, a matte layer, a polarizing layer, a colored layer, a design layer, a printed layer, an embossed layer, a conductive layer, a gas barrier layer, and a gas absorption layer.
  • the laminate may include two or more types of other functional layers in combination. Also, one functional layer may have two or more functions.
  • the laminate has a crack elongation of 100% or more at 120°C. This makes it possible to suppress the occurrence of defects such as cracks and whitening in the laminate when the laminate is laminated on a thermoplastic resin substrate and the thermoplastic resin substrate is covered with the laminate, particularly when the laminate is shaped by vacuum molding under heating and compressed air molding, or laminated onto a substrate, or when a molded product is obtained by insert injection molding after placing the shaped laminate on a mold surface as necessary, and the secondary moldability is good.
  • the crack elongation of the laminate at 120°C is preferably 110% or more, more preferably 120% or more, even more preferably 130% or more, and particularly preferably 140% or more. In this specification, the crack elongation of the laminate at 120°C can be measured by the method described in the Examples.
  • the laminate has no cracks on the surface of the hard coat layer even after an accelerated weathering test is performed for a total of 2000 hours, in which the laminate is placed so that the hard coat layer side faces the light source, a xenon lamp is used as the light source, and an irradiance of 180 W/m 2 (300 to 400 nm) is applied, and a cycle of 1000 cycles of 120 minutes in total consisting of step 1 with an exposure time of 102 minutes, a black panel temperature of 60 ⁇ 3°C, a relative humidity of 65 ⁇ 5%, and no rainfall, and step 2 with an exposure time of 18 minutes, an internal temperature of 38 ⁇ 3°C, a humidity of 95 ⁇ 5%, and rainfall is performed.
  • the color difference ⁇ E of the laminate after the accelerated weathering test relative to the laminate before the accelerated weathering test is preferably 0.5 or less, more preferably 0.3 or less.
  • the color difference ⁇ E of the laminate after the accelerated weather resistance test compared to the laminate before the accelerated weather resistance test is 0.5 or less, more preferably 0.3 or less.
  • the laminate preferably has a haze (Hz) of 2.0% or less, more preferably 1.5% or less, even more preferably 1.0% or less, even more preferably 0.8% or less, and particularly preferably 0.4% or less.
  • a haze Hz
  • the haze can be measured by the method described in the examples.
  • the laminate has excellent surface hardness, and from the viewpoint of enhancing the scratch resistance of a resin molded product using the laminate, the pencil hardness of the hard coat layer side is preferably B or higher under a load of 500 g, more preferably HB or higher, even more preferably F or higher, and particularly preferably H or higher.
  • the laminate shows no visible change in appearance when approximately 0.02 mL of isopropyl alcohol is dropped onto the surface of the hard coat layer and left at 23°C for 6 hours. Also, from the viewpoint of excellent chemical resistance, it is preferable that the laminate shows no visible change in appearance when approximately 0.02 mL of acetone is dropped onto the surface of the hard coat layer and left at 23°C for 6 hours.
  • the ⁇ haze ( ⁇ Hz) of the laminate when stretched 20% at room temperature is preferably 3% or less, more preferably 2% or less, and even more preferably 1.5% or less.
  • the ⁇ Hz of the laminate when stretched 20% at room temperature can be measured by the method described in the Examples.
  • the ⁇ Hz of the laminate when stretched 80% at 120°C is preferably 3% or less, more preferably 2% or less, even more preferably 1% or less, even more preferably 0.8% or less, and particularly preferably 0.4% or less.
  • the ⁇ Hz of the laminate when stretched 80% at 120°C can be measured by the method described in the Examples.
  • the resin molded product includes a thermoplastic resin substrate and a laminate, and at least a portion of the thermoplastic resin substrate is covered with the laminate arranged so that the acrylic resin film is on the thermoplastic resin substrate side.
  • the laminate has a high crack elongation at 120°C, and therefore a thermoplastic resin substrate having at least a portion of a non-flat curved shape and/or a three-dimensional shape can be covered with the laminate to suitably obtain a resin molded product having a three-dimensional shape.
  • the laminate can impart various functionalities such as long-term weather resistance, scratch resistance, and chemical resistance to the resin molded product by covering the thermoplastic resin substrate in various shapes of resin molded products.
  • the thermoplastic resin substrate may be composed of, for example, polycarbonate resin having a bisphenol-based skeleton, a fluorene-based skeleton, or an isosorbide-based skeleton, an acrylic resin, a styrene-based resin (AS resin, ABS resin, MAS resin, styrene maleimide-based resin, and styrene maleic anhydride resin, etc.), a saturated polyester resin, a polyvinyl chloride resin, a polyarylate resin, a PPS-based resin, a POM-based resin, a polyamide resin, a polylactic acid resin, a cellulose acylate-based resin, and a polyolefin-based resin.
  • polycarbonate resin having a bisphenol-based skeleton, a fluorene-based skeleton, or an isosorbide-based skeleton
  • an acrylic resin a styrene-based resin (AS resin, ABS resin, MAS resin, sty
  • polycarbonate resin one or more selected from the group consisting of polycarbonate resin, acrylic resin, styrene resin, and amorphous polyolefin-based resin are preferred because of their excellent transparency, and polycarbonate resin and/or acrylic resin are more preferred because of their good adhesion to the laminate, and polycarbonate resin is even more preferred from the viewpoints of high rigidity, high heat resistance, and high impact resistance.
  • the resin molded body can be used, for example, as an automobile interior material, an automobile exterior material, an optical component, a home appliance component, and an architectural exterior material. Since the laminate has excellent long-term weather resistance, the resin molded body using the laminate can be suitably used as an automobile exterior material or an architectural exterior material.
  • Automotive exterior materials are not particularly limited, but examples thereof include door mirrors, windows, headlamp covers, taillamp covers, windshield parts, weather strips, bumpers, bumper guards, side mudguards, body panels, spoilers, flon ruffles, strut mounts, wheel caps, center pillars, center ornaments, side moldings, door moldings, and window moldings.
  • Automotive exterior materials include exterior wall materials such as siding, fences, roofs, gates, and gable boards.
  • the method for producing the resin molded body is not particularly limited as long as it is a molding method that can cover at least a part of the thermoplastic resin substrate with a laminate arranged so that the acrylic resin film side is the thermoplastic resin substrate side.
  • the laminate may have other functional layers as described above formed thereon before lamination onto the substrate. Using such a laminate, for example, by insert injection molding, a resin molded body having a laminate arranged on its surface can be produced.
  • the laminate may be preformed by a method such as vacuum molding, pressure molding, and compression molding, as necessary.
  • the laminate may be heated and/or pressurized under reduced pressure and/or pressure, and the laminate may be arranged on the surface of a thermoplastic resin substrate having at least a part of a non-flat three-dimensional shape (curved shape) to produce a resin molded body, so-called three-dimensional laminate molding. Furthermore, the laminate may be heated and stretched appropriately, and laminated by hand onto the surface of the thermoplastic resin substrate to produce a resin molded body.
  • a differential scanning calorimeter (DSC, manufactured by Seiko Instruments, model number "SSC-5200") was used. The sample was heated to 200°C at a rate of 25°C/min, held for 10 minutes, preconditioned by lowering the temperature to 50°C at a rate of 25°C/min, and then heated to 200°C at a rate of 10°C/min, during which DSC measurements were performed.
  • a differential value (SSDC) was determined from the resulting DSC curve, and the glass transition temperature was determined from the maximum point.
  • the acrylic resin film was cut into a size of 10 mm (width) x 100 mm (length) in the machine direction (MD) during extrusion molding, and used as a sample.
  • a tensile test was performed using a Tensilon tensile tester (manufactured by Shimadzu Corporation, model number "AG-2000D") equipped with a high-temperature bath set at 120°C, under conditions of a preheat time of 2 minutes, a chuck distance of 40 mm, and a tensile speed of 200 mm/min. The elongation at the time the test piece broke was measured, and the average value of the test results obtained by measuring three samples was taken as the breaking elongation at 120°C.
  • the laminate was cut into a sample measuring 10 mm (width) x 100 mm (length), and a tensile test was performed using a Tensilon tensile tester (manufactured by Shimadzu Corporation, model number "AG-2000D") equipped with a high-temperature bath set at 120°C under the conditions of a preheat time of 2 minutes, a chuck distance of 40 mm, and a tensile speed of 200 mm/min. The elongation was measured when a crack occurred in the hard coat layer, and the average value of the test results obtained by performing the measurement on three samples was taken as the crack elongation at 120°C.
  • the thickness of the acrylic resin film was measured with a PEACOCK dial gauge No. 25 (manufactured by Ozaki Manufacturing Co., Ltd.).
  • the thickness of the hard coat layer was measured with an F20 film thickness measurement system (manufactured by Filmetrics, Inc.)
  • 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 to 1.49, and the refractive index of the hard coat layer was set to 1.50.
  • the laminate was cut into a size of 10 mm (width) x 100 mm (length) to prepare a sample, and a tensile test was performed using a Tensilon tensile tester (Shimadzu Corporation, AG-2000D) equipped with a high-temperature bath set at 120°C under the conditions of a pre-heating time of 2 minutes, a chuck distance of 40 mm, and a tensile speed of 200 mm/min.
  • the haze of the sample before the tensile test was measured to obtain the haze of the laminate before stretching, and the haze of the sample after 80% stretching was measured to obtain the haze of the laminate after 80% stretching at 120°C.
  • the laminate was cut into a size of 10 mm (width) x 100 mm (length) to prepare a sample, and a tensile test was performed at 23°C, chuck distance 40 mm, and tensile speed 200 mm/min using a Tensilon tensile tester (manufactured by Shimadzu Corporation, model number "AG-2000D") to stretch the sample by 20%.
  • the sample after 20% stretching was left to stand at 23°C for 12 hours, and then the haze was measured and used as the haze of the laminate after 20% stretching at room temperature.
  • the haze of the sample measured before the tensile test was used as the haze of the laminate before stretching.
  • ⁇ Hz after 20% stretching of the laminate at room temperature haze of the laminate after 20% stretching at room temperature - haze of the laminate before stretching
  • the pencil hardness was measured under a load of 500 g in accordance with JIS K 5600-5-4:1999.
  • a super xenon weather meter (SX2D-75, manufactured by Suga Test Instruments Co., Ltd.) was used.
  • the filter configuration used quartz glass on the inside and polysilicate #275 on the outside to simulate direct sunlight.
  • a laminate sample (40 mm x 50 mm) was placed with the hard coat layer side facing the light source, and an accelerated weather resistance test was performed by carrying out a cycle consisting of the following steps 1 and 2 (total of 120 minutes) for 1000 cycles (2000 hours).
  • Step 1 exposure time 102 minutes, irradiance 180 W/ m2 (300-400 nm), black panel temperature 60 ⁇ 3°C, relative humidity 65 ⁇ 5%, no rain
  • Step 2 exposure time 18 minutes, irradiance 180 W/ m2 (300-400 nm), chamber temperature 38 ⁇ 3°C, relative humidity 95 ⁇ 5%, rain
  • the surface of the hard coat layer of the sample after the accelerated weather resistance test was visually observed to check for cracks. If no cracks were found, the long-term weather resistance was judged to be good.
  • the color difference ( ⁇ E) of the laminate after the weather resistance test relative to the laminate before the weather resistance test was measured using a spectrophotometer SE7700 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) under the following conditions. Mode: Transmitted light, Light source: D65, Field of view: 2°, Measurement diameter: 28 mm
  • Methyl ethyl ketone (MEK) was added to a highly extensible curable resin composition (containing a urethane acrylate resin, manufactured by Daido Chemical Industry Co., Ltd., product name "P5820TA-20J", solid content 25%) so that the solid content became 23%.
  • Methyl ethyl ketone (MEK) was added to a low-stretch curable resin composition (containing a urethane acrylate resin, manufactured by DIC Corporation, product name "ENS-102", solid content 99%) so that the solid content became 23%.
  • Example 1 Preparation of acrylic resin film>
  • graft copolymer particles (A-1) multilayer structure particles (C4) having an average particle size of 85 nm prepared by the same method as in Production Example 4 of JP 2020-147653 A were used, and as the acrylic resin (D-1), poly(methyl methacrylate) (manufactured by Sumitomo Chemical, product name "Sumipex (registered trademark) MG”) was used.
  • a resin mixture 1 consisting of 38% graft copolymer particles (A-1) and 62% acrylic resin (D-1), 0.3 parts of a hindered phenol-based antioxidant (manufactured by BASF, product name "Irganox 1010”), and 1.5 parts of an ultraviolet absorber (benzotriazole-based ultraviolet absorber, manufactured by ADEKA, product name "Adekastab LA-31”) were mixed using a Henschel mixer.
  • melt-kneading was performed at a screw rotation speed of 150 rpm and a discharge rate of 180 kg / hr, taken up in a strand shape, cooled in a water tank, and cut using a pelletizer to obtain pellets.
  • the obtained pellets were melt-kneaded using a T-die-equipped single screw extruder with an extrusion diameter of 90 mm at a cylinder setting temperature of 180 to 240 ° C.
  • a hard coat layer curable resin composition was applied to one side of the obtained acrylic resin film using a bar coater. After that, the film was dried at 80°C for 2 minutes to volatilize the solvent, and then irradiated with an ultraviolet (UV) irradiator under a nitrogen atmosphere (oxygen concentration 1% or less) with an integrated UV light amount of 460 mJ to form a hard coat layer (thickness 5 ⁇ m), and a laminate was obtained.
  • UV ultraviolet
  • ADEKA STAB LA-82 reactive HALS
  • Example 2 An acrylic graft copolymer (A) having an average particle size of 80 nm, prepared in the same manner as in Reference Example 4 of JP-A-2004-137299, was used as the graft copolymer particles (A-2), and poly(methyl methacrylate) (Sumipex (registered trademark) EX, manufactured by Sumitomo Chemical) was used as the acrylic resin (D-2).
  • An acrylic resin film (D2) and a laminate were obtained in the same manner as in Example 1, except that 100 parts of a resin mixture 2 consisting of 70% of the graft copolymer particles (A-2) and 30% of the acrylic resin (D-2) was used, and the discharge rate from the T-die was set to 110 kg/hr.
  • Example 3 A multilayered acrylic resin having an average particle size of 130 nm, prepared in the same manner as in A-3 of Table 1 in JP-A-2015-7255, was used as the graft copolymer particles (A-3).
  • An acrylic resin film (D3) and a laminate were obtained in the same manner as in Example 1, except that 100 parts of a resin mixture 3 consisting of 40% of the graft copolymer particles (A-3) and 60% of the acrylic resin (D-2) was used.
  • Example 4 Graft copolymer particles (A-4) were prepared in the same manner as in Production Example 1 of WO 2019/181752, and graft copolymer particles (A) having an average particle diameter of 80 nm were used, and graft copolymer particles (B-1) were prepared in the same manner as in Production Example 12 of WO 2019/181752, and graft copolymer particles (B) having an average particle diameter of 230 nm were used.
  • An acrylic resin film (D4) and a laminate were obtained in the same manner as in Example 1, except that 100 parts of a resin mixture 4 consisting of 30% graft copolymer particles (A-4), 4% graft copolymer particles (B-1), and 66% acrylic resin (D-2) was used.
  • Comparative Example 1 An acrylic resin film and a laminate were obtained in the same manner as in Example 1, except that Coating 1 was used as the curable resin composition for the hard coat layer.
  • Comparative Example 2 An acrylic resin film and a laminate were obtained in the same manner as in Example 1, except that a composition in which a hydroxyphenyltriazine-based ultraviolet absorber (manufactured by BASF, product name "Tinuvin (registered trademark) 400", hereinafter also referred to as Tinuvin 400) was added to paint 1 in an amount of 2 parts per 100 parts of the solid content of paint 1 was used as the curable resin composition for the hard coat layer.
  • a hydroxyphenyltriazine-based ultraviolet absorber manufactured by BASF, product name "Tinuvin (registered trademark) 400", hereinafter also referred to as Tinuvin 400
  • Example 3 An acrylic resin film and a laminate were obtained in the same manner as in Example 1, except that a composition was used in which a hydroxyphenyltriazine-based ultraviolet absorber (manufactured by BASF, product name "Tinuvin (registered trademark) 479" (hereinafter also referred to as Tinuvin 479) was added to Paint 1 in an amount of 2 parts per 100 parts of the solid content of Paint 1 as the curable resin composition for the hard coat layer.
  • a hydroxyphenyltriazine-based ultraviolet absorber manufactured by BASF, product name "Tinuvin (registered trademark) 479” (hereinafter also referred to as Tinuvin 479) was added to Paint 1 in an amount of 2 parts per 100 parts of the solid content of Paint 1 as the curable resin composition for the hard coat layer.
  • Example 4 An acrylic resin film and a laminate were obtained in the same manner as in Example 1, except that a composition was used in which Tinuvin 400 and HALS (manufactured by BASF, product name "ADK STAB LA-81", hereinafter also referred to as LA81) were added to Coating 1 in amounts of 2 parts and 1 part, respectively, per 100 parts of the solid content of Coating 1, as the curable resin composition for the hard coat layer.
  • Tinuvin 400 and HALS manufactured by BASF, product name "ADK STAB LA-81”, hereinafter also referred to as LA81
  • Example 5 An acrylic resin film and a laminate were obtained in the same manner as in Example 1, except that a composition in which LA81 was added to Coating 1 so that the amount was 2 parts per 100 parts of the solid content of Coating 1 was used as the curable resin composition for the hard coat layer.
  • Example 6 An acrylic resin film and a laminate were obtained in the same manner as in Example 1, except that a composition in which LA82 was added to Coating 2 so that the amount was 2 parts per 100 parts of the solid content of Coating 2 was used as the curable resin composition for the hard coat layer.
  • Example 7 An acrylic resin film and a laminate were obtained in the same manner as in Example 2, except that Coating 1 was used as the curable resin composition for the hard coat layer.
  • Comparative Example 8 An acrylic resin film and a laminate were obtained in the same manner as in Example 2, except that a composition in which Tinuvin 400 was added to Coating 1 so that the amount was 2 parts per 100 parts of the solid content of Coating 1 was used as the curable resin composition for the hard coat layer.
  • Example 9 An acrylic resin film and a laminate were obtained in the same manner as in Example 2, except that a composition in which Tinuvin 479 was added to Coating 1 in an amount of 2 parts per 100 parts of the solid content of Coating 1 was used as the curable resin composition for the hard coat layer.
  • Example 10 An acrylic resin film and a laminate were obtained in the same manner as in Example 2, except that a composition in which Tinuvin 400 and LA81 were added to Coating 1 so that the amounts were 2 parts and 1 part, respectively, per 100 parts of the solid content of Coating 1 was used as the curable resin composition for the hard coat layer.
  • Example 11 An acrylic resin film and a laminate were obtained in the same manner as in Example 1, except that a composition in which LA81 was added to Coating 1 in an amount of 2 parts per 100 parts of the solid content of Coating 1 was used as the curable resin composition for the hard coat layer.
  • Reference Example 1 An acrylic resin film prepared in the same manner as in Example 1 was used as Reference Example 1.
  • the crack elongation at 120°C, ⁇ Hz after 80% stretching at 120°C, ⁇ Hz after 20% stretching at room temperature, haze, pencil hardness, chemical resistance and weather resistance of the laminate were measured as described above, and the results are shown in Tables 1 and 2 below.
  • the thickness of the acrylic resin film, the tensile breaking elongation at 120°C, and the glass transition temperature, as well as the thickness of the hard coat layer were measured as described above, and the results are shown in Tables 1 and 2 below. Tables 1 and 2 below also show the composition of the hard coat layer, and the blending amount is in parts by mass relative to 100 parts by mass of the solid content of the paint.
  • the laminates of Examples 1 to 4 have a crack elongation of 100% or more at 120°C, and have good secondary formability. Furthermore, even after 2000 hours of accelerated weather resistance testing, the laminates of Examples 1 to 4 did not develop cracks on the surface of the hard coat layer, and the color difference was 0.3 or less, indicating good long-term weather resistance.
  • the laminates of Comparative Examples 1 to 5 and 7 to 11 in which the hard coat layer does not contain reactive HALS, had cracks on the surface of the hard coat layer after 1000 hours or 2000 hours of accelerated weather resistance testing, and had poor long-term weather resistance.
  • the laminate of Comparative Example 6 in which a low-extensibility paint was used as the curable resin composition for the hard coat layer had a crack elongation of less than 100% at 120°C, and was poor in secondary formability.
  • a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one surface of the acrylic resin film,
  • the acrylic resin film has a tensile elongation at break of 200% or more at 120°C
  • the hard coat layer is formed of a cured product of a curable resin composition including a urethane acrylate resin and a hindered amine-based light stabilizer having a reactive functional group
  • the laminate has a tensile crack elongation of 100% or more at 120°C.
  • the curable resin composition contains 1 to 10 parts by mass of a hindered amine-based light stabilizer having a reactive functional group per 100 parts by mass of a urethane acrylate resin.
  • a resin molded article comprising the laminate according to any one of [1] to [7] and a thermoplastic resin substrate, wherein at least a portion of the thermoplastic resin substrate is covered with the laminate in such a manner that the acrylic resin film is on the thermoplastic resin substrate side.

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PCT/JP2024/010061 2023-03-30 2024-03-14 積層体及びそれを含む樹脂成形体 Ceased WO2024203401A1 (ja)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012207120A (ja) * 2011-03-29 2012-10-25 Dainippon Printing Co Ltd ハードコートフィルム及びそれを用いたハードコート樹脂成型体
JP2012210739A (ja) * 2011-03-30 2012-11-01 Dainippon Printing Co Ltd 耐候性ハードコートフィルムの製造方法
JP2012213926A (ja) * 2011-03-31 2012-11-08 Dainippon Printing Co Ltd 三次元成形用加飾シート、該加飾シートの製造方法、加飾樹脂成形品及び該加飾樹脂成形品の製造方法
JP5267700B1 (ja) * 2012-03-30 2013-08-21 大日本印刷株式会社 有機ガラス積層用フィルム
WO2015015553A1 (ja) * 2013-07-29 2015-02-05 大日本印刷株式会社 有機ガラス積層用フィルム
WO2022137768A1 (ja) * 2020-12-25 2022-06-30 株式会社カネカ 積層体およびその利用
WO2022185815A1 (ja) * 2021-03-05 2022-09-09 株式会社カネカ 積層体およびその製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012207120A (ja) * 2011-03-29 2012-10-25 Dainippon Printing Co Ltd ハードコートフィルム及びそれを用いたハードコート樹脂成型体
JP2012210739A (ja) * 2011-03-30 2012-11-01 Dainippon Printing Co Ltd 耐候性ハードコートフィルムの製造方法
JP2012213926A (ja) * 2011-03-31 2012-11-08 Dainippon Printing Co Ltd 三次元成形用加飾シート、該加飾シートの製造方法、加飾樹脂成形品及び該加飾樹脂成形品の製造方法
JP5267700B1 (ja) * 2012-03-30 2013-08-21 大日本印刷株式会社 有機ガラス積層用フィルム
WO2015015553A1 (ja) * 2013-07-29 2015-02-05 大日本印刷株式会社 有機ガラス積層用フィルム
WO2022137768A1 (ja) * 2020-12-25 2022-06-30 株式会社カネカ 積層体およびその利用
WO2022185815A1 (ja) * 2021-03-05 2022-09-09 株式会社カネカ 積層体およびその製造方法

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