WO2025004853A1 - 積層体、それを含む成形体、及び成形体の製造方法 - Google Patents

積層体、それを含む成形体、及び成形体の製造方法 Download PDF

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WO2025004853A1
WO2025004853A1 PCT/JP2024/021666 JP2024021666W WO2025004853A1 WO 2025004853 A1 WO2025004853 A1 WO 2025004853A1 JP 2024021666 W JP2024021666 W JP 2024021666W WO 2025004853 A1 WO2025004853 A1 WO 2025004853A1
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laminate
resin layer
cured resin
layer
group
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French (fr)
Japanese (ja)
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長谷部花子
石丸富士雄
小山治規
山口克己
嶋本幸展
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Kaneka Corp
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Kaneka Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings

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  • the present invention relates to a laminate containing an acrylic resin film, a molded body containing the same, and a method for producing the molded body.
  • Acrylic resin films formed from acrylic resin compositions containing elastomers have been used in a variety of applications, taking advantage of their excellent properties, such as transparency, hardness, weather resistance, and secondary formability.
  • applications for acrylic resin films include decorative and protective applications as an alternative to painting for interior and exterior vehicle components, decorative and protective applications for exterior components of electronic devices such as portable electronic devices, personal computers, and home appliances, and applications as building materials.
  • Patent Document 1 proposes a technology that achieves both secondary formability and scratch resistance by providing a hard coat layer on the surface of an acrylic resin film substrate that exhibits high surface hardness after curing and high secondary formability.
  • N,N-diethyl 3-ethylbenzamide (hereinafter also referred to as DEET) has little effect on the human body and is highly effective in repelling harmful insects such as mosquitoes, so it is widely used as the main ingredient in sprays and lotions for repelling insects.
  • Patent Document 2 proposes a laminated film that is given a certain degree of resistance to DEET by providing a cured resin layer made of a resin containing units derived from urethane resin on an acrylic resin film.
  • the present invention has been made in consideration of the above problems, and provides a laminate that contains an acrylic resin film, has high surface hardness and secondary formability, and has good chemical resistance to chemicals such as N,N-diethyl-3-ethylbenzamide, a molded product that contains the laminate, and a method for producing the molded product.
  • One or more embodiments of the present invention relate to a laminate including a base material layer and a cured resin layer, wherein the base material layer includes an acrylic resin film, and the acrylic resin film has a tensile elongation at break of 200% or more at 120°C.
  • the cured resin layer is formed of a cured product of an active energy ray-curable resin composition including a urethane acrylate resin, and the cured resin layer has a curing index represented by the following formula 1 of 0.013 or less, and the laminate has a tensile crack elongation of 80% or more at 120°C.
  • Hardening index B/D
  • B represents the area of an infrared absorption peak at a wave number of about 810 cm ⁇ 1 in FT-IR measurement of the cured resin layer
  • D represents the area of an infrared absorption peak at a wave number of about 1705 cm ⁇ 1 in FT-IR measurement of the cured resin layer.
  • One or more embodiments of the present invention relate to a molded body including the laminate and a molded body substrate, in which the laminate is laminated on the surface of the molded body substrate, and the cured resin layer of the laminate is disposed closer to the surface of the molded body than the substrate layer of the laminate.
  • One or more embodiments of the present invention relate to a method for manufacturing the molded body, in which the laminate is laminated onto the surface of the molded body substrate using one or more methods selected from the group consisting of vacuum forming, compressed air forming, film insert injection molding, and three-dimensional laminate molding.
  • the present invention provides a laminate that contains an acrylic resin film, has high surface hardness and secondary formability, and has good chemical resistance to chemicals such as N,N-diethyl-3-ethylbenzamide, a molded product that contains the laminate, and a method for producing the molded product.
  • FIG. 1 is a diagram illustrating a method for calculating a curing index based on the area of an infrared absorption peak at a wave number of about 810 cm ⁇ 1 and the area of an infrared absorption peak at a wave number of about 1705 cm ⁇ 1 in FT-IR measurement of a cured resin layer in Comparative Example 2.
  • the inventors of the present invention have conducted extensive research to solve the above problems. As a result, they have discovered that in a laminate including a substrate layer containing an acrylic resin film and a cured resin layer, by using an acrylic resin film having a tensile breaking elongation of 200% or more at 120°C, making the tensile crack elongation of the laminate at 120°C 80% or more, forming the cured resin layer from a cured product of an active energy ray curable resin composition containing a urethane acrylate resin, and setting the value of the curing index of the cured resin layer represented by the following formula 1 within a specific range, i.e., the degree of curing within a specific range, the surface hardness and secondary formability of the laminate are high, and the chemical resistance to high concentrations of DEET is enhanced.
  • Hardening index B/D
  • B represents the area of an infrared absorption peak at a wave number of about 810 cm ⁇ 1 in FT-IR measurement of the cured resin layer
  • D represents the area of an infrared absorption peak at a wave number of about 1705 cm ⁇ 1 in FT-IR measurement of the cured resin layer.
  • the curing index is a parameter indicating the degree of curing of the cured resin layer, and more specifically, depends on the degree of progress of the curing reaction in the active energy ray curable resin composition containing a urethane acrylate resin.
  • the infrared absorption peak at a wave number of about 810 cm ⁇ 1 in the FT-IR measurement corresponds to the out-of-plane bending vibration of the C-C double bond of the acryloyl group and/or methacryloyl group
  • B reflects the content of the uncured acryloyl group and methacryloyl group in the cured resin layer, and the value decreases with progress of the curing reaction.
  • the infrared absorption peak at a wave number of about 1705 cm ⁇ 1 in the FT-IR measurement corresponds to the stretching vibration of the C-O double bond of the ester group
  • D reflects the total amount of the uncured acryloyl group and methacryloyl group in the cured resin layer, and the ester group after the acryloyl group and methacryloyl group are cured, and the total amount of the C-O double bond functional group does not change in principle before and after the curing reaction.
  • the curing index B/D is obtained by dividing the peak area values corresponding to the acryloyl and methacryloyl groups, which are functional groups that decrease due to the curing reaction, by the peak area value that does not change in principle due to the curing reaction.
  • the value depends on the degree of progress of the curing reaction, is maximum when the curing reaction is unreacted, and is 0 when the curing reaction has progressed completely, and can be used as a parameter indicating the degree of curing of the cured resin layer.
  • the chemical resistance to high concentration for example, 30 w/v % DEET is improved.
  • the curing index B/D is set to 0.013 or less
  • the active energy ray curable resin composition contains, in addition to the urethane acrylate resin, a hindered amine-based light stabilizer having a reactive functional group, and a compound having a hydrophobic group and a reactive functional group, thereby improving weather resistance, particularly the weather resistance of physical properties including chemical resistance to chemicals such as DEET.
  • 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 cured resin layer, and the secondary moldability 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. In this specification, the tensile elongation at break of the acrylic resin film at 120°C can be measured by the method described in the examples.
  • the acrylic resin film is preferably formed from an acrylic resin composition containing 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.
  • structural units 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 WO 2005/54311, lactone ring structures as shown in JP-A-2004-168882 and JP-A-2006-171464, glutaric anhydride structures obtained by thermal 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 WO 2009/84541.
  • the introduction of these structures into an acrylic resin makes the molecular chain rigid. As a result, it is expected to have effects such as improved heat resistance, improved surface hardness, reduced heat shrinkage, and improved chemical
  • 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 crosslinked resin layer with a glass transition temperature of room temperature (20 ⁇ 5°C) or higher or a semi-hard crosslinked resin layer with a glass transition temperature in the range of 0°C to room temperature 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) is 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 deteriorate 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, the polyfunctional monomer, and the other vinyl monomers may be mixed together and polymerized in one step.
  • the acrylic acid ester, the polyfunctional monomer, and the other vinyl monomers may be polymerized in two or more stages by changing the composition of the acrylic acid ester, the polyfunctional monomer, and the other vinyl monomers as appropriate, or by keeping the composition the same.
  • acrylic acid esters aliphatic esters of acrylic acid are preferred, aliphatic alkyl acrylate esters are more preferred, and aliphatic 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 produce polymers with low glass transition temperatures (Tg).
  • the aliphatic alkyl may be linear, branched, or cyclic (also called alicyclic).
  • preferred aliphatic alkyl acrylates 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 aliphatic alkyl acrylate, more preferably an aliphatic alkyl acrylate with an alkyl group having 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 other than aliphatic alkyl acrylate esters such as phenyl acrylate and benzyl acrylate; methacrylic acid; methacrylic acid derivatives such as ⁇ -hydroxyethyl meth
  • 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 crack resistance 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 when folded, the resistance to whitening when folded, and the fluidity of the resin during molding of the acrylic resin film.
  • 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 particle (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 particle (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, and the melt viscosity of the acrylic resin composition can be reduced, which is expected to improve the melt processability and film processing accuracy of the acrylic resin film, as well as improve 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, and 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, and the like 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 for the purpose of reducing the double bond terminals of the polymer to control the thermal stability, etc.
  • 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) as a shell layer, the graft copolymer particle (A) can typically be obtained by graft copolymerizing a monomer mixture (a-2) containing 50 to 100% by mass of a methacrylic acid ester and 0 to 50% by 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% by 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, and octyl methacrylate, as well as aromatic methacrylic acid esters such as 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 is preferably at least one 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, more preferably at least one selected from the group consisting of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate, and particularly preferably n-butyl acrylate.
  • 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, methacrylic acid derivatives, acrylic acid, acrylic acid 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, methacrylic acid derivatives, acrylic acid, acrylic acid 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.
  • 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole is preferably used in terms of cost and ease of handling.
  • (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 ratio 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.
  • Such a chain transfer agent may be the same as the chain transfer agent that can be used in the polymerization of the crosslinked elastomer (A1).
  • the amount of the chain transfer agent used is preferably 0 to 2 parts by mass, 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 cause cracks during secondary molding. If the graft ratio exceeds 250%, the melt viscosity of the acrylic resin composition tends to increase during film molding, and the moldability of the acrylic resin film tends to decrease.
  • 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 particle (B), like the graft copolymer particle (A), comprises a crosslinked elastomer (B1) which is a rubber component.
  • the graft copolymer particle (B), like the graft copolymer particle (A), typically comprises a graft polymer layer (B2) located on the surface side of the crosslinked elastomer (B1).
  • the graft copolymer particle (B) preferably comprises a core layer of crosslinked elastomer (B1) and a shell layer of graft polymer layer (B2).
  • both the core layer and the shell layer may have a multilayer structure.
  • 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 diameter 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 WO 2014/41803.
  • a hard or semi-hard crosslinked resin layer it is possible to improve the transparency, resistance to whitening on bending, resistance to cracking on bending, etc. 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) having 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 than graft copolymer particles (A) having a small average particle size. For this reason, the graft copolymer particles (B) are extremely effective in imparting impact resistance and crack resistance to the acrylic resin material.
  • the graft copolymer particles (B) are inferior to the graft copolymer particles (A) in bending whitening resistance and/or solvent whitening resistance, etc.
  • 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) 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 reduced so that the surface hardness of the acrylic resin film and the laminate is not reduced, (b) when external stress is applied to the acrylic resin film, when a coating liquid containing an organic solvent is applied and/or during molding processing, the whitening property is unlikely to deteriorate, and (c) the crack resistance, secondary moldability, etc.
  • acrylic resin films that use graft copolymer particles (A) and a small amount of graft copolymer particles (B) in combination include those disclosed in International Publication No. 2013/051239 and International Publication No. 2019/181752.
  • 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 referred to as a mass basis), and can be measured in a latex state using a laser diffraction/scattering 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, and hydroxyacetone.
  • a catalyst such as ferrous sulfate and a reducing agent such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, and 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 with propylene oxide and/or ethylene oxide, and reaction products of aliphatic alcohols with 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 ammoni
  • 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 treating the latex with spray drying, freeze coagulation, freeze drying, or the like.
  • the latex of the graft copolymer particles (A) or the latex of the graft copolymer particles (B) may be filtered with a filter and/or mesh to remove environmental foreign matter and substances that may cause foreign matter defects, such as polymerization scale.
  • the filters and meshes may be any known filters and meshes used for filtering liquid media.
  • the type of filter and mesh, the mesh openings, filtering accuracy, and filtering capacity are appropriately selected depending on the intended use and the type, size, and amount of foreign matter to be removed.
  • the mesh openings 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 10 to 70% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 45% 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 range preferred for the intended use without impairing the quality of the laminate of the present invention.
  • 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-based resins, polycarbonate resins, and polyimide resins are preferred because they have excellent compatibility with acrylic resins and may be able to improve the flexural 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 conventionally known for use in acrylic resin films, within the scope of not impairing the objective of one embodiment of the present invention.
  • additives include antioxidants, ultraviolet absorbers, 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.
  • the additives are not limited to these. These additives can be used in any amount according to the type of additive, within the scope of not impairing the objective of one embodiment of the present invention, or to enhance the effect of one embodiment of the present invention.
  • 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 preferably, for example, 100°C or more.
  • the glass transition temperature of the acrylic resin film can be determined using a known method such as differential scanning calorimetry (DSC).
  • the thickness of the acrylic resin film is not particularly limited, but is preferably 50 to 350 ⁇ m, more preferably 60 to 300 ⁇ m, and particularly preferably 70 to 250 ⁇ m.
  • the film has sufficient stretchability and excellent handleability, and has the advantage of excellent appearance after lamination to a resin substrate (substrate for molded body) during production of the molded body.
  • 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 surface hardness and 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 form 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, it is preferable to use a filter or mesh to filter out environmental foreign matter, polymerization scale, deteriorated resin, etc., in the acrylic resin composition, which may cause defects in the appearance or internal foreign matter in the acrylic resin film, in order to improve the appearance quality of 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 any particular restrictions, so long as the filters and meshes have heat resistance and durability according to the melt processing conditions, or resistance to the casting solvent and dope, etc.
  • an automatic die device can be used to improve the thickness accuracy of the film, for example, by measuring the film thickness distribution in the TD direction (direction perpendicular to the extrusion direction) of the extruded film online and automatically adjusting the lip clearance of the T-die while extruding the film 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 maintained at a temperature of the glass transition temperature of the acrylic resin composition minus 80°C or higher, preferably the glass transition temperature minus 70°C or higher.
  • the upper limit of the temperature of the cooling roll or cooling belt is not particularly limited, but may be, for example, the glass transition temperature of the acrylic resin composition + 10°C or lower.
  • a roll having an elastic metal sleeve such as those disclosed in JP-A-2000-153547 and JP-A-11-235747 is used, and a low sandwiching pressure is used to transfer the roll mirror surface or a specific surface shape.
  • 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, and a method in which transverse stretching is performed while relaxing the longitudinal direction after longitudinal stretching, thereby suppressing the bowing phenomenon of the film.
  • the substrate layer includes an acrylic resin film.
  • the substrate layer may have a smooth surface, and may be provided with any surface shape such as hairline, prism, uneven shape, three-dimensional decoration, matte surface, rough surface having a certain surface roughness, knurling on the film end, etc., on one or both sides of the substrate layer, as needed for the application, within a range that does not impair the effects of the present invention.
  • the provision of such a surface shape can be carried out by a known method.
  • both surfaces (also called both sides) of a film immediately after extrusion or a molded film unwound from a winding device are sandwiched between two rolls or belts having a surface shape on at least one surface (also called one side) to transfer the surface shape of the roll
  • the substrate layer may also be provided with a printed decorative layer laminated on one or both sides of an acrylic resin film, as needed for the application, within a range that does not impair the effects of the present invention.
  • the cured resin layer is formed of a cured product of an active energy ray curable resin composition (hereinafter, also simply referred to as "curable resin composition") containing a urethane acrylate resin, or preferably a urethane acrylate resin, a hindered amine-based light stabilizer having a reactive functional group, and a compound having a hydrophobic group and a reactive functional group.
  • curable resin composition an active energy ray curable resin composition
  • the cured resin layer can be formed by coating a curable resin composition containing a urethane acrylate resin, or preferably a curable resin composition containing a urethane acrylate resin, a hindered amine-based light stabilizer having a reactive functional group, and a compound having a hydrophobic group and a reactive functional group, on a substrate layer containing an acrylic resin film, and then curing the resulting layer.
  • the cured resin layer may be formed on one side or both sides of the substrate layer containing an acrylic resin film.
  • the curable resin composition for the cured resin layer preferably has active energy curability, and it is more preferable that the urethane acrylate resin, the hindered amine-based light stabilizer having a reactive functional group, and the compound having a hydrophobic group and a reactive functional group have active energy curability.
  • the cured resin layer is required to have high crack elongation as well as improved surface hardness, so that when the laminate is subjected to secondary molding to fit the shape of a molded product, breakage or significant whitening does not occur due to stretching, folding, etc.
  • the cured product of the curable resin composition containing the curable resin is highly crosslinked and/or contains a filler with high hardness, so that deformation of the cured product surface due to external stress is suppressed, and the surface hardness and scratch resistance are exhibited.
  • 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 cured resin layer.
  • the curable resin (e.g., urethane acrylate resin) used in the cured resin layer can be designed, 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 cured resin layer may be appropriately used.
  • the glass transition temperature of the curable resin composition after curing is designed to be between room temperature and the secondary molding temperature (e.g., about 110 to 140°C), and the composition is designed to be hard at room temperature but soften and deformable at the secondary molding temperature.
  • the cured product of the curable resin (cured resin layer) 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 relatively hard part with a high crosslink density and a relatively soft part with a low crosslink density and large plastic deformation property, and to be non-uniform in microstructure.
  • the part with high crosslink density in the cured product of the curable resin (cured resin layer) exhibits high surface hardness, and the part with low crosslink density 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 a 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 (cured resin layer) while maintaining a certain degree of surface hardness.
  • low-crosslinking, non-crosslinking, or low-elastic modulus resin components include (a) 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; (b) 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-, polyurethane-, acrylic-, olefin-, styrene-, silicone-, and fluororesin-based materials; and (c) core-shell type rubber particles in which a thermoplastic resin is graft-polymer
  • 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.
  • Further examples of the urethane acrylate resin include resin compositions containing a urethane acrylate resin that are commercially available as a curable coating agent.
  • 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
  • isocyanurate examples include propyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, tolidine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,5-bis(isocyanatemethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatemethyl)-bicyclo[2.2.1]heptane, trimethylolpropane adduct of triethylene diisocyanate, isocyanurate of triethylene diisocyanate, oligomer of diphenylmethane-4,4'-diisocyanate, biuret of hexamethylene diisocyanate, isocyanurate of hexamethylene diisocyanate, uretdione of hexamethylene diisocyanate, and isocyanurate of iso
  • 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 superior 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- and di-)allyl ether, and N-methylol(meth)acrylamide, (b) or mixtures thereof, which can be added as necessary.
  • 2-hydroxypropyl (meth)acrylate 4-hydroxybutyl acrylate
  • polyethylene glycol mono(meth)acrylate polypropylene glycol mono(meth)
  • an organotin urethane catalyst may be 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 cured resin 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, and by using these, the crack elong
  • the curable resin composition for the cured resin layer preferably contains a light stabilizer.
  • a light stabilizer By containing a light stabilizer, the stability of the cured resin layer against ultraviolet degradation and light degradation is improved, and weathering deterioration such as surface cracking and peeling is suppressed in a portion or application exposed to sunlight outdoors or indoors of a molded article covered with a laminate containing the cured resin layer.
  • the curable resin composition for the cured resin layer more preferably contains a hindered amine light stabilizer having at least a reactive functional group (hereinafter also referred to as "reactive HALS") 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 hindered amine light stabilizer When the hindered amine light stabilizer has a reactive functional group, the hindered amine light stabilizer molecule reacts with the urethane acrylate resin when the urethane acrylate resin is cured, and is introduced in a chemically bonded state into the cured product that forms the cured resin layer. As a result, even under an environment such as outdoor exposure, migration or loss of the hindered amine light stabilizer from the surface of the cured resin layer is suppressed, and weather resistance deterioration of the cured resin layer can be suppressed 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-crotonoyloxy-2,
  • Reactive HALS may be, for example, commercially available products such as 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (also known as 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 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 also known as 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, manufactured by ADEKA Corporation under the trade name "ADEKA STAB LA
  • the curable resin composition for the cured resin layer preferably contains 0.1 to 10 parts by mass of reactive HALS per 100 parts by mass of urethane acrylate resin, more preferably 0.5 to 6 parts by mass, and even more preferably 1.0 to 4 parts by mass.
  • reactive HALS long-term weather resistance is improved.
  • weather resistance can be improved without impairing the quality of the cured resin layer.
  • the curable resin composition for the cured resin 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 cured resin layer may contain a total of 0.5 to 10 parts by mass, 0.8 to 6 parts by mass, or 1.0 to 4 parts by mass of light stabilizer per 100 parts by mass of urethane acrylate resin.
  • the curable resin composition for the cured resin layer preferably contains a compound having a hydrophobic group and a reactive group (hereinafter, also simply referred to as "hydrophobic reactive compound").
  • hydrophobic reactive compound Such compounds are generally referred to as leveling agents, surfactants, antifouling agents, water repellents, oil repellents, dispersants, and slipping agents.
  • Such compounds are appropriately adjusted and selected in terms of composition and structure according to the components such as the substrate, the curable resin, and the filler to be blended, and then blended into the curable resin composition and/or the paint containing the curable resin composition.
  • the molecules of the compound having a hydrophobic group and a reactive group are distributed toward the surface side or the interface side on the surface after application of the curable resin composition and/or the paint, and/or on the interface with other materials such as the substrate and filler, thereby reducing the surface tension of the curable resin composition and/or the paint containing the curable resin composition, or improving the wettability with other materials.
  • the surface of the cured resin layer is made hydrophobic, thereby more effectively suppressing the penetration of the DEET component into the cured resin layer, and it is presumed that, in particular, when used in combination with a reactive HALS, it shows an effect of improving the weather resistance of the DEET resistance.
  • the hydrophobic reactive compound contains a hydrophobic group in the molecule.
  • the hydrophobic group include saturated hydrocarbon groups, aromatic hydrocarbon groups, silicone groups, and fluorine-containing groups.
  • the silicone group include alkyl-substituted polysiloxane groups such as polydimethylsiloxane groups, and some of the alkyl substituents may have functional groups other than hydrocarbon groups, and some or all of the hydrogen groups of the alkyl substituents may be substituted with fluorine groups.
  • the fluorine-containing group examples include partially fluorinated hydrocarbon groups, perfluoroalkyl groups, partially fluorinated polyalkyleneoxy groups, polyperfluoroalkyleneoxy groups, and fluoroalkyl-substituted siloxane groups.
  • these hydrophobic groups it is presumed that the hydrophobic group has high hydrophobicity, is excellent in the performance of imparting leveling and wettability by adding a compound, is excellent in water repellency and oil repellency, and is excellent in the effect of improving DEET resistance, so that one or more selected from the group consisting of silicone groups and fluorine-containing groups are preferred, and fluorine-containing groups are more preferred.
  • a fluoroalkyl-substituted siloxane group can be appropriately used.
  • the hydrophobic reactive compound has a reactive group in addition to the hydrophobic group in the molecule, more preferably a functional group that can react with the urethane acrylate resin during the curing reaction.
  • a chemical bond is formed between the curable resin and the hydrophobic reactive compound (a compound having a hydrophobic group and a reactive group) during the curing reaction, so that the compound having the hydrophobic group and the reactive group does not flow out from the surface of the cured resin layer of the laminate and tends to remain on the surface of the cured resin layer, and it is expected that the functions such as hydrophobicity, water repellency, oil repellency, antifouling, slipperiness, scratch resistance, and DEET resistance can be maintained for a long period of time.
  • reactive groups include carbon-carbon double bond groups such as acryloyl groups, methacryloyl groups, vinyl groups, and allyl groups, as well as thiol groups.
  • carbon-carbon double bond groups such as acryloyl groups, methacryloyl groups, vinyl groups, and allyl groups, as well as thiol groups.
  • one or more selected from the group consisting of acryloyl groups and methacryloyl groups are preferred in terms of good reactivity with the urethane acrylate group, excellent weather resistance, and excellent maintenance of DEET resistance after weather resistance tests.
  • hydrophobic reactive compound commercially available products as reactive leveling agents, antifouling agents, surfactants, etc. may be used. Specific examples include commercially available products sold as leveling agents, surfactants, and surface conditioners, such as the "BYK-UV” series (manufactured by BYK Chemie), the "Megafac” series (manufactured by DIC Corporation), the “Ftergent” series (manufactured by Neos Co., Ltd.), the KP series and KY-1200 series (manufactured by Shin-Etsu Chemical Co., Ltd.), the "Disparlon” series (manufactured by Kusumoto Chemical Co., Ltd.), the "Polyflow” series (manufactured by Kyoeisha Chemical Co., Ltd.), and the “Surflon” series (manufactured by AGC Seimi Chemical Co., Ltd.), but are not limited to these.
  • BYK-UV manufactured by BYK Chemie
  • the curable resin composition for the cured resin layer preferably contains 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass of a compound having a hydrophobic group and a reactive group per 100 parts by mass of urethane acrylate resin.
  • 0.01 part by mass or more of a compound having a hydrophobic group and a reactive group the leveling properties of the curable resin composition for the cured resin layer are improved, the wettability to the substrate and filler components is improved, and defects such as cissing are prevented.
  • the compound having a hydrophobic group and a reactive group is 5 parts by mass or less, adverse effects such as reduced adhesion to the substrate and reduced recoatability due to excessive blending are unlikely to occur.
  • the curable resin composition for the cured resin layer may contain other components in addition to the above-mentioned components.
  • 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.
  • a 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 monofunctional (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(me
  • 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).
  • vinyl ester monomers obtained by reacting the epoxy group of an epoxy resin monomer having a skeleton such as a bisphenol-based, novolac-based, or biphenyl-based skeleton with acrylic acid can also be used as epoxy acrylate monomers.
  • a known method can be used to cure the resin layer (coated film of the curable resin composition).
  • 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.
  • 1-hydroxy-cyclohexyl-phenyl-ketone is preferred, as it has excellent compatibility with urethane acrylate resins.
  • a curable resin composition can be applied to one or both sides of a substrate layer containing an acrylic resin film, and the resin layer (coating film) made of the curable resin composition can be cured to form a cured resin layer.
  • a cured resin layer is formed by applying a curable resin composition for the cured resin layer to one or both sides of a substrate layer including an acrylic resin film and curing the coating film
  • various additives such as ultraviolet absorbers, defoamers, antioxidants, light diffusing agents, matting agents, lubricants, colorants such as pigments and dyes, organic particles, inorganic particles, and antistatic agents can be added to the curable resin composition as necessary.
  • the additives are not limited to these.
  • inorganic fine particles may be added to the curable resin composition for the cured resin layer, within a range that does not impair the object of the present invention.
  • inorganic fine particles include, but are not limited to, silica, alumina (aluminum oxide), titanium oxide, zinc oxide, zirconia, graphene, nanocarbon, carbon black, nanodiamond, mica, barium titanate, boron nitride, metallic silver, and metallic copper.
  • These inorganic fine 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 cured resin layer may be appropriately controlled.
  • the curable resin composition for the cured resin layer may contain anti-glare particles from the viewpoint of enhancing the anti-glare properties of the laminate.
  • anti-glare particles in order to obtain a balance of various properties such as the desired anti-glare properties, clarity of transmitted images, glare, jet black surface, surface hardness, slipperiness, and antistatic properties, the particle material, the number of parts blended, the type of particle dispersion solvent, particle diameter, dispersed particle diameter, thickness of the cured resin layer, the relative refractive index difference with the base layer containing an acrylic resin film, the affinity and reactivity of the particle surface with the base layer containing an acrylic resin film or with the 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 anti-glare particles to be blended into the cured resin layer is not particularly limited as long as it can enhance the anti-glare 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 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, and zirconia) and crosslinked organic resin particles (e.g., crosslinked silicone resin, crosslinked acrylic resin, and crosslinked aromatic vinyl resin), 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, and zirconia
  • crosslinked organic resin particles e.g., crosslinked silicone resin, crosslinked acrylic resin, and crosslinked aromatic vinyl resin
  • the particle is 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 by known methods such as using a silane coupling agent or reactive monomer that may have a reactive substituent, plasma treatment, corona treatment, etc.
  • the particles In order to improve the interfacial adhesion between the particle and the cured resin layer, and to improve the dispersibility of the particle, and cracks and/or whitening during stretching, it is preferable that at least some of the particles contain a reactive functional group that is reactive with urethane acrylate resin on the surface of the particle.
  • the "anti-glare particles” or “inorganic fine particles” may be dispersed as primary particles or may be dispersed as aggregates of multiple particles, depending on the size of the primary particles.
  • the size of the area (dispersion domain) in which these particles or fine particles, or their aggregates, are distributed is defined as the "average dispersed particle size.”
  • the average dispersed particle size may be the same as the primary (basic) particle size.
  • the average dispersed particle diameter of the anti-glare 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, at a magnification of 200,000 times measured with an electron microscope (Hitachi High-Technologies Corporation, H7650) is observed, the arithmetic mean value of the particle diameters of 10 dispersed domains of the anti-glare particles in the cured resin layer is calculated, and the obtained value is regarded as the average dispersed particle diameter of the anti-glare particles in the cured resin layer.
  • the average dispersed particle diameter of the inorganic fine particles is not particularly limited as long as the effects of the present invention are achieved, but may be, for example, 0.5 to 1000 nm, 1 to 500 nm, or 2 to 200 nm.
  • a cross-sectional photograph of a laminate measuring 1200 nm x 800 nm and magnification of 200,000 times measured with an electron microscope (Hitachi High-Technologies Corporation, H7650) is observed, the arithmetic mean value of the particle diameters of 10 dispersed domains of the inorganic fine particles in the cured resin layer is calculated, and the obtained value is regarded as the average dispersed particle diameter of the inorganic fine particles in the cured resin layer.
  • the content of the anti-glare particles in the curable resin composition for the cured resin layer is not particularly limited as long as it can increase the anti-glare 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.
  • the content of inorganic fine particles in the curable resin composition for the cured resin layer is not particularly limited as long as it can increase the abrasion resistance of the laminate within a range that does not impair the object of the present invention, but may be, for example, 0.1 to 30.0 mass %, 0.3 to 20.0 mass %, or 0.5 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 resin composition and form a cured resin layer with the desired thickness and performance. It is preferable for the boiling point of the organic solvent to be 50 to 150°C in terms of coatability and drying properties of the resin layer (coating film) formed.
  • 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 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-mentioned curable resin composition for the cured resin layer is applied to one or both sides of a substrate layer containing 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 cured resin 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 (cured resin 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 preferably 500 mJ/cm 2 or more, more preferably 550 mJ/cm 2 or more, and even more preferably 600 mJ/cm 2 or more.
  • the degree of curing of the cured resin layer can be increased, specifically, the curing index represented by the above formula 1 can be lowered, and/or the degree of curing represented by the following formula 2 can be increased, the crosslink density of the cured resin layer can be increased, and the hardness, DEET resistance, and weather resistance of the DEET resistance of the laminate (DEET resistance after weathering test) can be increased.
  • the upper limit of the integrated light amount may be appropriately set in consideration of energy efficiency while not causing deterioration of the cured resin layer due to excessive ultraviolet irradiation and heat generation caused by it.
  • it is preferably 1500 mJ/cm2 or less , and may be 1400 mJ/ cm2 or less, 1300 mJ/ cm2 or less, 1200 mJ/cm2 or less , 1100 mJ/cm2 or less , 1000 mJ/cm2 or less, 900 mJ/cm2 or less , or 800 mJ/cm2 or less .
  • the cured resin layer needs to have a curing index of 0.013 or less as described above. More preferably, the degree of curing of the cured resin layer, as represented by the following formula 2, is 75% or more.
  • the degree of crosslinking is generally quantified by quantifying the spectrum corresponding to the functional group before and after the reaction using an analytical method such as CP/MAS (Cross Polarization Magic Angle Spinning)-1H NMR, but in this specification, the degree of progress of the curing reaction of the cured resin layer formed of the cured product of the active energy ray curable resin composition containing a urethane acrylate resin can be shown by a curing index calculated by the following formula 1 and/or a curing degree calculated by the following formula 2 using FT-IR analysis in reflection mode.
  • A represents the area of an infrared absorption peak at a wavenumber of about 810 cm -1 in FT-IR measurement of a coating film of the active energy ray curable resin composition before curing
  • B represents the area of an infrared absorption peak at a wavenumber of about 810 cm -1 in FT-IR measurement of a cured resin layer
  • C represents the area of an infrared absorption peak at a wavenumber of about 1705 cm -1 in FT-IR measurement of a coating film of the active energy ray curable resin composition before curing
  • D represents the area of an infrared absorption peak at a wavenumber of about 1705 cm -1 in FT-IR measurement of a cured resin layer.
  • the peak at a wave number of about 810 cm ⁇ 1 in the infrared spectrum corresponds to the out-of-plane bending vibration of the C-C double bond of the acryloyl group and the methacryloyl group
  • A reflects the content of the acryloyl group and the methacryloyl group in the coating film of the active energy ray curable resin composition before curing
  • B reflects the content of the acryloyl group and the methacryloyl group in the cured resin layer, i.e., the coating film of the active energy ray curable resin composition after curing.
  • the values of A and B decrease with the progress of the curing reaction.
  • the infrared absorption peak at a wave number of about 810 cm ⁇ 1 in the FT-IR measurement corresponds to the stretching vibration of the C-O double bond of the ester group
  • C and D respectively reflect the total amount of the uncured acryloyl group and the methacryloyl group in the coating film of the active energy ray curable resin composition before and after the curing reaction, and the ester group after the acryloyl group and the methacryloyl group have been cured, and the total amount of the C-O double bond functional group does not change in principle before and after the curing reaction.
  • the above-mentioned curing index B/D is obtained by dividing the peak area value corresponding to the acryloyl group and methacryloyl group, which are functional groups that decrease due to the reaction, by the peak area value that does not change in principle due to the reaction, and is maximum in the unreacted state and becomes 0 when the curing reaction has progressed completely, and can be used as an index of the progress of the curing reaction.
  • the curing degree represented by the above formula 2 indicates the ratio of the remaining amount of acryloyl group and methacryloyl group after curing to the content of acryloyl group and methacryloyl group before curing, and can be used as an index of the progress of the curing reaction.
  • 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 molded article having the laminate disposed on its surface.
  • the laminate may include a substrate layer including an acrylic resin film and a cured resin layer laminated on one side of the substrate layer.
  • the cured resin layer may be laminated on both sides of the acrylic substrate layer.
  • the laminate may include other functional layers laminated between the substrate layer and the cured resin layer and/or on one or both sides of the laminate, as necessary, within a range that does not impair the effects of the present invention.
  • the other functional layers are not particularly limited, and conventionally known ones can be widely applied.
  • a printing layer a decorative layer, an adhesive layer, an antistatic layer, a conductive layer, a dielectric layer, a thermoplastic resin layer, and an optical functional layer can be mentioned.
  • the decorative layer may include a colored layer, a design layer, a surface unevenness layer, and an embossed layer.
  • the adhesive layer may include a primer layer.
  • the thermoplastic resin layer may include an anti-fouling layer, a fingerprint-resistant layer, a hard coat layer, a scratch-resistant layer, a gas barrier layer, and a gas absorption layer.
  • the optical functional layer may include a low refractive index layer, a high refractive index layer, an ultraviolet shielding layer, an infrared shielding (also called a reflective layer), a light diffusion layer, an anti-glare layer, a matte layer, a phase difference adjustment layer, a viewing angle adjustment layer, and a polarizing 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 80% 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 molded body substrate such as a thermoplastic resin substrate and the molded body substrate such as a thermoplastic resin substrate is covered with the laminate, particularly when the laminate is shaped by vacuum molding or pressure molding under heating, when laminating onto the substrate, or when the shaped laminate is placed on the mold surface as necessary and then a molded body is obtained by insert injection molding, and the secondary moldability is good.
  • the crack elongation of the laminate at 120°C is preferably 90% or more. There is no particular limit to the upper limit of the crack elongation of the laminate at 120°C. In this specification, the crack elongation of the laminate at 120°C can be measured by the method described in the Examples.
  • the laminate preferably has a change in haze ( ⁇ haze) when stretched 40% at 120°C of 0.5% or less, more preferably 0.3% or less, and particularly preferably 0.2% or less. Furthermore, from the viewpoint of suppressing whitening during molding, the laminate preferably has a change in haze ( ⁇ haze) when stretched 80% at 120°C of 0.5% or less, more preferably 0.3% or less, and particularly preferably 0.2% or less.
  • ⁇ haze of the laminate when stretched 40% at 120°C and the ⁇ haze of the laminate when stretched 80% at 120°C can both be measured by the method described in the Examples.
  • 40% stretching means that, when the size before stretching is L1 and the size after stretching is L2, [100 x (L2 - L1) / L1]% is 40%, and 80% stretching means that, when the size before stretching is L1 and the size after stretching is L2, [100 x (L2 - L1) / L1]% is 80%.
  • the laminate has excellent surface hardness, and from the viewpoint of enhancing the scratch resistance of molded articles using the laminate, the pencil hardness of the cured resin layer side under a load of 500 g is preferably B or higher, 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 cured resin 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 cured resin layer and left at 23°C for 6 hours.
  • the laminate preferably exhibits a change in haze ( ⁇ haze) of 0.5% or less, more preferably 0.4% or less, and even more preferably 0.3% or less, before and after an abrasion resistance test in which gauze is reciprocated 20 times against the surface of the cured resin layer under a load of 500 g/cm2.
  • the laminate preferably exhibits a change in haze ( ⁇ haze) of 2 % or less, more preferably 1.8% or less, and even more preferably 1.6% or less, before and after an abrasion resistance test in which steel wool (#0000) is reciprocated 10 times against the surface of the cured resin layer under a load of 100 g/cm2.
  • the laminate shows no visible change in appearance when the DEET resistance is evaluated under the following conditions. That is, it is desirable that there is no visible change in appearance when gauze coated with 0.05 g of an insect repellent consisting of a 30% ethanol solution of N,N-diethyl-3-methylbenzamide is placed on the surface of the cured resin layer of the laminate, and the laminate is left for 30 seconds under conditions of 23°C and relative humidity of 65%, and then left to stand for 1 hour in a thermostatic chamber at 74°C.
  • the laminate maintains DEET resistance after a weather resistance test according to the weather resistance level required, for example, in some applications for automobile interiors, i.e., has weather resistance of DEET resistance. That is, it is more preferable that the laminate is placed so that the cured resin layer side faces the light source, a xenon lamp is used as the light source, an irradiance of 180 W/m 2 (300 to 400 nm), a black panel temperature of 89° C.
  • the laminate is placed so that the cured resin layer side faces the light source, a xenon lamp is used as the light source, an irradiance of 180 W/m 2 is used, and a weather resistance test is performed for 300 hours under the conditions of no rain, and there is no visible change in appearance. It is even more preferable that a weather resistance test is carried out for 500 hours under conditions of a black panel temperature of 89° C.
  • the laminate preferably has a color difference ⁇ E of 0.5 or less, and more preferably 0.3 or less, between the laminate after the above-mentioned 300-hour or 500-hour weather resistance test and the laminate before the weather resistance test.
  • the laminate preferably has a ⁇ YI of 0.5 or less, and more preferably 0.3 or less, for the laminate after the above-mentioned 300-hour or 500-hour weather resistance test relative to the laminate before the weather resistance test.
  • ⁇ YI can be measured and calculated by the method described in the Examples.
  • the laminate preferably has a water contact angle of 105° or more on the surface of the cured resin layer.
  • the laminate preferably has a water contact angle of 95° or more on the surface of the cured resin layer after the above-mentioned 300-hour weather resistance test.
  • the laminate preferably has a water contact angle of 92° or more on the surface of the cured resin layer after the above-mentioned 500-hour weather resistance test.
  • the water contact angle can be measured by the method described in the Examples.
  • the laminate has an oleic acid contact angle of 65° or more on the surface of the cured resin layer.
  • the oleic acid contact angle of the surface of the laminate on the cured resin layer side can be measured by the method described in the Examples.
  • the laminate preferably has a haze 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, even more preferably 0.6% or less, and particularly preferably 0.4% or less.
  • the laminate preferably has a haze of 2.0% or less after the above-mentioned 300-hour weather resistance test, more preferably 1.5% or less, even more preferably 1.0% or less, even more preferably 0.8% or less, and even more preferably 0.6% or less.
  • the laminate preferably has a haze of 2.0% or less after the above-mentioned 500-hour weather resistance test, more preferably 1.5% or less, even more preferably 1.0% or less, even more preferably 0.8% or less, and even more preferably 0.6% or less.
  • haze can be measured by the method described in the examples.
  • the laminate preferably has a total light transmittance of 90% or more, and more preferably 91% or more. Furthermore, from the viewpoint of weather resistance of transparency, the laminate preferably has a total light transmittance of 90% or more after the above-mentioned 300-hour weather resistance test, and more preferably 91% or more. Furthermore, from the viewpoint of weather resistance of transparency, the laminate preferably has a total light transmittance of 90% or more after the above-mentioned 500-hour weather resistance test, and more preferably 91% or more. In this specification, the total light transmittance can be measured by the method described in the examples.
  • the laminate can be used as a decorative protective sheet that decorates and/or protects a molded body.
  • the laminate can further include, in addition to the substrate layer and cured resin layer, one or more layers selected from the group consisting of the above-mentioned printed layer, decorative layer, adhesive layer, antistatic layer, thermoplastic resin layer, and optical functional layer.
  • the laminate By using the laminate as a decorative protective sheet, it is possible to impart various functionalities to the molded body, such as DEET resistance, weather resistance, scratch resistance, and DEET resistance after weathering tests.
  • the molded body includes the above-mentioned laminate, and the laminate is laminated on the surface of the molded body substrate, and the cured resin layer of the laminate is disposed on the surface side of the molded body from the substrate layer of the laminate.
  • the laminate may be laminated on a part or all of the surface of the molded body substrate. Since the crack elongation of the laminate at 120 ° C. is high, at least a part of the molded body substrate having a non-planar three-dimensional shape can be covered with the laminate to preferably obtain a molded body having a three-dimensional shape, more specifically a resin molded body.
  • the laminate can impart various functionalities such as DEET resistance, weather resistance, scratch resistance, and DEET resistance after weathering test to the molded body by covering the molded body substrate.
  • the molded body substrate is not particularly limited, but a thermoplastic resin substrate can be suitably used.
  • the thermoplastic resin substrate may be, for example, a 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, 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 one or more selected from the group consisting of polycarbonate resin, acrylic resin, styrene-based 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 molded body has excellent weather resistance, scratch resistance, DEET resistance, and DEET resistance before and after weather resistance testing, and can be used, for example, as vehicle interior materials such as automobile interior materials, vehicle exterior materials such as automobile exterior materials, housings and exterior parts for portable electronic devices and personal computers, and home appliance exterior materials. It can be particularly suitably used as an automobile interior material.
  • vehicle interior materials include console boxes, meter covers, door panels, armrests, door lock bezels, steering wheels, various switch buttons and switch bases, shift levers, center clusters, dashboards, instrument panels, in-vehicle display front panels, sensor covers, plated parts such as emblems, and garnishes.
  • the method for producing the molded body is not particularly limited as long as it is a molding method that can cover at least a part of the molded body substrate, preferably a thermoplastic resin substrate, with the laminate.
  • a molded body having the laminate disposed on the surface can be produced, for example, by in-mold molding, film insert injection molding, etc.
  • the laminate may be pre-shaped, as necessary, by a method such as vacuum molding, compressed air molding, or compression molding.
  • the laminate may be heated and/or pressurized under reduced pressure to produce a resin molded body by disposing the laminate on the surface of a thermoplastic resin substrate having at least a part of a non-flat three-dimensional shape, so-called three-dimensional laminate molding may be performed. Furthermore, the laminate may be heated and stretched appropriately while being laminated by hand onto the surface of the thermoplastic resin substrate to produce a resin molded body.
  • the curing index and curing degree of the cured resin layer were measured by using FT/IR-4700 (manufactured by JASCO Corporation) and measuring the infrared absorption spectrum of the surface of the coating film (in a dry state) of the active energy ray curable resin composition before curing and the surface of the cured resin layer by the ATR method (total reflection measurement method) using a diamond prism, and after correcting the components derived from the infrared absorption spectrum of the prism material, the horizontal axis is the wave number (cm -1 ) and the vertical axis is the transmittance (%).
  • the horizontal axis is the wave number (cm -1 ) and the vertical axis is the transmittance (%)
  • a baseline that is a straight line connecting two points at the foot of each of the infrared absorption peaks at a wave number of about 810 cm -1 and the infrared absorption peak at about 1705 cm -1 was set by the method described below using the "spectral analysis" function of the instrument, and a numerical value corresponding to the peak area was obtained.
  • the horizontal axis is the wave number (cm -1 ) and the vertical axis is the transmittance (%)
  • the infrared absorption peak is observed downward.
  • a and C are obtained from the same infrared absorption spectrum chart, respectively, by using a straight line connecting two points at the foot of the corresponding peak as the baseline, and the area of the area surrounded by the curve of the baseline and the peak is obtained as the peak area
  • B and D are obtained from the same infrared absorption spectrum chart, respectively, by using a straight line connecting two points at the foot of the corresponding peak as the baseline, and the area of the area surrounded by the curve of the baseline and the peak is obtained as the peak area.
  • the peak at a wave number of about 810 cm -1 corresponds to the out-of-plane bending vibration of the carbon-carbon (C-C) double bond of the acrylate group, and the peak at a wave number of about 1705 cm -1 corresponds to the stretching vibration of the carbon-oxygen (C-O) double bond of the ester group.
  • IR spectrum infrared absorption spectrum
  • the two points at the foot of a given peak refer to the points at which the IR spectrum lines on either side of the peak start to bend downward toward the center of the peak.
  • FIG. 1 shows an example of the curing index B/D obtained from the IR spectrum chart for Comparative Example 2.
  • FIG. 1 shows an example of the curing index B/D obtained from the IR spectrum chart for Comparative Example 2.
  • peak 1 is an infrared absorption peak at a wave number of about 810 cm -1
  • peak 2 is an infrared absorption peak at a wave number of about 1705 cm -1
  • the numerical value corresponding to the peak area which is the area surrounded by the baseline Lb1, which is a straight line connecting the two points a and b at the base, and the curve of peak 1, i.e., B, is 23.5038
  • peak 2 the numerical value corresponding to the peak area, which is the area surrounded by the baseline Lb2, which is a straight line connecting the two points c and d at the base, and the curve of peak 2, i.e., D, is 1276.81.
  • the curing index B/D is calculated to be 0.0184.
  • points a and b where the IR spectrum lines on both sides adjacent to peak 1 start to bend downward toward the center of peak 1 are two points at the foot of peak 1.
  • points c and d where the IR spectrum lines on both sides adjacent to peak 2 start to bend downward toward the center of peak 2 are two points at the foot of peak 2.
  • the acrylic resin film was cut into a size of 10 mm (width) x 100 mm (length) to prepare a test piece.
  • the test piece was measured using a Tensilon tensile tester (Shimadzu Corporation, 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 at which the acrylic resin film broke was taken as the tensile breaking elongation.
  • the value of the tensile breaking elongation was the arithmetic mean value of the three values excluding the highest and lowest values among the measurement results obtained using five test pieces.
  • the laminate was cut into a sample measuring 10 mm (width) x 100 mm (length).
  • the sample was measured using a Tensilon tensile tester (Shimadzu Corporation, 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 which cracks occurred in the cured resin layer was taken as the crack elongation at 120°C.
  • the crack elongation value was the arithmetic mean value of the test results (three) obtained by measuring three samples.
  • the thickness (film thickness) of the acrylic resin film was measured with a PEACOCK dial gauge No. 25 (manufactured by Ozaki Manufacturing Co., Ltd.).
  • the thickness (film thickness) of the cured resin layer was measured using an F20 film thickness measurement system (manufactured by Filmetrics, Inc.)
  • the opposite surface of the cured resin 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 cured resin layer was set to 1.50.
  • Total Light Transmittance and Haze The total light transmittance and haze of the laminate were measured using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7375:2008 and JIS K 7136:2000, respectively.
  • the laminate was cut into a size of 10 mm (width) x 100 mm (length) to prepare a sample.
  • the sample was stretched by 40% or 80% using a Tensilon tensile tester (Shimadzu Corporation, AG-2000D) equipped with a thermostatic chamber 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, and the haze of the stretched portion of the laminate after stretching was measured in accordance with JIS K 7136:2000 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the chuck distance was 56 mm at 40% stretching and 72 mm at 80% stretching.
  • the absolute value of the difference between the haze of the laminate before stretching and the haze of the laminate after 40% or 80% stretching was defined as " ⁇ haze after 40% stretching at 120° C.” or " ⁇ haze after 80% stretching at 120° C.”
  • IPA isopropyl alcohol
  • acetone resistance test A laminate sample cut into a 5 cm x 5 cm square was placed on a horizontal surface with the cured resin layer side facing up, and one drop (approximately 0.02 mL) of isopropyl alcohol (hereinafter also referred to as IPA) or acetone taken with a dropper was dripped onto the sample. The sample was then left at room temperature (23°C) for 6 hours, after which the surface of the cured resin layer was visually observed and the chemical resistance was evaluated according to the following criteria. Good: No change in appearance. Bad: A mark remains along the outline of the drop and/or the surface of the drop dissolves.
  • Step wool abrasion test A surface property measuring instrument (HEIDON Type 14DR, manufactured by Shinto Scientific Co., Ltd.) was used. Steel wool #0000 was attached to a probe with a diameter of 1 mm, and a weight of 100 g was placed on it. Steel wool was placed on the surface of the cured resin layer of the laminate, and a test was performed 10 times with a stroke of 70 mm and a speed of 6000 mm/min. The presence or absence and the degree of scratches on the surface of the cured resin layer of the laminate after the steel wool (SW) abrasion test were visually observed. Furthermore, the haze value after the test was measured, and the absolute value of the difference between the haze value after the test and the haze value before the test was taken as ⁇ haze.
  • SW steel wool
  • Adhesion test A cutter knife was used to make cuts in a grid pattern of 100 squares at 1 mm intervals on the surface of the cured resin layer of the laminate, penetrating the cured resin layer until they reached the surface of the acrylic resin film. Cellophane tape was then firmly pressed from above, and one end of the tape was then quickly peeled off. Depending on the degree of peeling of the cured resin layer, the adhesion between the cured resin layer and the substrate was evaluated according to the following criteria. Good: No peeling in any of the 100 squares Average: Peeling in some squares Poor: Peeling in all 100 squares
  • the color tone of the laminate was measured under the following conditions using a spectrophotometer SE7700 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS Z 8781-4:2013.
  • the color difference ( ⁇ E) and YI value before and after the weather resistance test were calculated from the XYZ values and L*a*b* values obtained by measuring the laminate before and after the weather resistance test.
  • the absolute value of the difference between the YI value after the weather resistance test and the YI value before the weather resistance test was taken as ⁇ YI.
  • Mode Transmitted light
  • Light source D65
  • Field of view 2°
  • Measurement diameter 28 mm
  • a contact angle measuring device (DMo-501 type) manufactured by Kyowa Interface Science Co., Ltd. was used to measure the contact angle by dropping water or oleic acid onto the surface of the laminate on the side of the cured resin layer.
  • RUVA is a reactive ultraviolet absorber (2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2-H-benzotriazole, manufactured by Otsuka Chemical Co., Ltd., RUVA-93).
  • Monomer mixture 30 parts of vinyl monomer mixture (90% n-butyl acrylate (BA) and 10% methyl methacrylate (MMA)) 0.3 parts of RUVA 0.63 parts of allyl methacrylate (ALMA) 0.2 parts of cumene hydroperoxide (CHP).
  • BA n-butyl acrylate
  • MMA methyl methacrylate
  • CHP cumene hydroperoxide
  • 0.05 parts of sodium dioctyl sulfosuccinate was charged into the polymerization apparatus containing the particles of crosslinked elastomer (A1).
  • the internal temperature of the polymerization apparatus was set to 60°C, and a monomer mixture consisting of 70 parts of a vinyl monomer mixture (98% MMA, 1% BA, and 1% RUVA) for forming the graft polymer layer (A2), 0.5 parts of t-dodecyl mercaptan, and 0.5 parts of CHP was continuously added into the polymerization apparatus at a rate of 10 parts/hour.
  • the polymerization was continued for another hour to obtain a latex of graft copolymer particles (A) (average particle size 90 nm).
  • the polymerization conversion rate was 98.2%.
  • the obtained latex was salted out and coagulated with calcium chloride, and the coagulated solid was washed with water and dried to obtain powdered graft copolymer particles (A).
  • a mixed liquid consisting of 7 parts of a vinyl monomer mixture (97% MMA and 3% BA), 0.035 parts of allyl methacrylate, and 0.02 parts of t-dodecyl mercaptan was added into the polymerization apparatus. Then, 0.03 parts of t-butyl hydroperoxide was added into the polymerization apparatus. After 5 minutes, 0.065 parts of sodium formaldehyde sulfoxylate was added as a 5% aqueous solution. After 10 minutes, 0.05 parts of t-butyl hydroperoxide was added. After another 15 minutes, 0.01 parts of sodium hydroxide was added as a 2% aqueous solution.
  • polymerization was continued for 120 minutes to obtain a core layer polymer consisting of a two-layer structure of a hard crosslinked resin layer and a crosslinked elastomer layer.
  • the polymerization conversion rate was 99.0%, and the average particle size was 225 nm.
  • the obtained latex was salted out and coagulated with magnesium chloride, and the coagulated solid was washed with water and dried to obtain powdered graft copolymer particles (B).
  • the average particle size of the graft copolymer particles (B) was 240 nm.
  • the obtained pellets were melt-kneaded using a 90 mm ⁇ single-screw extruder with a T-die at a cylinder setting temperature of 180°C to 240°C and a discharge rate of 150 kg/hr, extruded from the T-die at a die temperature of 240°C, and cooled and solidified by contacting both sides with a metallic casting roll adjusted to 90°C and a touch roll equipped with an elastic metallic sleeve adjusted to 60°C, forming a film and winding it up to obtain an acrylic resin film with a thickness of 75 ⁇ m.
  • the tensile elongation at break of the acrylic resin film at 120°C measured as described above was 220%.
  • a curable resin composition containing a urethane acrylate resin (manufactured by Daido Chemical Industry Co., Ltd., product name "P-5820TAH-1", mainly composed of a urethane acrylate resin, containing a small amount of an acrylic acid ester, a trace amount of aluminum oxide nanoparticles (inorganic fine particles), and a photopolymerization initiator, solid content concentration 30 mass%, solvent: a mixed solvent of methyl ethyl ketone, propylene glycol, and methyl isobutyl ketone, hereinafter simply referred to as "P-5820TAH-1”) was diluted with methyl ethyl ketone to a solid content concentration of 24 mass%, and then a reactive HALS (manufactured by ADEKA, product name "ADEKA STAB”) was added to 100 parts of the solid content of the obtained resin composition.
  • a reactive HALS manufactured by ADEKA, product name "ADEKA STAB
  • a curable resin composition containing a urethane acrylate resin (manufactured by Daido Chemical Industry Co., Ltd., product name "P-5820TA-20J", consisting mainly of urethane acrylate resin with small amounts of acrylic ester and photopolymerization initiator, solids concentration 24%, solvent: mixed solvent of methyl ethyl ketone, propylene glycol and methyl isobutyl ketone, hereinafter also referred to simply as "P-5820TA-20J”) was used, and paints 4 to 6, 8 and 9 were prepared in the same manner as paint 1, except that the amounts of LA-82 and KY-1203 blended relative to 100 parts solids of the resin composition were as shown in Table 1 below. As paint 10, P-5820TA-20J was used as it was.
  • Example 1 On the acrylic resin film obtained in Production Example 3, the coating material 1 was applied using a bar coater to form a curable resin layer on the acrylic resin film. The curable resin layer was then dried at 80° C. for 1 minute to volatilize the solvent from the curable resin layer. Next, the dried curable resin layer (the coating film of the active energy ray curable resin composition before curing) was irradiated with ultraviolet light at the UV integrated light amount shown in Table 2 to cure the curable resin layer, forming a cured resin layer (cured product of the active energy ray curable resin composition) having a thickness shown in Table 2 below, and a laminate was obtained. The temperature of the cooling roll when forming the cured resin layer was 50° C.
  • Example 2 A laminate was prepared in the same manner as in Example 1, except that the coating material shown in Table 2 below was used.
  • Example 10 A laminate was prepared in the same manner as in Example 1, except that the coating material shown in Table 2 below was used and the thickness of the cured resin layer was set as shown in Table 2 below.
  • Example 2 A laminate was produced in the same manner as in Example 1, except that the coating material shown in Table 2 below was used and the thickness of the cured resin layer and the integrated UV light amount were set as shown in Table 2 below.
  • the laminates obtained in the Examples and Comparative Examples were measured and evaluated for various physical properties (initial) as described above, and the results are shown in Table 2 below. Furthermore, a weather resistance test was conducted using the laminates obtained in the Examples and Comparative Examples, and then various physical properties of the laminates were measured and evaluated as described above, and the results are shown in Table 3 below.
  • 300 hours means the physical properties of the laminate after 300 hours of weather resistance testing
  • 500 hours means the physical properties of the laminate after 500 hours of weather resistance testing.
  • the amounts of reactive HALS and fluorine-containing acrylic compound in the paint are in parts by mass per 100 parts by mass of the solid content (urethane acrylate resin) in the paint.
  • the laminates of the Examples have excellent transparency, good surface hardness and scratch resistance, excellent secondary formability, and good DEET resistance.
  • the laminates of Examples 1-3, 8, 10, and 11 in which the cured resin layer contains inorganic fine particles have excellent steel wool abrasion resistance and gauze abrasion resistance.
  • the laminate of the comparative example in which the cured resin layer had a curing index of more than 0.013 was poor in DEET resistance.
  • the laminates of Examples 2, 3, 5, and 6, in which the reactive HALS was contained in an amount of more than 0.5 parts by mass relative to 100 parts by mass of the urethane acrylate resin also had good DEET resistance after a 500-hour weather resistance test.
  • the laminates of Examples 7 to 11 in which the curable resin layer contains only one of a hindered amine-based light stabilizer having a reactive functional group and a compound having a hydrophobic group and a reactive functional group have good initial DEET resistance but poor DEET resistance after the weather resistance test.
  • the present invention is not particularly limited, but may include, for example, the following embodiments.
  • a laminate including a base layer and a cured resin layer The base layer includes an acrylic resin film, The acrylic resin film has a tensile elongation at break of 200% or more at 120°C, the cured resin layer is formed of a cured product of an active energy ray-curable resin composition containing a urethane acrylate resin, The cured resin layer has a curing index represented by the following formula 1 of 0.013 or less, The laminate has a tensile crack elongation of 80% or more at 120°C.
  • Hardening index B/D
  • B represents the area of an infrared absorption peak at a wave number of about 810 cm ⁇ 1 in FT-IR measurement of the cured resin layer
  • D represents the area of an infrared absorption peak at a wave number of about 1705 cm ⁇ 1 in FT-IR measurement of the cured resin layer.
  • Curing degree (%) 100 x [(A/C) - (B/D)]/(A/C)
  • A represents the area of an infrared absorption peak at a wavenumber of about 810 cm -1 in FT-IR measurement of a coating film of the active energy ray curable resin composition before curing
  • B represents the area of an infrared absorption peak at a wavenumber of about 810 cm -1 in FT-IR measurement of a cured resin layer
  • C represents the area of an infrared absorption peak at a wavenumber of about 1705 cm -1 in FT-IR measurement of a coating film of the active energy ray curable resin composition before curing
  • D represents the area of an infrared absorption peak at a wavenumber of about 1705 cm -1 in FT-IR measurement of a cured resin layer.
  • a molded article comprising the laminate according to any one of [1] to [19] and a molded article substrate, The laminate is laminated on a surface of the molded body substrate, and a cured resin layer of the laminate is disposed on the surface side of the molded body relative to the substrate layer of the laminate.
  • the molded body according to [20] wherein the surface of the molded body substrate on which the laminate is laminated has a three-dimensional shape.
  • a method for producing the molded article according to [20], comprising laminating the laminate according to any one of [1] to [19] on a surface of a molded article substrate using one or more methods selected from the group consisting of vacuum forming, pressure forming, film insert injection molding, and three-dimensional lamination molding.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2016199847A1 (ja) * 2015-06-12 2016-12-15 株式会社カネカ 積層フィルム
JP2017138626A (ja) * 2017-05-11 2017-08-10 リケンテクノス株式会社 防眩性ハードコート積層フィルム
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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2016199847A1 (ja) * 2015-06-12 2016-12-15 株式会社カネカ 積層フィルム
JP2017138626A (ja) * 2017-05-11 2017-08-10 リケンテクノス株式会社 防眩性ハードコート積層フィルム
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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