WO2019235160A1 - Stratifié de verre, son procédé de production et panneau avant de dispositif d'affichage utilisant celui-ci - Google Patents

Stratifié de verre, son procédé de production et panneau avant de dispositif d'affichage utilisant celui-ci Download PDF

Info

Publication number
WO2019235160A1
WO2019235160A1 PCT/JP2019/019483 JP2019019483W WO2019235160A1 WO 2019235160 A1 WO2019235160 A1 WO 2019235160A1 JP 2019019483 W JP2019019483 W JP 2019019483W WO 2019235160 A1 WO2019235160 A1 WO 2019235160A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
adhesive
film
glass
functional
Prior art date
Application number
PCT/JP2019/019483
Other languages
English (en)
Japanese (ja)
Inventor
長谷部花子
小山治規
嶋本幸展
Original Assignee
株式会社カネカ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社カネカ filed Critical 株式会社カネカ
Priority to JP2020523590A priority Critical patent/JP7142090B2/ja
Publication of WO2019235160A1 publication Critical patent/WO2019235160A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions

Definitions

  • the present invention relates to a glass laminate including a glass substrate, a method for producing the same, and a front plate of a display device using the same.
  • Display devices such as various electronic devices and in-vehicle devices are given anti-reflection and fingerprint resistance functions to improve visibility, and hard coat layers and scratch-resistant layers to improve durability during use. Or has been done.
  • glass materials are generally widely used as the material for the transparent portion, but in order to prevent fragments from being shattered when the glass that is a brittle material is broken, it is possible to impart anti-scattering properties.
  • Patent Document 1 describes an antireflective glass laminate having a plastic film layer on one side of a glass plate substrate with an adhesive adhesive layer and an antireflection layer formed on the surface of the plastic film layer. Has been.
  • Patent Document 2 describes a curved glass on which a scattering prevention film having a first base material, a first adhesive layer, and a hard coat layer is attached.
  • a glass substrate is widely used for building materials, electrical products, automobile parts, and the like, and is also used for a front plate of a display device such as an in-vehicle display.
  • Patent Document 1 does not describe a method of laminating into a curved surface, and a method of laminating a flat glass using a pressure-sensitive adhesive having a relatively low adhesive force is being studied. For this reason, for example, it is a difficult method to laminate a flat film around the main surface of the glass substrate and the end surface in contact with the main surface, or to laminate on a main surface having a deep curved shape or an uneven shape.
  • Patent Document 2 discloses a laminate of an anti-scattering film on a glass member having a curved surface shape, but does not describe a specific lamination method. For example, a flat film is formed on a glass substrate.
  • the inventors have coated at least one main surface of a glass substrate and at least a part of an end surface in contact with the main surface with a thermoplastic resin film having a functional layer, whereby the edge resistance of the glass substrate is improved. It has been found that cracking is improved and scattering is suppressed.
  • thermoplastic resin film having a functional layer
  • the main surface When covering at least a part of the end surface in contact with the film, after the lamination, the shrinkage of the thermoplastic resin film causes generation of a rubbing trace of the adhesive layer in the peripheral portion of the laminate, exposure of the edge portion, peeling of the film end portion, etc. It has been found that there is a case where an appropriate molded product may not be obtained due to the occurrence of springback, cracks in the thermoplastic resin film or functional layer, and the like.
  • the present invention has been made in view of the above-described problems, and has a high effect of preventing cracking of the entire glass substrate including the edge portion, and has a predetermined functionality, a method for producing the same, and a method for using the same.
  • a front panel of a display device Provided is a front panel of a display device.
  • the present invention is a glass laminate including a glass substrate, an adhesive layer, and a functional film, and the functional film is disposed on at least one main surface of the thermoplastic resin film and the thermoplastic resin film.
  • the functional film has a 120 ° C. crack elongation of 20% or more, and bonds at least one main surface of the glass substrate and at least a part of the end surface in contact with the main surface.
  • the present invention relates to a glass laminate having a 90 ° peel strength between the glass substrate and the functional film that is continuously covered through layers, and is 25 N / 25 mm or more.
  • the glass substrate is preferably a transparent glass plate having a total light transmittance of 85% or more.
  • One or both main surfaces of the glass substrate preferably have a curved surface portion.
  • the thermoplastic resin film is preferably an acrylic resin film composed of an acrylic resin composition including an acrylic resin and graft copolymer particles containing a rubber component.
  • the functional layer is selected from the group consisting of a hard coat layer, an antiglare layer, an antireflection layer, an antifouling layer, an anti-fingerprint layer, a scratch-resistant layer, an antistatic layer, an ultraviolet shielding layer, an infrared shielding layer, and a surface uneven layer.
  • One or more functional layers may be included.
  • the adhesive layer is preferably composed of at least one adhesive selected from the group consisting of a hot-melt adhesive, a reactive curable adhesive, and a reactive curable hot-melt adhesive.
  • the adhesive is selected from the group consisting of a styrene diene adhesive, a butyl rubber adhesive, a polyurethane adhesive, a polyamide adhesive, a polyester adhesive, an acrylic adhesive, an epoxy adhesive, and a silyl adhesive. It is preferably one or more selected.
  • the glass laminate preferably has a haze of 3.0% or less.
  • the glass laminate further includes a decorative layer, and the decorative layer is disposed so as to cover at least part of the main surface opposite to the main surface of the glass substrate on which the functional film is disposed. May be.
  • the present invention also relates to a front plate of a display device using the glass laminate.
  • the present invention is also a method for producing the above-mentioned glass laminate, and includes a step of laminating a functional film on a glass substrate via an adhesive layer by vacuum / pressure forming.
  • the present invention relates to a method for producing a glass laminate.
  • a glass laminate that has a high effect of preventing cracking of the entire glass substrate including the edge portion and has a predetermined functionality, and a front plate of a display device using the same. Further, according to the production method of the present invention, a glass laminate having a high functionality for preventing cracking of the entire glass substrate including the edge portion and having a predetermined functionality can be produced with good moldability.
  • FIG. 1 is a schematic cross-sectional view of a glass laminate according to one or more embodiments of the present invention.
  • FIG. 2 shows the results of an experiment for evaluating the crack resistance of the edge portion.
  • (A) shows the results of Example 1
  • (b) shows the results of Comparative Example 1
  • (c) shows the results of Comparative Example 2.
  • the inventors use a functional film having a functional layer disposed on at least one main surface of a thermoplastic resin film and a thermoplastic resin film, and the 120 ° C. crack elongation of the functional film is 20 %, And the 90 ° peel strength between the functional film and the glass substrate is 25 N / 25 mm or more, so that at least one main surface of the glass substrate is in contact with the main surface with good moldability. It has been found that at least a part of the end face can be continuously covered with a functional film.
  • one main surface (also referred to as a first main surface) refers to a surface having a relatively large area, and is a surface opposite to the first main surface.
  • the other main surface (also referred to as a second main surface).
  • the end surface substantially coincides with the side surface sandwiched between the first main surface and the second main surface.
  • an edge means an intersection of a main surface and an end surface.
  • FIG. 1 is a schematic cross-sectional view of a glass laminate according to one or more embodiments of the present invention.
  • the glass laminate 1 includes a glass substrate 2, an adhesive layer 3, and a functional film 4, and the functional film 4 has a first main surface 21 of the glass substrate 2 and the first through the adhesive layer 3.
  • the end surfaces 22a and 22b in contact with one main surface 21 are continuously covered.
  • the functional film 4 continuously covers all of the first main surface 21 and the end surfaces 22 a and 22 b in contact with the first main surface 21 through the adhesive layer 3.
  • the first main surface 21 and part of the end surfaces 22a and 22b in contact with the first main surface 21 may be continuously covered.
  • the edge portion is always covered, and therefore, the edge portion 32a (intersection portion of the first main surface 21 and the end surface 22a) and the edge portion 32b ( The crack resistance of the intersection of the first main surface 21 and the end surface 22b is improved.
  • the functional film 4 has the first main surface 21, all four end surfaces in contact with the first main surface 21, and part of the second main surface 23 continuously through the adhesive layer 3. May be coated.
  • the functional film includes a thermoplastic resin film and a functional layer disposed on at least one main surface of the thermoplastic resin film.
  • thermoplastic resin film is not particularly limited as long as it can be used for prevention of scattering of the glass substrate, and is not particularly limited, but an acrylic resin, a polyester resin, a polyurethane resin, a polyolefin resin, a polycarbonate resin, Triacetyl cellulose resin, diacetyl cellulose resin, acetate butyrate cellulose resin, polyether sulfone resin, polysulfone resin, polyether resin, trimethylpentene resin, polyether ketone resin, polyacrylonitrile resin, etc.
  • a thermoplastic resin film is used.
  • an acrylic resin film comprised by the acrylic resin composition containing the acrylic resin and the graft copolymer particle containing a rubber component.
  • the acrylic resin film is excellent in transparency, weather resistance, surface hardness, and secondary moldability, has good adhesion to a functional layer composed of various curable resins, and has a variety of curved surface shapes. It is easy to obtain a functional film for surface lamination excellent in followability to the surface shape.
  • the acrylic resin film is composed of an acrylic resin composition including an acrylic resin and graft copolymer particles containing a rubber component.
  • the graft copolymer particles containing a rubber component preferably include a graft copolymer particle (A) having an average particle size of 20 nm or more and 200 nm or less.
  • the graft copolymer particles (A) Graft copolymer particles (B) having an average particle size larger than that of the polymer particles (A) may be included.
  • the graft copolymer particles (A) are dispersed in the acrylic resin or a matrix containing the acrylic resin and other components, or the graft copolymer particles (A ) And graft copolymer particles (B) are dispersed.
  • the acrylic resin film preferably has a haze value of 1.3% or less, more preferably 1.1% or less, and even more preferably 0.8% or less. It is preferably 0.6% or less.
  • haze is measured according to JIS K 7136: 2000.
  • the elongation at break of the acrylic resin film is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more, and most preferably 40% or more.
  • the elongation at break is a value measured under the conditions of a temperature of 23 ° C. ⁇ 2 ° C. and a humidity of 50% ⁇ 5% using a Tensilon tensile tester at a distance between chucks of 40 mm and a tensile speed of 200 mm / min. It is. Further, the elongation at break value is measured as an average value excluding the highest value and the lowest value among the measurement results obtained using five or more test pieces, preferably five test pieces. Is done.
  • the acrylic hardness of the acrylic resin film measured according to JIS K 5600-5-4 is preferably 2B or more, more preferably B or more, and particularly preferably HB or more.
  • acrylic resin A conventionally well-known thing can be used as an acrylic resin used for an acrylic resin film.
  • the methyl methacrylate unit is 50% by mass to 100% by mass, and the other structural units are 0% by mass to 50%. It is preferable to contain 20% by mass or more and 100% by mass or less of a thermoplastic acrylic polymer composed of mass% or less.
  • Examples of other structural units include structural units derived from acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, aromatic vinyl derivatives, vinyl cyanide derivatives, vinylidene halides, and the like. 1 type may be sufficient as the other structural unit contained in an acrylic resin, and the combination of 2 or more types may be sufficient as it.
  • acrylic acid derivatives include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, and acrylic acid 2 -Acrylic acid esters such as phenoxyethyl, benzyl acrylate, 2- (N, N-dimethylamino) ethyl acrylate, and glycidyl acrylate.
  • methacrylic acid derivatives examples include ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-phenoxyethyl methacrylate.
  • methacrylic acid esters such as isobornyl methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate, and adamantyl methacrylate.
  • aromatic vinyl derivatives examples include styrene, vinyl toluene, and ⁇ -methylstyrene.
  • vinyl cyanide derivatives examples include acrylonitrile and methacrylonitrile.
  • Examples of the vinylidene halide include vinylidene chloride and vinylidene fluoride.
  • a structural unit having a specific structure with respect to the acrylic resin may be introduced by copolymerization, functional group modification and modification.
  • a specific structure include a glutarimide structure as disclosed in JP-A-62-89705, JP-A-02-178310, and WO2005 / 54311, JP-A-2004-168882, and the like.
  • examples thereof include an anhydride structure, a maleic anhydride structure as shown in JP-A-5-119217, and an N-substituted maleimide structure and an unsubstituted maleimide structure as shown in WO2009 / 84541.
  • these structures when these structures are introduced into an acrylic resin, the molecular chain becomes rigid. As a result, effects such as improved heat resistance, improved surface hardness, reduced heat shrinkage, and improved chemical resistance can be expected.
  • the production method of the acrylic resin is not particularly limited, and for example, a known suspension polymerization method, bulk polymerization method, solution polymerization method, emulsion polymerization method, dispersion polymerization method and the like can be applied.
  • a known suspension polymerization method bulk polymerization method, solution polymerization method, emulsion polymerization method, dispersion polymerization method and the like can be applied.
  • any of known radical polymerization methods, living radical polymerization methods, anionic polymerization methods, and cationic polymerization methods can be applied.
  • the acrylic resin film preferably includes the graft copolymer particles (A) as the graft copolymer particles containing a rubber component, and in addition to the graft copolymer particles (A) as necessary. Further, the graft copolymer particles (B) may be included.
  • the graft copolymer particles (A) have a core-shell structure (multilayer structure) comprising a crosslinked elastomer (A1) as a rubber component and a graft polymer layer (A2) located on the surface layer side of the crosslinked elastomer (A1). It is preferable.
  • the crosslinked elastomer (A1) may be a known crosslinked elastomer.
  • the cross-linked elastomer (A1) is an acrylic ester-based cross-linked elastomer (a cross-linked elastomer made of a polymer mainly composed of an acrylate ester).
  • the particles of the acrylic ester-based cross-linked elastomer (A1) may have a concentric spherical multilayer structure including a hard or semi-hard cross-linked resin layer inside the cross-linked elastomer layer.
  • a hard or semi-hard cross-linked resin layer include hard cross-linked methacrylic resin particles as disclosed in JP-B-55-27576, and methyl methacrylate-acrylic acid as disclosed in JP-A-4-270751.
  • Examples thereof include semi-rigid crosslinked particles composed of ester-styrene, and crosslinked rubber particles having a high degree of crosslinking.
  • the graft copolymer particles (A) have a core-shell structure formed by graft polymerization of the graft polymer layer (A2) in the presence of the above-mentioned acrylic ester-based crosslinked elastomer (A1) particles. preferable.
  • the average particle diameter of the graft copolymer particles (A) is from 20 nm to 200 nm, more preferably from 50 nm to 150 nm, and particularly preferably from 50 nm to 120 nm.
  • the average particle diameter of the graft copolymer particles (A) When the average particle diameter of the graft copolymer particles (A) is too small, the impact resistance and bending cracking resistance of the acrylic resin film tend to decrease. When the average particle diameter of the graft copolymer particles (A) is excessive, the transparency of the acrylic resin film tends to deteriorate and whitening due to bending tends to occur.
  • acrylic ester-based crosslinked elastomer (A1) it can be copolymerized with an acrylic ester, other vinyl monomers optionally copolymerizable with the acrylic ester, and an acrylic ester.
  • Cross-linked elastomer particles obtained by polymerizing a monomer mixture (a-1) containing a polyfunctional monomer having two or more non-conjugated double bonds can be preferably used.
  • the acrylic ester, other vinyl monomers, and polyfunctional monomers may be mixed in a single step and polymerized in one step.
  • the composition of the acrylic ester, other vinyl monomer, and the polyfunctional monomer may be appropriately changed or the same.
  • the acrylic ester, the other vinyl monomer, and the polyfunctional monomer may be polymerized in two or more stages in the composition.
  • an aliphatic ester of acrylic acid is preferable, an alkyl ester of acrylic acid is more preferable, and the number of carbon atoms of the alkyl group is preferable in view of excellent polymerizability, low cost, and giving a polymer having a low Tg. 1 to 22 can be particularly preferably used.
  • alkyl acrylates include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and isobornyl acrylate. Cyclohexyl acrylate, dodecyl acrylate, stearyl acrylate, heptadecyl acrylate, octadecyl acrylate, and the like. These may be used alone or in combination of two or more.
  • the amount of the acrylate ester is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 80% by mass or more in 100% by mass of the monomer mixture (a-1). preferable. If the amount of acrylic ester is 50% by mass or more, the impact resistance of the acrylic resin film and the elongation at the time of tensile break are good, and cracks are unlikely to occur during secondary molding.
  • vinyl monomers include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid Methacrylic acid esters such as cyclohexyl, phenoxyethyl methacrylate, isobornyl methacrylate, and dicyclopentenyl methacrylate; vinyl halides such as vinyl chloride and vinyl bromide; vinyl cyanide derivatives such as acrylonitrile and methacrylonitrile; formic acid Vinyl esters such as vinyl, vinyl acetate, and vinyl propionate; aromatic vinyl derivatives such as styrene, vinyltoluene, and ⁇ -methylstyrene; vinylidene halides such as vinylidene chloride and vinylidene fluoride Acrylic acid;
  • Methacrylic acid derivatives maleic anhydride; maleic acid derivatives such as N-alkylmaleimide and N-phenylmaleimide. These may be used individually by 1 type and 2 or more types may be used together. Among these, from the viewpoint of weather resistance and transparency, one or more selected from the group consisting of methacrylic acid esters and aromatic vinyl derivatives are particularly preferable.
  • the amount of the other vinyl monomer is preferably 0% by mass or more and 49.9% by mass or less, and 0% by mass or more and 30% by mass or less in 100% by mass of the monomer mixture (a-1). More preferably, it is most preferably 0% by mass or more and 20% by mass or less. If the amount of the other vinyl monomer exceeds 49.9% by mass, the impact resistance of the acrylic resin film tends to be lowered, the elongation at the time of tensile rupture is lowered, and cracks are likely to occur during secondary molding. There is a case.
  • polyfunctional monomer those usually used as a crosslinking agent and / or a graft crossing agent may be used.
  • examples of the polyfunctional monomer include 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, dipropylene glycol dimethacrylate, and the like can be used.
  • These polyfunctional monomers may be used individually by 1 type, and 2 or more types may be used together.
  • the amount of the polyfunctional monomer is preferably 0.1% by mass or more and 10% by mass or less, and 1.0% by mass or more and 4% by mass or less in 100% by mass of the monomer mixture (a-1). More preferably. If the blending amount of the polyfunctional monomer is within such a range, it is preferable from the viewpoint of the bending cracking resistance and bending whitening resistance of the acrylic resin film and the resin fluidity at the time of molding.
  • the amount of the polyfunctional monomer is increased between the inside of the cross-linked elastomer (A1) and the surface for the purpose of increasing the graft coating efficiency of the graft polymer layer (A2) described later. It may be changed in the vicinity. Specifically, as shown in Japanese Patent No. 1460364, Japanese Patent No. 1786959, etc., a polyfunctional monomer having a function as a graft crossing agent is formed in the vicinity of the surface of the crosslinked elastomer (A1).
  • the coating of the graft copolymer particles (A) with the graft polymer layer is improved, the dispersibility in the acrylic resin is improved, and the graft copolymer particles (A) and acrylic It is possible to suppress a decrease in crack resistance due to peeling of the resin interface.
  • the graft copolymer particles (A1) for introducing a predetermined amount of the crosslinked elastomer (A1) into the acrylic resin composition The melt viscosity of the acrylic resin composition is lowered, and the melt processability of the acrylic resin film, the improvement of the film processing accuracy, the improvement of the surface hardness, etc. can be expected.
  • the monomer mixture (a-1) contains a double bond terminal of the polymer that accompanies the control of the molecular weight and crosslinking density of the acrylate-based crosslinked elastomer (A1) and the disproportionation termination reaction during polymerization.
  • a chain transfer agent may be added for the purpose of controlling the thermal stability and the like by the decrease.
  • the chain transfer agent can be selected from those usually used for radical polymerization.
  • chain transfer agent examples 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, tetrachloride. Carbon or a mixture thereof is preferable.
  • the addition amount of the chain transfer agent is preferably 0 parts by mass or more and 1.0 parts by mass or less, more preferably 0 parts by mass or more and 0 parts by mass or less with respect to 100 parts by mass of the total amount of the monomer mixture (a-1). .2 parts by mass or less.
  • the particles of the crosslinked elastomer (A1) may be a single layer composed of the above-mentioned acrylic ester-based crosslinked elastomer (A1), and two or more layers composed of the above-mentioned acrylic ester-based crosslinked elastomer (A1).
  • a multilayer structure may be included, and at least one layer of multilayer particles including a hard or semi-hard cross-linked resin layer may have an acrylic ester-based cross-linked elastomer (A1).
  • Examples of monomers constituting the hard or semi-rigid cross-linked resin layer include methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, methacrylic acid esters such as phenoxyethyl methacrylate, methyl acrylate, and ethyl acrylate.
  • Acrylic acid alkyl esters such as propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate, and fragrances such as styrene and ⁇ -methylstyrene
  • fragrances such as styrene and ⁇ -methylstyrene
  • vinyl group derivatives vinyl cyanide derivatives such as acrylonitrile
  • maleic acid derivatives such as maleic anhydride and maleimides
  • polyfunctional monomers having two or more non-conjugated double bonds per molecule.
  • At least one selected from the group consisting of methyl methacrylate, butyl methacrylate, butyl acrylate, ethyl acrylate, styrene, acrylonitrile and the like is particularly preferable.
  • a polyfunctional monomer the thing similar to what is used for superposition
  • a chain transfer agent is used for the purpose of controlling the thermal stability by controlling the cross-link density or reducing the double bond terminal of the polymer. You may use together.
  • the same chain transfer agent as used in the polymerization of the acrylic ester-based crosslinked elastomer (A1) layer can be used.
  • the addition amount of the chain transfer agent is preferably 0 parts by mass or more and 2 parts by mass or less, more preferably 0 parts by mass or more and 0.5 parts by mass with respect to 100 parts by mass of the total amount of the hard or semi-rigid crosslinked resin layer. Or less.
  • the graft copolymer particle (A) has a two-layer structure of a crosslinked elastomer particle (A1) as a core particle and a graft polymer layer (A2)
  • the graft copolymer particle (A) is typically In the presence of the crosslinked elastomer particles (A1), 50% by mass to 100% by mass of the methacrylic acid ester and 0% by mass to 50% by mass of the other vinyl monomer copolymerizable with the methacrylic acid ester.
  • the obtained monomer mixture (a-2) can be obtained by graft copolymerization to form the graft polymer layer (A2).
  • the amount of the methacrylic acid ester in the monomer mixture (a-2) is such that the compatibility with the acrylic resin as the matrix is ensured and the toughness of the coating film is reduced due to the impregnation of the solvent when coating the acrylic resin film.
  • the content is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.
  • the graft polymer layer (A2) is preferably 70% by mass to 99% by mass of the alkyl methacrylate and the number of carbon atoms of the alkyl group in the presence of 5 to 90 parts by mass of the crosslinked elastomer particles (A1).
  • Monomer mixture (a-2) containing 10% by mass to 95% of 2 or more alkyl acrylate esters containing 0.5% by mass to 30% by mass and other vinyl monomers of 0% by mass to 19% by mass It can be obtained by graft copolymerizing at least one part by mass in at least one stage. However, the total amount of the crosslinked elastomer particles (A1) and the monomer mixture (a-2) satisfies 100 parts by mass.
  • examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, methacrylic acid.
  • examples include methacrylic acid alkyl esters such as cyclohexyl, 2-ethylhexyl methacrylate, octyl methacrylate, phenyl methacrylate, and benzyl methacrylate. Of these, methacrylic acid alkyl esters having 1 to 4 carbon atoms in the alkyl group are preferred.
  • an alkyl acrylate ester having 2 or more carbon atoms in the alkyl group can be used as the other vinyl monomer.
  • the alkyl acrylate ester having 2 or more carbon atoms in the alkyl group include ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, acrylic
  • One or more selected from the group consisting of octyl acid, dodecyl acrylate, stearyl acrylate, and the like are preferable, and selected from the group consisting of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate.
  • One or more are more preferable, and n-butyl acrylate is particularly preferable.
  • Examples of other vinyl monomers that can be used in the monomer mixture (a-2) include aromatic vinyl derivatives such as styrene and its nuclear substitution, vinyl cyanide derivatives such as acrylonitrile, methacrylic acid and its derivatives, Acrylic acid and its derivatives, N-substituted maleimides, maleic anhydride, methacrylamide, acrylamide and the like.
  • the monomer mixture (a-2) preferably contains a reactive ultraviolet absorber as another vinyl monomer. That is, it is preferable that the graft polymer layer (A2) includes a structural unit derived from a reactive ultraviolet absorber. When the monomer mixture (a-2) contains a reactive ultraviolet absorber, it is easy to obtain an acrylic resin film having good weather resistance and chemical resistance.
  • the reactive ultraviolet absorber As a reactive ultraviolet absorber, a well-known reactive ultraviolet absorber can be used, and it is not specifically limited. From the viewpoint of moldability and weather resistance of the acrylic resin film, the reactive ultraviolet 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 linear, Or a branched alkylene group having 2 to 10 carbon atoms
  • R 3 is a hydrogen atom or a methyl group.
  • the reactive ultraviolet absorber represented by the general formula (1) include 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazoles. More specifically, 2- (2′-hydroxy-5′-acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl-2H-benzotriazole, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-5′-methacryloyloxypropylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methacryloyloxyethyl-3′-t-butylphenyl) -2 -.
  • Benzotriazole Preferably, the cost and handling properties, 2- (2'-hydroxy-5'-methacryloyloxye
  • the content of the structural unit derived from the reactive ultraviolet absorber in the graft polymer layer (A2) is preferably 0.01% by mass or more and 5% by mass or less, and 0.1% by mass or more and 3% by mass or less. More preferably.
  • the graft copolymer particles (A) especially during the graft copolymerization of the monomer mixture (a-2) in the presence of the crosslinked elastomer particles (A1), for example, the acrylic ester-based crosslinked elastomer particles (A1).
  • a polymer component (free polymer) that is not graft-bonded to the acrylic ester-based crosslinked elastomer particles (A1) may be produced.
  • a free polymer can be used as what constitutes a part or all of the acrylic resin constituting the matrix phase of the acrylic resin composition and the acrylic resin film.
  • the molecular weight of the polymer is controlled, the graft ratio to the crosslinked elastomer (A1), the amount of free polymer not bonded to the crosslinked elastomer (A1), and the polymerization
  • a chain transfer agent may be added for the purpose of controlling thermal stability and the like by reducing the number of double bond ends of the polymer accompanying the disproportionation termination reaction.
  • the same chain transfer agent as that usable for the polymerization of the crosslinked elastomer (A1) can be used.
  • the chain transfer agent is used in an amount of 0 to 2 parts by weight, preferably 0 to 0.5 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture (a-2).
  • the graft ratio of the monomer mixture (a-2) to the crosslinked elastomer particles (A1) is preferably 5% or more and 250% or less, more preferably 10% or more and 200% or less, and further preferably 20% or more and 150% or less.
  • the graft ratio is less than 5%, the bending whitening resistance of the acrylic resin film is lowered, the transparency is lowered, the elongation at the time of tensile break is lowered, and cracks are easily generated during secondary molding. There is a tendency to become.
  • the graft ratio exceeds 250%, the melt viscosity of the acrylic resin composition tends to be high during film molding, and the moldability of the acrylic resin film tends to be lowered.
  • the average particle diameter d (nm) of the crosslinked elastomer particles (A1) in the acrylic resin film and the amount w (mass%) of the polyfunctional monomer used in the acrylic ester-based crosslinked elastomer are expressed by the following relational expression: It is preferable to satisfy 0.015d ⁇ w ⁇ 0.06d, and it is more preferable to satisfy 0.02d ⁇ w ⁇ 0.05d. If the amount of the polyfunctional monomer is within the range of the above relational expression, the elongation during secondary molding of the acrylic resin film is unlikely to decrease, and cracks are less likely to occur during molding and cutting, resulting in transparency. It has the advantage that it is excellent and stress whitening hardly occurs during bending or tensile deformation.
  • the graft copolymer particles (B) used as necessary also include a crosslinked elastomer (B1), which is a rubber component, like the graft copolymer particles (A).
  • the graft copolymer particles (B) typically include a graft polymer layer (B2) located on the surface layer side of the cross-linked elastomer (B1), like the graft copolymer particles (A). That is, it is preferable that the graft copolymer particles (B) include a crosslinked elastomer (B1) and a graft polymer layer (B2).
  • the graft copolymer particles (B) are substantially the same as the graft copolymer particles (A), raw materials, production methods, etc., except that the average particle size is larger than that of the graft copolymer particles (A). Also good.
  • the acrylic ester-based crosslinked elastomer (B1) particles have a concentric spherical multilayer structure including a hard or semi-hard cross-linked resin layer inside the cross-linked elastomer layer.
  • a hard or semi-hard cross-linked resin layer for example, hard cross-linked methacrylic resin particles as shown in Japanese Patent Publication No. Sho 55-27576, JP-A-4-270751, WO 2014/41803, etc.
  • Examples thereof include crosslinked particles having a semi-hard layer made of a methyl methacrylate-acrylic acid ester-styrene copolymer.
  • a hard or semi-rigid cross-linked resin layer By introducing such a hard or semi-rigid cross-linked resin layer, the transparency, bending whitening resistance, and folding resistance of the graft copolymer particles (B) having a particle diameter larger than that of the graft copolymer particles (A). Bending cracking properties and the like can be improved.
  • the average particle diameter of the graft copolymer particles (B) is preferably 150 nm or more and 400 nm or less, and more preferably 200 nm or more and 350 nm or less.
  • the average particle diameter of the graft copolymer particles (B) is larger than the average particle diameter of the graft copolymer particles (A).
  • Graft copolymer particles (B) having a large average particle diameter induce plastic deformation (craze) more effectively in the acrylic resin phase around the graft copolymer particles against the action of external force on the acrylic resin material. To do. For this reason, the graft copolymer particles (B) are very excellent in the effect of imparting impact resistance and crack resistance to the acrylic resin material.
  • the graft copolymer particles (B) are inferior in bending whitening resistance, solvent whitening resistance, etc., to the graft copolymer particles (A).
  • the soft component for the acrylic resin film by adding a small amount of the graft copolymer particles (B) to the acrylic resin composition containing the acrylic resin and the graft copolymer particles (A), the soft component for the acrylic resin film.
  • the whitening property when reducing the total content and not reducing the surface hardness of the acrylic resin film, when an external stress is applied to the acrylic resin film, or when a coating solution containing an organic solvent is applied or during molding It is difficult to deteriorate, and the effect of efficiently improving the crack resistance, secondary formability, etc. of the functional film can be expected.
  • the average particle size of the graft copolymer particles (A) and the graft copolymer particles (B) is a laser diffraction type such as a Microtrac particle size distribution measuring device MT3000 manufactured by Nikkiso Co., Ltd.
  • the particle size distribution measuring apparatus of No. 1 can be used, and it can measure using the light-scattering method in a latex state.
  • the method for producing the graft copolymer particles (A) and the graft copolymer particles (B) is not particularly limited, and a known emulsion polymerization method, miniemulsion polymerization method, suspension polymerization method, bulk polymerization method, solution weight A legal method or a dispersion polymerization method is applicable.
  • the emulsion polymerization method is particularly preferable from the viewpoint of a large adjustment range of the resin structure.
  • Initiators used in the emulsion polymerization of the graft copolymer particles (A) or the graft copolymer particles (B) include known initiators such as organic peroxides, inorganic peroxides, and azo compounds. Agents can be used.
  • t-butyl hydroperoxide 1,1,3,3-tetramethylbutyl hydroperoxide, succinic acid peroxide, peroxymaleic acid t-butyl ester, cumene hydroperoxide
  • Organic peroxides such as benzoyl peroxide and lauroyl peroxide
  • inorganic peroxides such as potassium persulfate, sodium persulfate and ammonium persulfate
  • azo compounds such as azobisisobutyronitrile can be used. These may be used alone or in combination of two or more.
  • initiators may be used as thermal decomposition type radical polymerization initiators, or sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, hydroxyacetic acid, ferrous sulfate, etc. It may be used as a redox type polymerization initiator system in combination with a reducing agent. Ferrous sulfate may be used in combination with a complex such as ethylenediaminetetraacetic acid-2-sodium.
  • inorganic peroxides such as potassium persulfate, sodium persulfate and ammonium persulfate are used from the viewpoint of polymerization stability and particle size control, or t-butyl hydroperoxide, cumene hydroperoxide, etc. It is possible to use a redox initiator system in which an organic process oxide of the above is combined with an inorganic reducing agent such as a divalent iron salt and / or an organic reducing agent such as sodium formaldehyde sulfoxylate, reducing sugar, ascorbic acid or the like. More preferred.
  • the above-mentioned inorganic peroxide or organic peroxide is added by a known method such as a method of adding to a polymerization system as it is, a method of adding by mixing with a monomer, a method of adding by dispersing in an aqueous emulsifier solution, or the like. be able to. From the viewpoint of the transparency of the acrylic resin film, a method of mixing and adding to a monomer and a method of adding by dispersing in an emulsifier aqueous solution are preferable.
  • surfactant also referred to as an emulsifier
  • emulsifier used for the emulsion polymerization of the graft copolymer particles (A) or the graft copolymer particles (B).
  • Known emulsions can be widely used for emulsion polymerization.
  • Preferred surfactants include, for example, alkyl sulfonic acid, alkyl benzene sulfonic acid, dioctyl sulfosuccinic acid, alkyl sulfuric acid, fatty acid sodium, polyoxyethylene alkyl ether acetic acid, alkyl phosphoric acid, alkyl ether phosphoric acid, alkylphenyl ether phosphoric acid.
  • Anionic surfactants such as sodium salts such as surfactin, potassium salts and ammonium salts, and nonionic surfactants such as reaction products of alkylphenols, aliphatic alcohols with propylene oxide and ethylene oxide, etc. Is mentioned.
  • alkyl ether phosphoric acid and its salt polyoxyethylene lauryl ether phosphoric acid and its sodium salt etc. can be used conveniently, for example.
  • These surfactants may be used alone or in combination of two or more.
  • the graft copolymer particles (A) or the graft copolymer particles ( B) can be separated and recovered. For example, after adding a water-soluble electrolyte such as calcium chloride and magnesium sulfate to the latex and coagulating it, or coagulating it by freezing, the graft copolymer particles are filtered, washed and dried. (A) or graft copolymer particles (B) can be separated and recovered. Further, the graft copolymer particles (A) or the graft copolymer particles (B) can be separated and recovered by a treatment such as spray drying or freeze drying on the latex.
  • a water-soluble electrolyte such as calcium chloride and magnesium sulfate
  • the graft copolymer particles (A) or the graft copolymer particles (B) are separated and collected in advance for the purpose of reducing the appearance defects and internal foreign matter of the acrylic resin film before the graft copolymer particles (B) are separated and collected.
  • the latex of (A) or the latex of graft copolymer particles (B) is filtered with a filter or mesh to remove substances that cause foreign matter defects such as environmental foreign matter and polymerization scale.
  • the filter or mesh a known filter or mesh used for filtration of a liquid medium can be used.
  • the form of the filter or mesh, the opening of the filter, the filtration accuracy, the filtration capacity, and the like are appropriately selected according to the intended application, the type, size, and amount of the foreign matter to be removed.
  • the openings of the filter and the mesh are preferably, for example, two times or more larger than the average particle diameter of the graft copolymer particles (A) or the graft copolymer particles (B).
  • the content of the graft copolymer particles (A) is not particularly limited, but is preferably 1% by mass or more and 70% by mass or less, and preferably 5% by mass or more and 65% by mass or less. More preferably, it is 10 mass% or more and 60 mass% or less.
  • the content of the graft copolymer particles (B) is not particularly limited, but is preferably 20% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less. Most preferably it is.
  • the acrylic resin film (acrylic resin composition constituting the acrylic resin film) is a range that does not impair the object of the present invention, and if necessary, a thermoplastic resin that is at least partially compatible with the acrylic resin. May be included.
  • thermoplastic resins examples include styrene resin, polyvinyl chloride resin, polycarbonate resin, amorphous saturated polyester resin, polyamide resin, phenoxy resin, polyarylate resin, olefin-methacrylic acid derivative resin, olefin- Acrylic acid derivative resin, cellulose derivative (cellulose acylate, etc.), vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polylactic acid resin, and PHBH (poly (3-hydroxybutyrate-co-3-hydroxyhexanoate)
  • the styrenic resin include styrene-acrylonitrile resin, styrene-methacrylic acid resin, styrene-acrylic acid resin, styrene-maleic anhydride resin, styrene-N-substituted maleimide resin, styrene- Examples thereof include substituted maleimide resins, styrene-acrylonitrile-butad
  • one or more kinds of heat selected from the group consisting of styrene resins, polycarbonate resins, and cellulose acylate resins. It is preferable because the plastic resin is excellent in compatibility with the acrylic resin and may improve the bending crack resistance, solvent resistance, low moisture absorption of the acrylic resin film, and the glass scattering prevention performance of the laminate. .
  • the acrylic resin film (acrylic resin composition constituting the acrylic resin film) is a conventionally known additive used for the acrylic resin film as necessary, as long as the object of the present invention is not impaired. May be included.
  • additives include antioxidants, ultraviolet absorbers, light stabilizers, light diffusing agents, matting agents, colorants such as lubricants, pigments and dyes, fibrous fillers, organic particles and inorganic particles. Examples thereof include an anti-blocking agent, an infrared reflector made of a metal or a metal oxide, a plasticizer, and an antistatic agent.
  • the additive is not limited to these. These additives can be used in any amount depending on the type of the additive within the range not impairing the object of the present invention or to enhance the effect of the present invention.
  • the acrylic resin film can be produced by a known processing method.
  • known processing methods include melt processing methods, calendar forming methods, press forming methods, and solvent casting methods.
  • the melt processing method include an inflation method and a T-die extrusion method.
  • the solvent casting method the acrylic resin composition is dissolved and dispersed in a solvent, and then the obtained dispersion is poured into a film on the belt-like substrate. Next, an acrylic resin film is obtained by volatilizing the solvent from the fluent film dispersion.
  • a melt processing method using no solvent, particularly a T-die extrusion method is preferable. According to the melt processing method, a film having excellent surface properties can be produced with high productivity, and the load on the natural environment and working environment due to the solvent, and the energy and cost for production can be reduced.
  • the acrylic resin composition When the acrylic resin composition is formed into a film by a melt processing method or a solvent casting method, from the viewpoint of improving the appearance quality of the acrylic resin film, by using a filter or a mesh, the appearance defect or the inside of the acrylic resin film is reduced. It is preferable to remove environmental foreign matter, polymerization scale, deteriorated resin, and the like in the acrylic resin composition that cause foreign matters and the like.
  • the pelletization of the molten acrylic resin composition, and the film formation process by the T-die Filtration can be performed.
  • the acrylic resin, the graft copolymer particles (A), and the graft copolymer particles (B) may be mixed with a solvent and then filtered before cast film formation.
  • a known filter or mesh can be used without particular limitation as long as the filter or mesh has heat resistance and durability according to melt processing conditions and resistance to a casting solvent.
  • the filtration capacity is large, which causes generation of resin degradation products and cross-linked products that impair the quality of the film.
  • a filter with less resin retention is preferred.
  • use of a leaf disk type filter or a pleat type filter is preferable in terms of filtration efficiency and productivity.
  • an acrylic resin film when molding the film, if necessary, by bringing the both sides of the molten film into contact with a cooling roll or a cooling belt at the same time (sandwiching), a film with better surface properties can be obtained. Can be obtained.
  • the molten film is simultaneously brought into contact with a roll or a metal belt maintained at a glass transition temperature of ⁇ 5 ° C. or less, preferably a glass transition temperature of ⁇ 10 ° C. or less of the acrylic resin composition.
  • a roll having a metal sleeve having elasticity as disclosed in, for example, Japanese Patent Application Laid-Open No. 2000-153547 and Japanese Patent Application Laid-Open No. 11-235747 is used as at least one of the rolls for performing such sandwiching.
  • a film having excellent smoothness and less internal distortion can be obtained.
  • uniaxial stretching or biaxial stretching can be performed following film formation.
  • Uniaxial stretching or biaxial stretching can be performed using a known stretching apparatus.
  • Biaxial stretching can be carried out in a known manner such as a method of reducing the bowing of the film by sequentially stretching biaxially, simultaneously biaxially stretching, and longitudinally stretching, then performing transverse stretching while relaxing the longitudinal direction. is there.
  • an arbitrary surface shape such as a hairline, a prism, a concavo-convex shape, or a matte surface may be imparted to one surface or both surfaces of the acrylic resin film as required for the application.
  • Such surface shape can be imparted by a known method.
  • the surface shape of the roll can be changed by sandwiching both sides of a film in a molten state immediately after extrusion or a formed film fed from a feeding device with two rolls or belts having a surface shape on at least one surface. There is a method of transferring.
  • the concavo-convex shape When a concavo-convex shape is imparted to one or both sides of the acrylic resin film, the concavo-convex shape may function as a surface concavo-convex layer described later. When one surface or both surfaces of the acrylic resin film is a matte surface, the matte surface may function as a matte layer described later.
  • the thickness of the acrylic resin film is preferably 20 ⁇ m or more and 500 ⁇ m or less, and more preferably 40 ⁇ m or more and 300 ⁇ m or less. If the thickness of the acrylic resin film is within such a range, the moldability is good, the acrylic resin film can be easily wound, and wrinkles are not easily generated when the acrylic resin film is wound.
  • the functional film has a functional layer disposed on at least one main surface of a thermoplastic resin film (preferably an acrylic resin film).
  • the functional layer may be one layer or two or more layers.
  • the functional layer may be arrange
  • the functional layer is preferably in direct contact with at least one surface of a thermoplastic resin film (preferably an acrylic resin film).
  • the functional layer is not particularly limited, and various conventionally known functional layers can be employed, for example.
  • Specific examples of the functional layer include a hard coat layer, an antireflection layer, an antiglare layer, an antifouling layer, an anti-fingerprint layer, a scratch-resistant layer, an antistatic layer, an ultraviolet shielding layer, an infrared shielding layer, a surface uneven layer, and a light diffusion layer. Examples include layers, matte layers, polarizing layers, colored layers, design layers, embossed layers, conductive layers, gas barrier layers, and gas absorption layers.
  • the functional film may include two or more of these functional layers in combination. One functional layer may have two or more functions.
  • the antireflection layer may be composed of a low refractive index layer, or may be composed of both a high refractive index layer and a low refractive index layer, and has a surface irregularity shape finer than the wavelength of visible light as a functional layer. You may comprise by forming in the surface of this.
  • each functional layer is not particularly limited, and is appropriately set according to the purpose and function of the glass laminate.
  • the thickness of the functional film is preferably 20 ⁇ m or more and 500 ⁇ m or less, and more preferably 40 ⁇ m or more and 300 ⁇ m or less.
  • the thickness of the functional layer may be, for example, 0.1 ⁇ m or more and 20 ⁇ m or less, or 1 ⁇ m or more and 10 ⁇ m or less.
  • the functional film can be provided with good chemical resistance and stain resistance, and a functional film suitable for use in the production of a molded product can be obtained, the functional film should have at least one hard coat layer.
  • the functional film having a hard coat layer preferably has a low refractive layer on the hard coat layer for the purpose of imparting an antireflection function, and a high refractive layer is provided between the hard coat layer and the low refractive layer. It is more preferable to comprise.
  • the functional film includes a low refractive layer or a low refractive layer and a high refractive layer on the hard coat layer, the reflectance of the functional film surface can be reduced.
  • the production method of the functional film is particularly limited as long as it is a method of providing a desired type and number of functional layers on the main surface of the above-described thermoplastic resin film (preferably an acrylic resin film) which is a base film.
  • a functional layer may be laminated
  • a functional layer may be laminated
  • a method for forming a functional layer it is easy for uniform processing even on a large-area substrate film, and because it can form a functional layer with excellent adhesion to the substrate film, it is used for forming a functional layer containing an organic solvent.
  • a method using a coating solution is preferred.
  • the surface of the base film is a functional layer at the interface between the base film and the functional layer.
  • a hybrid region in which a thermoplastic resin that constitutes the base film, such as an acrylic resin, and a constituent material of the functional layer are mixed may be formed.
  • the functional layer formed using the coating liquid for functional layer formation containing an organic solvent is hard to peel from a base film.
  • a coating film is formed by applying a coating liquid for forming a functional layer containing an organic solvent on at least one surface of the acrylic resin film described above. Or a coating layer is dried and cured to form a functional layer.
  • the method for applying the coating solution is not particularly limited, and examples thereof include a reverse coating method, a gravure coating method, a bar coating method, a die coating method, a spray coating method, a kiss coating method, a wire bar coating method, and a curtain coating method. .
  • the drying temperature of the coating film is not particularly limited as long as the organic solvent can be removed from the coating film.
  • the drying temperature is appropriately set to a temperature in a range that does not cause deformation of the acrylic resin film.
  • the curing method is not particularly limited as long as a desired functional layer can be formed.
  • the curing method is appropriately selected according to the composition of the coating solution.
  • the coating film is cured by heating or irradiating (exposing) energy rays such as ultraviolet rays.
  • exposing energy rays such as ultraviolet rays.
  • curing may be allowed to proceed by allowing the coating film to stand without heating or exposure.
  • the hard coat layer various hard coat layers that have been conventionally provided in various functional films, resin molded articles, and the like can be employed without particular limitation.
  • the hard coat layer is, for example, a monomer, oligomer, resin having radical reactive functional groups such as polyfunctional (meth) acrylate, epoxy acrylate, urethane acrylate, polyester acrylate, silicon acrylate, polycarbonate acrylate, and polyacryl acrylate, or these It can form by hardening the composition containing the mixture of these.
  • a hard-coat layer can be formed by hardening the composition containing the monomer, oligomer, resin, or these mixtures which have cation curable or anion curable functional groups, such as an epoxy group and an oxetane group, for example.
  • a hard coat layer can be formed by thermally curing a polysiloxane resin obtained by hydrolyzing and partially condensing an alkoxy group-substituted silyl compound.
  • a hard coat layer can be formed by introducing a reactive functional group into a silyl compound and reacting it to cure.
  • the said component used for formation of a hard-coat layer may be used individually by 1 type, and may mix and use 2 or more components suitably.
  • the polyfunctional (meth) acrylate is not particularly limited as long as it has at least two (meth) acryloyl groups. Specifically, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, penta Examples include polyfunctional (meth) acrylates such as erythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, hexanediol di (meth) acrylate, and diethylene glycol di (meth) acrylate.
  • (meth) acrylate is meant to include methacrylate and acrylate.
  • the (meth) acryloyl group is meant to include a methacryloyl group and an acryloyl group.
  • epoxy acrylate monomer there are no particular restrictions on the epoxy acrylate monomer. Specifically, glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and vinylcyclohexene monooxide (ie, 1,2-epoxy-4-vinylcyclohexane) ) And the like.
  • the urethane acrylate resin can be obtained, for example, by mixing a polyhydric alcohol, a polyvalent isocyanate, and a hydroxyl group-containing (meth) acrylate, and generating a urethane bond by a reaction between the isocyanate group and the hydroxyl group.
  • the hydroxyl group-containing (meth) acrylate is not particularly limited, and may be a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and, if necessary, at least one hydroxyl group.
  • the polyisocyanate is not particularly limited.
  • Examples of the polyvalent isocyanate compound that is a compound containing two or more isocyanate groups include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene diene.
  • polyhydric alcohol examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -Octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,8-octanediol, 1,4-cyclohexanedi Examples include methanol and polytetramethylene glycol. These polyhydric alcohols may be used alone or in combination of two or more.
  • An organotin urethanization catalyst is used to promote the reaction with the isocyanate group of the isocyanate component.
  • the organic tin-based urethanization catalyst any catalyst generally used in urethanization reactions may be used. Examples thereof include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dialkylmalate, tin stearate, and tin octylate. It is done.
  • the amount of the organotin-based urethanization catalyst used is not particularly limited, but is suitably used within a range of 0.005 mass% to 3 mass%. If the lower limit is not reached, the urethane reaction does not proceed sufficiently. If the upper limit is exceeded, the reaction control becomes difficult due to heat generation during the urethane reaction.
  • the composition for forming a hard coat comprising a polysiloxane-based resin composition is preferably the following general formula (2): R 4 - (SiR 5 a ( OR 6) 3-a) (2) (In general formula (2), at least a part of R 4 is an epoxy group, an oxetane group, a (meth) acryloyl group, a vinyl group, a hydroxyl group, a carboxyl group, an amino group, or a functional group-protected amino group.
  • a group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, substituted with a reactive substituent selected from the group consisting of R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and 7 carbon atoms.
  • the condensate (A) has a weight average molecular weight of 30,000 or less. Moreover, it is preferable that the usage-amount of the silane compound which has a reactive substituent is 10 mass% or more of the whole. In this case, the cured product as the hard coat layer is excellent in hardness, chemical resistance, durability, and the like.
  • the catalyst or curing agent (B) is preferably at least one catalyst or curing agent selected from a photo radical generator, a photo cation generator, and a photo anion generator from the viewpoint of photocurability of the composition.
  • the reactive substituent in the general formula (2) is an epoxy group or an oxetane group from the viewpoint of less curing shrinkage when forming a hard coat layer and easy to obtain a functional film excellent in durability and curling suppressed. Is preferred.
  • a neutral salt catalyst as a catalyst for the hydrolysis condensation reaction of the silane compound (Z). This is because when the reactive substituent is an epoxy group or an oxetane group, it is easy to suppress decomposition of the reactive substituent during hydrolysis condensation.
  • the number of moles of OR 6 groups bonded directly to silicon atoms condensate (A) has The Q ratio Q / P is more preferably 0.2 or less. This is because the cured product has excellent hardness, chemical resistance, durability, and the like.
  • a known method can be applied as a method of curing the resin composition when forming the hard coat layer.
  • a method of irradiating active energy rays typified by ultraviolet rays is preferable.
  • a photopolymerization initiator, a photoanion generator, a photocation generator, and the like are usually added to the composition for forming a hard coat layer.
  • the photopolymerization initiator include, for example, 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-morpholinopropane- Examples thereof include 1-one compounds. Of these, 1-hydroxy-cyclohexyl-phenyl-ketone, which is excellent in compatibility with the resin, is preferable.
  • photocation generator examples include CPI-100P, CPI-101A, CPI-200K, and CPI-200S manufactured by Sun Apro, Inc .; WPI-124, WPI-113, WPI- manufactured by Wako Pure Chemical Industries, Ltd. 116, WPI-169, WPI-170, and WPI-124; Rhodesil 2074 manufactured by Rhodia
  • the photoanion generator include, for example, acetophenone o-benzoyloxium, nifedipine, 2- (9-oxoxanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4.4.0].
  • Deca-5-ene 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3- [bis (dimeramino) methylene] guanidinium 2- (3-benzoylphenyl) propionate, 1, Examples include 2-dicyclohexyl-4,4,5,5-tetramethylpiguanidinium and n-butyltriphenylballate.
  • leveling agent a fluorine leveling agent, an acrylic leveling agent, a silicone leveling agent, and an adduct or a mixture thereof can be used.
  • compounding quantity of a leveling agent is not specifically limited, For example, it is the quantity in the range of 0.03 mass part or more and 3.0 mass part or less with respect to 100 mass parts of curable compositions.
  • the curable composition When a hard coat layer is formed by applying a curable composition, the curable composition includes an ultraviolet absorber, a light stabilizer, an antifoaming agent, an antioxidant, a light diffusing agent, a matting agent, Various additives such as stains, lubricants, colorants such as pigments and dyes, organic particles, inorganic fine particles, and antistatic agents can be added as necessary.
  • the additive is not limited to these.
  • an organic solvent is usually blended.
  • the organic solvent is not particularly limited as long as a desired coating property can be imparted to the curable composition and a hard coat layer having a desired film thickness and performance can be formed.
  • the boiling point of the organic solvent is preferably 50 ° C. or higher and 150 ° C. or lower from the viewpoints of coating properties and drying properties of the formed coating film.
  • organic solvents include saturated hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and methylene chloride; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol.
  • Esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, dioxane, propylene glycol monoethyl ether, methyl cellosolve, and ethyl cellosolve And amides such as N-methylpyrrolidone and dimethylformamide.
  • An organic solvent can be used individually by 1 type or in combination of 2 or more types.
  • thermoplastic resin film preferably an acrylic resin film
  • any method can be adopted as the application method without any particular limitation.
  • the coating method include reverse coating, gravure coating, bar coating, die coating, spray coating, kiss coating, wire bar coating, and curtain coating. These coating methods may be implemented singly or in combination.
  • the curable composition for forming the hard coat layer described above is applied to the surface of the thermoplastic resin film (preferably an acrylic resin film) that is a base film, the organic solvent is removed from the coating film by drying. Then, a hard coat layer is formed by curing with light such as ultraviolet irradiation.
  • the thermoplastic resin film preferably an acrylic resin film
  • the organic solvent is removed from the coating film by drying. Then, a hard coat layer is formed by curing with light such as ultraviolet irradiation.
  • the drying temperature of the coating film when the organic solvent is removed by drying is preferably 60 ° C. or higher and 120 ° C. or lower, and more preferably 70 ° C. or higher and 100 ° C. or lower. If the drying temperature is too low, the organic solvent may remain in the coating film. If the drying temperature is too high, the flatness of the functional film may be impaired due to thermal deformation of the base film.
  • the wavelength of ultraviolet rays irradiated when the coating film is cured is preferably in the range of 200 nm to 400 nm.
  • the irradiation conditions of ultraviolet rays are appropriately adjusted according to the type and composition of the constituent components of the curable composition.
  • Examples of the irradiation device for exposure light such as ultraviolet rays include pulse light sources such as high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, electrodeless lamps, and excimer lamps, and pulse or continuous lights such as argon ion lasers and helium neon lasers.
  • An irradiation apparatus including a laser light source or the like can be used.
  • Examples of the hard coat layer forming composition include the product name “Z-879” manufactured by Aika Industry Co., Ltd., the product name “Unidic ESS108” manufactured by DIC Corporation, “NSC-7712” manufactured by Dainichi Seika Kogyo Co., Ltd., and Arakawa.
  • Commercial products such as “FA-3280H” may be used. Since it has elongation even after curing, the 120 ° C. crack elongation of the functional film can be further increased.
  • the high refractive index layer is typically formed by curing a composition for a high refractive index layer.
  • the high refractive index layer is a layer for exhibiting an antireflection effect due to a significant refractive index difference from the hard coat layer described above and a significant refractive index difference from the low refractive index layer described later.
  • known layers conventionally used for antireflection films and the like can be used without particular limitation.
  • the composition for a high refractive index layer a composition in which an inorganic material for adjusting the refractive index is appropriately added to an organic material serving as a base can be used.
  • the same composition as the hard coat layer can be used without particular limitation.
  • fine particles such as zinc oxide, titanium oxide, cerium oxide, aluminum oxide, silane oxide, antimony oxide, zirconium oxide, tin oxide, and ITO can be used.
  • additives can be added as other components within a range not impairing the effects of the present invention.
  • additives include additives such as a polymerization initiator, a dispersant, a surfactant, a light stabilizer, and a leveling agent.
  • the low refractive index layer is typically formed by curing a composition for a low refractive index layer.
  • a composition for a low refractive index layer a known layer that has been conventionally used for an antireflection film or the like can be used without particular limitation.
  • the composition for a low refractive index layer a material obtained by appropriately adding a material for adjusting a refractive index to an organic material as a base can be used.
  • the same composition as the hard coat layer can be used without particular limitation.
  • a material for adjusting the refractive index for example, silica fine particles, hollow silica fine particles, fluoride fine particles and the like can be used.
  • the fluoride constituting the fluoride fine particles include magnesium fluoride, lithium fluoride, aluminum fluoride, and calcium fluoride.
  • a part of the organic material may be replaced with a water repellent material or an oil repellent material.
  • a water repellent material or an oil repellent material a wax-based material is generally used.
  • additives can be added as other components within a range not impairing the effects of the present invention.
  • additives include additives such as photopolymerization initiators, dispersants, surfactants, light stabilizers and leveling agents, and anti-fingerprint agents.
  • composition for the low refractive index layer examples include a product name “Z-824” manufactured by Aika Industry Co., Ltd., a product name “TU-2359” manufactured by Arakawa Chemical Industries, Ltd., and a product name “ELCOM manufactured by JGC Catalysts & Chemicals Co., Ltd.”
  • Commercial products such as “P-5062” may be used. Since it has elongation even after curing, the 120 ° C. crack elongation of the functional film can be further increased.
  • the functional film has a 120 ° C. crack elongation of 20% or more, preferably 25% or more, and more preferably 30% or more.
  • the functional film has a 120 ° C. crack elongation of 20% or more, preferably 25% or more, and more preferably 30% or more.
  • the 120 ° C. crack elongation is 20% or more, cracks occur in the functional film when the functional film is laminated with a glass substrate via an adhesive layer, particularly when vacuum forming or vacuum / pressure forming is performed. This can be suppressed, and a glass laminate can be obtained with good moldability.
  • the upper limit of 120 degreeC crack elongation of a functional film is not specifically limited, For example, 200% or less may be sufficient from a viewpoint of hardness.
  • the measurement of 120 degreeC crack elongation of a functional film is performed as mentioned later. By using a functional layer having an elongation, the 120 ° C. crack elongation of the functional film can be further increased.
  • the functional film preferably has a haze value of 3.0% or less, more preferably 2.0% or less, and even more preferably 1.3% or less, It is still more preferably 1.1% or less, still more preferably 0.8% or less, and particularly preferably 0.6% or less.
  • the haze value is not limited to the above range.
  • the glass substrate is not particularly limited, and examples thereof include alkali-free glass, soda lime glass, soda lime silicate glass, aluminosilicate glass, boron silicate glass, lithium aluminosilicate glass, and borosilicate glass.
  • the glass substrate may be subjected to processing such as chamfering.
  • the glass substrate is preferably a transparent glass plate having a total light transmittance of 85% or more from the viewpoint of excellent transparency.
  • the total light transmittance of the transparent glass plate is more preferably 90% or more.
  • the glass substrate may be a flat glass plate with both main surfaces flat, or may be a curved glass with one or both main surfaces having curved portions. Moreover, you may have a curved-surface part also in an end surface.
  • the curved surface portion may be bent two-dimensionally or may be bent three-dimensionally (three-dimensional shape).
  • the thickness of the glass substrate is not particularly limited, and can be appropriately determined according to the use of the glass laminate. For example, it may be from 0.1 mm to 50 mm, or from 1 mm to 20 mm.
  • the adhesive layer is composed of an adhesive (including a pressure sensitive adhesive).
  • the pressure sensitive adhesive is also referred to as a pressure sensitive adhesive. That is, in the present invention, the adhesive layer is an adhesive layer having a broad meaning including an adhesive layer.
  • the adhesive layer adheres the functional film and the glass substrate, and the adhesive layer needs to have an adhesive strength such that the 90 ° peel strength between the functional film and the glass substrate is 25 N / 25 mm or more. . The 90 ° peel strength between the functional film and the glass substrate is measured as described later.
  • the 90 ° peel strength between the functional film and the glass substrate is 25 N / 25 mm or more, when the functional film is laminated and formed with the glass substrate through the adhesive layer, particularly when vacuum forming or vacuum-compressed. Generation
  • production of a spring back can be suppressed and a glass laminated body can be obtained with a sufficient moldability.
  • the 90 ° peel strength between the functional film and the glass substrate is preferably 30 N / 25 mm or more, more preferably 35 N / 25 mm or more, and further preferably 40 N / 25 mm or more.
  • the upper limit of 90 degree peeling strength between a functional film and a glass base material is not specifically limited, For example, 100 N / 25mm or less may be sufficient from a viewpoint of handling property.
  • the thickness of the adhesive layer is not particularly limited, but is preferably 10 ⁇ m or more and 100 ⁇ m or less, and more preferably 20 ⁇ m or more and 50 ⁇ m or less from the viewpoint of handling properties, for example.
  • the adhesive is generally a hard adhesive having excellent adhesive strength or a curable adhesive having curability.
  • the hard or curable adhesive include a hot-melt adhesive that melts when heated and solidifies when cooled, and a reactive curable type that has reaction curability by light, heat, moisture, a curing agent, a curing catalyst, and the like.
  • examples thereof include an adhesive, a reaction curable hot melt adhesive having hot melt properties and reaction curability. From the viewpoint of further increasing the adhesive strength, it is more preferable to use a reaction curable adhesive or a reaction curable hot melt adhesive.
  • the adhesive is preferably excellent in adhesive strength to glass, which is generally said to be difficult to adhere, and does not impair the transparency of the glass laminate after adhesion.
  • adhesives such as styrene diene, butyl rubber, polyurethane, polyamide, polyester, acrylic, epoxy, and silyl are exemplified.
  • Specific examples of the styrene diene adhesive include a styrene butadiene adhesive.
  • the styrene-butadiene-based adhesive is not particularly limited.
  • commercially available products such as “Hamatite M Series” manufactured by Yokohama Rubber Co., Ltd. and “FB-ML60” (hot melt adhesive) manufactured by Nitto Shinko Co., Ltd. May be appropriately selected and used.
  • the polyester adhesive is not particularly limited, and for example, commercially available products such as “FB-ML80” (hot melt adhesive) manufactured by Nitto Shinko Co., Ltd. can be used.
  • the acrylic adhesive is not particularly limited.
  • “Mastuck (registered trademark) TS” thermosetting adhesive manufactured by Fujimori Kogyo Co., Ltd.
  • Commercial products such as (UV curable hot melt adhesive) can be used.
  • the epoxy adhesive is not particularly limited, and for example, commercially available products such as “GFT50UT7” (UV curable adhesive) manufactured by DIC Corporation can be used.
  • the polyurethane adhesive is not particularly limited.
  • commercially available products such as “TS23” manufactured by 3M and “Technomelt AS series” manufactured by Henkel may be used as appropriate.
  • the polyamide adhesive is not particularly limited, and examples thereof include “Technomelt PA series” manufactured by Henkel.
  • the silyl-based adhesive is not particularly limited.
  • commercially available products such as “Kanekazemlac” and “Syryl (registered trademark)” manufactured by Kaneka Co., Ltd. and “Super X” series of Cemedine Co., Ltd. are appropriately used. May be.
  • the adhesive layer may be formed by laminating a sheet-like (also called film-like) adhesive (adhesive sheet) on one main surface of the functional film. You may form by apply
  • the adhesive layer is a main surface opposite to the main surface of the thermoplastic resin film on which the functional layer is disposed. That is, it is preferably formed on the main surface where the functional layer is not disposed.
  • the functional film with an adhesive layer preferably has a haze value of 3.0% or less, more preferably 2.0% or less, and further preferably 1.3% or less. Preferably, it is 1.1% or less, more preferably 0.8% or less, and particularly preferably 0.6% or less.
  • the glass laminate may further include a decorative layer from the viewpoint of design.
  • the functional film is disposed so as to cover at least a part of one main surface of the glass substrate and the end surface in contact with the main surface
  • the decorative layer is formed of the glass substrate on which the functional film is not disposed. It can arrange
  • the decorative layer is preferably provided by printing ink on one main surface of the glass substrate by a general printing method from the viewpoint of preventing the occurrence of deviation during the molding of the glass laminate.
  • a general printing method examples include silk printing, screen printing, thermal transfer printing, and gravure printing.
  • the decorative layer is not particularly limited as long as it imparts various design properties to the glass laminate.
  • the glass laminate when used as a front plate of a display device such as a vehicle-mounted display, Examples thereof include characters and figures that are visually recognized in the surroundings, or a black border-like decorative layer provided in a frame shape on the display unit.
  • the thickness of a decoration layer is not specifically limited, For example, it is preferable that they are 1 micrometer or more and 30 micrometers or less from a viewpoint of printability and design property, It is more preferable that they are 1 micrometer or more and 15 micrometers or less, It is 2 micrometers or more and 10 micrometers or less. More preferably it is.
  • any inorganic ink or organic ink that can be used for printing on a glass substrate can be used.
  • the organic ink is not particularly limited, and for example, an organic ink such as a urethane resin, an acrylic resin, an epoxy resin, or a polyester resin may be used.
  • the ink may further contain a colorant.
  • a black colorant such as carbon black can be used.
  • Method for producing glass laminate As a method for laminating the functional film on the surface of the glass substrate, a known method can be used without particular limitation. In particular, as a method of laminating the functional film on the surface of a glass substrate having a curved shape, or as a method of laminating the functional film around the main surface of the glass substrate and an end surface adjacent thereto, And the same three-dimensional laminate molding method as those described in Japanese Patent No. 3733564, Japanese Patent No. 3924760, and Japanese Patent No. 5549036.
  • a functional film with an adhesive layer softened by heat after laminating an adhesive layer on the functional film described above is formed into a planar shape using a vacuum state or a compressed air state.
  • a decorative layer may be printed on the glass substrate in advance.
  • the resin temperature, molding conditions, and the like can be appropriately set in consideration of the shape, thermal and physical properties of the functional film, the shape and size of the glass substrate, and the like.
  • the present invention is not necessarily limited to the case where all the end faces are completely covered. For example, even if the end faces are partially exposed, it does not depart from the scope of the present invention.
  • Glass laminates protect the surfaces of various molded products or members that incorporate, for example, a display unit or an operation unit, by using glass substrates molded in various shapes according to the intended application. It can be used as a surface material that imparts various functions such as antireflection and scratch prevention. Specific uses of the glass laminate include, for example, automotive interior applications such as instrument panels, in-vehicle display front plates, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, and dashboards; , Windows, headlamp covers, tail lamp covers, windshield parts, etc.
  • buttons for portable electronic devices such as smartphones, mobile phones, tablets, etc .
  • TVs, DVD players, stereo devices, and other household electronic devices Use for housings such as furniture products, front panels, buttons, surface decorative materials, etc .; use for optical members such as various displays, lenses, mirrors, goggles, and window glass.
  • the glass laminate By using a glass laminate, it is possible to easily produce a molded article having a complicated three-dimensional shape and having a controlled appearance such as antifouling properties, reflection characteristics, and antiglare properties on the surface. For this reason, the glass laminate is preferably used for applications such as a front plate of a display device such as an in-vehicle display having various shapes such as a planar shape, a curved surface shape, and a three-dimensional shape, among the above applications.
  • mixture (II) (1) 70 parts of a vinyl monomer mixture (MMA 98%, BA 1%, and RUVA 1%), (2) t-dodecyl mercaptan (t-DM) 0.5 part (3) CHP 0.5 part RUVA is a reactive ultraviolet absorber (2- (2′-hydroxy-5′-methacryloyloxyethylphenyl)) -2-H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., RUVA-93)).
  • the internal temperature was set to 80 ° C., 0.027 part of potassium persulfate was added in a 2% aqueous solution, then 26.19 parts of methyl methacrylate, 0.2% of butyl acrylate.
  • a mixture comprising 81 parts, allyl methacrylate 0.135 parts, n-octyl mercaptan 0.3 parts and polyoxyethylene lauryl ether phosphoric acid 0.094 parts was continuously added over 81 minutes. Polymerization latex was further obtained by continuing the polymerization for 60 minutes. The polymerization conversion rate was 99.0%.
  • the graft polymer layer (B2) was formed on the front side of the crosslinked elastomer particles (B1) (core) having a two-layer structure to obtain a latex of the graft copolymer particles (B).
  • the polymerization conversion rate was 100.0%, and the average particle size of the graft copolymer (B) was 240 nm.
  • the obtained latex was filtered through a stainless steel mesh having an opening of 10 ⁇ m, and then salted out and coagulated with magnesium sulfate, washed with water and dried to obtain white powdered graft copolymer particles (B).
  • Example 1 [Production of functional film] ⁇ Production of acrylic resin film> 65 parts of an acrylic resin (manufactured by Sumitomo Chemical Co., Ltd., product name “SUMIPEX (registered trademark) EX”) and 31 parts of the graft copolymer particles (A) obtained in Production Example 1 were obtained in Production Example 2. 4 parts of the graft copolymer particles (B) and 0.6 part of a phenolic antioxidant (manufactured by ADEKA, product name “ADK STAB AO-60”) were mixed using a Henschel mixer.
  • SUMIPEX registered trademark
  • a phenolic antioxidant manufactured by ADEKA, product name “ADK STAB AO-60
  • the cylinder temperature was 200 ° C to 240 ° C, and the filter section And a die part set temperature of 250 ° C., a screw rotation speed of 200 rpm, a discharge amount of 180 kg / hr, melt-kneaded, taken in a strand shape, cooled in a water tank, cut with a pelletizer, Pellets were obtained.
  • the obtained acrylic resin composition pellets were melt kneaded at a cylinder set temperature of 190 ° C. to 240 ° C. at a discharge rate of 130 kg / hr using a 90 mm diameter single screw extruder with a T die, and a die temperature of 240 ° C.
  • the film was formed while being pressed between a cast roll discharged from a T die and touched with a cast roll adjusted to 95 ° C. and an elastic metal sleeve adjusted to 65 ° C. to obtain an acrylic resin film having a thickness of 175 ⁇ m. .
  • the haze of the acrylic resin film was 0.6%.
  • a hard coat layer forming composition manufactured by Aika Kogyo Co., Ltd., product name “Z-879” is made so that the solid content concentration becomes 30% with methyl ethyl ketone.
  • the diluted liquid was applied by a gravure coating method, dried at 80 ° C. for 1 minute, and then cured by ultraviolet irradiation to form a hard coat layer (thickness 3 ⁇ m).
  • a liquid obtained by diluting the composition for forming a low refractive index layer (manufactured by Aika Kogyo Co., Ltd., product name “Z-824”) to a solid content concentration of 30% on the main surface of the hard coat layer.
  • the film was applied by a gravure coating method, dried at 80 ° C. for 1 minute, and then cured by ultraviolet irradiation to form an antireflection layer (thickness 0.1 ⁇ m) to obtain a functional film.
  • the haze of the functional film was 0.3%.
  • the functional film covers the main surface opposite to the main surface on which the decorative layer of the glass substrate is arranged and all four end surfaces in contact with the main surface on the opposite side.
  • the glass substrate with the decorative layer was pressed against the functional film with the adhesive layer, and then pressurized air was introduced into the upper portion to 300 kPa to perform molding.
  • Example 2 A glass laminate was obtained in the same manner as in Example 1 except that the functional layer was formed as follows. ⁇ Formation of functional layer> A functional film was obtained in the same manner as in Example 1 except that the product name “Unidic ESS-108” manufactured by DIC Corporation was used as the hard coat layer forming composition. The haze of the functional film was 0.3%.
  • Example 3 A glass laminate was obtained in the same manner as in Example 1 except that the adhesive layer was formed as follows. [Formation of adhesive layer] On the main surface opposite to the main surface on which the functional layer of the functional film obtained above was formed, a polyester hot melt adhesive sheet (manufactured by Nitto Shinko Co., Ltd., product name “FB-”) was used. ML80 ”) was melted and laminated at 100 ° C. to form an adhesive layer (thickness 50 ⁇ m). The haze of the functional film with an adhesive layer was 66.1%.
  • Example 4 A glass laminate was obtained in the same manner as in Example 1 except that the adhesive layer was formed as follows. [Formation of adhesive layer] On the main surface opposite to the main surface on which the functional layer of the functional film is formed, using a roller laminating machine, an acrylic thermosetting pressure-sensitive adhesive sheet (manufactured by Fujimori Kogyo Co., Ltd., product name “Mastack (registered trademark) TS”) ) (Thickness 25 ⁇ m) was bonded to form a functional film with an adhesive layer. The haze of the functional film with an adhesive layer was 0.7%. The adhesive layer was cured by heat (130 ° C.) applied by vacuum / pressure forming, and the functional film and the glass substrate were joined.
  • an acrylic thermosetting pressure-sensitive adhesive sheet manufactured by Fujimori Kogyo Co., Ltd., product name “Mastack (registered trademark) TS”
  • Example 5 A functional film was obtained in the same manner as in Example 1.
  • [Formation of adhesive layer] On the main surface opposite to the main surface on which the functional layer of the functional film obtained above was formed, using a roller laminating machine, a urethane-epoxy UV curable adhesive sheet (product name “GFT50UT7, manufactured by DIC Corporation”). ]) (Thickness 50 ⁇ m) was bonded together to form a functional film with an adhesive layer. The haze of the functional film with an adhesive layer was 42.5%.
  • [Formation of decorative layer] In the same manner as in Example 1, a glass substrate with a decorative layer was obtained.
  • the functional film with an adhesive layer is irradiated with UV (integrated light quantity: 1500 mJ / cm 2 ), and before the adhesive layer is cured (within 30 minutes after UV irradiation), in the same manner as in Example 1, a vacuum / pressure forming machine ( A glass laminate was produced using NGF-0406-S) manufactured by Fuse Vacuum Co., Ltd. In addition, when about 30 minutes passed after UV irradiation, hardening of the contact bonding layer advanced and the functional film and the glass base material joined.
  • Example 6 A functional film was obtained in the same manner as in Example 1.
  • an acrylic UV curable hot melt adhesive sheet product name, manufactured by No Tape Industry Co., Ltd.
  • “Acrylic melt UV-120” thickness: 100 ⁇ m
  • the haze of the functional film with an adhesive layer was 0.8%.
  • [Formation of decorative layer] In the same manner as in Example 1, a glass substrate with a decorative layer was obtained.
  • Example 1 the glass laminate obtained by vacuum / pressure forming was irradiated with UV (integrated light amount: 300 mJ / cm 2 ), whereby the adhesive layer was cured and the functional film and the glass substrate were bonded.
  • UV integrated light amount: 300 mJ / cm 2
  • Comparative Example 2 With a decorative layer so that the functional film covers only the main surface opposite to the main surface on which the decorative layer of the glass substrate is arranged at the stage of heating to 80 ° C. during the production of the glass laminate A glass laminate was obtained in the same manner as in Example 1 except that the glass substrate was pressed against the functional film with an adhesive layer.
  • Example 3 A glass laminate was obtained in the same manner as in Example 1 except that the functional layer was formed as follows. ⁇ Formation of functional layer> A functional film was obtained in the same manner as in Example 1 except that the product name “Unidic EQS-1291” manufactured by DIC Corporation was used as the hard coat layer forming composition. The haze of the functional film was 0.3%.
  • Example 4 A glass laminate was obtained in the same manner as in Example 1 except that the adhesive layer was formed as follows.
  • Acrylic hot melt adhesive sheet product name “CS9862UA” manufactured by Nitto Denko Corporation
  • CS9862UA manufactured by Nitto Denko Corporation
  • the haze of the functional film with an adhesive layer was 0.6%.
  • Example 5 A glass laminate was obtained in the same manner as in Example 1 except that the adhesive layer was formed as follows. [Formation of adhesive layer] On the main surface opposite to the main surface on which the functional layer of the functional film is formed, a hot-melt adhesive sheet (product name: “18346” manufactured by Niei Kakko Co., Ltd.) is melted at 100 ° C. using a heat roller laminator. To form an adhesive layer (thickness: 50 ⁇ m). The haze of the functional film with an adhesive layer was 0.7%.
  • a hot-melt adhesive sheet product name: “18346” manufactured by Niei Kakko Co., Ltd.
  • Example 6 A glass laminate was obtained in the same manner as in Example 1 except that the adhesive layer was formed as follows. [Formation of adhesive layer] On the main surface opposite to the main surface on which the functional layer of the functional film is formed, a hot-melt adhesive sheet (manufactured by Nichiei Kako Co., Ltd., product name “18347”) is melted at 100 ° C. using a heat roller laminator. To form an adhesive layer (thickness: 50 ⁇ m). The haze of the functional film with an adhesive layer was 0.7%.
  • Example 7 A glass laminate was obtained in the same manner as in Example 1 except that the adhesive layer was formed as follows.
  • An acrylic adhesive sheet manufactured by Nichiei Kako Co., Ltd., pressure sensitive adhesive type, product name “G25” is bonded to the main surface opposite to the main surface on which the functional layer of the functional film is formed, and an adhesive layer (thickness) 25 ⁇ m) was formed.
  • the haze of the functional film with an adhesive layer (acrylic adhesive layer) was 0.8%.
  • Example 1 to 6 and Comparative Examples 1 to 7 the 120 ° C. crack elongation of the functional film and the 90 ° peel strength between the glass substrate and the functional film were measured as follows. Further, in Examples 1 to 6 and Comparative Examples 1 to 7, the edge portion and main surface portion of the glass laminate were evaluated for cracking, functional film cracking, and springback. In Examples 1 to 6 and Comparative Examples 1 to 7, the haze, total light transmittance, and reflectance of the glass laminate were measured as follows. These results are shown in Table 1. Table 1 also shows the haze of the functional film with an adhesive layer.
  • the “distance of the rubbing trace of the adhesive layer” means the maximum value selected from the measured values by measuring the vertical distance of the rubbing trace of the adhesive layer with respect to the edge of the glass laminate at the peripheral portion. .
  • haze The haze value was measured according to JIS K 7136: 2000. In addition, haze was measured in the location where the decoration layer is not provided.
  • Total light transmittance The total light transmittance of the glass laminate was measured according to JIS K 7375. The total light transmittance of the glass substrate was measured according to JIS R 3106. In addition, total light transmittance was measured in the location where the decoration layer is not provided.
  • the reflection spectrum (380 to 1050 nm) of the glass laminate was measured using a reflection spectrometer (manufactured by Filmetrics, model number “F20”), and the reflectance value at 550 nm was obtained. In addition, the reflectance was measured in the location where the decoration layer is not provided.
  • the cracking stress was calculated as follows. The appearance of the glass laminate was visually confirmed, and the degree of scattering of the glass laminate was evaluated according to the following five-stage criteria according to the degree of scattering.
  • FIG. 2 the photograph of the glass laminated body after the crack resistance test of the edge part of (a) Example 1, (b) Comparative example 1 and (c) Comparative example 2 was shown.
  • Cracking stress (kg ⁇ cm) height at which cracking occurs (cm) ⁇ weight of weight (kg) ⁇ Degree of scattering> A: Although the crack is generated in the impact portion, the glass substrate is bonded to the resin film, and the glass substrate is not scattered.
  • C The entire impact part is separated from the glass laminate or scattered as fragments and scattered.
  • D The glass substrate is cracked and a part of the glass substrate is scattered.
  • E The glass substrate is cracked and the glass. Most of the base material is scattered
  • edge part exposure is ⁇ % means the ratio of the length of the exposed edge part to the outer periphery of the edge part.
  • the crack resistance of the edge part was poor. Further, in the glass laminates of Examples 1 to 6 in which the functional film covers at least one main surface of the glass substrate and the end surface in contact with the glass substrate, the crack resistance of the main surface portion is comparative example 1 having no functional film. Compared to, it was much improved. In addition, the glass laminates of Examples 1 to 6 in which the functional film covered one main surface of the glass substrate and all of the end surfaces in contact with the glass substrate had good three-dimensional coverage, but the functional film was a glass substrate. The glass laminate of Comparative Example 2 covering only one main surface of the material had poor three-dimensional coverage.
  • the glass laminates of Examples 1 to 6 in which the glass substrate was coated with a functional film having a hard coat layer and an antireflection layer had a reflectivity of Comparative Example 1 (glass substrate) having no functional film. The antireflection property was good.
  • the glass laminates of Examples 1-2, 4 and 6 formed using a functional film with an adhesive layer having a haze of 3.0% or less have a haze of 3.0% or less and excellent transparency. It was.
  • the glass laminates of Examples 3 and 5 formed using a functional film with an adhesive layer with a haze exceeding 3.0% had high haze and poor transparency.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention se rapporte à un stratifié de verre comprenant un matériau de base en verre, une couche adhésive et un film fonctionnel, le film fonctionnel comprenant un film de résine thermoplastique et une couche fonctionnelle disposée sur au moins une surface principale du film de résine thermoplastique, le film fonctionnel présentant un allongement de fissure à 120 °C supérieur ou égal à 20 %, le film fonctionnel recouvrant de manière contiguë au moins une surface principale du matériau de base en verre et au moins une partie d'une face de bord qui est en contact avec la surface principale avec la couche adhésive intercalée entre elles, et la résistance au pelage à 90° entre le matériau de base en verre et le film fonctionnel étant supérieure ou égale à 25 N/25 mm. Il devient possible de proposer : un stratifié de verre comprenant un matériau de base en verre qui a un effet élevé pour empêcher la fissuration sur toute la surface du matériau de base en verre qui comprend une partie de bord, présente également une fonctionnalité spécifique et présente également une bonne aptitude au moulage ; un procédé permettant de produire le stratifié de verre ; et un panneau avant pour un dispositif d'affichage, dans lequel le stratifié de verre est utilisé.
PCT/JP2019/019483 2018-06-04 2019-05-16 Stratifié de verre, son procédé de production et panneau avant de dispositif d'affichage utilisant celui-ci WO2019235160A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020523590A JP7142090B2 (ja) 2018-06-04 2019-05-16 ガラス積層体、その製造方法、及びそれを用いた表示装置の前面板

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018107180 2018-06-04
JP2018-107180 2018-06-04

Publications (1)

Publication Number Publication Date
WO2019235160A1 true WO2019235160A1 (fr) 2019-12-12

Family

ID=68770342

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/019483 WO2019235160A1 (fr) 2018-06-04 2019-05-16 Stratifié de verre, son procédé de production et panneau avant de dispositif d'affichage utilisant celui-ci

Country Status (2)

Country Link
JP (1) JP7142090B2 (fr)
WO (1) WO2019235160A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021107000A1 (fr) * 2019-11-29 2021-06-03 大日本印刷株式会社 Corps multicouche, procédé de production d'un corps multicouche, film pour stratification et dispositif d'affichage d'image
WO2022092249A1 (fr) * 2020-10-30 2022-05-05 大日本印刷株式会社 Stratifié et dispositif d'affichage
WO2022137768A1 (fr) * 2020-12-25 2022-06-30 株式会社カネカ Stratifié et utilisation de celui-ci
WO2022185815A1 (fr) * 2021-03-05 2022-09-09 株式会社カネカ Stratifié et son procédé de production
KR20220134209A (ko) * 2021-03-26 2022-10-05 주식회사 아이델 테두리가 보강된 접합 시트
WO2022230892A1 (fr) * 2021-04-27 2022-11-03 日東電工株式会社 Corps stratifié
WO2023074250A1 (fr) * 2021-10-28 2023-05-04 日本電気硝子株式会社 Procédé de production d'un stratifié de résine de verre, et stratifié de résine de verre
WO2024095890A1 (fr) * 2022-10-31 2024-05-10 コニカミノルタ株式会社 Stratifié et dispositif d'affichage

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7092247B1 (ja) * 2021-09-24 2022-06-28 Ａｇｃ株式会社 積層体、及び積層体の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012214360A (ja) * 2011-03-31 2012-11-08 Hoya Corp 電子機器用カバーガラスの製造方法、電子機器用カバーガラス、及び電子機器に用いられるカバーガラス用ガラス基板、並びにタッチセンサモジュールの製造方法
JP2012254625A (ja) * 2011-05-13 2012-12-27 Nippon Electric Glass Co Ltd 積層体
JP2015223698A (ja) * 2014-05-26 2015-12-14 日立化成株式会社 透明基板
WO2017010483A1 (fr) * 2015-07-13 2017-01-19 大日本印刷株式会社 Film de sécurité et verre incurvé en trois dimensions doté du film de sécurité
WO2017026318A1 (fr) * 2015-08-10 2017-02-16 旭硝子株式会社 Feuille de verre à couche antisalissures

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012214360A (ja) * 2011-03-31 2012-11-08 Hoya Corp 電子機器用カバーガラスの製造方法、電子機器用カバーガラス、及び電子機器に用いられるカバーガラス用ガラス基板、並びにタッチセンサモジュールの製造方法
JP2012254625A (ja) * 2011-05-13 2012-12-27 Nippon Electric Glass Co Ltd 積層体
JP2015223698A (ja) * 2014-05-26 2015-12-14 日立化成株式会社 透明基板
WO2017010483A1 (fr) * 2015-07-13 2017-01-19 大日本印刷株式会社 Film de sécurité et verre incurvé en trois dimensions doté du film de sécurité
WO2017026318A1 (fr) * 2015-08-10 2017-02-16 旭硝子株式会社 Feuille de verre à couche antisalissures

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021107000A1 (fr) * 2019-11-29 2021-06-03 大日本印刷株式会社 Corps multicouche, procédé de production d'un corps multicouche, film pour stratification et dispositif d'affichage d'image
WO2022092249A1 (fr) * 2020-10-30 2022-05-05 大日本印刷株式会社 Stratifié et dispositif d'affichage
WO2022137768A1 (fr) * 2020-12-25 2022-06-30 株式会社カネカ Stratifié et utilisation de celui-ci
WO2022185815A1 (fr) * 2021-03-05 2022-09-09 株式会社カネカ Stratifié et son procédé de production
KR20220134209A (ko) * 2021-03-26 2022-10-05 주식회사 아이델 테두리가 보강된 접합 시트
KR102594264B1 (ko) * 2021-03-26 2023-10-30 주식회사 아이델 테두리가 보강된 접합 시트
WO2022230892A1 (fr) * 2021-04-27 2022-11-03 日東電工株式会社 Corps stratifié
WO2023074250A1 (fr) * 2021-10-28 2023-05-04 日本電気硝子株式会社 Procédé de production d'un stratifié de résine de verre, et stratifié de résine de verre
WO2024095890A1 (fr) * 2022-10-31 2024-05-10 コニカミノルタ株式会社 Stratifié et dispositif d'affichage

Also Published As

Publication number Publication date
JP7142090B2 (ja) 2022-09-26
JPWO2019235160A1 (ja) 2021-06-24

Similar Documents

Publication Publication Date Title
JP7142090B2 (ja) ガラス積層体、その製造方法、及びそれを用いた表示装置の前面板
JP5300385B2 (ja) 熱可塑性樹脂組成物とそれを用いたフィルム
WO2014002491A1 (fr) Matériau en résine non biréfringent et film
JP5666751B1 (ja) 光学樹脂材料および光学フィルム
WO2016139927A1 (fr) Composition de résine acrylique, produit moulé et film obtenu à partir de cellei-ci
WO2016158827A1 (fr) Corps en couches
JPWO2016199847A1 (ja) 積層フィルム
US20230416556A1 (en) Laminate and method for producing same
US11760855B2 (en) Acrylic resin film, laminated film, production method for laminated film, and molded article
US20230340218A1 (en) Laminate and use thereof
JPWO2017022704A1 (ja) 成型用コーティングフィルム
WO2020179524A1 (fr) Feuille de résine pour moulage très dur, article moulé mettant en œuvre celle-ci
JP2012056252A (ja) アクリル系樹脂フィルム
JP7245082B2 (ja) フィルム用アクリル樹脂組成物、及びアクリル樹脂フィルム
JP2015038173A (ja) 光硬化性樹脂組成物、積層シート、積層成形品及び積層成形品の製造方法
WO2021029266A1 (fr) Feuille de résine pour moulage et article moulé l'utilisant
JP2012177900A (ja) 積層体
JP7477281B2 (ja) 積層フィルム、成形体、及び車載ディスプレイ用前面板
CN116963907A (zh) 层叠体及其制造方法
JP2023145140A (ja) 樹脂成形体被覆用機能性フィルム、その製造方法、樹脂成形体、及びその製造方法
JP2023145141A (ja) 樹脂成形体被覆用機能性フィルム、その製造方法、樹脂成形体、及びその製造方法
WO2024057985A1 (fr) Stratifié antireflet et son procédé de fabrication
WO2022097677A1 (fr) Procédé de fabrication de produit de formation de courbure de feuille de résine, et produit de formation de courbure
TW202103965A (zh) 防眩性積層體
WO2021246295A1 (fr) Feuille de résine pour moulage, et article moulé mettant en œuvre celle-ci

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19816049

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020523590

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19816049

Country of ref document: EP

Kind code of ref document: A1