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WO2016158827A1 - Corps en couches - Google Patents

Corps en couches Download PDF

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Publication number
WO2016158827A1
WO2016158827A1 PCT/JP2016/059841 JP2016059841W WO2016158827A1 WO 2016158827 A1 WO2016158827 A1 WO 2016158827A1 JP 2016059841 W JP2016059841 W JP 2016059841W WO 2016158827 A1 WO2016158827 A1 WO 2016158827A1
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WO
WIPO (PCT)
Prior art keywords
layer
front plate
resin
adhesive sheet
monomer
Prior art date
Application number
PCT/JP2016/059841
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English (en)
Japanese (ja)
Inventor
大希 野澤
純 松井
谷口　浩一郎
Original Assignee
三菱樹脂株式会社
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 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Priority to CN201680020492.8A priority Critical patent/CN107531037B/zh
Priority to JP2017509955A priority patent/JP6508330B2/ja
Publication of WO2016158827A1 publication Critical patent/WO2016158827A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Definitions

  • the present invention relates to a laminate. Specifically, the present invention relates to a laminate that is used as a substrate material or a protective material, and can be suitably used as a cover material for a surface protection panel of an image display device, a mobile phone, a smartphone, a tablet device, a wearable terminal, or the like.
  • glass has been mainly used as a cover material for image display devices.
  • glass is easily broken by an impact and is heavy, substitution with a resin material has been studied.
  • the resin material as such a glass substitute material is mainly required to have impact resistance, surface hardness, and shape stability in a high temperature and high humidity environment.
  • Polycarbonate resin plates have transparency and are excellent in impact resistance and heat resistance, and thus are used for soundproof partitions, carports, signboards, glazing materials, lighting fixtures, and the like.
  • the surface hardness is low, it has a drawback of being easily scratched.
  • Patent Document 1 discloses a resin laminate obtained by subjecting a laminate obtained by coextruding a polycarbonate resin and an acrylic resin to a hard coat treatment.
  • Patent Document 2 discloses a resin laminate in which a methyl methacrylate-styrene copolymer resin (MS resin) is laminated on a polycarbonate resin.
  • MS resin methyl methacrylate-styrene copolymer resin
  • Patent Document 3 discloses a resin laminate in which the glass transition temperature difference and the water absorption difference of each layer in which a polycarbonate resin is laminated are defined.
  • a front plate having a polycarbonate resin layer and a layer made of a thermoplastic resin different from the polycarbonate resin is laminated on a base material via an adhesive sheet, for example, It is used as a surface protection panel and cover material.
  • the front plate having such a structure has a different coefficient of thermal expansion or moisture absorption between a polycarbonate resin and a thermoplastic resin different from the polycarbonate resin, for example, when placed in a high temperature and high humidity environment, one resin There was a problem that it was difficult to maintain the shape stability of the front plate, such as the layer absorbing moisture and changing dimensions.
  • the present invention relates to a laminate comprising a polycarbonate resin layer, a front plate having a thermoplastic resin layer different from the polycarbonate resin, and an adhesive sheet, and has excellent shape stability in a high temperature and high humidity environment.
  • a new laminate will be provided.
  • the present invention is a laminate including a front plate and an adhesive sheet, wherein the front plate includes a B layer mainly composed of a polycarbonate resin and a thermoplastic resin different from the polycarbonate resin as a main component.
  • the total thickness of the A layer is 10 to 250 ⁇ m
  • the ratio of the thickness (A) of the one A layer to the total thickness (T) of the A layer and the B layer is ((A) / (T)) is 0.05 to 0.40, and is determined by the formulas (1) and (2) described below, and the temperature is 85 ° C. and the humidity is 85% RH for 120 hours.
  • Proposed is a laminate in which the internal stress ( ⁇ ) of the front plate and the pressure-sensitive adhesive sheet is 0.47 MPa or less when the laminate is exposed.
  • the laminate proposed by the present invention includes a total thickness of a thermoplastic resin A layer mainly composed of a thermoplastic resin different from a polycarbonate resin in the configuration of the front plate, and A with respect to the total layer thickness of the A layer and the B layer.
  • a thickness ratio ((A) / (T)) for one layer and by defining the internal stress ( ⁇ ) within a predetermined range it has excellent shape stability in a high-temperature and high-humidity environment. Can be demonstrated. Therefore, the laminate proposed by the present invention can be suitably used as various substrate materials, protective materials, and the like, for example, by bonding them to a base material.
  • various substrate materials and protective materials as constituent materials for portable display devices such as mobile phone terminals, smartphones, portable electronic playground equipment, portable information terminals, tablet devices, mobile personal computers, wearable terminals, liquid crystal televisions, liquid crystal monitors
  • stationary display devices such as desktop personal computers, car navigation systems, and automobile meters.
  • the“ main component ”for each layer means a resin component having the highest content (mass%) in the resin composition forming each layer.
  • the total amount thereof corresponds to the content.
  • the“ main component ”of the polymer and its derivative means a monomer having the highest ratio among the monomer units constituting the polymer and its derivative.
  • a laminate according to an example of an embodiment of the present invention (hereinafter referred to as “the present laminate”) is a laminate including a front plate and an adhesive sheet. As described later, in a predetermined exposure test, the laminate and the front plate are adhered.
  • the laminate is characterized in that the internal stress of the sheet is within a predetermined range.
  • the front plate of this laminated body should just be provided with the B layer which has a polycarbonate-type resin as a main component, and the thermoplastic resin A layer which has a thermoplastic resin different from this polycarbonate-type resin as a main component.
  • the thermoplastic resin A layer which has a thermoplastic resin different from this polycarbonate-type resin as a main component.
  • thermoplastic resin A layer which has a thermoplastic resin different from this polycarbonate-type resin as a main component.
  • a front plate having a configuration in which an A layer is formed on one side or both sides of the B layer can be given.
  • the front plate preferably has characteristics such as transparency, rigidity, impact resistance, secondary workability, and high surface hardness.
  • the A layer is a layer mainly composed of a thermoplastic resin different from the polycarbonate resin.
  • “different” means that the types or composition ratios of the monomers constituting the polymer are not the same.
  • thermoplastic resin as the main component of the A layer is not particularly limited as long as it is different from the polycarbonate resin as the main component of the B layer described later.
  • polyethylene terephthalate polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate.
  • Polyester resins typified by aromatic polyesters such as poly-1,4-cyclohexylenedimethylene terephthalate, and aliphatic polyesters such as polylactic acid polymers, polyolefin resins such as polyethylene, polypropylene, and cycloolefin resins , Polycarbonate resin, acrylic resin, polystyrene resin, polyamide resin, polyether resin, polyurethane resin, polyphenylene sulfide resin, polyesteramide resin, polyether Steal resin, vinyl chloride resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, modified polyphenylene ether resin, polyarylate resin, polysulfone resin, polyetherimide resin, polyamideimide resin , Polyimide resins and copolymers containing these as main components, or mixtures of these resins. These may be one kind or a mixture of two or more kinds.
  • polycarbonate resin as a main component of A layer, what is necessary is just different from the polycarbonate-type resin used as the main component of B layer mentioned later, for example, aliphatic polycarbonate, alicyclic polycarbonate, and bisphenol C are contained. And aromatic polycarbonate.
  • the A layer is a surface layer
  • a resin having a higher hardness than the B layer it is preferable to select a resin having a higher hardness than the B layer.
  • an acrylic resin (a1) described later or a polycarbonate resin (a3) having a specific structure can be used.
  • a layer containing an acrylic resin (a1) as a main component resin can be exemplified.
  • the A layer comprises an acrylic resin (a1), a copolymer having an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic anhydride monomer unit.
  • a2 a layer containing a polycarbonate resin (a3) containing a structural unit derived from a dihydroxy compound in a part of the structure as a main component resin can also be mentioned.
  • the acrylic resin (a1) is a (co) polymer obtained by polymerizing a (meth) acrylic acid ester monomer unit as a main component and a derivative thereof.
  • (meth) acrylic acid ester monomer unit is meant to include an acrylic acid ester monomer unit or a methacrylic acid ester monomer unit.
  • Examples of the (meth) acrylic acid ester monomer unit include, for example, methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl.
  • the acrylic resin (a1) has a methyl methacrylate monomer, a methacrylic acid monomer, an acrylic acid monomer, a maleic anhydride monomer, and an aromatic vinyl monomer from the viewpoint of reducing internal stress.
  • a copolymer with at least one of a monomer and a vinyl cyanide monomer can be suitably used.
  • the three-dimensional structure of the (meth) acrylic acid ester monomer unit is preferred because the higher the proportion of the syndiotactic structure, the higher the glass transition temperature and the better the heat resistance.
  • the triad fractions of mm, mr, and rr those having a three-dimensional structure having the highest molar ratio of rr can be preferably used. This triad fraction can be measured by a known method using a nuclear magnetic resonance measuring apparatus (1H-NMR).
  • the A layer is preferably a layer containing the acrylic resin (a1) and the copolymer (a2). Among them, it is preferable to form the A layer by mixing the acrylic resin (a1) and the copolymer (a2).
  • the copolymer (a2) is a copolymer having an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic anhydride monomer unit.
  • aromatic vinyl monomer unit examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, ⁇ - Examples include units derived from styrene monomers such as methylstyrene and ⁇ -methyl-p-methylstyrene. These aromatic vinyl monomer units can be used alone or in combination of two or more. Of these, styrene units and ⁇ -methylstyrene units are preferred. Styrene monomer units are preferred because they are easily available industrially and are economical, and ⁇ -methylstyrene monomer units are preferred because they can improve the glass transition temperature.
  • (meth) acrylic acid ester monomer unit examples include methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, and isobornyl methacrylate. Mention may be made of units derived from ester monomers and acrylic ester monomers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate and decyl acrylate. These (meth) acrylic acid ester monomer units can be used alone or in combination of two or more. Among these, a methyl methacrylate monomer unit is preferable from the viewpoint of compatibility with the acrylic resin (a1) and appearance.
  • Examples of the “unsaturated dicarboxylic acid anhydride monomer unit” include units derived from respective anhydride monomers such as maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, aconitic acid anhydride and the like. be able to. These unsaturated dicarboxylic acid anhydride monomer units can be used alone or in combination of two or more. Among these, a maleic anhydride monomer unit is preferable from the viewpoint of compatibility with the acrylic resin (a1) and transparency.
  • the constituent unit of the copolymer (a2) is preferably 45 to 85% by mass of an aromatic vinyl monomer unit, 4 to 45% by mass of a (meth) acrylic acid ester monomer unit, an unsaturated dicarboxylic acid anhydride unit. 8 to 20% by mass of a monomer unit, more preferably 55 to 85% by mass of an aromatic vinyl monomer unit, 5 to 30% by mass of a (meth) acrylic acid ester monomer unit, an unsaturated dicarboxylic acid anhydride unit It is in the range of 10 to 18% by mass of the monomer unit.
  • the structural unit of the copolymer (a2) can be qualitatively and quantitatively analyzed by a known method, for example, a nuclear magnetic resonance (NMR) measuring device or other instrumental analyzer.
  • NMR nuclear magnetic resonance
  • the aromatic vinyl monomer unit occupies 45% by mass or more, particularly 55% by mass or more among all the structural units of the copolymer (a2), the thermal stability is improved, and the acrylic resin (a1) and When mixed, a good appearance can be obtained, and water absorption can be reduced, which is preferable.
  • a (meth) acrylic acid ester monomer unit occupies 4 mass% or more among all the structural units of a copolymer (a2), especially 5 mass% or more, it will be a phase with acrylic resin (a1). It is preferable because the solubility is improved and the transparency is improved.
  • unsaturated dicarboxylic anhydride monomer unit occupies 8 mass% or more among all the structural units of a copolymer (a2), especially 10 mass% or more, it is a phase with acrylic resin (a1). It is preferable because the solubility is improved and the transparency and heat resistance are improved.
  • the ratio of the aromatic vinyl monomer unit is 85% by mass or less in the total constituent units of the copolymer (a2), the heat resistance is maintained while maintaining the miscibility with the acrylic resin (a1). This is preferable because it can improve water resistance and reduce water absorption.
  • the ratio of a (meth) acrylic acid ester monomer unit is 45 mass% or less among all the structural units of a copolymer (a2), especially if it is 30 mass% or less, with acrylic resin (a1) It is preferable because water absorption can be suppressed while ensuring compatibility.
  • the proportion of the unsaturated dicarboxylic acid anhydride unit is 20% by mass or less, particularly 18% by mass or less among all the structural units of the copolymer (a2), the compatibility with the acrylic resin (a1) is improved. While ensuring, improvement in thermal stability and water absorption can be suppressed, which is preferable.
  • the copolymer (a2) includes the above three monomer units, that is, an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic anhydride monomer unit.
  • Other copolymerizable units may be contained. However, the content is preferably 5% by mass or less.
  • the “other copolymerizable units” include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, N-methylmaleimide, and N-ethyl.
  • N-alkylmaleimide monomers such as maleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-arylmaleimide monomers such as N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, etc. Mention may be made of units derived from a monomer. These copolymerizable units can be used alone or in combination of two or more.
  • the copolymer (a2) preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 100,000 to 200,000 as measured by gel permeation chromatography (GPC).
  • Mw polystyrene-equivalent weight average molecular weight
  • GPC gel permeation chromatography
  • the production method of the copolymer (a2) can be produced by a known polymerization method and is not particularly limited.
  • solution polymerization, bulk polymerization, and the like can be applied, and batch, semi-batch, and continuous methods can be appropriately employed as the polymerization process.
  • this laminate there are few by-products, and it is easy to control molecular weight adjustment and transparency, so that a batch polymerization process can be suitably used in solution polymerization.
  • (a1) / (a2) 70/30 to 40/60, particularly 70/30 to 60 / More preferably, it is 40.
  • the A layer is also preferably composed mainly of a polycarbonate resin (a3) having a specific structure. Thereby, a high surface hardness can be imparted to the laminate.
  • the polycarbonate resin (a3) is a polycarbonate resin containing a structural unit derived from a dihydroxy compound represented by the following (Chemical Formula 1) in a part of the structure.
  • Examples of the dihydroxy compound represented by the above (Chemical Formula 1) include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship. These may be used alone or in combination of two or more.
  • the dihydroxy compound represented by the above is an ether diol that can be produced from a saccharide using a biogenic material as a raw material.
  • isosorbide can be produced at low cost by hydrogenating and dehydrating D-glucose obtained from starch, and can be obtained in abundant resources. For these reasons, isosorbide is most preferred.
  • the content ratio of the structural unit derived from the dihydroxy compound represented by the above (Chemical Formula 1) is preferably 50 mol% or more, and 60 mol% or more. More preferably, it is preferably 90 mol% or less, and more preferably 80 mol% or less.
  • the content ratio of the structural unit derived from the dihydroxy compound represented by (Chemical Formula 1) is in the above range, and thus the hardness of the polycarbonate resin (a3) is:
  • the intermediate value between the aromatic polycarbonate resin and the acrylic resin is taken, and the punching workability is dramatically improved as compared with the display front plate in which the acrylic resin layer is arranged on the surface layer. More specifically, when the content of the structural unit is 90 mol% or less, the surface hardness and heat resistance are excellent, and the impact resistance and the lowering of interlayer adhesion with the B layer described later can be suppressed.
  • this laminated body can obtain further sufficient surface hardness by disposing a hard coat layer on at least one surface, and is suitable for any use of a display front plate and a transparent building material.
  • the polycarbonate resin (a3) may have a structural unit other than the structural unit.
  • a structural unit derived from an aliphatic dihydroxy compound described in International Publication No. 2004/111106 pamphlet The structural unit derived from the alicyclic dihydroxy compound as described in 2007/148604 pamphlet can be mentioned.
  • structural units derived from the above aliphatic dihydroxy compounds selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. It is preferable to have a structural unit derived from at least one dihydroxy compound.
  • the structural units derived from the above alicyclic dihydroxy compounds those containing a 5-membered ring structure or a 6-membered ring structure are preferable.
  • the six-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond.
  • the heat resistance of the obtained polycarbonate can be increased.
  • the number of carbon atoms contained in the alicyclic dihydroxy compound is usually preferably 70 or less, more preferably 50 or less, and further preferably 30 or less.
  • Examples of the alicyclic dihydroxy compound containing the 5-membered ring structure or the 6-membered ring structure include those described in the above-mentioned International Publication No. 2007/148604.
  • cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol and pentacyclopentadecanedimethanol can be preferably exemplified.
  • cyclohexanedimethanol is preferably selected, and 1,4-cyclohexanedimethanol is particularly preferable.
  • tricyclododecane secondary methanol when importance is attached to heat resistance and interlayer adhesion with the B layer described later, it is preferable to select tricyclododecane secondary methanol.
  • the polycarbonate resin (a3) used for the A layer can be produced by a generally used polymerization method, and may be either a phosgene method or a transesterification method in which it reacts with a carbonic acid diester.
  • a polymerization catalyst in the presence of a polymerization catalyst, a dihydroxy compound represented by the above (Chemical Formula 1) in a part of the structure, an aliphatic and / or alicyclic hydroxy compound, and other dihydroxy compounds used as necessary And a transesterification method in which carbonic acid diester is reacted.
  • the transesterification method includes a dihydroxy compound represented by the above (Chemical Formula 1) as a part of the structure, an aliphatic and / or alicyclic hydroxy compound, other dihydroxy compounds used as necessary, and a carbonic acid diester. Is a basic catalyst, and further, an acidic substance that neutralizes the basic catalyst is added to perform a transesterification reaction.
  • carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Is mentioned. Of these, diphenyl carbonate is particularly preferably used.
  • the molecular weight of the polycarbonate resin (a3) can be represented by a reduced viscosity.
  • the lower limit of the reduced viscosity is preferably 0.20 dl / g or more, more preferably 0.30 dL / g or more, and 0.35 dL / g or more.
  • the upper limit of the reduced viscosity is preferably 1.20 dL / g or less, more preferably 1.00 dL / g or less, and even more preferably 0.80 dL / g or less. If the reduced viscosity of the polycarbonate resin is too low, the mechanical strength of the molded product may be small. If it is too large, the fluidity at the time of molding tends to decrease, and the productivity and moldability tend to decrease.
  • the layer A can appropriately contain various additives, modifiers and the like as long as the effects of the present invention are not impaired.
  • the additive include an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a flame retardant, and a colorant.
  • the modifier include impact resistance improvers, compatibilizers and antistatic agents.
  • B layer is a layer which shares the function which expresses especially impact resistance, heat resistance, etc. among the functions of this laminated body.
  • the polycarbonate resin (b1) can be used alone as a main component resin, and various modifiers (b2) described later are mixed with the polycarbonate resin (b1) as the main component resin. It can also be used.
  • Polycarbonate resin (b1)) examples include aromatic polycarbonate resins and aliphatic polycarbonate resins.
  • the polycarbonate resin (b1) may be a homopolymer or a copolymer with another copolymerizable monomer.
  • the structure of the polycarbonate resin (b1) may be a branched structure, a linear structure, or a mixture of a branched structure and a linear structure.
  • the polycarbonate resin (b1) may be obtained by any known production method such as a phosgene method, a transesterification method, or a pyridine method.
  • the weight-average molecular weight of the polycarbonate resin (b1) may be 10,000 to 100,000, particularly 20,000 or more and 40,000 or less, particularly 22,000 or more and 28,000 or less. Further preferred. As the polycarbonate resin (b1), only one kind can be used alone, or two or more kinds having different weight average molecular weights can be used in combination. If the weight average molecular weight of polycarbonate-type resin (b1) exists in the said range, since impact resistance is ensured and extrusion moldability is also favorable, it is preferable.
  • the polycarbonate resin (b1) and the modifier (b2) are preferably mixed and used to form the B layer.
  • a specific acrylic resin (b2) can be exemplified.
  • the acrylic resin (b2) is preferably an acrylic copolymer composed of 5 to 80% by mass of aromatic (meth) acrylate monomer units and 95 to 20% by mass of methyl methacrylate monomer units.
  • the acrylic resin (b2) if the content ratio of the aromatic (meth) acrylate monomer unit and the methyl methacrylate monomer unit is within the above range, the compatibility and the surface hardness with the polycarbonate resin (b1). Since the improvement effect can be expressed, it is preferable.
  • the aromatic (meth) acrylate monomer unit is preferably 10 to 70% by mass and the methyl methacrylate monomer unit 90 to 30% by mass, and the aromatic (meth) acrylate monomer unit 25 to More preferably, it is 60% by mass and 75 to 40% by mass of methyl methacrylate monomer units.
  • aromatic (meth) acrylate monomer unit examples include phenyl (meth) acrylate and benzyl (meth) acrylate. These can be used alone or in combination of two or more. Of these, phenyl methacrylate and benzyl methacrylate are preferred, and phenyl methacrylate is more preferred from the viewpoint of compatibility with the polycarbonate resin (b1).
  • the acrylic resin (b2) can contain other copolymerizable monomer units other than the aromatic (meth) acrylate monomer unit and the methyl methacrylate monomer unit, if necessary. When other monomer units are contained, the content is preferably 0.1 to 10% by mass in the acrylic resin (b2).
  • the acrylic resin (b2) preferably has a polystyrene-reduced weight average molecular weight (Mw) of 5,000 to 30,000 as measured by gel permeation chromatography (GPC).
  • Mw weight average molecular weight
  • the compatibility with the polycarbonate resin (b1) is good, and the moldability and surface hardness improvement effect and appearance of the obtained B layer are good. It is preferable because it is excellent.
  • the range of the weight average molecular weight (Mw) of the acrylic resin (b2) is more preferably 10,000 to 28,000.
  • the polycarbonate resin as the main component resin of the B layer is preferably as the glass transition temperature is higher. It is particularly preferable to use the homopolymer (b1). On the other hand, when importance is attached to the surface hardness of the laminate, those containing the polycarbonate resin (b1) and the modifier (b2) are preferable.
  • the B layer can be blended with the above-described various additives and other resins as long as the effects of the present invention are not impaired.
  • the additive include an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a flame retardant, a colorant, and a hydrolysis inhibitor.
  • the glass transition temperature of the A layer is preferably as small as the difference from the glass transition temperature of the B layer from the viewpoint of suppressing internal stress generated in a high-temperature and high-humidity environment, and is preferably 100 to 140 ° C. Above or 140 ° C. or less , among them 115 ° C. or more, more preferably 120 ° C. or more.
  • the glass transition temperature of the B layer is preferably as high as possible from the viewpoint of suppressing internal stress generated in a high-temperature and high-humidity environment, preferably 100 ° C. to 160 ° C., and more preferably 120 ° C. or more or 155 ° C. or less. Further preferred.
  • the absolute value of the difference between the glass transition temperature of the A layer and the glass transition temperature of the B layer is 30 ° C. or less, the warpage of the front plate after the high temperature and high humidity environment test at a temperature of 85 ° C. and a humidity of 85% RH It is preferable because it can be further suppressed.
  • the absolute value of the difference is preferably 30 ° C. or less, more preferably 20 ° C. or less, more preferably 10 ° C. or less, and particularly preferably 5 ° C. or less. More preferably.
  • the glass transition temperature is a value obtained by measuring at a heating rate of 10 ° C./min according to JIS K7121 using a differential scanning calorimeter.
  • the glass transition temperature can also be measured by other known instrument analyzers such as a dynamic viscoelastic device.
  • the front plate may further include a hard coat layer (C layer) as an outermost surface layer on one side or both sides.
  • the hard coat layer (C layer) may not be provided.
  • the hard coat layer (C layer) is a layer that imparts excellent surface hardness and scratch resistance to the front plate.
  • the hard coat layer (C layer) is cured by irradiating an energy beam such as an electron beam, radiation, or ultraviolet ray to cure the curable resin composition for forming the C layer, or curing for forming the C layer by heating. It can be formed by curing the functional resin composition. Among these, from the viewpoint of molding time and productivity, it is preferable to form a hard coat layer (C layer) by irradiating ultraviolet rays to cure the C layer forming curable resin composition.
  • the curable resin composition for forming the C layer for forming the hard coat layer (C layer) may be a resin composition containing the curable resin C1. As described above, when the C layer forming curable resin composition is cured by irradiating ultraviolet rays, the C layer forming curable resin composition starts photopolymerization in addition to the curable resin C1. A resin composition containing an agent is preferred.
  • curable resin C1 examples include, for example, acrylate compounds, urethane acrylate compounds, epoxy acrylate compounds, carboxyl group-modified epoxy acrylate compounds, polyester acrylate compounds, copolymer acrylates, alicyclic epoxy resins, glycidyl ether epoxy resins. , Vinyl ether compounds, oxetane compounds and the like. These curable resins can be used alone or in combination of two or more.
  • the curable resin C1 that imparts more excellent surface hardness
  • a polyfunctional acrylate compound a polyfunctional urethane acrylate compound, a polyfunctional epoxy acrylate compound, or the like
  • a radical polymerization curable compound an alkoxysilane, an alkylalkoxysilane, etc.
  • a thermopolymerizable curable compound can be mentioned, and further, an organic / inorganic composite curable resin composition obtained by adding an inorganic component to the curable resin may be used.
  • An organic / inorganic hybrid curable resin composition may be mentioned as a curable resin composition for forming a C layer that gives particularly excellent surface hardness.
  • the organic / inorganic hybrid curable resin composition include those composed of a curable resin composition containing an inorganic component having a reactive functional group in the curable resin. Utilizing such an inorganic component having a reactive functional group, for example, an organic / inorganic composite in which this inorganic component is copolymerized and crosslinked with a radical polymerizable monomer, so that the organic binder simply contains the inorganic component.
  • an organic / inorganic hybrid curable resin composition containing ultraviolet-reactive colloidal silica as an inorganic component having a reactive functional group can be mentioned as a more preferable example.
  • the concentration of the inorganic component contained in the hard coat layer (C layer), particularly the inorganic component having a reactive functional group is preferably 10 to 65% by mass. If the said density
  • the hard coat layer (C layer) can be filled with an inorganic component, particularly an inorganic component having a reactive functional group, with excellent surface hardness. Can be effectively imparted.
  • the concentration is preferably 10 to 65% by mass, more preferably 20% by mass or more and 60% by mass or less, and particularly preferably 40% by mass or more and 55% by mass or less.
  • the main component resin of a hard-coat layer (C layer) is an adhesive sheet.
  • the same resin as the main component resin is preferred.
  • the main component resin of the pressure-sensitive adhesive sheet is an acrylic resin
  • the main component resin of the hard coat layer (C layer) is also preferably an acrylic resin.
  • the curable resin composition for forming the C layer contains a photopolymerization initiator, and the photopolymerization initiator absorbs ultraviolet rays to be excited and activated to cause a polymerization reaction, thereby curing the ultraviolet curable resin. Those where the reaction takes place are preferred.
  • the photopolymerization initiator include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyldimethyl ketals, ⁇ hydroxyalkylphenones, ⁇ -hydroxyacetophenones, hydroxyketones, aminoalkylphenones, acylphosphine oxides, and the like. Can be mentioned.
  • ⁇ -hydroxyalkylphenones are preferred because they hardly cause yellowing during curing and a transparent cured product is obtained.
  • aminoalkylphenones are preferable because they have very high reactivity and a cured product having excellent hardness can be obtained.
  • the said photoinitiator can be used individually by 1 type or in combination of 2 or more types.
  • the addition amount of the photopolymerization initiator is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin.
  • the curable resin composition for forming a C layer can contain a leveling agent as a surface adjustment component.
  • the leveling agent include silicone leveling agents and acrylic leveling agents.
  • those having a reactive functional group at the terminal are preferable, and those having a reactive functional group having two or more functionalities are more preferable.
  • Specific examples include polyether-modified polydimethylsiloxane having an acrylic group having double bonds at both ends, and a polyester-modified polydimethylsiloxane having acrylic groups having two double bonds at the ends. be able to.
  • polyester-modified polydimethylsiloxane having an acrylic group that has a stable haze value and contributes to improvement of scratch resistance is particularly preferable.
  • the curable resin composition for forming the C layer includes, for example, a lubricant such as a silicon compound, a fluorine compound, or a mixed compound thereof, an antioxidant, an ultraviolet absorber, and an antistatic agent.
  • a lubricant such as a silicon compound, a fluorine compound, or a mixed compound thereof
  • an antioxidant such as a sulfur compound
  • an ultraviolet absorber such as a sulfur compound
  • an antistatic agent such as sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate
  • the thickness of the hard coat layer (C layer) is not particularly limited.
  • the thickness is preferably 1 ⁇ m to 30 ⁇ m, more preferably 3 ⁇ m or more and 25 ⁇ m or less, especially 5 ⁇ m or more and 20 ⁇ m or less, and particularly preferably 7 ⁇ m or more and 15 ⁇ m or less.
  • the thickness of the hard coat layer (C layer) is in the above range, scratch resistance can be imparted and cracks due to stress are unlikely to occur, which is preferable.
  • the thickness of each hard coat layer may be the same or different.
  • the thickness of each hard coat layer is in the range of 7 ⁇ m to 15 ⁇ m, and the hard coat layer on the surface of the acrylic resin layer (A layer) is hard coat on the surface of the polycarbonate resin layer (B layer).
  • the thickness is preferably equal to or greater than the thickness of the layer.
  • the front plate may have a layer structure having a thermoplastic resin layer (A layer) different from the polycarbonate resin on one side or both sides of the polycarbonate resin layer (B layer), and includes other layers. May be.
  • a layer thermoplastic resin layer
  • it may be a laminate having an acrylic resin layer (A layer) on one side or both sides of a polycarbonate resin layer (B layer), and other layers may be provided.
  • a hard coat layer (C layer) may be provided on the single-sided outermost surface or the double-sided outermost surface.
  • the layers may have the same composition or different compositions.
  • (A) / (B), (A) / (B) / (A), (C) / (A) / (B), (C) / (A) / (B) / (C ), (C) / (A) / (B) / (A) / (C) configurations are preferred.
  • (viewing side) (C) / (A) / (B) / (C) (light source side) or (viewing side) (C) / (A) / (B) It is more preferable to arrange on the light source side.
  • the thickness (a 1 ) of the front plate is not particularly limited, and is preferably, for example, 0.1 mm to 3.0 mm, particularly 1.5 mm or less, of which 0.15 mm or more or 1 More preferably, it is 2 mm or less.
  • the thickness (a 1 ) of the front plate has a preferable range depending on the application application of the laminate.
  • it is preferably 0.1 to 2.0 mm, 0.15 mm or more or 1.5 mm or less, 0.2 mm or more or 0.8 mm or less, More preferably, it is 0.2 mm or more or 0.7 mm or less. If it is in this range, it is preferable because it is excellent in lightness and rigidity and shape stability in a high temperature and high humidity environment.
  • the thickness of the front plate ( a 1 ) is preferably from 0.1 mm to 0.6 mm, more preferably from 0.15 mm to 0.5 mm.
  • the thickness (a 1 ) of the front plate is thinner in terms of reducing the internal stress ( ⁇ ) of the laminate.
  • the thickness (a 1 ) of the front plate is preferably 0.7 mm or less, more preferably 0.6 mm or less, and further preferably 0.5 mm or less.
  • the total thickness of layer A is preferably as small as possible in order to suppress internal stress generated in the high temperature and high humidity environment of the laminate, and further shape stability.
  • the thickness is preferably a certain thickness or more, and is preferably adjusted within an appropriate range according to the intended physical properties. From such a viewpoint, the total thickness of the A layer is preferably 10 ⁇ m to 250 ⁇ m, more preferably 30 ⁇ m or more and 200 ⁇ m or less, and particularly preferably 50 ⁇ m or more or 150 ⁇ m or less.
  • the total thickness for the two layers is the total thickness of the A layer.
  • the thermoplastic resin relative to the total thickness (T) of the thermoplastic resin layer A and the polycarbonate resin layer B layer.
  • the ratio (A) / (T) of the thickness (A) of layer A to layer 1 is preferably 0.05 to 0.40, more preferably 0.07 or more and 0.35 or less. More preferably, it is 10 or more or 0.30 or less.
  • the thickness of each A layer is mutually the same thickness.
  • the elastic modulus (E 1 ) of the front plate is preferably 1500 to 4500 (MPa) from the viewpoint of reducing the internal stress of the laminate in a high temperature and high humidity environment and improving the shape stability. 1800 or more or 4000 (MPa) or less, more preferably 2000 or more or 3500 (MPa) or less.
  • the front plate is allowed to stand for 120 hours in a temperature 85 ° C. and humidity 85% RH environment, and then the temperature 23 ° C.
  • the average value of the amount of warping at the four corners after leaving for 4 hours in a humidity 50% RH environment is preferably 1.5 mm or less, more preferably 1.0 mm or less, and most preferably 0.3 mm or less. Particularly preferred.
  • the lower limit value of the warpage amount ( ⁇ ) is preferably 0.01 mm or more, and more preferably 0.05 mm or more.
  • the total thickness of the A layer is reduced and the thickness of one A layer with respect to the total layer thickness (T) of the A layer and the B layer (A ) Ratio ((A) / (T)) and a method of balancing the elastic modulus, cure shrinkage, and thickness of the hard coat layers on the front and back sides are preferably employed.
  • a method of balancing the elastic modulus, cure shrinkage, and thickness of the hard coat layers on the front and back sides are preferably employed.
  • a film forming method for laminating the A layer and the B layer a known method can be adopted.
  • an extrusion casting method using a T-die having a melt mixing facility such as a single-screw extruder, a multi-screw extruder, a Banbury mixer, a kneader, etc. can be suitably used from the viewpoints of handling properties and productivity.
  • a method of co-extrusion molding of melt-kneaded resin with a T-die having a feed block or a multi-manifold can be suitably used.
  • a forming roll such as a metal elastic roll or a polishing roll
  • the molding temperature in the extrusion casting method using a T die is appropriately adjusted depending on the flow characteristics and film-forming properties of the resin composition used, but is generally 300 ° C. or less, preferably 230 to 260 ° C.
  • the molding roll temperature is approximately 90 to 160 ° C., preferably 95 to 150 ° C.
  • each layer extruder when each layer is extruded, a single screw extruder or a multi-screw extruder can be suitably used, and each layer extruder preferably has a vent function and a filter function.
  • the vent function is preferable because it can be used for drying the resin composition used for each layer, removing a small amount of volatile components, and the like, and a laminate having few defects such as bubbles can be obtained.
  • filter functions there are various types, and specific examples include a leaf disk filter, a back disk filter, a cone filter, a candle filter, and a cylindrical filter. Among them, a leaf disk filter that can easily secure an effective filtration area is preferable.
  • the filter function can remove foreign matters, minute gels, and the like, and a laminated body with few appearance defects can be obtained.
  • the resin composition for forming each layer may be used by mixing each component in advance with a mixer such as a tumbler, V-type blender, Banbury mixer, extruder, etc.
  • the components may be supplied directly, or the components weighed separately may be supplied to each supply port of an extruder having two or more supply ports.
  • the mixing method of various additives can use a well-known method. For example, (a) a master batch in which various additives are mixed in a suitable base resin at a high concentration (typically about 3 to 60% by mass) is prepared separately, and the concentration is added to the resin used. And (b) a method of directly mixing various additives into the resin to be used.
  • resin layer surface After coating the surface of layer A or layer B (referred to as “resin layer surface”) laminated as described above as a paint in which the above-described curable resin composition for C layer formation is dissolved or dispersed in an organic solvent
  • a method of forming and laminating on the surface of the resin layer can be exemplified. However, it is not limited to this method.
  • a method of laminating on the surface of the resin layer a known method can be used. For example, laminating method using cover film, dip coating method, natural coating method, reverse coating method, comma coater method, roll coating method, spin coating method, wire bar method, extrusion method, curtain coating method, spray coating method, The gravure coat method etc. are mentioned.
  • a method of using a transfer sheet in which a hard coat layer (C layer) is formed on a release layer and laminating the hard coat layer (C layer) on the surface of the resin layer may be employed.
  • various surface treatments such as corona treatment, plasma treatment and primer treatment can be performed on the resin layer surface.
  • the curable resin composition is cured by irradiating energy rays such as electron beam, radiation, and ultraviolet rays, or
  • the curable resin composition is preferably cured by heating.
  • curing by ultraviolet irradiation is preferable.
  • the light source that emits ultraviolet rays for example, an electrodeless high-pressure mercury lamp, an electroded high-pressure mercury lamp, an electrodeless metal halide lamp, an electroded metal halide lamp, a xenon lamp, an ultrahigh-pressure mercury lamp, or a mercury xenon lamp can be used.
  • an electrodeless high-pressure mercury lamp is preferable because it is easy to obtain ultraviolet rays with high illuminance and is advantageous for curing an ultraviolet curable resin.
  • the C-layer-forming curable resin composition is made of an ultraviolet curable resin and cured by irradiating with ultraviolet rays, since the transparency to the ultraviolet rays is high, the internal curing of the curable resin composition proceeds quickly. In some cases, the curing of the surface of the curable resin composition is delayed due to the inhibition effect of oxygen (referred to as oxygen damage).
  • oxygen damage it is preferable to irradiate the resin composition with a nitrogen gas atmosphere by supplying nitrogen gas and then irradiate with ultraviolet rays, since the curing of the surface can proceed rapidly together with the inside of the resin composition. .
  • the resin laminate may be heat treated.
  • the resin laminate is heat-treated in a temperature range lower by 5 ° C. to 30 ° C. than the glass transition temperature of the A layer, particularly in a temperature range lower by 5 ° C. to 25 ° C., particularly in a temperature range lower by 5 ° C.-20 ° C. Is preferred.
  • the outermost surface on one side or both sides of the front plate can be subjected to any one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment.
  • Each processing method is not particularly limited, and a known method can be used. For example, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be exemplified.
  • the composition of the pressure-sensitive adhesive sheet used in the laminate is not particularly limited. However, it is preferable to use a pressure-sensitive adhesive sheet obtained by crosslinking a pressure-sensitive adhesive composition containing an acrylic resin as a main component resin from the viewpoint of adhesiveness, transparency, weather resistance, and the like.
  • the pressure-sensitive adhesive composition preferably contains an acrylic resin, a crosslinking monomer, and, if necessary, a crosslinking initiator, a reaction catalyst, and the like.
  • an acrylate polymer (including a copolymer) is preferable.
  • Acrylic acid ester polymers (including copolymers) have properties such as glass transition temperature (Tg) depending on the types and composition ratios of acrylic monomers and methacrylic monomers used to polymerize them, and polymerization conditions. It is possible to adjust appropriately.
  • acrylic monomer and methacrylic monomer used for polymerizing the acrylate polymer examples include 2-ethylhexyl acrylate, n-octyl acrylate, n-butyl acrylate, ethyl acrylate, methyl methacrylate, and the like.
  • Vinyl acetate, hydroxyethyl acrylate, acrylic acid, glycidyl acrylate, acrylamide, acrylonitrile, methacrylonitrile, fluorine acrylate, silicone acrylate, etc., which are copolymerized with a hydrophilic group or an organic functional group, can also be used.
  • (meth) acrylic acid alkyl ester copolymers are particularly preferable.
  • the (meth) acrylate used for forming the (meth) acrylic acid alkyl ester copolymer that is, the alkyl acrylate or alkyl methacrylate component
  • the alkyl group is n-octyl, isooctyl, 2-ethylhexyl, n-butyl
  • alkyl acrylate or alkyl methacrylate which is any one of isobutyl, methyl, ethyl and isopropyl, or a mixture of two or more selected from these is preferable.
  • an acrylate or methacrylate having an organic functional group such as a carboxyl group, a hydroxyl group, or a glycidyl group
  • an acrylate or methacrylate having an organic functional group such as a carboxyl group, a hydroxyl group, or a glycidyl group
  • a monomer component obtained by appropriately and selectively combining the alkyl (meth) acrylate component and the (meth) acrylate component having an organic functional group as a starting material is subjected to heat polymerization to form a (meth) acrylate ester copolymer.
  • a polymer polymer can be obtained.
  • alkyl acrylates such as iso-octyl acrylate, n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture of two or more selected from these, or iso-octyl acrylate
  • alkyl acrylates such as iso-octyl acrylate, n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture of two or more selected from these, or iso-octyl acrylate
  • alkyl acrylates such as iso-octyl acrylate, n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture of two or more selected from these, or iso-octyl acrylate
  • examples include those obtained by copolymerizing at
  • crosslinking monomers include organic compounds such as polyfunctional (meth) acrylates having two or more (meth) acryloyl groups, isocyanate groups, epoxy groups, melamine groups, glycol groups, siloxane groups, and amino groups.
  • a polyfunctional organic functional group resin having two or more functional groups, an organometallic compound having a metal complex such as zinc, aluminum, sodium, zirconium, or calcium can be used.
  • polyfunctional (meth) acrylates include, for example, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, trimethylolpropane triacrylate, and the like. be able to.
  • the content of the crosslinking monomer may be adjusted in combination with other factors so as to obtain a desired holding force, but is generally 0.01 to 40.0 parts by mass, preferably 100 parts by mass with respect to 100 parts by mass of the main component resin. Is preferably adjusted within a range of 0.1 to 30.0 parts by mass, particularly 0.5 to 30.0 parts by mass. However, this range may be exceeded in balance with other elements.
  • cross-linking initiators peroxidation initiators, photoinitiators
  • reaction catalysts tertiary amine compounds, quaternary ammonium compounds, tin laurate compounds, etc.
  • UV crosslinking In the case of UV irradiation crosslinking (also referred to as “UV crosslinking”), it is preferable to add a photoinitiator.
  • a photoinitiator either a cleavage type photoinitiator or a hydrogen abstraction type photoinitiator may be used, but both may be used in combination.
  • the cleavage type photoinitiator include benzoin butyl ether, benzyl dimethyl ketal, and hydroxyacetophenone.
  • examples of the hydrogen abstraction type photoinitiator include benzophenone, Michler's ketone, dibenzosuberone, 2-ethylanthraquinone, and isobutylthioxanthone. However, it is not limited to the substances listed above.
  • the addition amount of the photoinitiator may be adjusted as appropriate, but in general, the photoinitiator should be adjusted within a range of 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the main component resin. It is preferable to use a mold and a cleavage type photoinitiator in a ratio of 1: 1. However, this range may be exceeded in balance with other elements.
  • pigments such as pigments and dyes having near-infrared absorption characteristics, tackifiers, antioxidants, antioxidants, hygroscopic agents, ultraviolet absorbers, silane coupling agents, natural products, Various additives such as synthetic resins, glass fibers and glass beads can be appropriately blended.
  • the above pressure-sensitive adhesive sheet is mixed with an acrylic resin as a main component resin and, if necessary, a cross-linking agent and a reaction initiator or a reaction catalyst, and the mixture is stirred and mixed so that a desired thickness is obtained on the release film.
  • the film can be formed into a pressure-sensitive adhesive sheet by crosslinking by heat drying or ultraviolet irradiation.
  • the thickness (a 2 ) of the pressure-sensitive adhesive sheet is preferably 10 ⁇ m to 300 ⁇ m from the viewpoint of reducing the internal stress of the laminate and increasing the shape stability in a high-temperature and high-humidity environment, and more preferably 30 ⁇ m or more or 250 ⁇ m or less. Among them, the thickness is particularly preferably 50 ⁇ m or more or 200 ⁇ m or less.
  • the elastic modulus (E 2 ) of the pressure-sensitive adhesive sheet is preferably 0.001 MPa or more from the viewpoint of enhancing shape stability in a high temperature and high humidity environment. From this viewpoint, it is more preferably 0.01 MPa or more, and further preferably 0.1 MPa or more. Further, from the viewpoint of improving tackiness, the elastic modulus (E 2 ) is 30 MPa or less, preferably 20 MPa or less, more preferably 10 MPa or less. Tack is defined as “representing the adhesive strength at the moment of bonding to an adherend”, and “is often judged qualitatively by fingers, etc.” (Mr.
  • the elastic modulus (E 2 ) of the pressure-sensitive adhesive sheet can be measured by performing a tensile test at a test speed of 300 mm / min in the length direction of the pressure-sensitive adhesive sheet cut out using a tensile tester.
  • Tg of the pressure-sensitive adhesive sheet is measured using a rheometer (“MARS” manufactured by Eihiro Seiki Co., Ltd.), pressure-sensitive adhesive jig: ⁇ 25 mm parallel plate, strain: 0.5%, frequency: 1 Hz, temperature: ⁇ 50 to 200 ° C. It can be measured by a loss tangent (tan ⁇ ) of dynamic viscoelasticity measurement by a shear method at a rate of 3 ° C./min.
  • This laminate is obtained by the following formula (1) and formula (2), and the front plate when the laminate of the front plate and the pressure-sensitive adhesive sheet is exposed for 120 hours in an environment of temperature 85 ° C. and humidity 85% RH.
  • the internal stress ( ⁇ ) of the pressure-sensitive adhesive sheet is 0.47 MPa or less.
  • each character in the said Formula (1) and Formula (2) is as follows.
  • ⁇ When the front plate is exposed to a temperature of 85 ° C. and a humidity of 85% RH for 120 hours, the front plate is warped in a convex shape and the front plate end surface Lifting height from the stationary surface
  • L Sample length (10 cm)
  • ⁇ The front plate warp shape when only the front plate is exposed to a temperature of 85 ° C. and a humidity of 85% RH for 120 hours, and the front plate is left in a horizontal shape with a convex downward shape.
  • this laminate is warped in a high-temperature and high-humidity environment as long as the internal stress ( ⁇ ) determined by the above formulas (1) and (2) is 0.47 MPa or less. It has been confirmed that can be effectively suppressed. From this point of view, the internal stress ( ⁇ ) in the laminate is preferably 0.47 MPa or less, particularly 0.46 MPa or less, and particularly preferably 0.45 MPa or less. Furthermore, 0.40 MPa or less is preferable, and 0.30 MPa or less is more preferable.
  • the internal stress ( ⁇ ) in this laminate is mainly the ratio of the thickness (A) of one layer (A layer) to the total thickness (T) of the A layer and the (A) layer and (B) layer ( (A) / (T)), the materials of the A layer and the B layer, the thickness and material of the pressure-sensitive adhesive sheet, and the like.
  • a temperature of 85 ° C. and a humidity of 85% RH are adopted as the high temperature and high humidity environment, but other environmental conditions such as a temperature of 60 ° C., Environmental conditions such as a humidity of 90% RH, a temperature of 70 ° C., and a humidity of 90% RH can also be adopted as the high temperature and high humidity environment.
  • the laminate is excellent in shape stability in a high temperature and high humidity environment, and can also improve transparency, impact resistance, surface hardness, and the like. Therefore, this laminated body can be suitably used as various substrate materials, protective materials, and the like by bonding them to various applications, for example, a base material.
  • a base material for example, in addition to various substrate materials and protective materials as constituent materials for image display devices such as mobile phone terminals, smartphones, portable electronic playground equipment, portable information terminals, tablet devices, mobile personal computers, wearable terminals, liquid crystal televisions, liquid crystal monitors, desktops It can be suitably used as various substrate materials and protective materials as constituent materials for stationary display devices such as personal computers, car navigation systems, and automobile meters.
  • This laminate can also be given a shape by various processing methods. For example, in addition to the method of heating and pressurizing using a mold, a pressure forming method, a vacuum forming method, a roll homing method and the like can be exemplified as the forming method. By imparting a shape to the laminate, it can be used for an image display device having a curved surface and various flexible devices.
  • “Sheet” generally refers to a product that is thin by definition in JIS and has a thickness that is small and flat for the length and width.
  • “film” is thicker than the length and width.
  • JISK6900 Japanese Industrial Standard
  • the term “sheet” is included and the term “sheet” is used.
  • “film” is included.
  • the expression “panel” such as an image display panel and a protection panel includes a plate, a sheet and a film, or a laminate thereof.
  • X to Y (X and Y are arbitrary numbers) is described, it means “preferably greater than X” or “preferably,” with the meaning of “X to Y” unless otherwise specified. The meaning of “smaller than Y” is also included. Further, when described as “X or more” (X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and described as “Y or less” (Y is an arbitrary number). In the case, unless otherwise specified, the meaning of “preferably smaller than Y” is included.
  • Thickness It measured using the commercially available thickness measuring device (made by MITUTOYO).
  • FIG. 1 a schematic diagram of the internal stress calculation model is shown in FIG.
  • the warpage amount ( ⁇ ) actually measured by the wet heat exposure test of the front plate alone is substituted into the equation (1), and only the front plate is placed in a temperature 85 ° C., humidity 85% RH environment for 120 hours.
  • the curvature radius ( ⁇ 1 ) of the warp shape of the front plate when exposed was calculated.
  • the sectional moments (I 1 and I 2 ) of the front plate and the pressure-sensitive adhesive were calculated from the following formulas (3) and (4).
  • the calculated ⁇ 1 and other physical property values were substituted into Equation (2) to calculate the internal stress ( ⁇ ).
  • Adhesive sheet As the pressure-sensitive adhesive sheet, a pressure-sensitive adhesive resin composition comprising an acrylic acid ester copolymer, a crosslinking agent and a photopolymerization initiator is sandwiched between two peeled polyethylene terephthalate films, and is formed into a sheet shape having a thickness of 150 ⁇ m.
  • Glass plate A commercially available soda lime glass (width: 100 mm ⁇ length: 100 mm ⁇ thickness: 0.5 mm) was used as the glass plate.
  • Example 1 100 parts by mass of a resin composition obtained by mixing 60 parts by mass of an acrylic resin (a1-1) and 40 parts by mass of a copolymer acrylic resin (a2-1), and a polycarbonate resin (b1-1) 100
  • the mass parts are respectively supplied to separate extruders having a vent function and a filter function, melt-kneaded at a resin temperature of 240 to 265 ° C., and a layered structure of (A layer) / (B layer) is formed by a feed block.
  • a resin composition obtained by mixing 60 parts by mass of an acrylic resin (a1-1) and 40 parts by mass of a copolymer acrylic resin (a2-1), and a polycarbonate resin (b1-1) 100
  • the mass parts are respectively supplied to separate extruders having a vent function and a filter function, melt-kneaded at a resin temperature of 240 to 265 ° C., and a layered structure of (A layer) / (B layer) is formed by a feed block
  • the product is cooled by sequentially passing through a first cooling roll set to 100 ° C., a second cooling roll set to 110 ° C., and a third cooling roll set to 150 ° C.
  • a front plate having a total thickness of 0.675 mm and a thickness of each layer (A layer) / (B layer) 0.075 mm / 0.600 mm was obtained.
  • the curable resin composition (cf) consisting of 60 parts by mass of the curable resin composition (c-1) and 40 parts by mass of the curable resin composition (c-2) is prepared using the bar coater. It was applied to the surface of the acrylic resin layer (A layer) of the face plate, dried in this state at 90 ° C. for 1 minute, and then exposed to ultraviolet rays at an exposure amount of 700 mJ / cm 2 to obtain a curable resin composition (c). Was cured to form a hard coat layer (Cf).
  • the curable resin composition (cb) consisting of 60 parts by mass of the curable resin composition (c-2) and 40 parts by mass of the curable resin composition (c-3) is mixed with the resin using a bar coater.
  • the pressure-sensitive adhesive surface exposed by peeling off one release film of the pressure-sensitive adhesive sheet was superimposed on the surface of the hard coat layer (Cb) of the front plate and adhered with a hand roller.
  • the remaining peeled film was peeled off, soda lime glass (thickness: 0.5 mm) was stacked on the exposed adhesive surface, and press-bonded under reduced pressure (absolute pressure 5 kPa), followed by autoclave treatment (50 ° C., 0.00 mm). (2 MPa, 20 minutes) was applied and pasted to prepare a laminate.
  • the pressure-sensitive adhesive sheet was cured by irradiating the laminated body with ultraviolet rays so that 365 nm ultraviolet rays reached 2000 mJ / cm 2 with a high pressure mercury lamp through soda lime glass, and the front plate / adhesive sheet / glass. A bonded body was prepared.
  • Example 1 As shown in Table 1, in Example 1, the front plate and the front plate / adhesive sheet were the same as in Example 1 except that the thickness ratio and total thickness of each of the A layer and B layer of the front plate were changed. / A glass laminate was produced.
  • thermoplastic resin (a3-1) and part by mass of polycarbonate resin (b1-1) are supplied to separate extruders having a vent function and a filter function, respectively, and are melt-kneaded at a resin temperature of 240 to 265 ° C. Then, after co-extrusion molding with a T die at 240 ° C.
  • thermoplastic resin (a3-1) and part by mass of polycarbonate resin (b1-1) are supplied to separate extruders having a vent function and a filter function, respectively, and are melt-kneaded at a resin temperature of 240 to 265 ° C. Then, after co-extrusion molding with a T die at 240 ° C.
  • the factors of the front plate that affect the internal stress include elastic modulus, thickness, and warpage amount from the formulas (1) and (2).
  • the internal stress can be reduced mainly by reducing the thickness or reducing the amount of warpage. Even if either is larger, the internal stress can be reduced and peeling can be suppressed by adjusting the other parameter to an appropriate range.
  • adjustments such as the layer configuration of the A layer and the B layer, the thickness ratio of the A layer and the B layer, the thickness ratio of the front and back coat layers, and the processing conditions such as the roll temperature condition during production Can be mentioned.
  • the layer configuration of the A layer and the B layer a 2-layer / 3-layer symmetrical configuration of A layer / B layer / A layer.
  • the difference between the expansion and contraction behaviors of the A layer and the B layer can be canceled on both sides, which is effective in reducing warpage.
  • the amount of warpage of the front plate is compared with that using the two types / two-layer configuration of A layer / B layer. It can be confirmed that the internal stress can be kept small.
  • the thickness of one layer (A layer) with respect to the total thickness (T) of the (A) layer and the (B) layer in a two-layer / two-layer configuration of A layer / B layer (A ) Ratio ((A) / (T)) is effective.
  • the cause of warping is due to the difference in expansion and contraction behavior of the two layers. For example, if the A layer is made extremely thin and the thickness ratio is made non-uniform so as to approach the single layer body of the B layer, the influence of the A layer Since it becomes difficult to express, warping behavior can be suppressed.
  • the front and back hard coat layers (C layers) As another means for reducing the amount of warpage, it is effective to bring the front and back hard coat layers (C layers) closer to the front and back objects.
  • the hard coat layer (C layer) When the hard coat layer (C layer) is exposed to the moist heat test, the hard coat layer itself shrinks due to the progress of curing shrinkage, which causes warpage.
  • the material composition of the hard coat layer is the same on the front and back sides, it is preferable to make the thicknesses close to each other. In consideration of the above, it is preferable to adjust the thickness so that the front and back are balanced.
  • the thermal strain in the cooling process is effective to reduce the thermal strain in the cooling process by adjusting the film forming conditions at the time of coextrusion. For example, by setting the third cooling roll to a high temperature within a range that does not cause poor appearance, the thermal distortion can be reduced by the annealing effect.
  • Comparative Examples 1 to 8 peeling occurs due to a large internal stress.
  • Comparative Example 1 even when the total thickness was as large as 1000 ⁇ m and the amount of warpage was small, the internal stress increased due to the large contribution of the thickness.
  • Comparative Examples 2 to 4 since the thickness ratio of the A layer to the B layer was large, the amount of warpage of the front plate was large and the internal stress was large.
  • Comparative Examples 5 to 6 the thickness of the back side hard coat layer (Cf) was thin and the front and back hard coat layers were not balanced, so the amount of warpage of the front plate was large and the internal stress was large.
  • Comparative Examples 7 to 8 the third cooling roll temperature was not sufficiently high, the amount of thermal distortion of the front plate was large, the amount of warpage was large, and the internal stress was large.
  • ⁇ Lifting height of the front plate end surface from the stationary surface
  • L Sample length
  • ⁇ Radius of curvature of the front plate warp shape
  • ⁇ Vertical line from the center of curvature of the front plate warp shape to the contact point of the front plate, and the front Angle formed by a straight line connecting the center of curvature of the face plate warp shape and the end point of the front plate 10:
  • Front plate 20 Adhesive sheet

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

La présente invention vise à procurer un nouveau corps en couches, qui est un corps en couches qui a une feuille adhésive et un panneau avant comprenant une couche de résine à base de polycarbonate et une résine thermoplastique différente de cette résine à base de polycarbonate, et qui a également une excellente stabilité de forme dans un environnement à haute température et à humidité élevée. A cet effet, l'invention porte sur un corps en couches, lequel corps a un panneau avant et une feuille adhésive, et lequel corps en couches est caractérisé en ce que : le panneau avant comprend une couche B ayant une résine à base de polycarbonate comme résine de constituant principal et une couche A ayant une résine thermoplastique différente de la résine à base de polycarbonate comme constituant principal ; l'épaisseur totale de la couche A est de 10 à 250 µm, et le rapport ((A)/(T)) de l'épaisseur (A) d'une une couche A à l'épaisseur totale (T) de la couche A et de la couche B est de 0,05 à 0,40 ; et la contrainte interne (σ) du panneau avant et de la feuille adhésive quand le corps en couches du panneau avant et de la feuille adhésive est exposé pendant 120 heures à un environnement avec une température de 85° C et une humidité de 85 % d'humidité relative est de 0,47 MPa ou moins.
PCT/JP2016/059841 2015-03-31 2016-03-28 Corps en couches WO2016158827A1 (fr)

Priority Applications (2)

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CN201680020492.8A CN107531037B (zh) 2015-03-31 2016-03-28 叠层体
JP2017509955A JP6508330B2 (ja) 2015-03-31 2016-03-28 積層体

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JP2015-072075 2015-03-31
JP2015072075 2015-03-31

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WO2018143194A1 (fr) * 2017-02-03 2018-08-09 帝人株式会社 Corps multicouche
JPWO2017141787A1 (ja) * 2016-02-15 2018-12-13 三菱瓦斯化学株式会社 透明樹脂積層体
JP2020003448A (ja) * 2018-07-02 2020-01-09 凸版印刷株式会社 刺激応答性可逆変形構造体及びその製造方法
WO2020162395A1 (fr) 2019-02-07 2020-08-13 三菱瓦斯化学株式会社 Film adhésif et procédé de fabrication d'un film adhésif
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CN111816077B (zh) * 2020-07-13 2022-04-26 武汉华星光电半导体显示技术有限公司 可折叠显示模组

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WO2020162395A1 (fr) 2019-02-07 2020-08-13 三菱瓦斯化学株式会社 Film adhésif et procédé de fabrication d'un film adhésif
KR20210123292A (ko) 2019-02-07 2021-10-13 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 점착 필름, 및 점착 필름의 제조 방법
WO2021241426A1 (fr) * 2020-05-27 2021-12-02 三菱瓦斯化学株式会社 Corps multicouche en résine

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TWI723985B (zh) 2021-04-11
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JP6508330B2 (ja) 2019-05-08
CN107531037B (zh) 2019-10-01
TW201700300A (zh) 2017-01-01

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