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WO2018070480A1 - Stratifié de verre - Google Patents

Stratifié de verre Download PDF

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Publication number
WO2018070480A1
WO2018070480A1 PCT/JP2017/037023 JP2017037023W WO2018070480A1 WO 2018070480 A1 WO2018070480 A1 WO 2018070480A1 JP 2017037023 W JP2017037023 W JP 2017037023W WO 2018070480 A1 WO2018070480 A1 WO 2018070480A1
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WO
WIPO (PCT)
Prior art keywords
methyl methacrylate
mass
glass
resin composition
light
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2017/037023
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English (en)
Japanese (ja)
Inventor
祐作 野本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
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Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to JP2018545053A priority Critical patent/JP7010832B2/ja
Publication of WO2018070480A1 publication Critical patent/WO2018070480A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the present invention relates to a laminate (also referred to as a glass laminate) in which a hard resin sheet including a layer made of a methacrylic resin composition containing light diffusing particles is bonded to a glass plate via an adhesive layer.
  • methacrylic resin is particularly excellent in transparency, scratch resistance, weather resistance, and the like, and is suitable as a resin material for a glass laminate.
  • methacrylic resins generally have a glass transition temperature (Tg) as low as about 110 ° C. Therefore, a glass laminate using a methacrylic resin may cause an appearance defect or deformation due to heat during the lamination process of the methacrylic resin sheet and the glass plate or in the actual use environment of the glass laminate.
  • a method for increasing the glass transition temperature (Tg) of a material containing a methacrylic resin a method for increasing the syndiotacticity of the methacrylic resin (for example, Patent Document 1), and a methacrylic resin containing styrene and maleic anhydride.
  • a method of blending a copolymer resin for example, Patent Document 2 is known.
  • the glass laminated body containing the layer and glass layer which consist of a methacryl resin composition containing the copolymer resin of styrene and a maleic anhydride is disclosed (for example, patent document 3).
  • An object of the present invention is to provide a glass laminate excellent in light weight, transparency, durability, and light guiding performance.
  • the laminated body in which the said hard resin sheet contains the layer which consists of a methacryl resin composition which contains a methyl methacrylate (co) polymer and light-diffusion particle
  • the methyl methacrylate (co) polymer is composed of 60 to 100% by mass of methyl methacrylate units and 40 to 0% by mass of (meth) acrylic acid ester units other than methyl methacrylate.
  • Methyl methacrylate in which the methyl methacrylate (co) polymer comprises 10 to 35% by mass of methyl methacrylate units, 15 to 40% by mass of maleic anhydride units, and 50 to 75% by mass of aromatic vinyl compound units.
  • the methacrylic resin composition is 5 to 80% by mass of methyl methacrylate (co) polymer (A) comprising 60 to 100% by mass of methyl methacrylate units and 40 to 0% by mass of (meth) acrylic acid ester units other than methyl methacrylate, and 95 to 20% by mass of a methyl methacrylate copolymer (B) comprising 10 to 35% by mass of methyl methacrylate units, 15 to 40% by mass of maleic anhydride units and 50 to 75% by mass of aromatic vinyl compound units [1 ] To [4].
  • the hard resin sheet is a laminated sheet including a layer made of the methacrylic resin composition and a layer made of another thermoplastic resin, The laminate according to any one of [1] to [9], wherein the laminate has the adhesive layer on the surface of the layer made of the other thermoplastic resin.
  • a vehicle member including the laminate according to any one of [1] to [12].
  • An automobile glazing material comprising the laminate according to any one of [1] to [12].
  • An automobile sunroof material including the laminate according to any one of [1] to [12].
  • the present invention it is possible to provide a glass laminate excellent in light weight, transparency, durability, and light guiding performance.
  • the glass laminate of the present invention has a multilayer structure in which glass plates are laminated on one surface of a hard resin sheet via an adhesive layer containing a soft resin.
  • the hard resin sheet comprises a layer (hereinafter referred to as a methacrylic resin composition) containing a methyl methacrylate (co) polymer and light diffusing particles and having a glass transition temperature (Tg) of 120 ° C. or higher.
  • Tg glass transition temperature
  • the glass laminated body of this invention can be used conveniently as a window glass member for vehicles, a window glass member of a building, a glass member for doors, etc.
  • FIG. 1 the schematic cross section of the glass laminated body of 1st Embodiment is shown.
  • reference numeral 10X denotes a glass laminate of the present embodiment
  • reference numeral R1 denotes a hard resin sheet made of the methacrylic resin composition layer 11
  • reference numeral 12 denotes an adhesive layer
  • reference numeral 13 denotes a glass plate.
  • the glass laminated body of this invention is not limited to a 3 layer structure.
  • the hard resin sheet R1 includes one or more methacrylic resin composition layers 11 and, if necessary, a layer made of a thermoplastic resin (composition) other than the methacrylic resin composition (hereinafter referred to as “other heat”).
  • a layer made of a thermoplastic resin (composition) other than the methacrylic resin composition hereinafter referred to as “other heat”.
  • One or more arbitrary layers such as a plastic resin (composition) layer ")
  • the glass laminate of the present invention may include a plurality of hard resin sheets R1, may include a plurality of adhesive layers 12, or may include a plurality of glass plates 13. Further, the stacking order of at least one hard resin sheet R1, at least one adhesive layer 12, and at least one glass plate 13 is appropriately designed.
  • the glass laminate of the present invention may include one or more other arbitrary layers.
  • FIG. 2 the schematic cross section of the glass laminated body of 2nd Embodiment is shown.
  • This glass laminated body is an aspect containing the layer which consists of other thermoplastic resins (composition) other than a methacrylic resin composition.
  • reference numeral 10Y denotes a glass laminate of the present embodiment
  • reference numeral 14 denotes another thermoplastic resin (composition) layer.
  • Reference numerals 11 to 13 are the same as those in FIG.
  • the glass laminate 10Y of the present embodiment includes a hard resin sheet R2 composed of a methacrylic resin composition layer 11 and another thermoplastic resin (composition) layer 14.
  • the aspect containing the layer which consists of other thermoplastic resins (composition) other than a methacrylic resin composition can change a design suitably.
  • FIGS. 3 and 4 show schematic cross-sectional views of the glass laminates of the third and fourth embodiments, respectively.
  • Each of these glass laminates is an embodiment including an abrasion-resistant layer.
  • reference numeral 20X denotes a glass laminate of the third embodiment
  • reference numeral 20Y denotes a glass laminate of the fourth embodiment
  • reference numeral 21 denotes a scratch-resistant layer.
  • Reference numerals 10X, 10Y, and 11 to 14 are the same as those in FIGS. The design including the scratch-resistant layer can be changed as appropriate.
  • the hard resin sheet constituting the glass laminate of the present invention comprises a methacrylic resin composition containing a methyl methacrylate (co) polymer and light diffusing particles and having a glass transition temperature (Tg) of 120 ° C. or higher.
  • Tg glass transition temperature
  • the hard resin sheet contains one or more methyl methacrylate (co) polymers.
  • the methyl methacrylate (co) polymer is polymethyl methacrylate (PMMA), which is a homopolymer of methyl methacrylate (MMA), or a copolymer of MMA and one or more other monomers. It is a coalescence.
  • the methacrylic resin composition comprises a methyl methacrylate (co) polymer (A) comprising 60 to 100% by mass of methyl methacrylate (MMA) units and 40 to 0% by mass of (meth) acrylic acid ester units other than methyl methacrylate. It is preferable to include.
  • the hard resin sheet containing the methyl methacrylate (co) polymer (A) is excellent in scratch resistance and is preferable.
  • the content of the MMA monomer unit in the methyl methacrylate (co) polymer (A) is 60% by mass or more, preferably 80% by mass or more, more preferably, because the scratch resistance of the hard resin sheet is excellent. It is 90% by mass or more, particularly preferably 99% by mass or more, and most preferably 100% by mass.
  • the content of the MMA monomer unit in the methyl methacrylate (co) polymer was purified by reprecipitation of the methyl methacrylate (co) polymer in methanol, and then pyrolyzed using pyrolysis gas chromatography. And volatile components can be separated and calculated from the ratio of peak areas of MMA and copolymer components.
  • the methyl methacrylate (co) polymer (A) can contain (meth) acrylic acid ester units other than MMA in all monomer units.
  • (Meth) acrylic acid ester units other than MMA include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate.
  • Methacrylic acid alkyl esters such as heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, and dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate , and methacrylic acid tricyclo [5.2.1.0 2, 6] cycloalkyl methacrylate esters such as deca-8-yl (TCDMA); phenyl methacrylate, etc.
  • TCDMA deca-8-yl
  • phenyl methacrylate etc.
  • Methacrylic acid aryl ester methacrylic acid aralkyl ester such as benzyl methacrylate; methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-acrylic acid Butyl, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, acrylic Cyclohexyl acid, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, acrylic acid group
  • Examples
  • the content of (meth) acrylic acid ester units other than MMA units in the methyl methacrylate (co) polymer (A) is 40% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably. Is 1% or less.
  • the methyl methacrylate (co) polymer (A) may not contain (meth) acrylic acid ester units other than MMA.
  • the methyl methacrylate (co) polymer (A) can be obtained by polymerizing MMA and other monomers as required.
  • a plurality of types of monomers are mixed to prepare a monomer mixture, which is then subjected to polymerization.
  • the polymerization method is not particularly limited, but radical polymerization and anionic polymerization are preferable from the viewpoints of productivity and heat resistance.
  • the methyl methacrylate (co) polymer (A) has a lower limit of the triplet-syndiotacticity (rr), preferably 50% or more, more preferably 55% or more, particularly preferably. Is 58% or more, most preferably 60% or more.
  • the upper limit of the triplet-represented syndiotacticity (rr) is preferably 99%, more preferably 85%, particularly preferably. 77%, most preferably 65%.
  • syndiotacticity (rr) (simply referred to as “syndiotacticity (rr)” or “rr ratio”) in triplet display is a chain of three consecutive structural units (triplet, triad). ) Is a ratio in which both chains (doublet, diad) are racemo (represented as rr). In the chain of molecular units (doublet, diad) in the polymer molecule, those having the same configuration are referred to as “meso”, and those opposite to each other are referred to as “racemo”, which are expressed as m and r, respectively.
  • the rr ratio (%) of the methyl methacrylate (co) polymer (A) was determined by measuring a 1 H-NMR spectrum at 30 ° C. in deuterated chloroform. Tetramethylsilane (TMS) was found to be 0 ppm from the spectrum. The area (X) of the region of 0.6 to 0.95 ppm and the area (Y) of the region of 0.6 to 1.35 ppm are measured and calculated by the formula: (X / Y) ⁇ 100 can do.
  • the weight average molecular weight (Mw) of the methyl methacrylate (co) polymer (A) is preferably 40,000 to 500,000, more preferably 60,000 to 300,000, and particularly preferably 80,000 to 200,000. preferable.
  • Mw is 40,000 or more
  • the glass laminate of the present invention has excellent mechanical strength
  • the Mw is 500,000 or less
  • the glass laminate of the present invention has excellent moldability. .
  • the glass transition temperature (Tg) of the methyl methacrylate (co) polymer (A) is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher.
  • Tg is 100 ° C. or higher
  • the methacrylic resin composition has excellent heat resistance.
  • the glass transition temperature (Tg) of the whole methacrylic resin composition should just be 120 degreeC or more, and comprises a methacrylic resin composition.
  • the glass transition temperature (Tg) of some methyl methacrylate (co) polymers may be less than 120 ° C.
  • the glass transition temperature (Tg) in this specification is a value calculated by a midpoint method, using a differential scanning calorimeter and measuring at a temperature rising rate of 10 ° C./min.
  • the melt flow rate (MFR) of the methyl methacrylate (co) polymer (A) is preferably in the range of 1 to 10 g / 10 min.
  • the lower limit value of MFR is more preferably 1.2 g / 10 minutes, and particularly preferably 1.5 g / 10 minutes.
  • the upper limit value of MFR is more preferably 7.0 g / 10 minutes, and particularly preferably 4.0 g / 10 minutes.
  • MFR in this specification is a value measured using a melt indexer at a temperature of 230 ° C. and a load of 3.8 kg.
  • the methacrylic resin composition is used in place of the methyl methacrylate (co) polymer (A) or in combination with the methyl methacrylate (co) polymer (A), and has a methyl methacrylate (MMA) unit of 10 to 35 mass. %, A methyl methacrylate copolymer (B) comprising 15 to 40% by weight of maleic anhydride units and 50 to 75% by weight of aromatic vinyl compound units.
  • MMA methyl methacrylate copolymer
  • the content of the MMA unit in the methyl methacrylate copolymer (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. Most preferably, it is 10 mass% or more.
  • the content of the MMA unit in the methyl methacrylate copolymer (B) is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 26% by mass or less. When the content of the MMA unit is in the range of 1 to 35% by mass, the methacrylic resin composition is excellent in transparency and thermal stability.
  • the content of maleic anhydride units in the methyl methacrylate copolymer (B) is preferably 15% by mass or more, more preferably 18% by mass or more, and particularly preferably 20% by mass or more. preferable.
  • the content of maleic anhydride units in the methyl methacrylate copolymer (B) is preferably 49% by mass or less, more preferably 45% by mass or less, and particularly preferably 40% by mass or less. .
  • the content of maleic anhydride units is in the range of 15 to 49% by mass, the methacrylic resin composition is excellent in heat resistance and transparency.
  • the content of the aromatic vinyl compound unit in the methyl methacrylate copolymer (B) is preferably 50% by mass or more, more preferably 55% by mass or more, and particularly preferably 60% by mass or more. preferable.
  • the content of the aromatic vinyl compound unit in the methyl methacrylate copolymer (B) is preferably 84% by mass or less, more preferably 82% by mass or less, and particularly preferably 80% by mass or less. preferable.
  • the content of the aromatic vinyl compound unit is in the range of 50 to 84% by mass, the methacrylic resin composition is excellent in moisture resistance and transparency.
  • aromatic vinyl compound examples include styrene; alkyl-substituted styrene such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, and 4-tert-butylstyrene; ⁇ -methylstyrene, and 4 And ⁇ -alkyl-substituted styrenes such as -methyl- ⁇ -methylstyrene. Styrene is preferred from the viewpoint of availability.
  • These aromatic vinyl compounds can be used alone or in combination of two or more.
  • the methyl methacrylate copolymer (B) may have a structural unit derived from a monomer other than MMA, maleic anhydride, and an aromatic vinyl compound.
  • Other monomers include MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, Nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, acrylic acid 3-methoxybutyl, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroeth
  • the content of other monomer units in the methyl methacrylate copolymer (B) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.
  • the methyl methacrylate copolymer (B) can be obtained by polymerizing MMA, maleic anhydride, an aromatic vinyl compound, and other monomers as required. In this polymerization, usually, a plurality of types of monomers are mixed to prepare a monomer mixture, and then subjected to polymerization.
  • the polymerization method is not particularly limited, but from the viewpoint of productivity, a radical polymerization method such as a bulk polymerization method and a solution polymerization method is preferable.
  • the Mw of the methyl methacrylate copolymer (B) is preferably in the range of 40,000 to 300,000.
  • a methacrylic resin composition is excellent in mechanical strength because Mw is 40,000 or more.
  • the moldability of a methacrylic resin composition can be improved because Mw is 300,000 or less.
  • the glass transition temperature (Tg) of the methyl methacrylate copolymer (B) is preferably 115 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 125 ° C. or higher.
  • Tg glass transition temperature
  • the methacrylic resin composition is excellent in heat resistance, and the appearance defect and deformation of the glass laminate due to heat can be suppressed.
  • the MFR of the methyl methacrylate copolymer (B) is preferably in the range of 1 to 10 g / 10 minutes.
  • the lower limit value of MFR is more preferably 1.2 g / 10 minutes, and particularly preferably 1.5 g / 10 minutes.
  • the upper limit of MFR is more preferably 7.0 g / 10 minutes, and particularly preferably 4.0 g / 10 minutes. When the MFR is in the range of 1 to 10 g / 10 minutes, the stability of heat-melt molding is good.
  • the hard resin sheet preferably includes a methacrylic resin composition layer containing a methyl methacrylate (co) polymer (A) and a methyl methacrylate copolymer (B).
  • the mass ratio (mass ratio (A) / (B)) of the methyl methacrylate (co) polymer (A) to the methyl methacrylate copolymer (B) is a viewpoint of heat resistance, transparency, and scratch resistance. To 5/95 to 90/10.
  • the mass ratio (A) / (B) is more preferably 10/90 or more, particularly preferably 15/85 or more, and most preferably 20/80 or more. Further, the mass ratio (A) / (B) is more preferably 85/15 or less, particularly preferably 80/20 or less, and most preferably 75/25 or less.
  • Examples of the mixing method of the methyl methacrylate (co) polymer (A) and the methyl methacrylate copolymer (B) include a melt mixing method and a solution mixing method.
  • a melt mixing method for example, an inert gas such as nitrogen gas, argon gas, and helium gas is used as necessary using a melt kneader such as a uniaxial or multiaxial kneader, an open roll, a Banbury mixer, and a kneader. Melt kneading can be performed under an atmosphere.
  • the methyl methacrylate (co) polymer (A) and the methyl methacrylate copolymer (B) can be dissolved and mixed in an organic solvent such as toluene, tetrahydrofuran, and methyl ethyl ketone.
  • the methacrylic resin composition may contain a polymer other than the methyl methacrylate (co) polymer (A) and the methyl methacrylate copolymer (B) as long as the effects of the present invention are not impaired.
  • Other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene, ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene Styrene resin such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, and MBS resin; methyl methacrylate-styrene copolymer; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66 , And polyamide resins such as polyamide elastomers; polyphenylene sulfide, polyether ether ketone, poly
  • the methacrylic resin composition constituting the hard resin sheet of the glass laminate of the present invention contains light diffusing particles.
  • the light diffusing particles are particles that have a refractive index different from that of the methyl methacrylate (co) polymer, which is a matrix resin (base resin other than the light diffusing particles) of the hard resin sheet, and scatter light.
  • the glass laminate of the present invention is opposed to light while scattering light in the thickness direction of the glass laminate when light is introduced from the light source to one end surface of the glass laminate. Light can be guided in the direction of the surface of the laminate toward the other end surface.
  • the light diffusing particles are contained in the hard resin sheet, it is possible to provide a laminate having excellent light guiding performance at low cost without the need to separately provide a light diffusing layer by printing, surface unevenness processing, or the like.
  • the concentration of the light diffusing particles in the methacrylic resin composition is preferably 0.00005 to 0.1% by mass, more preferably 0.0001 to 0.01% by mass, and 0.0002 to 0.001. Particularly preferred is 001% by weight.
  • concentration of the light diffusing particles increases, the transparency of the glass laminate including the hard resin sheet tends to decrease. For this reason, in order to keep the haze value of the hard resin sheet low, it is preferable to keep the concentration of the light diffusing particles low.
  • the concentration of the light diffusing particles is too low, light may not be sufficiently scattered when light is introduced from the light source to the hard resin sheet, and the light guide performance of the glass laminate may be insufficient. .
  • the concentration of the light diffusing particles in the methacrylic resin composition is in the range of 0.00005 to 0.1% by mass, both good transparency and good light guiding performance can be achieved.
  • the volume average particle diameter (volume average diameter) d of the light diffusing particles is preferably 0.5 to 5 ⁇ m, more preferably 0.75 to 4 ⁇ m, and particularly preferably 1 to 3 ⁇ m.
  • the volume average particle diameter d of the light diffusing particles is smaller than 0.5 ⁇ m, there may be a difference in color between the vicinity of the light incident end face of the glass laminate and the position away from it.
  • the volume average particle diameter d of the light diffusing particles is larger than 5 ⁇ m, the light diffusing particles having a relatively large particle diameter may become a bright spot when the light source is turned on, thereby impairing the appearance.
  • the volume average particle diameter d in the present specification is a particle diameter obtained by taking an electron micrograph of primary particles and using image analysis type particle size distribution measurement software.
  • the difference in refractive index ( ⁇ n) between the methyl methacrylate (co) polymer as the matrix resin and the light diffusing particles is preferably 0.3 to 3.
  • the difference in refractive index ( ⁇ n) is more preferably 0.4 or more.
  • the refractive index difference ( ⁇ n) is larger than 3, the scattered light is dominated by backscattering, so that the light cannot be extracted efficiently, and the transparency is inferior to the brightness when the light source is turned on. There is a case.
  • inorganic compound particles having a large refractive index difference with respect to the matrix resin are preferably used.
  • titanium oxide and zinc oxide are preferably used.
  • the volume average particle diameter d of the light diffusing particles is excessively small, a color change such as coloring that may be caused by the Rayleigh scattering phenomenon may occur.
  • the refractive index difference ( ⁇ n) is too small, there may be a change in color such as coloring that may be caused by the Rayleigh scattering phenomenon.
  • the scattered light may be bluish in the vicinity of the light source and yellowish in the position away from the light source.
  • ⁇ d) of the volume average particle diameter d ( ⁇ m) of the light diffusing particles and the absolute value of the refractive index difference ( ⁇ n) ) Is preferably 0.1 ⁇ m or more.
  • the methacrylic resin composition may contain various additives as required in addition to the light diffusing particles.
  • additives include antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, bluing agents, matting agents, Examples thereof include impact resistance modifiers and phosphors.
  • the methacrylic resin composition preferably contains 0.0001 to 0.01% by mass of a bluing agent for color matching.
  • the timing of adding the optional components is not particularly limited, and the methyl methacrylate (co) polymer (A) and / or methyl methacrylate is not limited.
  • the copolymer (B) is polymerized, any timing such as when the polymerized methyl methacrylate (co) polymer (A) and the methyl methacrylate copolymer (B) are mixed or after mixing may be used.
  • the glass transition temperature (Tg) of the methacrylic resin composition is 120 ° C. or higher, preferably 130 ° C. or higher, and more preferably 140 ° C. or higher. When the glass transition temperature (Tg) is 120 ° C. or higher, the methacrylic resin composition has excellent heat resistance.
  • the MFR of the methacrylic resin composition is preferably in the range of 1 to 10 g / 10 minutes.
  • the lower limit value of MFR is more preferably 1.2 g / 10 minutes, and particularly preferably 1.5 g / 10 minutes.
  • the upper limit value of MFR is more preferably 7.0 g / 10 minutes, and particularly preferably 4.0 g / 10 minutes. When the MFR is in the range of 1 to 10 g / 10 minutes, the stability of heat-melt molding is good.
  • Sheet molding methods for methacrylic resin compositions include co-extrusion molding, T-die lamination molding, and extrusion coating methods; insert injection molding, two-color injection molding, core back injection molding, sandwich Examples thereof include injection molding methods such as injection molding methods and injection breath molding methods; blow molding methods; calendar molding methods; press molding methods; slush molding methods.
  • film”, “sheet”, and “plate” are used depending on the thickness of the thin film molded body. In the present specification, these are not clearly distinguished and are collectively referred to as a “sheet”.
  • the adhesive layer is a transparent layer that adheres the hard resin sheet and the glass plate, and includes a tough soft resin.
  • the soft resin polyvinyl butyral, ethylene-vinyl acetate copolymer, ethylene ionomer, thermoplastic polyurethane, and modified products thereof can be suitably used.
  • the adhesive layer relaxes the difference in thermal expansion coefficient or the difference in water absorption between the hard resin sheet and the glass plate, and in durability tests such as a heat cycle test. It preferably has a function of suppressing cracking and delamination of the glass laminate and a function of improving the impact resistance of the glass laminate.
  • thermoplastic polyurethane can be particularly preferably used as the soft resin.
  • the thermoplastic polyurethane is obtained by reacting a polyisocyanate, a polyol and a curing agent.
  • polyisocyanates include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethyl-1,6-hexane diisocyanate; bis (4-isocyanatocyclohexyl) methane, Alicyclic diisocyanate compounds such as 2,2-bis (4-isocyanatocyclohexyl) propane, 1,4-cyclohexyl diisocyanate, and 1-methyl-2,4- (or 2,6) -diisocyanatecyclohexane; isophorone diisocyanate, etc. And an aliphatic / alicyclic mixed diisocyanate compound.
  • polystyrene resin examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol.
  • a polyester diol obtained by a polyesterification reaction of an aliphatic dibasic acid or an anhydride thereof with a dihydric alcohol, preferably an aliphatic dihydric alcohol can also be suitably used.
  • Aliphatic dibasic acids can be represented by the formula: HOOC-R-COOH.
  • R in the formula is an alkylene group having 2 to 12 carbon atoms, preferably 4 to 8 carbon atoms, and examples thereof include adipic acid, succinic acid, palmitic acid, suberic acid, azelaic acid, and sebacic acid.
  • the dihydric alcohol is preferably an alcohol having 2 to 15 carbon atoms, and specific examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and the like.
  • polyol examples include polyoxytetramethylene diol having an oxymethylene group; polyoxyalkylene diol having an oxypropylene group or a combination of an oxyethylene group and an oxypropylene group; an oxyalkylene group such as an oxyethylene group and an oxypropylene group; Polyether diols having combinations with methylene groups can also be used.
  • curing agent examples include fatty acid diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol; aminoalcohols such as monoethanolamine; 1,2-ethanediamine And diamines.
  • the adhesive layer can be formed using a thermoplastic resin sheet such as a thermoplastic polyurethane sheet and an ethylene / vinyl acetate copolymer sheet.
  • the thermoplastic resin sheet can be produced by a known sheet molding method such as an extrusion molding method.
  • Glass plate The kind of glass plate used for the glass laminated body of this invention is not specifically limited.
  • float plate glass, polished plate glass, mold plate glass, mesh plate glass, heat ray absorbing plate glass, special glass (for example, metal (for example, silver or indium tin oxide) sputtered for the purpose of controlling sunlight), low E glass and tempered glass can be used. These may be either colorless or colored. These can be used alone or in combination of two or more.
  • the hard resin sheet, the adhesive layer, and the glass plate may each be singular or plural.
  • the glass laminated body of this invention may have other layers other than these layers.
  • the constituent material of the other layer is not particularly limited, and one or two or more kinds of thermoplastic resins, one kind or two or more kinds of thermosetting resins excluding the methacrylic resin composition and the soft resin, one kind or two kinds or more are used. Examples include energy ray curable resins and combinations thereof.
  • the function of other resin layers is not particularly limited, and is a support layer for supporting a hard resin sheet, etc .; scratch-resistant layer, antistatic layer, antifouling layer, friction reducing layer, antiglare layer, antireflection layer, adhesive layer, heat ray You may function as various functional layers, such as an absorption layer, a sound insulation layer, and an impact strength provision layer.
  • the other resin layer may be singular or plural. When there are a plurality of other resin layers, the composition may be the same or non-identical.
  • the hard resin sheet can have a laminated structure including a methacrylic resin composition layer and another thermoplastic resin (composition) layer.
  • thermoplastic resins are not particularly limited, for example, polyolefins such as polyethylene and polypropylene, polystyrene, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinylidene fluoride, modified polyphenylene ether, polyphenylene sulfide, Examples include silicone-modified resins, polyether ether ketone, polysulfone, polyphenylene oxide, polyimide, polyether imide, and phenoxy resin.
  • polycarbonate is preferable from the viewpoints of transparency, heat resistance, and impact resistance.
  • the thickness of the other plastic resin (composition) layer is preferably 0.04 to 3 mm, more preferably 0.05 to 1.5 mm, and particularly preferably 0.06 to 1.0 mm. preferable. If the thickness of the other plastic resin (composition) layer is 0.04 mm or more, the impact resistance of the glass laminate tends to be excellent, and if it is 3 mm or less, the warp of the glass laminate There is a tendency to be able to suppress.
  • the hard resin sheet can have a laminated structure including a scratch-resistant layer and a methacrylic resin composition layer.
  • the scratch-resistant layer can be usually formed by applying a fluid curable composition containing a monomer, an oligomer, a resin, and the like to the surface of another layer (for example, a methacrylic resin composition layer) and curing it.
  • the curable composition is, for example, a thermosetting composition that is cured by heat; an energy beam curable composition that is cured by an energy beam such as an electron beam, radiation, or ultraviolet rays.
  • the thickness of the scratch-resistant layer is preferably 2 to 10 ⁇ m, more preferably 3 to 8 ⁇ m, and particularly preferably 4 to 7 ⁇ m.
  • the thickness of the scratch-resistant layer is 2 ⁇ m or more, the scratch resistance tends to be well expressed, and when it is 10 ⁇ m or less, the impact resistance of the glass laminate tends to be excellent.
  • thermosetting composition examples include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-urea cocondensation. Examples thereof include resins, silicon resins, and polysiloxane resins.
  • the thermosetting composition may contain a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, or the like, if necessary.
  • isocyanates and organic sulfonic acids are usually used for polyester resins and polyurethane resins
  • amines are used for epoxy resins
  • peroxides such as methyl ethyl ketone peroxide and azobisisobutyl are used for unsaturated polyester resins.
  • a radical initiator such as an ester is used.
  • the energy ray curable composition examples include a composition containing an oligomer and / or a monomer having a group containing a polymerizable unsaturated bond such as an acryloyl group and a methacryloyl group, a thiol group, or an epoxy group in the molecule. It is done. From the viewpoint of enhancing the scratch resistance, a composition containing an oligomer and / or monomer having a plurality of acryloyl groups and / or methacryloyl groups is preferred.
  • the energy beam curable composition may contain a photopolymerization initiator and / or a photosensitizer.
  • Photopolymerization initiators include carbonyl compounds such as benzoin methyl ether, acetophenone, 3-methylacetophenone, benzophenone, and 4-chlorobenzophenone; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2, 4, 6 -Trimethylbenzoyldiphenylphosphine oxide and benzoyldiethoxyphosphine oxide;
  • Examples of the photosensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.
  • the thickness of each layer is not particularly limited.
  • the thickness of the hard resin sheet is preferably from 0.1 to 10 mm, more preferably from 0.5 to 5 mm, particularly preferably from 1.0 to 3.0 mm, from the viewpoint of scratch resistance, weather resistance, impact resistance, and the like. preferable.
  • the thickness of the adhesive layer is preferably 0.03 to 8.0 mm, more preferably 0.1 to 7.0 mm, and more preferably 0.4 to 6 in terms of interlayer adhesion, impact resistance, and internal stress relaxation performance. 0.0 mm is particularly preferable.
  • the thickness of the glass plate is preferably from 0.1 to 4.0 mm, more preferably from 0.5 to 3.0 mm, and particularly preferably from 1.0 to 2.0 mm from the viewpoints of rigidity and weight reduction.
  • the manufacturing method in particular of the glass laminated body of this invention is not restrict
  • a hard resin sheet produced by a known method, a thermoplastic resin sheet for an adhesive layer produced by a known method, and a glass plate are stacked, and an autoclave process is performed on the obtained pre-laminated body.
  • a glass laminate can be produced.
  • the preliminary laminate is placed in a bag that can maintain a vacuum (vacuum bag), air is sucked from the vacuum bag by a vacuum line or other means, and heated and pressurized in the autoclave while maintaining the vacuum. It is.
  • the heating temperature and the heating time can be arbitrarily set within a conventionally known range.
  • the heating temperature is preferably 120 ° C. or lower, and more preferably 110 ° C. or lower so that the hard resin sheet is not thermally deformed. It should be noted that at least one surface of the glass plate may be subjected to a known adhesion enhancing treatment in advance prior to the lamination step.
  • the adhesion enhancing process is described, for example, in US Pat. No. 7,625,627.
  • Other manufacturing methods include a method in which a laminated sheet including a hard resin sheet and an adhesive layer is obtained by a known multilayer molding, and then the obtained laminated sheet is bonded to a glass plate.
  • multilayer molding include multilayer extrusion molding; multilayer blow molding; multilayer press molding; multicolor injection molding; insert injection molding;
  • the glass laminate of the present invention includes a hard resin sheet including a methacrylic resin composition layer including a methyl methacrylate (co) polymer and light diffusing particles, an adhesive layer, and a glass plate. . Since the glass laminate of the present invention is a composite material including a hard resin sheet and a glass plate, the weight can be reduced as compared with a single glass. Moreover, even if it receives a strong impact from the outside, it is difficult to break, and even if the glass is broken, the glass fragments do not scatter and the safety is excellent. In the glass laminate of the present invention, the heat resistance of the hard resin sheet is high, and the adhesive layer contains a soft resin.
  • the appearance defect and deformation due to heat are suppressed during the lamination process of the hard resin sheet and the glass plate or in the actual use environment, and the interlayer due to the difference in linear expansion coefficient between the resin and glass. Is prevented from peeling. Therefore, according to the present invention, a high-quality glass laminate having high transparency and excellent durability can be provided.
  • the glass laminate of the present invention is also excellent in light guiding performance because the hard resin sheet contains light diffusing particles.
  • a planar light-emitting body can be provided by combining the glass laminate of the present invention and a light source.
  • the use of the glass laminate of the present invention is not particularly limited, for example, building parts such as safety window glass and partitions; optics such as liquid crystal protection plates, light guide plates, light guide films, front plates of various displays, and diffusion plates Related parts: Automotive interior / exterior parts (side visor, rear visor, head wing, headlight cover, bumper, sunroof, glazing, etc.) and other vehicle parts; other greenhouses, large tanks, box tanks, bathroom parts, clock panels, Bath, sanitary, desk mat, game parts, toy, and mask for face protection when welding.
  • the planar light emitter using the glass laminate of the present invention is suitable as a vehicle member or the like, and is suitable as an automobile glazing material, particularly an automobile sunroof material.
  • planar light emitter using the glass laminate of the present invention, it is possible to provide a high-performance automotive glazing material such as an automobile sunroof material that functions as a transparent plate when the light source is turned off and functions as interior lighting when the light source is turned on. It becomes possible.
  • a high-performance automotive glazing material such as an automobile sunroof material that functions as a transparent plate when the light source is turned off and functions as interior lighting when the light source is turned on. It becomes possible.
  • ⁇ Durability> The produced glass laminate is allowed to stand for 1 hour in an environment of 20% humidity and 20 ° C., and then left for 1 hour in an environment of 20% humidity and 80 ° C. under an environment of 100% humidity and 20 ° C. And left for 1 hour in an environment of 100% humidity and 80 ° C. The above operation was made into 1 cycle, and 100 cycles were repeated. After carrying out this heat cycle test, the presence or absence of delamination and the appearance of the glass laminate of the laminate were evaluated by the same method as the initial performance.
  • the pencil scratch hardness of the surface was measured using the table movement-type pencil scratch test machine (model P, Toyo Seiki company make).
  • the evaluation target surface was the surface of the hard resin sheet shown in Table 3. Under the conditions of an angle of 45 degrees and a load of 750 g, scratching was performed while pressing a pencil lead against the surface of the glass laminate, and the presence or absence of scratches was confirmed.
  • the hardness of the pencil lead increased in order, and the hardness of the lead that was one step softer than the point at which the scar was generated was used as scratch resistance data.
  • the Taber abrasion resistance performance of the surface was measured using a Taber abrasion tester (AB-101) (manufactured by Tester Sangyo Co., Ltd.).
  • the evaluation target surface was the surface of the hard resin sheet shown in Table 3.
  • the measurement was performed according to the method of ASTM D-1044.
  • the wear wheel was CS-10F, the load was 500 g, and the rotation speed was 1000 times.
  • the haze difference ( ⁇ H (%)) before and after the Taber abrasion test was measured. The smaller ⁇ H (%), the better the Taber wear performance.
  • FIG. 5 shows a schematic cross-sectional view of the evaluation system.
  • a planar light emitter 50 shown in FIG. 5 includes a light source 51 and a glass laminate 52.
  • the glass laminate 52 has been subjected to a known light absorption treatment 54 in advance on the other end surface 52B facing the end surface 52A on the light incident side.
  • a light source 51 and a light reflecting cover 55 are disposed adjacent to the end surface 52A on the light incident side of the glass laminate 52.
  • the light source 51 seven LEDs arranged in a line in a parallel direction with respect to the light incident side end face of the glass laminate at intervals of 10 mm were used.
  • LED NFSW036BT diameter of light emitting part: 3 mm
  • a voltage of 2.8 V was applied to each LED.
  • a light absorbing sheet 53 that absorbs light emitted to the back side is disposed on the back side of the planar light emitter 50.
  • Light emitted from the light source 51 enters from the end surface 52A on the light incident side of the glass laminate 52, and is guided through the glass laminate 52 toward the other end surface 52B on which the light absorption processing 54 is performed.
  • the distance from the end surface 52A on the light incident side to the other end surface 52B subjected to the light absorption processing 54 was set to 300 mm.
  • the position of the end surface 52A on the light incident side was set to 0 mm, and the distance to an arbitrary point between the other end surface 52B subjected to the light absorption process 54 was defined as “light guide distance”.
  • ⁇ Methyl methacrylate homopolymer (A-2)> The inside of the autoclave equipped with the stirrer and the sampling tube was replaced with nitrogen. To this, 100 parts by mass of purified methyl methacrylate (MMA), 2,2′-azobis (2-methylpropionitrile (hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.) 0.0065 parts by mass And 0.290 parts by mass of n-octyl mercaptan were added and stirred to obtain a raw material liquid, and nitrogen was fed into the raw material liquid to remove dissolved oxygen in the raw material liquid. The raw material liquid was put to 2/3 of the capacity in a tank reactor connected to the autoclave by piping.
  • MMA purified methyl methacrylate
  • 2,2′-azobis (2-methylpropionitrile hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.
  • the temperature was maintained at 120 ° C., and the polymerization reaction was first started in a batch mode.
  • the polymerization conversion rate reaches 55% by mass
  • the raw material liquid is supplied from the autoclave to the tank reactor at a flow rate at which the average residence time is 120 minutes while maintaining the temperature at 120 ° C., and the supply flow rate of the raw material liquid
  • the reaction liquid was withdrawn from the tank reactor at a flow rate corresponding to 1 and switched to a continuous flow polymerization reaction. After switching, the polymerization conversion in the steady state was 45% by mass.
  • the reaction liquid extracted from the tank reactor in a steady state was heated by supplying it to a multitubular heat exchanger having an internal temperature of 230 ° C. at a flow rate with an average residence time of 2 minutes.
  • the heated reaction liquid was introduced into a flash evaporator, and volatile components mainly composed of unreacted monomers were removed to obtain a molten resin.
  • a methyl methacrylate homopolymer (A-2) (MMA ratio 100%) was obtained.
  • ⁇ Methyl methacrylate homopolymer (A-3)> The inside of the autoclave equipped with the stirrer and the sampling tube was replaced with nitrogen. To this, 100 parts by mass of purified methyl methacrylate (MMA), 2,2′-azobis (2-methylpropionitrile (hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.) 0.0094 parts by mass And 0.26 parts by mass of n-octyl mercaptan were added and stirred to obtain a raw material liquid, and nitrogen was fed into the raw material liquid to remove dissolved oxygen in the raw material liquid. The raw material liquid was put to 2/3 of the capacity in a tank reactor connected to the autoclave by piping.
  • MMA purified methyl methacrylate
  • 2,2′-azobis (2-methylpropionitrile hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.
  • the temperature was maintained at 100 ° C., and the polymerization reaction was first started in a batch mode.
  • the temperature is maintained at 120 ° C., and the raw material liquid is supplied from the autoclave to the tank reactor at a flow rate that makes the average residence time 120 minutes.
  • the reaction solution was extracted from the tank reactor and switched to a continuous flow polymerization reaction. After switching, the polymerization conversion in the steady state was 49% by mass.
  • the reaction liquid withdrawn from the tank reactor in a steady state was heated by supplying it to a multi-tubular heat exchanger having an internal temperature of 230 ° C. at a flow rate with an average residence time of 2 minutes.
  • the heated reaction liquid was introduced into a flash evaporator, and volatile components mainly composed of unreacted monomers were removed to obtain a molten resin.
  • a methyl methacrylate homopolymer (A-3) (MMA ratio 100%) was obtained.
  • Method (A-4) The inside of a 5 L glass reaction vessel equipped with a stirring blade and a three-way cock was replaced with nitrogen. To this, at room temperature, 1600 g of toluene, 2.49 g (1,0.8 mmol) of 1,1,4,7,10,10-hexamethyltriethylenetetramine, isobutyl bis (2,6-dioxy) having a concentration of 0.45M. 5.
  • ⁇ Methyl methacrylate copolymer (A-5)> The inside of a 5 L glass reaction vessel equipped with a stirring blade and a three-way cock was replaced with nitrogen. To this, 630 g of methyl methacrylate (MMA), 350 g of tricyclo [5.2.1.0 2,6 ] decanyl (TCDMA) methacrylate, 20 g of methyl acrylate (MA), azobisisobutyronitrile 0.6 g, 2.0 g of n-octyl mercaptan, 2500 g of ion exchange water, 0.9 g of a dispersant, and 10.7 g of a pH adjuster were charged. While stirring, the liquid temperature was raised from room temperature to 70 ° C.
  • ADEKA STAB LA-46 manufactured by ADEKA Corporation was used as an ultraviolet absorber.
  • thermoplastic polyurethane sheet > “High-Grass DUS203” manufactured by Seadom Co., Ltd. (polyester-based thermoplastic polyurethane having aromatic diisocyanate and polyester diol as main reaction components, thickness 500 ⁇ m) was used as the thermoplastic polyurethane sheet.
  • PC-1 Polycarbonate resin
  • a-1 light diffusing particles
  • an ultraviolet absorber supplied to the hopper of the twin screw extruder at the compounding ratio shown in Table 1, and melt kneaded at a cylinder temperature of 250 ° C. Extrusion molding was performed to obtain a pellet-shaped polycarbonate resin composition (12). The composition and physical properties of this polycarbonate resin composition are shown in Table 1-2.
  • Hard resin sheets (1) to (7) and (10) to (14) were produced using the methacrylic resin compositions (1) to (7) and (10) to (14) by the following method. .
  • the pellets of the methacrylic resin composition shown in Table 2 were continuously charged into a vent-type single-screw extruder having a shaft diameter of 50 mm, and melt-extruded under conditions of a cylinder temperature of 190 to 250 ° C. and a discharge rate of 30 kg / hour.
  • the molten methacrylic resin composition was extruded from a T-die having a width of 400 mm set to 250 ° C., and niped with a pair of metal rigid rolls set to 100 ° C. and 120 ° C., respectively. It was taken up at a speed of 47 m / min. As described above, a methacrylic resin sheet having a width of 300 mm, a length of 400 mm, and a thickness of 2 mm was obtained.
  • the pellets of the methacrylic resin composition (1) were continuously charged into a vent type single-screw extruder having a shaft diameter of 50 mm, and melt-extruded under conditions of a cylinder temperature of 190 to 250 ° C. and a discharge rate of 24 kg / hour.
  • a pellet of a methacrylic resin composition (6) or a polycarbonate resin composition (12) is continuously charged into a vent type single screw extruder having a shaft diameter of 30 mm, under conditions of a cylinder temperature of 190 to 300 ° C. and a discharge amount of 6 kg / hour. And melt extruded.
  • the molten methacrylic resin composition (1) and the methacrylic resin composition (6) or the polycarbonate resin composition (12) are introduced into a junction block and laminated by a multi-manifold die having a width of 400 mm set at 250 ° C. Extrusion (co-extrusion) was performed by niping with a pair of rigid metal rolls set at 100 ° C. and 120 ° C., respectively, and taken up at a speed of 0.47 m / min. As described above, the first resin layer (thickness 1.6 mm) made of the methacrylic resin composition (1) and the second resin made of the methacrylic resin composition (6) or the polycarbonate resin composition (12).
  • a two-layer laminated resin sheet (width 300 mm, length 400 mm, thickness 2 mm) obtained by laminating layers (thickness 0.4 mm) was obtained.
  • a scratch-resistant layer (about 4 ⁇ m) was formed on the surface of the first resin layer of the obtained laminated resin sheet in the same manner as in Production Example 2-1, to obtain a hard resin sheet with a scratch-resistant layer.
  • Table 2 shows the structure of the hard resin sheet obtained in each production example.
  • a polycarbonate resin sheet having a width of 300 mm, a length of 400 mm, and a thickness of 2 mm was obtained.
  • a scratch-resistant layer (about 4 ⁇ m) was formed on one surface of the obtained polycarbonate resin sheet in the same manner as in Production Example 2-1, to obtain a hard resin sheet with a scratch-resistant layer.
  • Table 2 shows the structure of the obtained hard resin sheet.
  • Examples 1 to 7, 9 to 11 On the hard resin sheet shown in Table 3, a thermoplastic polyurethane sheet as an adhesive layer and a commercially available float glass plate (G1) (thickness: 2.8 mm) were sequentially stacked. In addition, when the hard resin sheet containing an abrasion-resistant layer was used, the adhesive layer was overlaid on the non-formation surface of the abrasion-resistant layer of the hard resin sheet.
  • the obtained preliminary laminated body was heated by a vacuum bag method (temperature profile: heated from 30 ° C. to 110 ° C. over 60 minutes and then held at 110 ° C. for 30 minutes) and pressurized to produce a glass laminated body. Tables 3 and 4 show the structures and evaluation results of the glass laminates produced in each example.
  • Example 8 A glass laminate was produced in the same manner as in Example 7 except that an ethylene-vinyl acetate copolymer (EVA) sheet was used instead of the thermoplastic polyurethane sheet. Tables 3 and 4 show the structure and evaluation results of the glass laminate produced in Example 8.
  • EVA ethylene-vinyl acetate copolymer
  • a hard resin sheet comprising a methacrylic resin composition layer containing a methyl methacrylate (co) polymer and light diffusing particles and having a glass transition temperature (Tg) of 120 ° C. or higher, and a thermoplastic polyurethane
  • Tg glass transition temperature
  • thermoplastic polyurethane A glass laminate having a three-layer structure of an adhesive layer made of a sheet or an ethylene / vinyl acetate copolymer sheet and a glass plate was obtained. None of the glass laminates obtained in Examples 1 to 11 using a hard resin sheet containing a highly heat-resistant methacrylic resin composition layer produced layer peeling and poor appearance immediately after production and after a heat cycle test. The transparency and durability were good.
  • Examples 1 to 11 By using the glass laminates of Examples 1 to 11 using a hard resin sheet containing a methacrylic resin composition layer containing an appropriate amount of appropriate light diffusing particles, transparency is good when the light source is turned off, and light is emitted when the light source is turned on. A planar light-emitting body having good emission characteristics and excellent surface light-emitting properties could be produced.
  • two kinds of light diffusing particles having different refractive indexes and average particle diameters were used.
  • the refractive index difference between the matrix resin of the methacrylic resin composition and the light diffusing particles When the refractive index difference between the matrix resin of the methacrylic resin composition and the light diffusing particles is larger, the light emission property when the light source is lit tends to be improved.
  • the particle size of the light diffusing particles When the particle size of the light diffusing particles is larger, the light emission property when the light source is lit tends to be improved. The smaller the particle size of the light diffusing particles, the better the transparency when the light source was turned off.
  • the planar light emitter using the glass laminate of Comparative Example 4 using the hard resin sheet (14) containing a methacrylic resin composition layer not containing light diffusing particles has insufficient brightness when the light source is turned on.
  • the glass laminate obtained in Comparative Example 5 using the hard resin sheet (15) containing the polycarbonate resin composition layer is optically strained immediately after production and after the heat cycle test, and has insufficient scratch resistance. there were.
  • the planar light-emitting body using the glass laminate of Comparative Example 5 had insufficient transparency when the light source was turned off, and had insufficient brightness and uneven color when the light source was turned on.

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Abstract

La présente invention concerne un stratifié de verre léger ayant de meilleures transparence, durabilité et performance de guide de lumière. Le stratifié de verre selon la présente invention comporte une plaque de verre disposée sur un premier côté d'une feuille de résine dure avec une couche adhésive interposée entre celles-ci. La feuille de résine dure comprend une couche formée d'une composition de résine méthacrylique qui contient un (co)polymère de méthacrylate de méthyle et des particules de diffusion de lumière, et a une température de transition vitreuse (Tg) de 120 °C ou plus. Le (co)polymère de méthacrylate de méthyle comprend de préférence un (co)polymère de méthacrylate de méthyle (A) contenant de 60-100 % en masse d'une unité méthacrylate de méthyle, et de 40-0 % en masse d'une unité ester d'acide (méth)acrylique autre que le méthacrylate de méthyle.
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WO2018159520A1 (fr) * 2017-02-28 2018-09-07 株式会社クラレ Stratifié de verre et son procédé de production
JP2022032733A (ja) * 2020-08-13 2022-02-25 旭化成株式会社 積層体
JP2023547489A (ja) * 2020-10-30 2023-11-10 ユーロケラ ソシエテ オン ノーム コレクティフ 強化ガラスセラミック物品

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CN112365805B (zh) * 2020-12-09 2022-07-26 合肥维信诺科技有限公司 盖板和显示模组的制作方法

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