WO2018159520A1 - Stratifié de verre et son procédé de production - Google Patents

Stratifié de verre et son procédé de production Download PDF

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Publication number
WO2018159520A1
WO2018159520A1 PCT/JP2018/006904 JP2018006904W WO2018159520A1 WO 2018159520 A1 WO2018159520 A1 WO 2018159520A1 JP 2018006904 W JP2018006904 W JP 2018006904W WO 2018159520 A1 WO2018159520 A1 WO 2018159520A1
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Prior art keywords
hard resin
resin sheet
glass laminate
glass
light
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PCT/JP2018/006904
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English (en)
Japanese (ja)
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祐作 野本
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株式会社クラレ
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Priority to JP2019502970A priority Critical patent/JP7107915B2/ja
Publication of WO2018159520A1 publication Critical patent/WO2018159520A1/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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor

Definitions

  • the present invention relates to a glass laminate and a method for producing the same.
  • planar light emitters In applications using glass members such as automobile glazing, development of a glass laminate in which an inorganic glass plate and a transparent hard resin sheet are laminated has been promoted for the purpose of reducing the weight of the member and improving safety. Furthermore, in recent years, examinations of planar light emitters in which a light source is combined with a glass laminate using a transparent resin excellent in light guide performance such as methacrylic resin and a light guide method is applied have begun. Such planar light emitters can be preferably used for high-performance automotive glazing materials such as automotive sunroof materials that can also function as interior lighting.
  • a conventional glass laminate in which an inorganic glass plate and a general methacrylic resin sheet are bonded has the following problems.
  • a soft resin sheet such as a polyvinyl butyral sheet serving as an intermediate film and an methacrylic resin sheet are stacked, and then heat-pressed by a hot press method, a vacuum bag method, or an autoclave method.
  • a hot press method under the heating conditions in which the interlayer film is not completely melted, there is a risk of poor adhesion between the inorganic glass plate and the methacrylic resin sheet or distortion of the glass laminate. Therefore, it is preferable to sufficiently heat the interlayer film so that it completely melts.
  • the temperature required for this is generally above 80 ° C. However, when heating is performed at such a temperature, the methacrylic resin softens and melts and further flows under pressure, which may cause surface roughness.
  • Patent Document 1 discloses a glass laminate including a glass layer and a resin layer comprising a methacrylic resin composition containing a methacrylic resin and a styrene / maleic anhydride copolymer resin and having an increased Tg. (Claim 1).
  • a glass laminate described in Patent Document 1 is applied to a planar light emitter, there is a risk that light emission defects such as color unevenness may occur in the emitted light due to the influence of the styrene / maleic anhydride copolymer resin.
  • the difference in linear expansion coefficient between the inorganic glass plate and the hard resin sheet is the cause, and the glass laminate after thermocompression bonding is brought to room temperature.
  • the glass laminate may be warped, resulting in defects such as delamination and cracking.
  • Patent Document 2 discloses a glass laminate having a laminated structure of plastic plate / first intermediate film / second intermediate film / inorganic glass plate (claims 1 and 19).
  • Patent Document 3 discloses a glass laminate in which an inorganic glass plate and a resin plate are laminated via first and second intermediate films (first and second pressure-sensitive adhesive layers) having different viscoelastic properties. (Claims 1 and 6).
  • the glass laminate of Patent Document 3 preferably includes a transparent water vapor barrier layer between the first and second intermediate films (Claim 3).
  • the glass laminates described in Patent Documents 2 and 3 do not require high-temperature and high-pressure treatment during the production of the glass laminate, it is possible to suppress the occurrence of defects such as warpage, delamination, and cracking.
  • the method for producing a glass laminate described in Patent Document 2 has a first laminate having a laminated structure of a plastic plate / first intermediate film and a laminated structure of a second intermediate film / inorganic glass plate. This is a method in which the two laminated bodies are bonded together after the second laminated body is produced separately (claim 1). Therefore, there are many steps and the cost is high.
  • the glass laminate described in Patent Document 3 needs to have a transparent water vapor barrier layer between the first and second intermediate films, and is poor in productivity.
  • the glass laminate used for vehicles and the like can be exposed to any environment such as a high temperature environment, a low temperature environment, a temperature change environment, a high humidity environment, and a rainy environment. Even when used in such an environment, it is preferable that defects such as surface roughness, warpage, delamination, and cracking hardly occur and have good durability. In addition, defects such as warpage, delamination, and cracking can occur not only due to the difference in the linear expansion coefficient between the inorganic glass plate and the resin sheet, but also due to the difference in water absorption between these members.
  • the present invention has been made in view of the above circumstances, can be reduced in weight, has good transparency, and has surface roughness, warpage, delamination, cracking, and the like in the step of bonding the inorganic glass plate and the resin sheet. It is an object to provide a glass laminate that can suppress the occurrence of defects, has good durability, and has excellent light guiding performance.
  • the present invention provides the following glass laminates [1] to [14], a manufacturing method thereof, a planar light emitter, and a vehicle member.
  • the hard resin sheet comprises a hard resin composition having the following characteristics (a) and (b):
  • the glass laminated body which the said intermediate film consists of a soft resin composition which has the following characteristic (c) and (d).
  • the storage elastic modulus G ′ at a set temperature of 25 ° C. and a frequency of 1.0 Hz is 1.0 ⁇ 10 7 Pa or less.
  • the peak temperature at which the loss tangent tan ⁇ at the frequency of 1.0 Hz is maximum is 25 ° C. or less.
  • the hard resin composition includes a methyl methacrylate (co) polymer composed of 60 to 100% by mass of methyl methacrylate units and 0 to 40% by mass of (meth) acrylic acid ester units other than methyl methacrylate.
  • the glass laminate according to [2], wherein the tridentate syndiotacticity (rr) of the methyl methacrylate (co) polymer is 50 to 85%.
  • the hard resin composition further contains 0.0001 to 0.001 of light diffusing particles having an absolute value of a refractive index difference ( ⁇ n) of 0.3 to 3 with respect to the refractive index of the matrix resin of the hard resin sheet.
  • the soft resin composition includes a thermoplastic polyurethane resin.
  • the intermediate film has a surface uneven structure on at least one side.
  • a planar light-emitting body comprising the glass laminate of any one of [1] to [8] and a light source for introducing light into at least one end face of the glass laminate.
  • a vehicle member comprising the glass laminate of any one of [1] to [8] or the planar light emitter of [9].
  • the vehicle member according to [10] which is an automobile glazing material or an automobile sunroof material.
  • the weight can be reduced, the transparency is good, and the occurrence of defects such as surface roughness, warpage, delamination, and cracking in the process of bonding the inorganic glass plate and the resin sheet is suppressed. It is possible to provide a glass laminate having good durability and excellent light guiding performance.
  • the glass laminate of the present invention includes a laminated structure in which a hard resin sheet is laminated on an inorganic glass plate via an intermediate film.
  • the hard resin sheet is made of a hard resin composition having specific heat resistance characteristics and optical characteristics, specifically, the following characteristics (a) and (b).
  • the interlayer film is made of a soft resin composition having specific viscoelastic characteristics, specifically, the following characteristics (c) and (d).
  • Tg Glass transition temperature
  • B The light transmittance at a wavelength of 420 nm with an optical path length of 200 mm is 60% or more.
  • C The storage elastic modulus G ′ at a set temperature of 25 ° C. and a frequency of 1.0 Hz is 1.0 ⁇ 10 7 Pa or less.
  • the peak temperature at which the loss tangent tan ⁇ at the frequency of 1.0 Hz is maximum is 25 ° C. or less.
  • various parameters such as the peak temperature at which the weight average molecular weight (Mw), glass transition temperature (Tg), light transmittance, storage elastic modulus G ′, and loss tangent tan ⁇ are maximized are [implementing the invention]. Measured value measured by the method described in the section of [Form for Use] or [Example]. In the present specification, arbitrary numerical ranges A to B indicate a numerical range of A to B.
  • the glass laminate of the present invention is a composite material including an inorganic glass plate and a hard resin sheet, 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.
  • the hard resin sheet has specific heat resistance (characteristic (a)). Therefore, in the process of bonding the inorganic glass plate and the hard resin sheet, the hard resin sheet can be used even if sufficient heating is performed so that the intermediate film completely melts in order to bond the inorganic glass plate and the hard resin sheet well. Softening, melting, and flow are suppressed. As a result, the occurrence of surface roughness of the hard resin sheet is suppressed, and a uniform glass laminate having a uniform thickness can be obtained.
  • the interlayer film has specific viscoelastic properties (characteristics (c) and (d)).
  • the intermediate film can have a function of favorably bonding the inorganic glass plate and the hard resin sheet and a function of improving the impact resistance of the glass laminate.
  • the interlayer film further has an internal stress relaxation performance, and in this step, in the step of bonding the inorganic glass plate and the hard resin sheet, the thermocompression bonding is caused by the difference in the linear expansion coefficient between the inorganic glass plate and the hard resin sheet. It can have a function of suppressing the occurrence of defects such as warpage, delamination, and cracking of the glass laminate that may occur in the process in which the subsequent glass laminate returns to room temperature.
  • the above-mentioned effects due to the heat resistance of the hard resin sheet and the viscoelastic properties of the interlayer film are not limited to the production of the glass laminate, but can be used in any environment such as high temperature environment, low temperature environment, temperature change environment, high humidity environment, and rain environment. It can be obtained in the same way under the environment. Therefore, even if the glass laminate of the present invention is used in an arbitrary environment, the surface roughness due to softening and melting of the hard resin sheet and flow, the difference in linear expansion coefficient between the inorganic glass plate and the hard resin sheet, and the water absorption rate The occurrence of defects such as warpage, delamination, and cracking that may occur due to the difference in resistance is unlikely to occur, and good durability can be achieved.
  • the glass laminate of the present invention since the hard resin sheet has specific optical characteristics (characteristic (b)), transparency is good and light guiding performance is excellent. Therefore, the glass laminate of the present invention can be used as a light guide plate. By combining the glass laminate of the present invention with a light source that introduces light into one end face of the glass laminate, a planar light emitter having good light emission performance can be provided.
  • Inorganic glass plate There is no particular limitation on the inorganic glass plate, and float plate glass, polished plate glass, mold plate glass, mesh plate glass, heat ray absorbing plate glass, special glass (for example, metal such as silver or metal such as indium tin oxide for the purpose of controlling sunlight) Oxide-sputtered), low-E glass, tempered glass, and combinations thereof. These may be colorless or colored.
  • the hard resin sheet is made of a hard resin composition having a glass transition temperature (Tg) of 120 ° C. or higher and a light transmittance of 60% or more at a wavelength of 420 nm with an optical path length of 200 mm.
  • the hard resin sheet may have a single layer structure or a laminated structure composed of a plurality of hard resin composition layers having different compositions.
  • the hard resin composition has a glass transition temperature (Tg) of 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 140 ° C. or higher.
  • Tg glass transition temperature
  • the light transmittance of the hard resin composition at a wavelength of 420 nm at an optical path length of 200 mm is 60% or more, preferably 70% or more, and more preferably 80% or more.
  • the wavelength of 420 nm is a wavelength in a region close to 470 nm which is a peak wavelength of a general blue LED (light emitting diode) used as one of light sources of an optical member such as a light guide plate. If the light transmittance at this wavelength of 420 nm is low, there is a possibility that yellowishness may slightly increase.
  • the spectral light transmittance at a wavelength of 420 nm is measured using an injection molded long optical path molded product (200 mm ⁇ 50 mm ⁇ 2 mm) under the condition of an optical path length of 200 mm. Shall.
  • the hard resin composition is a methacrylic resin composition containing a methyl methacrylate (co) polymer (A).
  • the methyl methacrylate (co) polymer (A) is a polymethyl methacrylate (PMMA) that is a homopolymer of methyl methacrylate (MMA), or a co-polymer of MMA and one or more other monomers. It is a coalescence.
  • PMMA polymethyl methacrylate
  • MMA polymethyl methacrylate
  • MMA polymethyl methacrylate
  • MMA polymethyl methacrylate
  • MMA polymethyl methacrylate
  • MMA polymethyl methacrylate
  • MMA homopolymer of methyl methacrylate
  • co-polymer of MMA MMA
  • It is a coalescence.
  • One or more methyl methacrylate (co) polymers (A) can be used.
  • the content of the MMA unit in the methyl methacrylate (co) polymer (A) is not particularly limited, and is preferably 60% by mass or more, more preferably 80% by mass or more, because the hard resin sheet has excellent scratch resistance. More preferably, it is 90% by mass or more, particularly preferably 99% by mass or more, and most preferably 100% by mass.
  • the content of MMA units in the methyl methacrylate (co) polymer (A) was purified by reprecipitation of the methyl methacrylate (co) polymer (A) in methanol, and then pyrolysis gas chromatography was used. Thus, thermal decomposition and separation of volatile components can be carried out, and calculation can be made 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 units.
  • (meth) acrylic acid esters 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
  • the content of (meth) acrylic acid ester units other than MMA units in the methyl methacrylate (co) polymer (A) is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less. Particularly preferably, it is 1% by mass or less, and most preferably 0% by mass.
  • the methyl methacrylate (co) polymer (A) is obtained by polymerizing one or more monomers including MMA.
  • a plurality of types of monomers in the 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, and radical polymerization and anionic polymerization are preferable from the viewpoints of productivity and heat resistance.
  • the methyl methacrylate (co) polymer (A) preferably has a triadic syndiotacticity (rr) (hereinafter also referred to as “rr ratio”) from the viewpoint of heat resistance and moldability. 85%.
  • the lower limit of the rr ratio is more preferably 53%, still more preferably 55%, particularly preferably 58%, and most preferably 60%.
  • the upper limit of the rr ratio is more preferably 77%, and particularly preferably 65%.
  • the rr ratio is a ratio in which two chains (doublet, diad) of three consecutive structural unit chains (triplet, triad) are both racemo (represented as rr).
  • chains doublet, diad
  • racemo those having the same configuration
  • racemo those opposite to each other
  • the rr ratio of the methyl methacrylate (co) polymer (A) was determined by measuring a 1 H-NMR spectrum in deuterated chloroform at 30 ° C., from which tetramethylsilane (TMS) was 0 ppm.
  • TMS tetramethylsilane
  • 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 it can.
  • 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, particularly preferably 80,000 to 200,000. 000.
  • Mw is 40,000 or more, the hard resin sheet is excellent in mechanical strength, and when it is 500,000 or less, the hard resin sheet is excellent in moldability.
  • the methyl methacrylate (co) polymer (A) has a glass transition temperature (Tg) of preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and particularly preferably 140 ° C. or higher.
  • Tg glass transition temperature
  • the methyl methacrylate (co) polymer (A) has a light transmittance at a wavelength of 420 nm at an optical path length of 200 mm, preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more.
  • the light transmittance is 60% or more, the hard resin sheet is excellent in transparency and light guiding performance.
  • the melt flow rate (MFR) of the methyl methacrylate (co) polymer (A) is preferably 1 to 10 g / 10 min.
  • the lower limit value of MFR is more preferably 1.2 g / 10 minutes, 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 is a value measured using a melt indexer at a temperature of 230 ° C. and a load of 3.8 kg unless otherwise specified.
  • the hard resin composition contains one or more polycarbonate resins (PC) in place of the methyl methacrylate (co) polymer (A) or in combination with the methyl methacrylate (co) polymer (A). be able to.
  • the polycarbonate-based resin (PC) is a polymer having a basic structure including a carbonic acid bond represented by a general formula: — (— O—X—O—C ( ⁇ O) —) —.
  • X is generally a hydrocarbon group, but a hydrocarbon group into which a hetero atom or a hetero bond is introduced may be used for imparting various properties.
  • PC Polycarbonate resins
  • aromatic polycarbonate resins can be classified into aromatic polycarbonate resins and aliphatic polycarbonate resins, based on the type of hydrocarbons that are directly bonded to carbonic acid bonds. Any of them may be used, but an aromatic polycarbonate resin is more preferable from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.
  • the aromatic polycarbonate resin can be obtained, for example, by reacting an aromatic dihydroxy compound, a carbonate precursor, and, if necessary, a polyhydroxy compound.
  • the aromatic polycarbonate resin may be linear or branched.
  • the aromatic polycarbonate resin may be a homopolymer composed of one type of repeating unit or a copolymer having a plurality of repeating units.
  • the form of the copolymer is arbitrary such as a random copolymer and a block copolymer.
  • aromatic dihydroxy compound bis (hydroxyaryl) alkanes are preferable. Among them, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A) is particularly preferable from the viewpoint of impact resistance and heat resistance.
  • the carbonate precursor include carbonyl halide and carbonate ester. One or more aromatic dihydroxy compounds and carbonate precursors can be used.
  • Examples of the method for producing a polycarbonate resin (PC) include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization of a cyclic carbonate compound, and a solid phase transesterification of a prepolymer.
  • PC polycarbonate resin
  • SD Polycarbonate SD2201W, SD2211W manufactured by Sumika Stylon Polycarbonate Co., Ltd.
  • Iupilon HL-Series manufactured by Mitsubishi Engineering Plastics Co., Ltd., and the like
  • the viscosity average molecular weight (Mv) of the polycarbonate-based resin (PC) is only required to be moldable, and is usually 12,000 to 50,000, preferably 14,000 to 40,000, more preferably 16,000 to 30,000. It is. If the Mv of the polycarbonate resin (PC) is less than 12,000, the mechanical strength may decrease. If Mv exceeds 50,000, the melt fluidity is lowered and the moldability may be insufficient.
  • the polycarbonate resin (PC) may be a mixture of a plurality of polycarbonate resins (PC) having different Mvs. In this case, if the molecular weight of the mixture is within the above range, a polycarbonate resin (PC) having Mv outside the above range may be included.
  • viscosity average molecular weight (Mv) uses methylene chloride as a solvent and measures the intrinsic viscosity [ ⁇ ] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. It is a value calculated from the viscosity formula of Schnell of the following formula (1).
  • the intrinsic viscosity [ ⁇ ] is a value calculated from the following formula (2) by measuring the specific viscosity ⁇ sp at the solution concentration c (g / dl).
  • the polycarbonate resin (PC) has a glass transition temperature (Tg) of preferably 140 ° C. or higher, more preferably 145 ° C. or higher, and particularly preferably 150 ° C. or higher.
  • Tg glass transition temperature
  • the hard resin sheet has excellent heat resistance.
  • the polycarbonate resin (PC) preferably has a light transmittance at an optical path length of 200 mm and a wavelength of 420 nm of 60% or more, more preferably 70% or more, and particularly preferably 80% or more.
  • the light transmittance is 60% or more, the hard resin sheet is excellent in transparency and light guiding performance.
  • the hard resin composition containing methyl methacrylate (co) polymer (A) and / or polycarbonate-based resin (PC) can further contain light diffusing particles.
  • the light diffusing particles are particles that have a refractive index different from that of the matrix resin and scatter light.
  • the hard resin sheet contains light diffusing particles, when light is introduced from the light source to the one end surface of the glass laminate of the present invention, the light is scattered in the thickness direction of the glass laminate, toward the opposite other end surface. It becomes possible to guide light well in the surface direction of the glass laminate.
  • the light diffusing particles are contained in the hard resin sheet
  • a glass laminate that is excellent in light guide performance and suitable as a light guide plate for a planar light emitter without the need to separately provide a light diffusing layer by printing, surface unevenness processing, etc.
  • the body can be provided.
  • the hard resin sheet may be formed of only a hard resin such as methyl methacrylate (co) polymer (A) and / or polycarbonate resin (PC). In the present invention, even when the hard resin sheet is formed of only the hard resin, the hard resin sheet is considered to be made of the hard resin composition for convenience.
  • the hard resin sheet preferably has good transparency when the light source is turned off.
  • the light diffusing particle diameter, content, and light diffusing particle so that the light guide performance can be effectively improved by the light scattering action of the light diffusing particle after sufficiently ensuring the transparency of the hard resin sheet.
  • the difference in refractive index between the matrix resin and the matrix resin is designed.
  • the volume average particle diameter d ( ⁇ m) 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” is a particle diameter obtained by a laser diffraction scattering method.
  • the content of the light diffusing particles in the hard resin composition is preferably 0.0001 to 0.1% by mass, more preferably 0.000125 to 0.01% by mass. Particularly preferred is 0.00025 to 0.001 mass%.
  • the absolute value of the refractive index difference ( ⁇ n) between the matrix resin (preferably methyl methacrylate (co) polymer (A) and / or polycarbonate resin (PC)) in the hard resin composition and the light diffusing particles is too small. Then, since the light scattering effect cannot be obtained effectively, it is difficult to extract light efficiently. When the light is excessively large, backscattering is dominant and it is difficult to extract light efficiently.
  • the absolute value of the refractive index difference ( ⁇ n) is too small or too large, it is necessary to increase the content of the light diffusing particles in order to obtain sufficient luminance, which may result in insufficient transparency.
  • the absolute value of the difference in refractive index ( ⁇ n) is preferably 0.3 to 3, more preferably 0.4 to 3, from the balance between brightness and transparency during lighting.
  • the product ( ⁇ n ⁇ d) of the absolute value of the refractive index difference ( ⁇ n) and the volume average particle diameter d ( ⁇ m) is preferably 0.1 ⁇ m or more, more preferably 0, from the balance between brightness and transparency at the time of lighting. .5 ⁇ m or more.
  • inorganic compound particles having a large refractive index difference with respect to the matrix resin are preferable, and metal oxide particles such as titanium oxide particles and zinc oxide particles are preferable. These can be used alone or in combination of two or more.
  • the hard resin composition may contain a polymer other than the methyl methacrylate (co) polymer (A) and the polycarbonate resin (PC) 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, styrene- Styrenic resins such as maleic anhydride-MMA copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, and MBS resin; methyl methacrylate-styrene copolymer; polyethylene terephthalate and poly Polyester resins such as butylene terephthalate; polyamide resins such as nylon 6, nylon 66, and polyamide elastomers; polyphenylene sul
  • thermoplastic resins thermosetting resins such as phenol resins, melamine resins, silicone resins, and epoxy resins
  • acrylic rubbers, silicone rubbers styrene thermoplastic elastomers such as SEPS, SEBS, SIS
  • IR And olefin rubbers such as EPR and EPDM.
  • the content of the other polymer in the hard resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.
  • the hard resin composition may contain other various additives as required.
  • Other additives include antioxidants, thermal degradation inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes / pigments, matting agents , Impact resistance modifiers, and phosphors.
  • the content of these additives can be appropriately set within a range not impairing the effects of the present invention.
  • the content of the antioxidant is 0.01 to 1% by mass
  • the content of the ultraviolet absorber is 0.01 to 3%.
  • the content of the light stabilizer is 0.01 to 3% by mass
  • the content of the lubricant is 0.01 to 3% by mass
  • the content of the dye / pigment is 0.01 to 3% by mass.
  • the ultraviolet absorber is a compound having an ability to absorb ultraviolet rays.
  • the ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy.
  • Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, and formamidines.
  • benzotriazoles, triazines, or ultraviolet absorbers having a maximum molar extinction coefficient ⁇ max at a wavelength of 380 to 450 nm of 1200 dm 3 ⁇ mol ⁇ 1 cm ⁇ 1 or less are preferable.
  • Benzotriazoles are preferably used when the glass laminate is applied to optical applications because it has a high effect of suppressing deterioration in optical properties such as coloring due to ultraviolet irradiation.
  • benzotriazoles include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (such as “trade name TINUVIN329” manufactured by BASF Japan Ltd.), 2 -(2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (such as “trade name TINUVIN234” manufactured by BASF Japan Ltd.), and 2,2′-methylenebis [ 6- (2H-benzotriazol-2-yl) -4-t-octylphenol] (“ADEKA STAB LA-31” manufactured by ADEKA Corporation) and the like are preferable.
  • a triazine UV absorber is preferably used.
  • Such UV absorbers include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (“ADEKA STAB LA-F70” manufactured by ADEKA Corporation) And hydroxyphenyltriazine-based ultraviolet absorbers (such as “TINUVIN477” and “TINUVIN460” manufactured by BASF Japan Ltd.) which are analogs thereof.
  • the light stabilizer is a compound that is said to have a function of capturing radicals generated mainly by oxidation by light.
  • Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6 monotetraalkylpiperidine skeleton. Examples thereof include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (“ADEKA STAB LA-77Y” manufactured by ADEKA Corporation) and the like.
  • a hard fat composition preferably containing methyl methacrylate (co) polymer (A) and / or polycarbonate resin (PC)
  • the timing of adding the optional component is not particularly limited, and the methyl methacrylate (co) polymer (A) polymerized during polymerization of the methyl methacrylate (co) polymer (A) and / or the polycarbonate resin (PC) (A) ) And polycarbonate resin (PC) may be mixed at any timing or after mixing.
  • the MFR of the hard resin composition is preferably 1 to 10 g / 10 minutes.
  • the lower limit value of MFR is more preferably 1.5 g / 10 minutes, and particularly preferably 2.0 g / 10 minutes.
  • the upper limit value of MFR is more preferably 7.0 g / 10 minutes, particularly preferably 4.0 g / 10 minutes.
  • the molding method of the hard resin sheet is not particularly limited, and examples thereof include an extrusion molding method, a cast molding method, and an injection molding method, and the extrusion molding method and the like are preferable.
  • a hard resin sheet having a laminated structure composed of a plurality of hard resin composition layers can be formed by known multilayer molding.
  • the hard resin sheet can also be multilayer extruded with an interlayer or any other layer.
  • the intermediate film is a transparent layer that bonds the inorganic glass plate and the hard resin sheet.
  • the intermediate film is made of a soft resin composition having specific viscoelastic properties.
  • the interlayer film may have a single layer structure or a laminated structure composed of a plurality of soft resin composition layers having different compositions.
  • the soft resin composition has a storage elastic modulus G ′ at a set temperature of 25 ° C. and a frequency of 1.0 Hz of 1.0 ⁇ 10 7 Pa or less, preferably 5.0 ⁇ 10 6 Pa or less, more preferably 1. 0 ⁇ 10 6 Pa or less.
  • the storage elastic modulus G ′ is 1.0 ⁇ 10 7 Pa or less, the difference in linear expansion coefficient and the difference in water absorption between the inorganic glass plate and the hard resin sheet during the production and actual use of the glass laminate. It is possible to effectively suppress the occurrence of defects such as warpage, delamination, and cracking that may occur due to.
  • the soft resin composition has a peak temperature at which the loss tangent tan ⁇ at a frequency of 1.0 Hz is maximized at 25 ° C. or lower, preferably 20 ° C. or lower, more preferably 15 ° C. or lower.
  • the maximum peak temperature of the loss tangent tan ⁇ is 25 ° C. or less, the glass laminate of the present invention can suppress the occurrence of the above-described defects and has excellent impact resistance.
  • the soft resin constituting the soft resin composition examples include polyvinyl butyral, ethylene-vinyl acetate copolymer, ethylene ionomer, thermoplastic polyurethane resin, and modified products thereof. These can be used alone or in combination of two or more.
  • the intermediate film has a function of favorably bonding the inorganic glass plate and the hard resin sheet and a function of improving the impact resistance of the glass laminate. Furthermore, it has internal stress relaxation performance, which may occur during manufacturing and actual use of glass laminates due to differences in linear expansion coefficient and water absorption between inorganic glass plates and hard resin sheets. It has a function of suppressing the occurrence of defects such as warping, delamination, and cracking.
  • a thermoplastic polyurethane resin is particularly preferred because of its excellent function.
  • the intermediate film may be formed of only a soft resin such as a thermoplastic polyurethane resin, or may further contain various additives in addition to the soft resin as described above. In the present invention, even when such an intermediate film is formed of only a soft resin, for convenience, the intermediate film is considered to be formed of a soft resin composition.
  • the thermoplastic polyurethane resin is obtained by reacting a polyisocyanate, a polyol and a chain extender.
  • the thermoplastic polyurethane-based resin is preferably a block copolymer composed of a hard segment formed by a reaction between a chain extender and polyisocyanate and a soft segment formed by a reaction between a polyol and polyisocyanate.
  • diisocyanate is preferable, and aliphatic diisocyanate compounds such as hexamethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethyl-1,6-hexane diisocyanate; bis (4-isocyanatocyclohexyl) Alicyclic diisocyanate compounds such as methane, 2,2-bis (4-isocyanatocyclohexyl) propane, 1,4-cyclohexyl diisocyanate, and 1-methyl-2,4- (or 2,6) -diisocyanatecyclohexane; isophorone Aliphatic and alicyclic mixed diisocyanate compounds such as diisocyanate; toluene diisocyanate, diphenylmethane diisocyanate (MDI), polymeric MD , Tolylene diisocyanate, p- phenylene diisocyanate,
  • MDI dipheny
  • polyol examples include polyester diols obtained by a polyesterification reaction of an aliphatic dibasic acid or an anhydride thereof with a dihydric alcohol (preferably an aliphatic dihydric alcohol).
  • the aliphatic dibasic acid is represented by the general formula HOOC—R—COOH (wherein R is an alkylene group having 2 to 12 carbon atoms, preferably 4 to 8 carbon atoms), adipic acid, succinic acid, Examples include palmitic acid, suberic acid, azelaic acid, and sebacic acid.
  • the dihydric alcohol is preferably an alcohol having 2 to 15 carbon atoms, and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol.
  • polyols include polyoxytetramethylene diol having an oxymethylene group, oxypropylene group or polyoxyalkylene diol having an oxyethylene group and an oxypropylene group, and the above oxyalkylene group and oxytetramethylene group.
  • polyether diol examples include polyether diol.
  • polystyrene resin examples include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; polycarbonate diols obtained by polycondensation of compounds such as phosgene, chloroformate, diallyl carbonate, and alkylene carbonate with low molecular weight polyols. .
  • dialkyl carbonates such as dimethyl carbonate and diethyl carbonate
  • polycarbonate diols obtained by polycondensation of compounds such as phosgene, chloroformate, diallyl carbonate, and alkylene carbonate with low molecular weight polyols.
  • One or more polyols can be used.
  • chain extender examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and bishydroxyethoxybenzene.
  • the storage elastic modulus G ′ and the loss tangent tan ⁇ peak temperature of the thermoplastic polyurethane resin are determined by the hard segment (reaction site between the chain extender and the polyisocyanate) and the soft segment (polyol and polyisocyanate) constituting the thermoplastic polyurethane resin. It is possible to adjust by selecting the mass ratio to the reaction site), the glass transition temperature (Tg) of the soft segment, and the weight average molecular weight (Mw) or type of each component. For example, the storage modulus G ′ tends to decrease when a soft segment having a high mass ratio is used, and the tan ⁇ peak temperature tends to decrease when a soft segment having a low glass transition temperature (Tg) is used.
  • the surface shape of the intermediate film is not particularly limited, and may have a surface uneven structure such as an embossed structure on at least one surface, preferably both surfaces.
  • a surface uneven structure such as an embossed structure
  • the height of the surface uneven structure is not particularly limited, and is preferably 5 to 500 ⁇ m, more preferably 7 to 300 ⁇ m, and particularly preferably 10 to 200 ⁇ m.
  • the height of the surface concavo-convex structure is less than 5 ⁇ m, when the inorganic glass plate and the hard resin sheet are laminated, air bubbles formed between the inorganic glass plate and the intermediate film and between the hard resin sheet and the intermediate film are efficiently formed. In some cases, it cannot be removed.
  • the thickness exceeds 500 ⁇ m, it is difficult to form a surface uneven structure.
  • the shape of the surface uneven structure may be regular or irregular. Examples of the method for forming the surface uneven structure include an emboss roll method, a calender roll method, and a profile extrusion method. Among these, the embossing roll method is preferable because a relatively large amount of the uneven pattern can be easily formed.
  • the intermediate film can be formed using a soft resin sheet.
  • the molding method of the soft resin sheet is not particularly limited, and examples thereof include an extrusion molding method, a cast molding method, and an injection molding method, and the extrusion molding method and the like are preferable.
  • a soft resin sheet having a laminated structure composed of a plurality of soft resin composition layers can be formed by known multilayer molding.
  • the soft resin sheet can also be multilayer extruded with a hard resin sheet or any other layer.
  • the uneven surface structure can be imparted during or after the cooling step when molding the soft resin sheet, or after the production of the soft resin sheet.
  • a glass laminate 1 according to the first embodiment shown in FIG. 1 is a glass laminate having a three-layer structure in which an intermediate film 12 and a hard resin sheet 13 are sequentially provided on an inorganic glass plate 11.
  • the thickness of each component is not particularly limited.
  • the thickness of the inorganic glass plate 11 is preferably 0.1 to 4.0 mm, more preferably 0.5 to 3.0 mm, and particularly preferably 1.0 to 2.0 mm from the viewpoint of rigidity and weight reduction. .
  • the thickness of the intermediate film 12 is preferably 0.03 to 8.0 mm, more preferably 0.1 to 7.0 mm, and particularly preferably 0 from the viewpoints of interlayer adhesion, impact resistance, and internal stress relaxation performance. .4 to 6.0 mm.
  • the thickness of the hard resin sheet 13 is preferably 0.1 to 10 mm, more preferably 0.5 to 5 mm, and particularly preferably 1.0 to 3 in terms of scratch resistance, weather resistance, impact resistance, and the like. 0.0 mm.
  • the manufacturing method in particular of the glass laminated body 1 of 1st Embodiment is not restrict
  • the method to match is mentioned.
  • the inorganic glass plate 11 may be subjected to adhesion enhancement treatment on at least one surface in advance, if necessary.
  • the adhesion enhancing process is described in, for example, US Pat. No. 7,625,627.
  • the thermocompression bonding method is not particularly limited, and examples thereof include a hot press method, a vacuum bag method, and an autoclave method.
  • a pre-laminated body in which a soft resin sheet that becomes an inorganic glass plate 11 and an intermediate film 12 and a hard resin sheet 13 are placed in a vacuum bag, air is sucked from the vacuum bag by means of a vacuum line or the like, and the vacuum bag A method of heating and pressurizing inside an autoclave or the like while maintaining the inside vacuum state is preferable.
  • the heating temperature required for this is generally above 80 ° C, preferably above 90 ° C.
  • the upper limit of the heating temperature is preferably 120 ° C, more preferably 110 ° C.
  • a laminated sheet composed of the intermediate film 12 and the hard resin sheet 13 is prepared in advance, and this laminated sheet is laminated on the inorganic glass plate 11 and bonded by thermocompression bonding.
  • a laminated sheet composed of the intermediate film 12 and the hard resin sheet 13 can be performed by known multilayer molding.
  • the multilayer molding method include a multilayer extrusion molding method, a multilayer blow molding method, a multilayer press molding method, a multicolor injection molding method, and an insert injection molding method. From the viewpoint of productivity, multilayer extrusion molding in which the intermediate film 12 and the hard resin sheet 13 are laminated by melt coextrusion is preferable.
  • multilayer extrusion molding using a molding apparatus provided with a flat T die and a plurality of cooling rolls adjacent to each other is preferable.
  • the T-die method include a feed block method in which a plurality of types of heat-melted resins are laminated before the T-die flows, and a multi-manifold method in which a plurality of types of heat-melted resins are laminated inside the T die. It is done. From the viewpoint of improving the smoothness of the interface between layers, the multi-manifold method is preferable.
  • the cooling roll in contact with at least the hard resin sheet among the plurality of cooling rolls is preferably a polishing roll having a mirror-finished surface.
  • the glass laminated body of this invention is not limited to the three-layer structure shown in figure, A design change is possible suitably.
  • Each of the inorganic glass plate 11, the intermediate film 12, and the hard resin sheet 13 may be singular or plural.
  • the glass laminate can include other optional layers as required.
  • the constituent material of the other layer is not particularly limited, and examples thereof include various resins (thermoplastic resin, thermosetting resin, energy ray curable resin, and combinations thereof) having different compositions from the intermediate film and the hard resin sheet. .
  • the function of other layers is not particularly limited, and is a support layer that supports other elements, an abrasion-resistant layer, an antistatic layer, an antifouling layer, a friction reducing layer, an antiglare layer, an antireflection layer, an adhesive layer, and heat ray absorption.
  • You may function as various functional layers, such as a layer, a sound insulation layer, and an impact strength provision layer.
  • Other layers may be singular or plural. When there are a plurality of other layers, the composition may be the same or non-identical.
  • the glass laminate 2 of the second embodiment shown in FIG. 2 has the glass laminate 1 of the first embodiment as a basic structure, and further, between the intermediate film 12 and the hard resin sheet 13, the hard resin sheet 13 is It is the aspect provided with the thermoplastic resin layer 14 from which a composition differs.
  • the thermoplastic resin layer 14 may have a single layer structure or a laminated structure.
  • the constituent resin of the thermoplastic resin layer 14 is not particularly limited.
  • Methacrylic resin Polyolefin resin such as polyethylene and polypropylene; Polystyrene resin; Polyester resin; Polyamide resin; Polycarbonate resin; Polyvinyl chloride, Polychlorinated resin Vinylidene, polyvinyl alcohol, polyvinylidene fluoride; modified polyphenylene ether, polyphenylene sulfide; silicone modified resin; polyether ether ketone; polysulfone; polyphenylene oxide; polyimide, polyetherimide; Among these, methacrylic resins and polycarbonate resins are preferable from the viewpoints of transparency, heat resistance, and impact resistance.
  • the thickness of the thermoplastic resin layer 14 is not particularly limited, and is preferably 0.04 to 3 mm, more preferably 0.05 to 1.5 mm, and particularly preferably 0.06 to 1.0 mm.
  • the impact resistance of a glass laminated body can be improved because the thickness of the thermoplastic resin layer 14 is 0.04 mm or more, and the curvature of a glass laminated body can be suppressed because it is 3 mm or less.
  • the manufacturing method in particular of the glass laminated body 2 of 2nd Embodiment is not restrict
  • a method of preparing a laminated sheet composed of the intermediate film 12, the thermoplastic resin layer 14, and the hard resin sheet 13 in advance, and laminating the laminated sheet on the inorganic glass plate 11 and bonding them by thermocompression bonding. is mentioned.
  • a design change is possible suitably similarly to 1st Embodiment.
  • the glass laminated body 3 of 3rd Embodiment shown in FIG. 3 is the aspect which equipped the glass laminated body 1 of 1st Embodiment as basic structure, and also was equipped with the abrasion-resistant layer 21 on the hard resin sheet 13.
  • FIG. The glass laminate 4 of the fourth embodiment shown in FIG. 4 is a mode in which the glass laminate 2 of the second embodiment is a basic structure and the scratch-resistant layer 21 is further provided on the hard resin sheet 13.
  • the glass laminate 5 of the fifth embodiment shown in FIG. 5 is a mode in which the glass laminate 1 of the first embodiment is a basic structure and the scratch-resistant layers 21 are provided on both surfaces of the hard resin sheet 13.
  • the scratch-resistant layer 21 can be formed, for example, by applying a fluid curable composition composed of a monomer, an oligomer, a resin, and the like to the surface of the hard resin sheet 13 and curing it.
  • the curable composition is, for example, a thermosetting composition that is cured by heat, or an energy beam curable composition that is cured by an energy beam such as an electron beam, radiation, or ultraviolet rays.
  • Thermosetting compositions include phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, unsaturated polyester resins, polyurethane resins, epoxy resins, aminoalkyd resins, melamine-urea cocondensation resins, It includes a thermosetting resin such as silicon resin and polysiloxane resin.
  • 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.
  • Curing agents include isocyanates for polyurethane resins, organic sulfonic acids for polyester resins, amines for epoxy resins, peroxides such as methyl ethyl ketone peroxide and azobisisobutyl esters for unsaturated polyester resins, etc. These radical initiators are preferably 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. From the viewpoint of enhancing the scratch resistance, a composition containing an oligomer and / or monomer having a plurality of acryloyl groups 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.
  • the photosensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.
  • the thickness of the scratch-resistant layer 21 is not particularly limited, and 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, good scratch resistance can be expressed, and when the thickness is 10 ⁇ m or less, the impact resistance of the glass laminate tends to be excellent.
  • the manufacturing method in particular of the glass laminated body 3 of 3rd Embodiment is not restrict
  • seat 13 in this order is mentioned.
  • a laminated sheet composed of the intermediate film 12, the hard resin sheet 13, and the scratch-resistant layer 21 is prepared in advance, and this laminated sheet is laminated on the inorganic glass plate 11 and bonded by thermocompression bonding. Can be mentioned.
  • thermoplastic resin layer 14 is previously formed in one surface by the inorganic glass plate 11, the soft resin sheet used as the intermediate film 12, and the other There is a method in which the hard resin sheet 13 having the scratch-resistant layer 21 formed on the surface is superposed in this order, followed by thermocompression bonding.
  • a laminated sheet composed of the intermediate film 12, the thermoplastic resin layer 14, the hard resin sheet 13, and the scratch-resistant layer 21 is prepared in advance, and this laminated sheet is laminated on the inorganic glass plate 11 and thermocompression bonded. And pasting them together.
  • the manufacturing method in particular of the glass laminated body 5 of 5th Embodiment is not restrict
  • a laminated sheet composed of the intermediate film 12, the first scratch-resistant layer 21, the hard resin sheet 13, and the second scratch-resistant layer 21 is prepared in advance, and this laminated sheet is used as the inorganic glass plate 11. There is a method of stacking them on top of each other and applying them by thermocompression bonding.
  • the hard resin sheet 13 having the scratch-resistant layers 21 on both sides has the same distortion caused by curing of the curable composition on both sides of the hard resin sheet 13, so that warpage is suppressed and the soft resin composition constituting the intermediate film 12. Adhesion with objects is improved. Note that the glass laminates 3 to 5 of the third to fifth embodiments can be appropriately changed in design as in the first embodiment.
  • the present invention weight reduction is possible, transparency is good, and defects such as surface roughness, warpage, delamination, and cracking in the process of bonding the inorganic glass plate and the resin sheet are performed.
  • production can be suppressed, durability can be provided, and the glass laminated body excellent in the light guide performance can be provided.
  • the planar light-emitting body of the present invention includes the above-described glass laminate of the present invention and a light source for introducing light from one or both end surfaces of the glass laminate.
  • FIG. 6 the schematic cross section of the planar light-emitting body of one Embodiment which concerns on this invention is shown.
  • the planar light-emitting body 6 of this embodiment includes a glass laminate 61, a light source 62 disposed adjacent to both end faces of the hard resin sheet 61C of the glass laminate 61, and light for efficiently using light.
  • a reflective cover 63 is shown.
  • the glass laminate 61 is a glass laminate of the present invention including a laminated structure in which a hard resin sheet 61C is laminated on an inorganic glass plate 61A via an intermediate film 61B.
  • the glass laminate 61 of the first embodiment shown in FIGS. ⁇ A laminated structure of any one of the glass laminates 1 to 5 of the fifth embodiment.
  • Light emitted from the light source 62 is incident from both end surfaces that are the light incident side end surfaces of the hard resin sheet 61 ⁇ / b> C of the glass laminate 61, and is guided toward the center of the glass laminate 61.
  • a planar light-emitting body 7 having a design change shown in FIG. 7 includes a glass laminate 61, and a light source 62 and a light reflection cover 63 arranged adjacent to one end face of the glass laminate 61.
  • FIG. 7 the same components as those in FIG. 6 are denoted by the same reference numerals.
  • the glass laminate of the present invention includes, for example, building parts such as safety window glass and partitions; optical parts such as liquid crystal protective plates, light guide plates, front plates of various displays, and diffusion plates; automobile interior / exterior members (side visors, Vehicle components such as rear visor, head wing, headlight cover, bumper, sunroof, and glazing); bathroom components such as greenhouses, large aquariums, box aquariums, bathtubs, sanitary components, clock panels, desk mats, game parts, toys And a mask for protecting the face during welding.
  • the glass laminate and the planar light emitter of the present invention are suitable as a vehicle member, and are suitable as an automobile glazing material, particularly an automobile sunroof material.
  • a high-performance automobile 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.
  • Evaluation items and evaluation methods are as follows. (Glass transition temperature (Tg) of hard resin composition) 10 mg of the hard resin composition was dried at 80 ° C. for 24 hours, and then placed in an aluminum pan. After performing nitrogen substitution for 30 minutes or more using a differential scanning calorimeter (TA Instruments “Q20”), the temperature was increased from 25 ° C. to 200 ° C. at a rate of 20 ° C./min in a nitrogen stream of 10 ml / min. After being held at 200 ° C. for 10 minutes, it was naturally cooled to 25 ° C. (primary scanning). Next, the temperature was raised again to 200 ° C. at a rate of 10 ° C./min (secondary scanning), and the glass transition temperature (Tg) was calculated by the midpoint method.
  • Tg Glass transition temperature
  • a planar light emitter 7 as shown in FIG. 7 was prepared and evaluated.
  • the glass laminate 61 was previously subjected to a light absorption process 64 on the other end face facing the end face on the light incident side.
  • a light source 62 and a light reflection cover 63 are disposed adjacent to the end surface on the light incident side of the glass laminate 61.
  • the light source 62 one in which seven LEDs are arranged in a line in a parallel direction with respect to the end surface on the light incident side of the glass laminate at an interval of 10 mm was used.
  • “LED NFSW036BT” diameter of light emitting part: 3 mm
  • a voltage of 2.8 V was applied to each LED.
  • the light emitted from the light source 62 enters from the end surface on the light incident side of the glass laminate 61 and is guided through the glass laminate 61 to the other end surface subjected to the light absorption process 64.
  • the distance from the end surface on the light incident side to the other end surface on which the light absorption process 64 was performed was set to 300 mm.
  • the position of the end face on the light incident side was set to 0 mm, and the distance to an arbitrary point between the other end face subjected to the light absorption process 64 was set as the “light guide distance”.
  • the brightness at the time of light source lighting in 200 mm of light guide distances, and the change of a color eye were evaluated visually from the hard resin sheet 61C side. Even when the light guide distance was 200 mm, high luminance surface light emission could be confirmed, the change in chromaticity due to the light guide distance was small, and the change in the color from the end surface on the light incident side to the other end surface was not determined to be “good”. A case where surface emission was low in luminance or color unevenness was observed was judged as “bad”.
  • ⁇ Methacrylic resin (A2)> 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 capacity: 1%, 1 hour half-life temperature: 83 ° C.) 0.0065 Part by mass and 0.290 parts by mass of n-octyl mercaptan were added and stirred to obtain a raw material liquid. Nitrogen was fed into the raw material liquid to remove dissolved oxygen in the raw material liquid. The raw material liquid was put in a tank reactor connected to the autoclave through a pipe up to 2/3 of the capacity.
  • MMA purified methyl methacrylate
  • 2,2′-azobis (2-methylpropionitrile) hydrogen abstraction capacity: 1%, 1 hour half-life temperature: 83 ° C.
  • the polymerization reaction was first started by a batch method.
  • the raw material liquid is supplied from the autoclave to the tank reactor at a flow rate with an average residence time of 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 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.
  • the molten resin from which volatile components were removed was supplied to a twin-screw extruder having an internal temperature of 230 ° C., discharged into a strand, and cut with a pelletizer.
  • ⁇ Methacrylic resin (A3)> 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.
  • ⁇ Methacrylic resin (A4)> 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 ] dec-8-yl (TCDMA) methacrylate, 20 g of methyl acrylate (MA), azobisiso 0.6 g of butyronitrile, 2.0 g of n-octyl mercaptan, 2500 g of ion-exchanged 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.
  • MMA methyl methacrylate
  • TCDMA tricyclo [5.2.1.0 2,6 ] dec-8-yl
  • MA methyl acrylate
  • MA methyl acrylate
  • Table 1 shows the monomer unit composition, MMA ratio, rr ratio, and Mw of the methacrylic resin used.
  • PU1 ⁇ Thermoplastic polyurethane sheet (PU1)> Lubrizol “Estane AG-8451” was calendered and then embossed on both sides to obtain a 760 ⁇ m-thick thermoplastic polyurethane sheet (PU1).
  • Polyvinyl butyral sheet (PVB1)> As a plasticizer for 61.5 parts by mass of Kuraray Co., Ltd. polyvinyl butyral (raw material polyvinyl alcohol with a viscosity average polymerization degree of 1700, acetalization degree of 74 mol%, vinyl alcohol unit 19 mol%, vinyl acetate unit 7 mol%) , “Kuraray polyol P-510” (manufactured by Kuraray Co., Ltd., having a number average molecular weight of 500 per two hydroxyl groups, a polyester diol composed of 3-methyl-1,5-pentanediol and adipic acid) 38.5 parts by mass Added. The obtained polyvinyl butyral resin composition was extruded and then subjected to double-sided embossing to obtain a polyvinyl butyral sheet (PVB1) having a thickness of 760 ⁇ m.
  • Polyvinyl butyral sheet (PVB3) As the polyvinyl butyral sheet (PVB3), “Trosifol Extra-Stiff” (thickness: 760 ⁇ m) manufactured by Kuraray Co., Ltd. was prepared.
  • EI1 ⁇ Ethylene ionomer sheet (EI1)> As an ethylene ionomer sheet (EI1), “SentryGlas” (thickness: 760 ⁇ m) manufactured by Kuraray Co., Ltd. was prepared.
  • the product ( ⁇ n ⁇ d) is shown in Table 2.
  • As the ultraviolet absorber a hydroxyphenyl triazine ultraviolet absorber (“TINUVIN479” manufactured by BASF) was used.
  • the obtained pellet-shaped hard resin compositions (HRC1) to (HRC8) are continuously charged into a vent type single-screw extruder having a shaft diameter of 50 mm, under conditions of a cylinder temperature of 190 to 260 ° C.
  • the hard resin composition in a molten state is extruded from a T-die having a width of 400 mm set at 260 ° C., and formed into a sheet by niping with a pair of metal rigid rolls set at 100 ° C. and 130 ° C., 0.47 m / min I picked up at the speed of.
  • hard resin sheets (HRS1) to (HRS9) width 300 mm, length 400 mm, thickness 2 mm
  • an ultraviolet curable hard coat paint containing a polyfunctional acrylic resin on one surface of each of the obtained hard resin sheets (“UV-1700B” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) ) was used to form a scratch-resistant layer (thickness of about 4 ⁇ m) by a roll coating method.
  • an ultraviolet curable hard coat coating material containing a polyfunctional acrylic resin (“Aika Itron Z-850-3AF” manufactured by Aika Kogyo Co., Ltd.) was used on both sides of the obtained hard resin sheet.
  • a scratch-resistant layer (thickness of about 4 ⁇ m) was formed by a coating method. As described above, a hard resin sheet having a scratch-resistant layer on at least one surface was obtained.
  • Examples 1 to 7, Comparative Examples 1 to 6 In each of Examples 1 to 7 and Comparative Examples 1 to 6, a hard resin having an inorganic glass plate, a soft resin sheet serving as an intermediate film, and a scratch-resistant layer on at least one surface, by changing the materials used After the sheets are stacked in this order, they are thermocompression-bonded to form a glass laminate (FIG. 3) having a laminated structure of scratch-resistant layer / hard resin sheet / intermediate film / inorganic glass plate, or scratch-resistant layer / hard.
  • a glass laminate (FIG. 5) having a laminate structure of resin sheet / scratch resistant layer / intermediate film / inorganic glass plate was prepared and evaluated.
  • thermocompression bonding was performed by a vacuum bag method under a temperature profile condition in which the temperature was raised from 30 ° C. to 110 ° C. over 60 minutes and then maintained at 110 ° C. for 30 minutes.
  • a planar light emitter as shown in FIG. 7 was prepared and evaluated. Table 3 shows the materials and characteristics used in each layer and the evaluation results in each example.
  • the hard resin composition includes a laminated structure of a hard resin sheet / intermediate film / inorganic glass plate, and the hard resin sheet has specific heat resistance characteristics and optical characteristics (characteristics (a) and (b)).
  • Each of the obtained glass laminates had a high light transmittance even at a long light guide distance of the hard resin sheet, preferably contained an appropriate amount of light diffusing particles, and excellent in light guide performance. Therefore, a planar light emitting body having high luminance and uniform surface light emission without color unevenness was obtained.
  • Comparative Example 3 in which a hard resin sheet (HRS9) made of a polycarbonate resin having low light transmittance was used as the hard resin sheet, optical distortion occurred immediately after production and after a heat cycle test, and the obtained planar light emission The body had low brightness and color unevenness.
  • Comparative Examples 4 to 6 in which a soft resin having a high storage elastic modulus G ′ at 20 ° C. and a high peak temperature of loss tangent tan ⁇ was used for the intermediate film, warping occurred immediately after production, and the heat cycle test over time The amount of warpage increased and eventually the glass plate was cracked.
  • the present invention is not limited to the above-described embodiments and examples, and can be appropriately modified without departing from the gist of the present invention.

Abstract

La présente invention a trait à un stratifié de verre qui peut être réduit en poids, tout en ayant une bonne transparence, une bonne durabilité et d'excellentes performances de guidage de lumière, et qui peut être supprimé lors de l'apparition de défauts tels que la rugosité de surface, le gauchissement, la séparation des couches et la fissuration dans une étape de collage d'une plaque de verre inorganique et d'une feuille de résine. Ce stratifié de verre (1) comprend une structure multicouche dans laquelle une feuille de résine dure (13) est stratifiée sur une plaque de verre inorganique (11) avec un film intermédiaire (12) intercalé entre celles-ci. La feuille de résine dure est formée d'une composition de résine dure qui a des caractéristiques (a) et (b); et le film intermédiaire est formé à partir d'une composition de résine souple qui a des caractéristiques (c) et (d). (a) La température de transition vitreuse est supérieure ou égale à 120 °C. (b) La transmittance pour une longueur de trajet optique de 200 mm à une longueur d'onde de 420 nm est supérieure ou égale à 60 %. (c) Le module d'élasticité de stockage G' à une température de consigne de 25 °C à une fréquence de 1,0 Hz est inférieur ou égale à 1.0 × 107 Pa. (d) La température maximale à laquelle la tangente de perte δ à une fréquence de 1,0 Hz est maximale est inférieure ou égale à 25 °C.
PCT/JP2018/006904 2017-02-28 2018-02-26 Stratifié de verre et son procédé de production WO2018159520A1 (fr)

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WO2021117833A1 (fr) * 2019-12-11 2021-06-17 積水化学工業株式会社 Film intermédiaire pour verre feuilleté et verre feuilleté
US11339931B1 (en) 2019-07-16 2022-05-24 Apple Inc. Light-control panel with gradual index transition
EP3901113A4 (fr) * 2018-12-21 2022-08-31 Sekisui Chemical Co., Ltd. Film intercouche pour verre feuilleté, et verre feuilleté
EP4198085A4 (fr) * 2020-08-14 2024-02-07 Asahi Chemical Ind Composition de résine méthacrylique et corps moulé

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JPH01244843A (ja) * 1988-03-28 1989-09-29 Bridgestone Corp 防音・安全ガラス構造体
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EP3901113A4 (fr) * 2018-12-21 2022-08-31 Sekisui Chemical Co., Ltd. Film intercouche pour verre feuilleté, et verre feuilleté
US11850827B2 (en) 2018-12-21 2023-12-26 Sekisui Chemical Co., Ltd. Interlayer film for laminated glass and laminated glass
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WO2021117833A1 (fr) * 2019-12-11 2021-06-17 積水化学工業株式会社 Film intermédiaire pour verre feuilleté et verre feuilleté
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EP4198085A4 (fr) * 2020-08-14 2024-02-07 Asahi Chemical Ind Composition de résine méthacrylique et corps moulé

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