JPWO2020080162A1 - Glass plate - Google Patents
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- JPWO2020080162A1 JPWO2020080162A1 JP2020553081A JP2020553081A JPWO2020080162A1 JP WO2020080162 A1 JPWO2020080162 A1 JP WO2020080162A1 JP 2020553081 A JP2020553081 A JP 2020553081A JP 2020553081 A JP2020553081 A JP 2020553081A JP WO2020080162 A1 JPWO2020080162 A1 JP WO2020080162A1
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- 239000011521 glass Substances 0.000 title claims abstract description 131
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 claims abstract description 28
- 239000000805 composite resin Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 abstract 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 239000005357 flat glass Substances 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 230000035939 shock Effects 0.000 description 12
- 238000004031 devitrification Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- 239000005361 soda-lime glass Substances 0.000 description 6
- 230000002238 attenuated effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 238000006124 Pilkington process Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910018921 CoO 3 Inorganic materials 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 125000001475 halogen functional group Chemical group 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000006103 coloring component Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000007500 overflow downdraw method Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000009774 resonance method Methods 0.000 description 2
- 238000007372 rollout process Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910000500 β-quartz Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Glass Compositions (AREA)
- Joining Of Glass To Other Materials (AREA)
Abstract
本発明のガラス板は、樹脂板と複合一体化して、ガラス樹脂複合体を作製するためのガラス板であって、ガラス組成として、モル%で、SiO245〜80%、Al2O35〜30%、Li2O+Na2O+K2O 0〜20%、MgO 3〜35%、CaO 0.1〜35%、SrO+BaO 0〜15%を含有することを特徴とする。The glass plate of the present invention is a glass plate for producing a glass-resin composite by compositely integrating with a resin plate, and has a glass composition of 425-80% SiO, 35-30% Al2O, Li2O + Na2O + K2O 0 in terms of glass composition. It is characterized by containing ~ 20%, MgO 3 to 35%, CaO 0.1 to 35%, and SrO + BaO 0 to 15%.
Description
本発明は、樹脂板と複合一体化して、ガラス樹脂複合体を作製するためのガラス板に関し、特に自動車のフロントガラスやドアガラスに好適なガラス樹脂複合体に用いるガラス板に関する。 The present invention relates to a glass plate for producing a glass-resin composite by compositely integrating with a resin plate, and particularly to a glass plate used for a glass-resin composite suitable for windshields and door glasses of automobiles.
車両等の窓ガラスには、一般的に、複数枚のソーダライムガラス板を有機樹脂中間層で複合一体化した合わせガラスが使用されており、軽量化を目的として、複数枚のソーダライムガラス板と樹脂板とを有機樹脂中間層で複合一体化したガラス樹脂複合体が用いられることもある(特許文献1〜4参照)。 Generally, laminated glass in which a plurality of soda lime glass plates are compositely integrated with an organic resin intermediate layer is used for window glass of a vehicle or the like, and a plurality of soda lime glass plates are used for the purpose of weight reduction. A glass-resin composite in which the resin plate and the resin plate are compositely integrated with an organic resin intermediate layer may be used (see Patent Documents 1 to 4).
車両等の窓ガラスに使用されるソーダライムガラス板は、走行中の飛び石等の飛散片の先端形状を変形させて、その衝撃抵抗を増大させることで、飛散片の衝突エネルギーを減衰する機能を有している。 The soda lime glass plate used for the window glass of vehicles, etc. has the function of attenuating the collision energy of the scattered pieces by deforming the tip shape of the scattered pieces such as flying stones while increasing the impact resistance. Have.
しかし、ソーダライムガラス板は、飛散片の衝撃抵抗を増大させる効果が十分であるとは言えない。現状、ソーダライムガラス板の板厚を大きくするか、積層枚数を多くして、飛散片の衝撃抵抗を高めているが、これに伴い、窓ガラスの厚みや質量の増大を招いている。 However, it cannot be said that the soda lime glass plate has a sufficient effect of increasing the impact resistance of the scattered pieces. At present, the thickness of the soda lime glass plate is increased or the number of laminated sheets is increased to increase the impact resistance of the scattered pieces, but this has led to an increase in the thickness and mass of the window glass.
そこで、飛散片の衝撃抵抗を高めるために、ソーダライムガラス板の代わりに結晶化ガラス板を用いることが検討されている。例えば、主結晶としてβ−石英固溶体(Li2O・Al2O3・nSiO2[但し、n≧2])等のLi2O−Al2O3−SiO2系結晶を析出してなる結晶化ガラス板が検討されている。Therefore, in order to increase the impact resistance of the scattered pieces, it is considered to use a crystallized glass plate instead of the soda lime glass plate. For example, a crystal formed by precipitating a Li 2 O-Al 2 O 3 -SiO 2 system crystal such as a β-quartz solid solution (Li 2 O · Al 2 O 3 · nSiO 2 [however, n ≧ 2]) as a main crystal. Glass-ceramic plates are being considered.
ところで、結晶化ガラスの結晶化度を高めると、結晶化ガラスの硬度が上昇し、飛散片の衝突エネルギーを減衰し得るが、析出結晶が軟化変形を阻害するため、曲げ加工が困難になり、自動車のフロントガラス等に適用できなくなる。また、結晶化ガラスの厚みを大きくすることでも、飛散片の衝突エネルギーを減衰し得るが、この場合、窓ガラスの質量が増大してしまい、また透明性を損なう虞がある。 By the way, when the crystallinity of the crystallized glass is increased, the hardness of the crystallized glass is increased and the collision energy of the scattered pieces can be attenuated. It cannot be applied to the front glass of automobiles. Further, the collision energy of the scattered pieces can be attenuated by increasing the thickness of the crystallized glass, but in this case, the mass of the window glass may increase and the transparency may be impaired.
そこで、本発明は、上記事情に鑑みなされたものであり、その技術的課題は、曲げ加工性に優れると共に、厚みや結晶化度が小さくても、飛散片の衝突エネルギーを有効に減衰し得るガラス板を創案することである。 Therefore, the present invention has been made in view of the above circumstances, and its technical problem is that it is excellent in bending workability and can effectively attenuate the collision energy of scattered pieces even if the thickness and crystallinity are small. It is to create a glass plate.
本発明者等は、ガラス板のガラス組成範囲を厳密に規制することにより、上記技術的課題を解決し得ることを見出し、本発明として提案するものである。すなわち、本発明のガラス板は、樹脂板と複合一体化して、ガラス樹脂複合体を作製するためのガラス板であって、ガラス組成として、モル%で、SiO2 45〜80%、Al2O3 5〜30%、Li2O+Na2O+K2O 0〜20%、MgO 3〜35%、CaO 0.1〜35%、SrO+BaO 0〜15%を含有することを特徴とする。ここで、「Li2O+Na2O+K2O」は、Li2O、Na2O及びK2Oの合量を指す。「SrO+BaO」は、SrOとBaOの合量を指す。The present inventors have found that the above technical problems can be solved by strictly regulating the glass composition range of the glass plate, and propose the present invention. That is, the glass plate of the present invention is to composite integrated with the resin plate, a glass plate for making glass resin composite, as a glass composition, in mol%, SiO 2 45~80%, Al 2 O 3 5~30%, Li 2 O + Na 2 O + K 2 O 0~20%, MgO 3~35%, CaO 0.1~35%, characterized in that it contains 0~15% SrO + BaO. Here, "Li 2 O + Na 2 O + K 2 O" refers to the total amount of Li 2 O, Na 2 O and K 2 O. "SrO + BaO" refers to the total amount of SrO and BaO.
本発明のガラス板は、樹脂板と複合一体化して、ガラス樹脂複合体を作製するためのガラス板である。ガラス樹脂複合体において、ガラス板は、透明性を有し、衝撃抵抗を高める材料である。樹脂板は、飛散片の衝突による衝撃を緩和し、また飛散片の衝撃によるガラス片の飛散を防止する材料である。両者を備えることにより、耐衝撃性能を確保し易くなる。 The glass plate of the present invention is a glass plate for producing a glass-resin composite by compositely integrating with a resin plate. In the glass-resin composite, the glass plate is a material that has transparency and enhances impact resistance. The resin plate is a material that cushions the impact caused by the collision of the scattered pieces and prevents the glass pieces from scattering due to the impact of the scattered pieces. By providing both, it becomes easy to secure the impact resistance performance.
図1は、ガラス樹脂複合体の一例を説明するための概略図である。ガラス樹脂複合体10は、外側から順に、ガラス板11と、ガラス板12と、樹脂板13と、を有しており、これらは3次元的に湾曲した曲面形状を有しており、図示しない有機樹脂中間層により複合一体化されている。ガラス板11は、ガラス組成として、モル%で、SiO2 45〜80%、Al2O3 5〜30%、Li2O+Na2O+K2O 0〜20%、MgO 3〜35%、CaO 0.1〜35%、SrO+BaO 0〜15%を含有している。樹脂板13は、ポリカーボネートである。FIG. 1 is a schematic view for explaining an example of a glass resin composite. The glass-
本発明者等が飛散片の衝突を詳細に解析したところ、まずガラス板が飛散片の衝突による衝撃波により破損した後、飛散片がガラス板内を貫通していくことが判明した。そして、飛散片の衝突による衝撃波を分散させると、飛散片の衝突エネルギーを減衰させ、飛散片の貫通を防止し得ることが判明した。更にその衝撃波について詳細に解析したところ、衝撃波が飛散片の進行方向とその垂直方向に対して分散して減衰していく時、衝撃波の速度は、ガラス板のヤング率に比例して速くなる。そこで、本発明のガラス板は、上記のガラス組成を有するため、ヤング率を高めることができる。これにより、飛散片の衝突を受けた時に、衝撃波の分散領域が広くなって、衝撃波のエネルギー吸収が大きくなり、飛散片自体の速度を有効に低下させることができる。結果として、飛散片がガラス板内を貫通し難くなる。 When the present inventors analyzed the collision of the scattered pieces in detail, it was found that the glass plate was first damaged by the shock wave caused by the collision of the scattered pieces, and then the scattered pieces penetrated the inside of the glass plate. Then, it was found that by dispersing the shock wave due to the collision of the scattered pieces, the collision energy of the scattered pieces can be attenuated and the penetration of the scattered pieces can be prevented. Further analysis of the shock wave in detail shows that when the shock wave is dispersed and attenuated with respect to the traveling direction of the scattered pieces and the direction perpendicular to the traveling direction, the speed of the shock wave increases in proportion to the Young's modulus of the glass plate. Therefore, since the glass plate of the present invention has the above-mentioned glass composition, Young's modulus can be increased. As a result, when the collision of the scattered pieces is received, the dispersed region of the shock wave is widened, the energy absorption of the shock wave is increased, and the velocity of the scattered pieces themselves can be effectively reduced. As a result, it becomes difficult for the scattered pieces to penetrate the inside of the glass plate.
また、本発明のガラス板は、ヤング率が80GPa以上であることが好ましい。このようにすれば、ガラス板中で衝撃波の速度が速くなるため、衝撃波の分散領域が広がり、飛散体の衝突エネルギーを大きく減衰させることができる。ここで、「ヤング率」は、周知の共振法で測定した値を指す。 Further, the glass plate of the present invention preferably has a Young's modulus of 80 GPa or more. In this way, since the velocity of the shock wave is increased in the glass plate, the dispersed region of the shock wave is widened, and the collision energy of the scattered body can be greatly attenuated. Here, "Young's modulus" refers to a value measured by a well-known resonance method.
また、本発明のガラス板は、液相粘度が102.0d・Pa以上であることが好ましい。このようにすれば、ブツや失透が生じ難くなり、連続的な溶融が可能となる。ここで、「液相粘度」は、液相温度におけるガラスの粘度を白金球引き上げ法で測定した値を指す。「液相温度」は標準篩30メッシュ(500μm)を通過し50メッシュ(300μm)に残るガラス粉末を白金ボートに入れ、温度勾配炉で24時間保持した後、結晶が析出する温度を指す。Further, the glass plate of the present invention preferably has a liquid phase viscosity of 10 2.0 d · Pa or more. In this way, lumps and devitrification are less likely to occur, and continuous melting becomes possible. Here, the "liquid phase viscosity" refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by the platinum ball pulling method. "Liquid phase temperature" refers to the temperature at which crystals precipitate after passing glass powder that has passed through a standard sieve of 30 mesh (500 μm) and remains in 50 mesh (300 μm) in a platinum boat and holding it in a temperature gradient furnace for 24 hours.
また、本発明のガラス板は、結晶化度が30%以下であることが好ましい。このようにすれば、ガラス板の曲げ加工性を高めることができる。ここで、「結晶化度」は、粉末法によりXRDを測定することにより、非晶質の質量に相当するハローの面積と、結晶の質量に相当するピークの面積とをそれぞれ算出した後、[ピークの面積]×100/[ピークの面積+ハローの面積](%)の式により求めた値を指す。 Further, the glass plate of the present invention preferably has a crystallinity of 30% or less. By doing so, the bending workability of the glass plate can be improved. Here, the "crystallinity" is determined by measuring the XRD by the powder method to calculate the area of the halo corresponding to the amorphous mass and the area of the peak corresponding to the crystal mass, respectively. Peak area] x 100 / [Peak area + Hello area] (%) indicates the value obtained by the formula.
また、本発明のガラス板は、板厚が3〜15mmであることが好ましい。 Further, the glass plate of the present invention preferably has a plate thickness of 3 to 15 mm.
また、本発明のガラス板は、3次元的に湾曲した曲面形状を有することが好ましい。このようにすれば、自動車のフロントガラス等に適用し易くなる。 Further, the glass plate of the present invention preferably has a curved surface shape that is three-dimensionally curved. In this way, it becomes easy to apply to the windshield of an automobile or the like.
本発明のガラス板は、ガラス組成として、モル%で、SiO2 45〜80%、Al2O3 5〜30%、Li2O+Na2O+K2O 0〜20%、MgO 3〜35%、CaO 0.1〜35%、SrO+BaO 0〜15%を含有する。上記のように各成分の含有範囲を規制した理由を下記に示す。なお、各成分の含有範囲の説明において、%表示はモル%を指すものとする。The glass plate of the present invention has a glass composition, in mol%, SiO 2 45~80%, Al 2 O 3 5~30%, Li 2 O + Na 2 O + K 2 O 0~20%, MgO 3~35%, CaO It contains 0.1 to 35% and SrO + BaO 0 to 15%. The reasons for restricting the content range of each component as described above are shown below. In the description of the content range of each component, the% indication shall indicate mol%.
SiO2は、ガラスのネットワークを形成する成分である。SiO2の含有量は、好ましくは45〜80%、52〜75%、特に58〜72%である。SiO2の含有量が少な過ぎると、ガラス化し難くなり、また耐候性が低下し易くなる。一方、SiO2の含有量が多過ぎると、溶融性や成形性が低下し易くなり、また熱膨張係数が低くなり過ぎて、樹脂板や有機樹脂中間層の熱膨張係数に整合させ難くなる。SiO 2 is a component that forms a network of glass. The content of SiO 2 is preferably 45 to 80%, 52 to 75%, and particularly 58 to 72%. If the content of SiO 2 is too small, it becomes difficult to vitrify and the weather resistance tends to decrease. On the other hand, if the content of SiO 2 is too large, the meltability and moldability tend to decrease, and the coefficient of thermal expansion becomes too low, making it difficult to match the coefficient of thermal expansion of the resin plate or the organic resin intermediate layer.
Al2O3は、ヤング率や耐候性を高める成分である。Al2O3の含有量は、好ましくは5〜30%、9〜25%、10〜20%、特に12〜18%である。Al2O3の含有量が少な過ぎると、ヤング率や耐候性が低下し易くなる。一方、Al2O3の含有量が多過ぎると、溶融性、成形性及び耐失透性が低下し易くなる。Al 2 O 3 is a component that enhances Young's modulus and weather resistance. The content of Al 2 O 3 is preferably 5 to 30%, 9 to 25%, 10 to 20%, particularly 12 to 18%. If the content of Al 2 O 3 is too small, Young's modulus and weather resistance tend to decrease. On the other hand, if the content of Al 2 O 3 is too large, the meltability, moldability and devitrification resistance tend to decrease.
Li2O、Na2O及びK2Oは、高温粘度を低下させて、溶融性、成形性及び曲げ加工性を高める成分である。Li2O、Na2O及びK2Oの合量は、好ましくは0〜20%、1〜15%、特に2〜10%である。Li2Oの含有量は、好ましくは0〜15%、1〜12%、特に2〜10%である。Na2O及びK2Oのそれぞれの含有量は、好ましくは0〜15%、0〜3%、特に0〜1%未満である。Li2O、Na2O及びK2Oの合量が多過ぎると、耐候性が低下し易くなる。Li2Oの含有量が多過ぎると、耐失透性が低下し易くなる。Na2O及びK2Oの含有量が多過ぎると、ヤング率が低下し易くなる。Li 2 O, Na 2 O and K 2 O are components that reduce high-temperature viscosity and enhance meltability, moldability and bendability. The total amount of Li 2 O, Na 2 O and K 2 O is preferably 0 to 20%, 1 to 15%, and particularly 2 to 10%. The content of Li 2 O is preferably 0 to 15%, 1 to 12%, and particularly 2 to 10%. The respective contents of Na 2 O and K 2 O are preferably 0 to 15%, 0 to 3%, and particularly less than 0 to 1%. If the total amount of Li 2 O, Na 2 O and K 2 O is too large, the weather resistance tends to decrease. If the content of Li 2 O is too large, the devitrification resistance tends to decrease. If the contents of Na 2 O and K 2 O are too high, Young's modulus tends to decrease.
MgOは、ヤング率を大幅に高める成分であり、また高温粘度を低下させて、溶融性、成形性及び曲げ加工性を高める成分である。MgOの含有量は、好ましくは3〜35%、8〜30%、12〜25%、特に14〜20%である。MgOの含有量が少な過ぎると、上記効果を享受し難くなる。一方、MgOの含有量が多過ぎると、耐失透性が低下し易くなる。 MgO is a component that significantly increases Young's modulus and lowers high-temperature viscosity to improve meltability, moldability, and bendability. The content of MgO is preferably 3 to 35%, 8 to 30%, 12 to 25%, and particularly 14 to 20%. If the content of MgO is too small, it becomes difficult to enjoy the above effect. On the other hand, if the content of MgO is too large, the devitrification resistance tends to decrease.
CaOは、ヤング率を高める成分であり、また高温粘度を低下させて、溶融性、成形性及び曲げ加工性を高める成分である。また、MgOを含有量が多い組成領域において、CaOを導入すると、液相温度が低下し、耐失透性の低下が緩和される。CaOの含有量は、好ましくは0.1〜35%、1〜25%、2〜20%、特に4〜15%である。CaOの含有量が少な過ぎると、上記効果を享受し難くなる。一方、CaOの含有量が多過ぎると、ガラス組成のバランスが崩れて、かえって耐失透性が低下し易くなる。 CaO is a component that increases Young's modulus and lowers high-temperature viscosity to improve meltability, moldability, and bendability. Further, when CaO is introduced in the composition region containing a large amount of MgO, the liquidus temperature is lowered and the decrease in devitrification resistance is alleviated. The CaO content is preferably 0.1-35%, 1-25%, 2-20%, especially 4-15%. If the CaO content is too low, it becomes difficult to enjoy the above effects. On the other hand, if the CaO content is too large, the balance of the glass composition is lost, and the devitrification resistance tends to decrease.
SrO及びBaOは、高温粘度を低下させて、溶融性、成形性及び曲げ加工性を高める成分である。SrO及びBaOの合量は、好ましくは0〜15%、0〜5%、特に0〜1%未満である。SrO及びBaOのそれぞれの含有量は、好ましくは0〜12%、0〜5%、0〜2%、特に0〜1%未満である。SrOとBaOの含有量が多過ぎると、耐失透性、ヤング率等が低下し易くなり、また密度が増加するため、ガラス樹脂複合体の質量が増大し過ぎる慮がある。 SrO and BaO are components that reduce high-temperature viscosity and enhance meltability, moldability, and bendability. The total amount of SrO and BaO is preferably 0 to 15%, 0 to 5%, particularly less than 0 to 1%. The respective contents of SrO and BaO are preferably 0 to 12%, 0 to 5%, 0 to 2%, and particularly less than 0 to 1%. If the contents of SrO and BaO are too large, the devitrification resistance, Young's modulus, etc. tend to decrease, and the density increases, so that the mass of the glass resin complex may increase too much.
液相温度を下げる観点から、モル比MgO/(MgO+CaO+SrO+BaO)は、好ましくは0.95以下、0.9以下、特に0.85以下である。なお、「MgO/(MgO+CaO+SrO+BaO)」は、MgOの含有量をMgO、CaO、SrO及びBaOの合量で除した値である。 From the viewpoint of lowering the liquidus temperature, the molar ratio MgO / (MgO + CaO + SrO + BaO) is preferably 0.95 or less, 0.9 or less, and particularly 0.85 or less. In addition, "MgO / (MgO + CaO + SrO + BaO)" is a value obtained by dividing the content of MgO by the total amount of MgO, CaO, SrO and BaO.
ヤング率を高める観点から、モル比CaO/(CaO+SrO+BaO)は、好ましくは0.5以上、0.7以上、0.8以上、特に0.9以上である。「CaO/(CaO+SrO+BaO)」は、CaOの含有量をCaO、SrO及びBaOの含量で除した値を指す。 From the viewpoint of increasing Young's modulus, the molar ratio CaO / (CaO + SrO + BaO) is preferably 0.5 or more, 0.7 or more, 0.8 or more, and particularly 0.9 or more. "CaO / (CaO + SrO + BaO)" refers to a value obtained by dividing the content of CaO by the contents of CaO, SrO and BaO.
上記成分以外にも、例えば以下の成分を添加してもよい。 In addition to the above components, for example, the following components may be added.
B2O3は、ガラスのネットワークを形成すると共に、高温粘度を低下させて、溶融性、成形性及び曲げ加工性を高める成分である。よって、B2O3の含有量は、好ましくは0〜15%、0〜10%、特に0〜5%である。一方、B2O3の含有量が多過ぎると、ヤング率や耐候性が低下し易くなる。B 2 O 3 is a component that forms a network of glass, lowers high-temperature viscosity, and enhances meltability, moldability, and bendability. Therefore, the content of B 2 O 3 is preferably 0 to 15%, 0 to 10%, and particularly 0 to 5%. On the other hand, if the content of B 2 O 3 is too large, Young's modulus and weather resistance tend to decrease.
P2O5は、ガラスのネットワークを形成すると共に、溶融性、成形性及び曲げ加工性を高める成分であり、特に液相温度付近における粘度を高める成分である。P2O5の含有量は、好ましくは0〜15%、0〜10%、特に0〜5%である。一方、P2O5の含有量が多過ぎると、ヤング率や耐候性が低下し易くなり、また分相が生じ易くなる。P 2 O 5 is a component that forms a network of glass and enhances meltability, moldability, and bendability, and is a component that enhances viscosity particularly in the vicinity of the liquid phase temperature. The content of P 2 O 5 is preferably 0 to 15%, 0 to 10%, and particularly 0 to 5%. On the other hand, if the content of P 2 O 5 is too large, Young's modulus and weather resistance are likely to decrease, and phase separation is likely to occur.
Y2O3とLa2O3は、ヤング率を大幅に高める成分であり、また溶融性を高める成分である。Y2O3とLa2O3の合量及び個別含有量は、好ましくは0〜15%、0〜10%、特に0〜5%である。一方、Y2O3とLa2O3の含有量が多過ぎると、耐失透性が低下し易くなり、また密度が増加するため、ガラス樹脂複合体の質量が増大し過ぎる慮がある。Y 2 O 3 and La 2 O 3 are components that significantly increase Young's modulus and enhance meltability. The total amount and individual content of Y 2 O 3 and La 2 O 3 are preferably 0 to 15%, 0 to 10%, and particularly 0 to 5%. On the other hand, if the contents of Y 2 O 3 and La 2 O 3 are too large, the devitrification resistance tends to decrease and the density increases, so that the mass of the glass resin complex may increase too much.
TiO2は、耐候性を高める成分であるが、ガラスを着色させる成分である。よって、TiO2の含有量は、好ましくは0〜0.5%、特に0〜0.1%未満である。TiO 2 is a component that enhances weather resistance, but is a component that colors glass. Therefore, the content of TiO 2 is preferably 0 to 0.5%, particularly less than 0 to 0.1%.
ZrO2は、ヤング率や耐候性を高める成分であるが、耐失透性を低下させる成分である。よってZrO2の含有量は、好ましくは0〜0.5%、特に0〜0.1%未満である。ZrO 2 is a component that increases Young's modulus and weather resistance, but is a component that lowers devitrification resistance. Therefore, the content of ZrO 2 is preferably 0 to 0.5%, particularly less than 0 to 0.1%.
清澄剤として、SnO2、Cl、SO3、CeO2の群(好ましくはSnO2、SO3の群)から選択された一種又は二種以上を0.05〜0.5%添加してもよい。As a clarifying agent, one or more selected from the group of SnO 2 , Cl, SO 3 , and CeO 2 (preferably the group of SnO 2 , SO 3 ) may be added in an amount of 0.05 to 0.5%. ..
Fe2O3は、ガラス原料に不純物として不可避的に混入する成分であり、着色成分である。よって、Fe2O3の含有量は、好ましくは0.5%以下、特に0.01〜0.07%である。Fe 2 O 3 is a component that is inevitably mixed with the glass raw material as an impurity and is a coloring component. Therefore, the content of Fe 2 O 3 is preferably 0.5% or less, particularly 0.01 to 0.07%.
V2O5、Cr2O3、CoO3及びNiOは、着色成分である。よって、V2O5、Cr2O3、CoO3及びNiOのそれぞれの含有量は、好ましくは0.1%以下、特に0.01%未満である。V 2 O 5 , Cr 2 O 3 , CoO 3 and NiO are coloring components. Therefore, the content of each of V 2 O 5 , Cr 2 O 3 , CoO 3 and NiO is preferably 0.1% or less, particularly less than 0.01%.
環境的配慮から、ガラス組成として、実質的にAs2O3、Sb2O3、PbO、Bi2O3、Fを含有しないことが好ましい。ここで、「実質的に〜を含有しない」とは、ガラス成分として積極的に明示の成分を添加しないものの、不純物として混入する場合を許容する趣旨であり、具体的には、明示の成分の含有量が0.05%未満であることを指す。From the viewpoint of environmental consideration, it is preferable that the glass composition does not substantially contain As 2 O 3 , Sb 2 O 3 , PbO, Bi 2 O 3, and F. Here, "substantially free of ~" means that although an explicit component is not positively added as a glass component, it is allowed to be mixed as an impurity. It means that the content is less than 0.05%.
本発明のガラス板は、以下の特性を有することが好ましい。 The glass plate of the present invention preferably has the following characteristics.
ヤング率は、好ましくは80GPa以上、85GPa以上、90GPa以上、特に95〜150GPaである。ヤング率が低過ぎると、飛散片の衝突による衝撃波の速度が遅くなるため、衝撃波が狭い領域にしか広がらず、飛散片の衝突エネルギーを減衰し難くなる。 Young's modulus is preferably 80 GPa or more, 85 GPa or more, 90 GPa or more, and particularly 95 to 150 GPa. If the Young's modulus is too low, the velocity of the shock wave due to the collision of the scattered pieces becomes slow, so that the shock wave spreads only in a narrow region, and it becomes difficult to attenuate the collision energy of the scattered pieces.
液相粘度は、好ましくは102.0dPa・s以上、102.5dPa・s以上、103.0dPa・s以上、103.5dPa・s以上、特に104.0dPa・s以上である。このようにすれば、失透結晶が発生し難くなるため、フロート法やロールアウト法で成形し易くなる。結果として、ガラス板の製造コストを低廉化し得ると共に、ガラス板の品位を高めることができる。液相粘度の上限は特に限定されてないが、ガラス板に要求される種々の特性を満たすためのバランスを考慮すると、106.5dPa・s以下に設計することが目安となる。The liquidus viscosity is preferably 10 2.0 dPa · s or higher, 10 2.5 dPa · s or higher, 10 3.0 dPa · s or higher, 10 3.5 dPa · s or higher, and particularly 10 4.0 dPa · s or higher. s or more. In this way, devitrified crystals are less likely to occur, and thus it becomes easier to mold by the float method or the rollout method. As a result, the manufacturing cost of the glass plate can be reduced and the quality of the glass plate can be improved. The upper limit of the liquidus viscosity is not particularly limited, considering the balance to meet the various properties required for a glass plate, it is to design the following 10 6.5 dPa · s is a measure.
歪点は、好ましくは600℃以上、650℃以上、700℃以上、特に720〜850℃である。歪点が低過ぎると、耐熱性が低下し易くなる。 The strain point is preferably 600 ° C. or higher, 650 ° C. or higher, 700 ° C. or higher, particularly 720 to 850 ° C. If the strain point is too low, the heat resistance tends to decrease.
軟化点は、好ましくは1100℃以下、1020℃以下、980℃以下、特に950℃以下である。軟化点が高過ぎると、曲げ加工性が低下し易くなる。 The softening point is preferably 1100 ° C. or lower, 1020 ° C. or lower, 980 ° C. or lower, and particularly 950 ° C. or lower. If the softening point is too high, the bending workability tends to decrease.
高温粘度102.0dPa・sにおけるガラスのおける温度は、好ましくは1600℃以下、1580℃以下、1560℃以下、特に1550℃以下である。高温粘度102.0dPa・sにおけるガラスの温度が高過ぎると、溶融性や成形性が低下し易くなる。The temperature of the glass at a high temperature viscosity of 10 2.0 dPa · s is preferably 1600 ° C. or lower, 1580 ° C. or lower, 1560 ° C. or lower, and particularly 1550 ° C. or lower. If the temperature of the glass at a high temperature viscosity of 10 2.0 dPa · s is too high, the meltability and moldability tend to decrease.
結晶化度は、好ましくは30%以下、10%以下、5%以下、1%以下、特に0%、つまり非晶質である。結晶化度が高過ぎると、曲げ加工性が低下し易くなる。 The crystallinity is preferably 30% or less, 10% or less, 5% or less, 1% or less, particularly 0%, that is, amorphous. If the crystallinity is too high, the bending workability tends to decrease.
ガラス板の板厚は、好ましくは15mm以下、12mm以下、10mm以下、特に8mm以下であり、好ましくは3mm以上、4mm以上、5mm以上、6mm以上、特に7mm以上である。ガラス板の板厚が小さ過ぎると、耐衝撃性能を確保し難くなる。一方、ガラス板の板厚が大き過ぎると、窓ガラスを薄型化し難くなり、視認性が低下し易くなる。また窓ガラスの質量が増大して、自動車等の燃費が高騰してしまう。 The thickness of the glass plate is preferably 15 mm or less, 12 mm or less, 10 mm or less, particularly 8 mm or less, preferably 3 mm or more, 4 mm or more, 5 mm or more, 6 mm or more, and particularly 7 mm or more. If the thickness of the glass plate is too small, it becomes difficult to secure impact resistance. On the other hand, if the thickness of the glass plate is too large, it becomes difficult to make the window glass thin, and the visibility tends to decrease. In addition, the mass of the window glass increases, and the fuel consumption of automobiles and the like rises.
本発明のガラス板は、樹脂板と複合一体化して、ガラス樹脂複合体を作製するためのガラス板である。ガラス樹脂複合体において、ガラス板は複数枚であることが好ましい。なお、ガラス樹脂複合体中に複数のガラス板を有する場合、本発明のガラス板以外のガラス板(例えば、ソーダガラス板)を含んでいてもよいが、本発明の効果を的確に享受する観点から、全てのガラス板が本発明のガラス板であることが好ましい。 The glass plate of the present invention is a glass plate for producing a glass-resin composite by compositely integrating with a resin plate. In the glass-resin composite, it is preferable that the number of glass plates is plurality. When a plurality of glass plates are contained in the glass resin composite, a glass plate other than the glass plate of the present invention (for example, a soda glass plate) may be included, but from the viewpoint of accurately enjoying the effect of the present invention. Therefore, it is preferable that all the glass plates are the glass plates of the present invention.
ガラス樹脂複合体において、樹脂板は複数枚でもよいが、視認性を高める観点から、1枚であることが好ましい。樹脂板はアクリル、ポリカーボネート等の種々の樹脂が使用可能であるが、透明性、衝撃緩和性、軽量化の観点から、ポリカーボネートが特に好ましい。 In the glass-resin composite, a plurality of resin plates may be used, but one is preferable from the viewpoint of improving visibility. Various resins such as acrylic and polycarbonate can be used as the resin plate, but polycarbonate is particularly preferable from the viewpoint of transparency, impact mitigation, and weight reduction.
樹脂板の板厚は、好ましくは10mm以下、8mmm以下、7mm以下、6mm以下、特に5mm以下であり、好ましくは0.5mm以上、0.7mm以上、1mm以上、2mm以上、特に3mm以上である。樹脂板の板厚が小さ過ぎると、飛散片が衝突した時にその衝撃を緩和し難くなる。一方、樹脂板の板厚が大き過ぎると、窓ガラスを薄型化し難くなり、また窓ガラスの視認性が低下し易くなる。 The thickness of the resin plate is preferably 10 mm or less, 8 mm or less, 7 mm or less, 6 mm or less, particularly 5 mm or less, preferably 0.5 mm or more, 0.7 mm or more, 1 mm or more, 2 mm or more, and particularly 3 mm or more. .. If the thickness of the resin plate is too small, it becomes difficult to alleviate the impact when the scattered pieces collide. On the other hand, if the thickness of the resin plate is too large, it becomes difficult to make the window glass thinner, and the visibility of the window glass tends to decrease.
ガラス樹脂複合体において、ガラス板同士、ガラス板と樹脂板は、有機樹脂中間層により複合一体化されていることが好ましい。有機樹脂中間層の厚みは、好ましくは0.1〜2mm、0.3〜1.5mm、0.5〜1.2mm、特に0.6〜0.9mmである。有機樹脂中間層の厚みが小さ過ぎると、飛散片が衝突した時に、衝撃波のエネルギーが室内側に伝搬し易くなる。一方、有機樹脂中間層の厚みが大き過ぎると、窓ガラスの視認性が低下し易くなる。 In the glass-resin composite, it is preferable that the glass plates are compositely integrated with each other by an organic resin intermediate layer. The thickness of the organic resin intermediate layer is preferably 0.1 to 2 mm, 0.3 to 1.5 mm, 0.5 to 1.2 mm, and particularly 0.6 to 0.9 mm. If the thickness of the organic resin intermediate layer is too small, the energy of the shock wave tends to propagate to the indoor side when the scattered pieces collide. On the other hand, if the thickness of the organic resin intermediate layer is too large, the visibility of the window glass tends to decrease.
有機樹脂中間層の熱膨張係数は、ガラス板の熱膨張係数以上、且つ樹脂板の熱膨張係数以下であることが好ましい。このようにすれば、窓ガラスが直射日光で加熱された時に、ガラス板と樹脂板が分離、変形し難くなる。なお、「熱膨張係数」は、0〜300℃の温度範囲における平均線熱膨張係数を指す。 The coefficient of thermal expansion of the organic resin intermediate layer is preferably equal to or greater than the coefficient of thermal expansion of the glass plate and less than or equal to the coefficient of thermal expansion of the resin plate. In this way, when the window glass is heated by direct sunlight, the glass plate and the resin plate are less likely to be separated and deformed. The "coefficient of thermal expansion" refers to the average coefficient of linear thermal expansion in the temperature range of 0 to 300 ° C.
有機樹脂中間層として、種々の有機樹脂が使用可能であり、例えば、ポリエチレン(PE)、エチレン酢酸ビニル共重合体(EVA)、ポリプロピレン(PP)、ポリスチレン(PS)、メタクリル樹脂(PMA)、ポリ塩化ビニル(PVC)、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート(PBT)、セルロースアセテート(CA)、ジアリルフタレート樹脂(DAP)、ユリア樹脂(UP)、メラミン樹脂(MF)、不飽和ポリエステル(UP)、ポリビニルブチラール(PVB)、ポリビニルホルマール(PVF)、ポリビニルアルコール(PVAL)、酢酸ビニル樹脂(PVAc)、アイオノマー(IO)、ポリメチルペンテン(TPX)、塩化ビニリデン(PVDC)、ポリスルフォン(PSF)、ポリフッ化ビニリデン(PVDF)、メタクリル−スチレン共重合樹脂(MS)、ポリアレート(PAR)、ポリアリルスルフォン(PASF)、ポリブタジエン(BR)、ポリエーテルスルフォン(PESF)、又はポリエーテルエーテルケトン(PEEK)、ポリウレタン(PU)等が使用可能である。その中でも、透明性と固着性の観点から、EVA、PVB、PUが好適であり、特にPVBは遮音性を付与し得るため好ましい。 Various organic resins can be used as the organic resin intermediate layer, for example, polyethylene (PE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), polystyrene (PS), methacrylic resin (PMA), poly. Vinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), cellulose acetate (CA), diallyl phthalate resin (DAP), urea resin (UP), melamine resin (MF), unsaturated polyester (UP) , Polyvinylbutyral (PVB), Polyvinylformal (PVF), Polyvinyl alcohol (PVAL), Vinyl acetate resin (PVAc), Ionomer (IO), Polymethylpentene (TPX), Vinylidene chloride (PVDC), Polysulphon (PSF), Vinylidene fluoride (PVDF), methacrylic-styrene copolymer resin (MS), polyarate (PAR), polyallyl sulfone (PASF), polybutadiene (BR), polyether sulfone (PESF), or polyether ether ketone (PEEK), Polyethylene (PU) or the like can be used. Among them, EVA, PVB, and PU are preferable from the viewpoint of transparency and adhesiveness, and PVB is particularly preferable because it can impart sound insulation.
有機樹脂中間層中に着色剤を添加してもよく、赤外線、紫外線等の特定波長光線を吸収する吸収剤を添加してもよい。 A colorant may be added to the organic resin intermediate layer, or an absorbent that absorbs specific wavelength rays such as infrared rays and ultraviolet rays may be added.
有機樹脂中間層には、上記有機樹脂を複数種類組み合わせたものを用いてもよい。例えば、ガラス板と樹脂板の複合一体化に2層の有機樹脂中間層を用いると、ガラス板と樹脂板が異なる有機樹脂で固着されるため、窓ガラスの反りを低減し易くなる。 As the organic resin intermediate layer, a combination of a plurality of types of the above organic resins may be used. For example, when a two-layer organic resin intermediate layer is used for the composite integration of the glass plate and the resin plate, the glass plate and the resin plate are fixed by different organic resins, so that the warp of the window glass can be easily reduced.
ガラス樹脂複合体の総板厚は、好ましくは65mm以下、60mm以下、55mm以下であり、好ましくは4mm以上、5mm以上、7mm以上、特に10mm以上である。ガラス樹脂複合体の総板厚が小さ過ぎると、窓ガラスの耐衝撃性能が低下し易くなる。一方、ガラス樹脂複合体の総板厚が大き過ぎると、窓ガラスの質量が重くなり、また窓ガラスの視認性が低下し易くなる。 The total plate thickness of the glass resin complex is preferably 65 mm or less, 60 mm or less, 55 mm or less, preferably 4 mm or more, 5 mm or more, 7 mm or more, and particularly 10 mm or more. If the total plate thickness of the glass-resin composite is too small, the impact resistance performance of the window glass tends to deteriorate. On the other hand, if the total thickness of the glass-resin composite is too large, the mass of the window glass becomes heavy, and the visibility of the window glass tends to decrease.
以下のようにして、ガラス板を作製することができる。 A glass plate can be produced as follows.
まず所定のガラス組成になるように調合したガラス原料を連続溶融炉に投入して、1500〜1700℃で加熱溶融し、清澄、攪拌した後、成形装置に供給して板状に成形し、徐冷することにより、ガラス板を作製することができる。 First, a glass raw material prepared to have a predetermined glass composition is put into a continuous melting furnace, melted by heating at 1500 to 1700 ° C., clarified and stirred, and then supplied to a molding apparatus to be molded into a plate shape. By cooling, a glass plate can be produced.
ガラス板を成形する方法として、フロート法を採用することが好ましい。フロート法は、ガラス板を安価に作製し得る方法である。 It is preferable to adopt the float method as a method for molding the glass plate. The float method is a method capable of producing a glass plate at low cost.
フロート法以外にも、ロールアウト法やオーバーフローダウンドロー法を採用してもよい。オーバーフローダウンドロー法は、表面が未研磨の状態で、薄いガラス板を大量に作製し得る方法である。なお、表面が未研磨であると、ガラス板の製造コストを低廉化することができる。 In addition to the float method, a rollout method or an overflow downdraw method may be adopted. The overflow down draw method is a method capable of producing a large number of thin glass plates with the surface unpolished. If the surface is unpolished, the manufacturing cost of the glass plate can be reduced.
ガラス板は、必要に応じて、面取り加工されていることが好ましい。その場合、#800のメタルボンド砥石等により、C面取り加工を行うことが好ましい。このようにすれば、端面強度を高めることができる。必要に応じて、ガラス板の端面をエッチングして、端面に存在するクラックソースを低減することも好ましい。 The glass plate is preferably chamfered, if necessary. In that case, it is preferable to perform C chamfering with a # 800 metal bond grindstone or the like. In this way, the end face strength can be increased. If necessary, it is also preferable to etch the end face of the glass plate to reduce the crack source existing on the end face.
次に、得られたガラス板について、必要に応じて、曲面加工を行う。曲面加工の方法として、種々の方法を採用することができる。特に、金型によりガラス板を1枚ずつ或いは積層してプレス成形する方法が好ましく、所定の形状の金型でガラス板を挟み込んだ状態で熱処理炉を通過させることが好ましい。このようにすれば、曲面形状の寸法精度を高めることができる。また、所定形状の金型上にガラス板を1枚ずつ或いは積層して配置した後、ガラス板の一部又は全体を熱処理することにより、金型の形状に沿って、ガラス板を自重で軟化変形させる方法も好ましい。このようにすれば、曲面加工の効率を高めることができる。 Next, the obtained glass plate is subjected to curved surface processing as necessary. Various methods can be adopted as the method for processing the curved surface. In particular, it is preferable to press-mold the glass plates one by one or by laminating them with a mold, and it is preferable to pass the glass plates through the heat treatment furnace with the glass plates sandwiched between the molds having a predetermined shape. In this way, the dimensional accuracy of the curved surface shape can be improved. Further, after the glass plates are arranged one by one or laminated on a mold having a predetermined shape, a part or the whole of the glass plates is heat-treated to soften the glass plates by their own weight along the shape of the mold. A method of deforming is also preferable. By doing so, the efficiency of curved surface processing can be improved.
次に、ガラス板(好ましくは複数枚のガラス板)と樹脂板とを有機樹脂中間層で複合一体化して、ガラス樹脂複合体を作製することができる。複合一体化の方法として、ガラス板同士又はガラス板と樹脂板の間に有機樹脂を注入した後に有機樹脂を硬化させる方法、ガラス板同士又はガラス板と樹脂板の間に有機樹脂シートを配置した後に加圧加熱処理(熱圧着)する方法等が挙げられる。前者の方法は、ガラス板と樹脂板の膨張不整合による樹脂板の変形を抑制することができる。後者の方法の方は、複合一体化が容易である。 Next, a glass resin composite can be produced by compositely integrating a glass plate (preferably a plurality of glass plates) and a resin plate with an organic resin intermediate layer. As a method of composite integration, a method of injecting an organic resin between glass plates or between glass plates and a resin plate and then curing the organic resin, a method of arranging an organic resin sheet between glass plates or between glass plates and a resin plate, and then pressurizing and heating. Examples include a method of processing (thermocompression bonding). The former method can suppress the deformation of the resin plate due to the expansion mismatch between the glass plate and the resin plate. The latter method is easier to integrate.
また、複合一体化した後に、最外層のガラス板の外表面に、ハードコート膜、赤外線反射膜等の機能膜を形成してもよい。また複合一体化する前に、最外層のガラス板の内表面に、機能膜を形成してもよい。 Further, after the composite integration, a functional film such as a hard coat film or an infrared reflective film may be formed on the outer surface of the outermost glass plate. Further, a functional film may be formed on the inner surface of the outermost glass plate before the composite integration.
以下、実施例に基づいて、本発明を詳細に説明する。なお、以下の実施例は単なる例示である。本発明は以下の実施例に何ら限定されない。 Hereinafter, the present invention will be described in detail based on Examples. The following examples are merely examples. The present invention is not limited to the following examples.
表1は、本発明の実施例(試料No.1〜12)と比較例(試料No.13〜16)を示している。 Table 1 shows Examples (Samples Nos. 1 to 12) and Comparative Examples (Samples Nos. 13 to 16) of the present invention.
次のようにしてガラス板を作製した。表1に記載のガラス板が得られるように、ガラス原料を調合した。次に、調合済みのガラスバッチを連続溶融炉に投入し、1600℃で20時間溶融した後、清澄、攪拌して、均質な溶融ガラスを得た上で、板厚8.0mmの板状に成形した。得られたガラス板について、密度、ヤング率、液相温度、液相粘度、歪点、軟化点、高温粘度102.0dPa・sにおけるガラスの温度及び結晶化度を評価した。なお、試料No.1〜12に係るガラス板は、Fe2O3の混入不純物量が0.05モル%であり、V2O5、Cr2O3、CoO3及びNiOの混入不純物量がそれぞれ0.01モル%未満であった。A glass plate was produced as follows. The glass raw materials were prepared so as to obtain the glass plates shown in Table 1. Next, the prepared glass batch was put into a continuous melting furnace, melted at 1600 ° C. for 20 hours, clarified and stirred to obtain homogeneous molten glass, and then formed into a plate having a thickness of 8.0 mm. Molded. The obtained glass plate was evaluated for density, Young's modulus, liquidus temperature, liquidus viscosity, strain point, softening point, and glass temperature and crystallinity at a high temperature viscosity of 10 2.0 dPa · s. In addition, sample No. In the glass plates according to 1 to 12, the amount of impurities mixed in Fe 2 O 3 is 0.05 mol%, and the amount of impurities mixed in V 2 O 5 , Cr 2 O 3 , CoO 3 and Ni O is 0.01 mol, respectively. Was less than%.
密度は、周知のアルキメデス法で測定した値である。 Density is a value measured by the well-known Archimedes method.
ヤング率は、周知の共振法で測定した値である。 Young's modulus is a value measured by a well-known resonance method.
各試料を粉砕し、標準篩30メッシュ(500μm)を通過し、50メッシュ(300μm)に残るガラス粉末を白金ボートに入れて、温度勾配炉中に24時間保持した後、白金ボートを取出し、ガラス中に失透(結晶異物)が認められた温度を液相温度とした。更に、液相温度における粘度を白金球引き上げ法で測定し、これを液相粘度とした。 Each sample is crushed, passed through a standard sieve of 30 mesh (500 μm), the glass powder remaining in 50 mesh (300 μm) is placed in a platinum boat, held in a temperature gradient furnace for 24 hours, and then the platinum boat is taken out and the glass is taken out. The temperature at which devitrification (crystal foreign matter) was observed was defined as the liquidus temperature. Further, the viscosity at the liquidus temperature was measured by the platinum ball pulling method, and this was taken as the liquidus viscosity.
歪点、軟化点はASTM C336の方法に基づいて測定した値である。 The strain point and softening point are values measured based on the method of ASTM C336.
高温粘度102.0dPa・sにおけるガラスのおける温度を白金球引き上げ法で測定した値である。It is a value measured by a platinum ball pulling method at a temperature of glass at a high temperature viscosity of 10 2.0 dPa · s.
結晶化度は、粉末法によりXRDを測定することにより、非晶質の質量に相当するハローの面積と、結晶の質量に相当するピークの面積とをそれぞれ算出した後、[ピークの面積]×100/[ピークの面積+ハローの面積](%)の式により求めた値を指す。 The crystallinity is determined by measuring the XRD by the powder method, calculating the area of the halo corresponding to the amorphous mass and the peak area corresponding to the crystal mass, respectively, and then [peak area] ×. It refers to the value obtained by the formula of 100 / [peak area + halo area] (%).
表1から分かるように、試料No.1〜12は、ヤング率が高いため、耐衝撃性能が高く、結晶化度が低いため、曲げ加工も容易である。また液相粘度が高いため、連続的な溶融が可能であると考えられる。よって、試料No.1〜12は、樹脂板と複合一体化して、ガラス樹脂複合体を作製するためのガラス板として好適であると考えられる。一方、試料No.13〜15は、ヤング率が低いため、耐衝撃性能が低い。試料No.16は液相粘度が低いため、連続的な溶融が困難であると考えられる。 As can be seen from Table 1, Samples Nos. 1 to 12 have high Young's modulus, therefore have high impact resistance, and have low crystallinity, so that they can be easily bent. Moreover, since the liquidus viscosity is high, it is considered that continuous melting is possible. Therefore, the sample No. It is considered that 1 to 12 are suitable as a glass plate for producing a glass resin composite by compositely integrating with the resin plate. On the other hand, sample No. 13 to 15 have low Young's modulus and therefore have low impact resistance. Sample No. Since the liquid phase viscosity of No. 16 is low, it is considered that continuous melting is difficult.
次に、試料No.1に係るガラス板を所定の形状の金型で挟み込んだ状態で熱処理炉を通過させることにより、板幅方向の全体が円弧状に湾曲し、且つ長さ方向の全体が円弧状に湾曲した曲面形状に曲面加工した。その後、曲面加工後のガラス板の端面について#800のメタルボンド砥石によりC面取り加工及び研磨加工を行った。 Next, sample No. By passing the glass plate according to 1 in a state of being sandwiched between molds having a predetermined shape and passing through the heat treatment furnace, a curved surface in which the entire plate width direction is curved in an arc shape and the entire length direction is curved in an arc shape. The curved surface was processed into a shape. Then, the end face of the glass plate after the curved surface was chamfered and polished with a # 800 metal bond grindstone.
続いて、ガラス板と同様の曲面形状を有するポリカーボネート板(板厚4.0mm)を用意した。 Subsequently, a polycarbonate plate (plate thickness 4.0 mm) having a curved surface shape similar to that of the glass plate was prepared.
最後に、厚み0.8mmのポリビニルブチラール(PVB)を用いて、外側(大気側)から、試料No.1に係るガラス板(外層のガラス板)、試料No.1に係るガラス板(内層のガラス板)、ポリカーボネート板の順になるように、オートクレーブ処理により複合一体化して、試料No.1に係るガラス樹脂複合体を得た。更に、試料No.2〜12についても、同様の実験を行い、試料No.2〜12に係るガラス樹脂複合体を得た。 Finally, using polyvinyl butyral (PVB) having a thickness of 0.8 mm, from the outside (atmospheric side), the sample No. The glass plate (outer layer glass plate) according to No. 1 and sample No. The glass plate (inner layer glass plate) and the polycarbonate plate according to No. 1 were combined in the order of the sample No. 1 by autoclave treatment. The glass resin composite according to No. 1 was obtained. Furthermore, the sample No. The same experiment was performed for 2 to 12, and the sample No. A glass resin complex according to 2 to 12 was obtained.
本発明のガラス板は、樹脂板と複合一体化して、ガラス樹脂複合体を作製するためのガラス板として好適であり、そのガラス樹脂複合体は、自動車、鉄道、航空機等の窓ガラスに好適であり、それ以外にも、高層ビル等の建築物の窓ガラスにも好適である。 The glass plate of the present invention is suitable as a glass plate for producing a glass-resin composite by compositely integrating with a resin plate, and the glass-resin composite is suitable for window glass of automobiles, railways, aircraft, etc. In addition to that, it is also suitable for window glass of buildings such as high-rise buildings.
10 ガラス樹脂複合体
11 ガラス板
12 ガラス板
13 樹脂板10
Claims (6)
ガラス組成として、モル%で、SiO2 45〜80%、Al2O3 5〜30%、Li2O+Na2O+K2O 0〜20%、MgO 3〜35%、CaO 0.1〜35%、SrO+BaO 0〜15%を含有することを特徴とするガラス板。It is a glass plate for producing a glass resin composite by compositely integrating with a resin plate.
As a glass composition, in mol%, SiO 2 45~80%, Al 2 O 3 5~30%, Li 2 O + Na 2 O + K 2 O 0~20%, MgO 3~35%, CaO 0.1~35%, A glass plate containing 0 to 15% of SrO + BaO.
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