WO2010095479A1 - Stratifié diélectrique, verre stratifié, procédé de production d'un stratifié diélectrique, et procédé pour produire du verre stratifié - Google Patents

Stratifié diélectrique, verre stratifié, procédé de production d'un stratifié diélectrique, et procédé pour produire du verre stratifié Download PDF

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Publication number
WO2010095479A1
WO2010095479A1 PCT/JP2010/050444 JP2010050444W WO2010095479A1 WO 2010095479 A1 WO2010095479 A1 WO 2010095479A1 JP 2010050444 W JP2010050444 W JP 2010050444W WO 2010095479 A1 WO2010095479 A1 WO 2010095479A1
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WO
WIPO (PCT)
Prior art keywords
refractive index
dielectric film
dielectric
gas
laminate
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Application number
PCT/JP2010/050444
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English (en)
Japanese (ja)
Inventor
良孝 後藤
Original Assignee
コニカミノルタホールディングス株式会社
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Application filed by コニカミノルタホールディングス株式会社 filed Critical コニカミノルタホールディングス株式会社
Publication of WO2010095479A1 publication Critical patent/WO2010095479A1/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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/10009—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/1055—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal

Definitions

  • It has a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film are alternately laminated on a resin support, and glass is pasted on the front and back surfaces of the dielectric laminate.
  • the dielectric laminate is bonded to the glass with polyvinyl butyral, the resin support is polyethylene naphthalate, and the low refractive index dielectric film and the high refractive index
  • a laminated glass wherein a difference in hardness measured by a nanoindentation method with respect to a dielectric film is 1.4 GPa or more and 3.0 GPa or less.
  • a dielectric laminate manufacturing method for manufacturing a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film having different hardnesses are alternately laminated on a resin support the resin The support is polyethylene naphthalate, and the difference in hardness measured by the nanoindentation method between the low refractive index dielectric film and the high refractive index dielectric film is 1.4 GPa or more and 3.0 GPa or less
  • the dielectric film introduces a gas into the discharge space under atmospheric pressure or pressure near the atmosphere to form a high-frequency electric field in the discharge space, thereby bringing the gas into a plasma state, and A method for producing a dielectric laminate, wherein the dielectric laminate is formed by exposure to a gas in a plasma state.
  • a dielectric laminate in which a low refractive index dielectric film and a high refractive index dielectric film are alternately laminated on a resin support is polyethylene naphthalate, and the difference in hardness measured by the nanoindentation method between the low refractive index dielectric film and the high refractive index dielectric film is 1.4 GPa or more, A dielectric laminate characterized by being 3.0 GPa or less, or a dielectric laminate obtained by alternately laminating a low refractive index dielectric film and a high refractive index dielectric film on a resin support And the dielectric laminate is laminated to the glass with polyvinyl butyral, and the resin support is polyethylene naphthalate.
  • the low refractive index dielectric film and the high refractive index dielectric film according to the present invention have different hardnesses between the dielectric films. Therefore, after stacking a plurality of dielectric films, polyvinyl butyral It was found that there was a failure that caused cracks in the interface of the dielectric film and in the film when it was bonded to the glass using a glass, and there was a failure that deteriorated the performance.
  • the difference in hardness measured by the nanoindentation method between the low refractive index dielectric film formed on the resin support and the high refractive index dielectric film on the resin support is 1.4 GPa or more. It has been found that the above-mentioned problem can be achieved by setting the pressure to 0.0 GPa or less.
  • the resin support is a support for laminating dielectric films.
  • polyethylene naphthalate hereinafter abbreviated as PEN
  • PEN polyethylene naphthalate
  • the surface of the resin support on which the dielectric film is laminated may be subjected to easy contact treatment, or may be subjected to easy contact treatment on the opposite surface side where the dielectric film is not laminated.
  • PEN which is a resin support body is transparent, high light resistance, and high weather resistance.
  • the PEN that is the resin support may be an unstretched film or a stretched film.
  • fillers applicable to the PEN according to the present invention include calcium carbonate, calcium oxide, aluminum oxide, kaolin, silicon oxide, zinc oxide, carbon black, silicon carbide, tin oxide, crosslinked acrylic resin particles, and crosslinked polystyrene resin particles. , Melamine resin particles, crosslinked silicon resin particles, and the like.
  • the average particle size of the filler is 0.01 to 10 ⁇ m, and the content is within the range in which the PEN film maintains transparency, and is preferably 0.0001 to 5% by mass.
  • a material mainly composed of calcium, barium, lithium and magnesium fluorides can be used for the low refractive index film.
  • at least one layer can have a graded configuration.
  • the dielectric laminate of the present invention is characterized by being formed by alternately laminating low refractive index dielectric films and high refractive index dielectric films.
  • the dielectric film is defined as a film having a refractive index of 1.60 or more with respect to light having a wavelength of 633 nm, preferably a dielectric film having a refractive index of 1.70 or more.
  • the refractive index of the dielectric film the reflectance is measured under the condition of regular reflection at 5 degrees using, for example, a spectrophotometer 1U-4000 type (manufactured by Hitachi, Ltd.).
  • examples of the optical film thickness measuring apparatus include a USB simplified film thickness measuring apparatus, Solid Lambda Thickness (manufactured by Spectra Corp.). Or the cross-sectional part of the formed dielectric film laminated body is cut out using a microtome etc., The cross-sectional part is observed using an electron microscope etc., and the total film thickness of a dielectric film can be calculated
  • a dielectric film is an oxide or nitride oxide containing Si or Al by selecting conditions such as an organometallic compound, a decomposition gas, a decomposition temperature, and an input power as a raw material (also referred to as a raw material) in an atmospheric pressure plasma method.
  • a dielectric film having a refractive index different from that of a ceramic layer containing nitride as a main component can be formed.
  • silicon compounds include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide
  • the dielectric film is formed by mixing the discharge gas and the reactive gas and supplying the mixed gas as a dielectric film forming (mixed) gas to a plasma discharge generator (plasma generator).
  • a plasma discharge generator plasma generator
  • the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.
  • the high frequency referred to in the present invention means one having a frequency of at least 0.5 kHz.
  • the present invention is not limited to this, and both pulse waves may be used, one may be continuous waves and the other may be pulse waves. Further, it may have a third electric field having a different frequency.
  • a first filter that makes it difficult to pass a high-frequency electric field current from the second power source between the first electrode and the first power source or between them, and the second electrode, the second power source, or between them It is preferable to connect a 2nd filter to either.
  • the jet type atmospheric pressure plasma discharge processing apparatus is not shown in FIG. And an electrode temperature adjusting means.
  • the dielectric film forming gas G described above is introduced into the gap (discharge space) 13 between the first electrode 11 and the second electrode 12 from the gas supply means as shown in FIG.
  • a power source 21 and a second power source 22 form the above-described high-frequency electric field between the first electrode 11 and the second electrode 12 to generate a discharge.
  • the substrate is blown out in the form of a jet on the lower side (the lower side of the paper), and the processing space created by the lower surface of the counter electrode and the base material F is filled with a gas G ° in a plasma state.
  • a dielectric film is formed in the vicinity of the processing position 14 on the base material F that is unwound and transported or transported from the previous process.
  • the atmospheric pressure plasma discharge treatment apparatus is an apparatus having at least a plasma discharge treatment apparatus 30, an electric field application means 40 having two power supplies, a gas supply means 50, and an electrode temperature adjustment means 60.
  • the roll rotating electrode 35 receives a high-frequency electric field having a frequency ⁇ 1 from the first power source 41, and the fixed electrode group 36 has a second power source 42.
  • a second high-frequency electric field having a frequency ⁇ 2 is applied.
  • the medium whose temperature is adjusted by the electrode temperature adjusting means 60 is sent to both electrodes via the pipe 61 by the liquid feed pump P, Adjust the temperature from the inside of the electrode.
  • Reference numerals 68 and 69 denote partition plates that partition the plasma discharge processing vessel 31 from the outside.
  • the shape of the fixed electrode 36a shown in FIG. 4 is not particularly limited, and may be a cylindrical electrode or a rectangular tube electrode.
  • a roll electrode 35a and an electrode 36a are formed by spraying ceramics as dielectrics 35B and 36B on conductive metallic base materials 35A and 36A, respectively, and then using a sealing material of an inorganic compound. Sealed.
  • the ceramic dielectric may be covered by about 1 mm with a single wall.
  • As the ceramic material used for thermal spraying alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed.
  • the dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.
  • SPG5-4500 5 kHz
  • Shinko Electric Co., Ltd. AGI-023 (15 kHz) manufactured by Kasuga Electric Co., Ltd.
  • PHF-6k manufactured by HEIDEN Laboratory (100 kHz *)
  • commercially available products such as CF-2000-200k (200 kHz) manufactured by Pearl Industry, and any of them can be used.
  • an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.
  • the film quality can be further improved by supplying power (power density) of 1 W / cm 2 or more to the first electrode (first high-frequency electric field). Preferably it is 5 W / cm 2 or more.
  • the upper limit value of the power supplied to the first electrode is preferably 50 W / cm 2 .
  • the waveform of the high-frequency electric field is not particularly limited.
  • a continuous sine wave continuous oscillation mode called a continuous mode
  • an intermittent oscillation mode called ON / OFF intermittently called a pulse mode
  • the second electrode side second
  • the high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.
  • the discharge gas is nitrogen gas
  • the high-frequency electric field applied to the discharge space is a superposition of the first high-frequency electric field and the second high-frequency electric field, and the frequency ⁇ 1 of the first high-frequency electric field
  • the frequency ⁇ 2 of the second high-frequency electric field is high, and the relationship among the first high-frequency electric field strength V1, the second high-frequency electric field strength V2, and the discharge start electric field strength IV is V1 ⁇ IV> V2.
  • the glass material used for the laminated glass of the present invention is a transparent glass substrate, and there is no particular limitation other than that as long as it has high light transmissivity, its raw material, manufacturing method, shape, structure, thickness, hardness, etc. Can be appropriately selected from known ones.
  • quartz glass, soda lime glass, silicate glass, aluminosilicate glass, borosilicate glass, phosphate glass, and fluorophosphate glass can be used.
  • the nanoindentation probe is a Berkovich indenter in which a diamond triangular pyramid with a tip radius of curvature of 25 nm or less, a ridge angle of 60 degrees, and a height of 100 ⁇ m is fixed to a base having a length of 350 ⁇ m, a width of 100 ⁇ m, a thickness of 13 ⁇ m, and a spring constant of 263 N / m. Was used.
  • a polyvinyl butyral film (ST type, manufactured by Sekisui Chemical Co., Ltd.) having a thickness of 0.38 mm is bonded to both surfaces of the obtained dielectric film laminate 1, and the pressure is 9.8 N / cm 2 at room temperature.
  • a laminate was obtained by laminating with a roller. It was 300 g / cm when the adhesive force between the dielectric film laminated body 1 of the obtained laminated body and polyvinyl butyral was measured.
  • the laminate was stored for 2 weeks in an environment of 25 ° C. and 10% RH, and then left for 5 hours in an environment of 25 ° C. and 80% RH. Then, bending was performed and a peel test was performed.
  • the laminated body is squeezed with a glass plate having a thickness of 3 mm, laminated with a roller, put in a vacuum bag, reduced in pressure with a vacuum pump so that the laminated glass is subjected to atmospheric pressure, After heat-processing at 90 degreeC for 40 minutes, it put into the autoclave, the pressure of 1.3 MPa was applied under 130 degreeC, and it processed for 40 minutes, and the laminated glass 1 was produced.
  • Sample 5 was obtained in the same manner except that three layers (thickness: 190 nm, refractive index 1.46) were alternately provided in the layer configuration shown below, and a dielectric film laminate having a total film thickness of 430 nm was formed. .
  • Sample 8 In the production of the dielectric film laminate 1 of Sample 1, the resin support was changed to a triacetylcellulose film (thickness: 100 ⁇ m, abbreviated as TAC) instead of a PEN (polyethylene naphthalate) film (thickness: 100 ⁇ m). Sample 8 was produced in the same manner as Sample 1 except that.
  • TAC triacetylcellulose film
  • PEN polyethylene naphthalate

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  • Laminated Bodies (AREA)

Abstract

L'invention concerne un stratifié diélectrique qui a une force adhésive élevée quand il est collé à une feuille de polybutyral de vinyle et qui, quand il est utilisé dans un verre stratifié, offre des améliorations en termes de régularité de la qualité (résistance à la fissuration, absence d'inclusions de bulles d'air, et résistance au voilage) et présente d'excellentes propriétés d'isolation thermique ; un verre stratifié ; et des procédés de production du stratifié et du verre. Le stratifié diélectrique comprend un support en résine et, superposé dessus, des films diélectriques à indice réduit de réfraction alternés avec des films diélectriques à indice élevé de réfraction, et caractérisé en ce que le support de résine est en polyéthylène naphtalate, et la différence de dureté mesurée par un procédé de nanoindentation entre les films diélectriques à indice réduit de réfraction et les films diélectriques à indice élevé de réfraction est de 1,4 à 3,0 GPa.
PCT/JP2010/050444 2009-02-20 2010-01-16 Stratifié diélectrique, verre stratifié, procédé de production d'un stratifié diélectrique, et procédé pour produire du verre stratifié WO2010095479A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-037650 2009-02-20
JP2009037650 2009-02-20

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WO2010095479A1 true WO2010095479A1 (fr) 2010-08-26

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5412603B1 (ja) * 2013-07-31 2014-02-12 株式会社クラレ 透明性、熱割れ現象抑制に優れるポリビニルアセタールフィルム
JP2015030850A (ja) * 2013-11-11 2015-02-16 株式会社クラレ 透明性、熱割れ現象抑制に優れるポリビニルアセタールフィルム

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000355701A (ja) * 1999-06-10 2000-12-26 Honda Motor Co Ltd 複合材製コーティング部材
JP2005002457A (ja) * 2003-06-13 2005-01-06 Fuji Kihan:Kk 複合表面改質方法及び複合表面改質成品
JP2008062460A (ja) * 2006-09-06 2008-03-21 Konica Minolta Holdings Inc 光学フィルムとそれを用いた画像表示素子
JP2009035438A (ja) * 2007-07-31 2009-02-19 Central Glass Co Ltd 赤外線反射合せガラス

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000355701A (ja) * 1999-06-10 2000-12-26 Honda Motor Co Ltd 複合材製コーティング部材
JP2005002457A (ja) * 2003-06-13 2005-01-06 Fuji Kihan:Kk 複合表面改質方法及び複合表面改質成品
JP2008062460A (ja) * 2006-09-06 2008-03-21 Konica Minolta Holdings Inc 光学フィルムとそれを用いた画像表示素子
JP2009035438A (ja) * 2007-07-31 2009-02-19 Central Glass Co Ltd 赤外線反射合せガラス

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5412603B1 (ja) * 2013-07-31 2014-02-12 株式会社クラレ 透明性、熱割れ現象抑制に優れるポリビニルアセタールフィルム
WO2015015601A1 (fr) * 2013-07-31 2015-02-05 株式会社クラレ Film de poly(acétal de vinyle) ayant une transparence et une résistance au phénomène de fissuration thermique exceptionnelles
CN105452350A (zh) * 2013-07-31 2016-03-30 株式会社可乐丽 透明性、抑制热裂现象优异的聚乙烯醇缩醛薄膜
JP2015030850A (ja) * 2013-11-11 2015-02-16 株式会社クラレ 透明性、熱割れ現象抑制に優れるポリビニルアセタールフィルム

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