WO2011074639A1 - Film intermédiaire pour verre feuilleté et verre feuilleté associé - Google Patents

Film intermédiaire pour verre feuilleté et verre feuilleté associé Download PDF

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Publication number
WO2011074639A1
WO2011074639A1 PCT/JP2010/072672 JP2010072672W WO2011074639A1 WO 2011074639 A1 WO2011074639 A1 WO 2011074639A1 JP 2010072672 W JP2010072672 W JP 2010072672W WO 2011074639 A1 WO2011074639 A1 WO 2011074639A1
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group
carbon atoms
laminated glass
alkyl group
formula
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PCT/JP2010/072672
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English (en)
Japanese (ja)
Inventor
努 安藤
和幸 矢原
圭吾 大鷲
大輔 中島
恵市 小佐野
敦 和田
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積水化学工業株式会社
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Priority to JP2011501038A priority Critical patent/JP4886096B2/ja
Publication of WO2011074639A1 publication Critical patent/WO2011074639A1/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
    • B32B17/1055—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

  • the present invention relates to an interlayer film for laminated glass having a very short time from application of a voltage to completion of a change in light transmittance. Further, the present invention relates to a laminated glass using the interlayer film for laminated glass.
  • a light control body including a light control film whose light transmittance is changed by applying a voltage is widely used. Studies have been repeated for the purpose of applying this light control body to a display device such as a building or a lightning board.
  • a laminated glass using a light control film as an interlayer film for laminated glass has been proposed in order to control the temperature inside a vehicle such as an automobile. It is considered that the light transmittance of the laminated glass can be controlled by using such an interlayer film for laminated glass.
  • the dimmer is roughly classified into a dimmer using a liquid crystal material and a dimmer using an electrochromic compound.
  • a light control body using an electrochromic compound has excellent properties such as less light scattering and no influence of polarization compared to a light control body using a liquid crystal material.
  • electrochromic compounds inorganic electrochromic compounds and organic electrochromic compounds are known. Moreover, as an organic electrochromic compound, the low molecular weight organic electrochromic compound and the high molecular compound which shows electrochromic property are examined.
  • Patent Document 1 and Patent Document 2 include two laminates in which three layers of an electrochromic layer containing an inorganic oxide, an ion conductive layer, and an electrochromic layer containing an inorganic oxide are sequentially laminated.
  • a light control member sandwiched between conductive substrates is disclosed.
  • Patent Document 3 and Patent Document 4 disclose a light adjuster in which an electrochromic layer containing an organic electrochromic compound and an electrolyte layer are sandwiched between a pair of opposing electrode substrates.
  • the conventional light adjuster since the conventional light adjuster has poor responsiveness, there is a problem that it takes time to complete the change in light transmittance even when a voltage is applied.
  • JP 2004-062030 A Japanese Patent Laying-Open No. 2005-062772 Special Table 2002-526801 JP-T-2004-53770
  • An object of the present invention is to provide an interlayer film for laminated glass in which the time from application of voltage to completion of change in light transmittance is extremely short. It is another object of the present invention to provide a laminated glass using the interlayer film for laminated glass.
  • the present invention is an interlayer film for laminated glass having an electrolyte layer and an electrochromic layer formed on at least one side of the electrolyte layer, and the electrolyte layer includes a supporting electrolyte salt, a binder resin, and the following formula ( It is an interlayer film for laminated glass containing a compound represented by 1) or a compound represented by the following formula (2).
  • n represents an integer of 2 to 4
  • R 1 represents a hydrogen atom, an acyl group having an organic group having 1 to 7 carbon atoms, or an organic group having 1 to 8 carbon atoms
  • R 2 represents ethylene
  • R 3 represents a hydrogen atom, an acyl group having an organic group having 1 to 7 carbon atoms or an organic group having 1 to 8 carbon atoms
  • at least one of R 1 and R 3 represents an acyl group.
  • R 4 represents an organic group having 2 to 8 carbon atoms and having an oxygen atom
  • R 5 represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 12 carbon atoms
  • R 6 has 2 to 8 carbon atoms and represents an organic group having an oxygen atom.
  • R 4 and R 6 may be the same or different. The present invention is described in detail below.
  • the present inventors have extremely high responsiveness by adding a compound having a specific structure to the electrolyte layer, and the transmittance of light after voltage is applied.
  • the inventors have found that an interlayer film for laminated glass can be obtained with a very short time until the change is completed, and have completed the present invention.
  • the interlayer film for laminated glass of the present invention is a laminate of an electrolyte layer and an electrochromic layer.
  • the electrolyte layer has a role of applying a voltage to the electrochromic layer by conducting ions to change the light transmittance of the electrochromic layer.
  • the electrolyte layer contains a supporting electrolyte salt, a binder resin, and a compound represented by the above formula (1) or a compound represented by the above formula (2).
  • a supporting electrolyte salt By laminating the electrolyte layer containing the compound represented by the above formula (1) or the compound represented by the above formula (2) on the electrochromic layer, the change in light transmittance is completed after the voltage is applied. It is possible to obtain an interlayer film for laminated glass having a very short time.
  • the compound represented by the above formula (1) or the compound represented by the above formula (2) may be used alone or in combination.
  • the interlayer film for laminated glass having improved durability and a shorter time from application of voltage to completion of change in light transmittance can be obtained. It is preferable to contain the compound.
  • R 1 represents a hydrogen atom, an acyl group having an organic group having 1 to 7 carbon atoms, or an organic group having 1 to 8 carbon atoms.
  • R 1 is preferably an acyl group having an organic group having 1 to 7 carbon atoms or an organic group having 1 to 8 carbon atoms in order to further improve the compatibility with the binder resin.
  • An acyl group having an organic group of ⁇ 7 is more preferred, and an acyl group having an alkyl group having 1 to 7 carbon atoms is more preferred.
  • the preferable lower limit of the carbon number of the organic group is 2, and the preferable upper limit is 6.
  • the carbon number is 2 or more, the durability of the electrolyte layer is improved, and when it is 6 or less, the time from application of voltage to completion of change in light transmittance is shorter. Is obtained.
  • the more preferable lower limit of the carbon number is 3, a more preferable upper limit is 5, and a more preferable upper limit is 4.
  • the organic group having 1 to 7 carbon atoms may be an organic group having a linear structure or an organic group having a branched structure, and may be an alkyl group having a linear structure or an alkyl group having a branched structure. Preferably there is.
  • the organic group or the branched chain of the alkyl group preferably has 3 or less carbon atoms, more preferably 2 or less, and more preferably 1 or less. Is more preferable.
  • the acyl group having an organic group having 1 to 7 carbon atoms is an acyl group having 1 to 7 carbon atoms and an organic group having a linear structure, or 1 to 7 carbon atoms, and An acyl group having an alkyl group having a chain structure is preferred.
  • the acyl group having an organic group having 1 to 7 carbon atoms is an acyl group having 1 to 7 carbon atoms and an organic group having a branched structure, or has 1 to 7 carbon atoms, and has a branched structure. It is preferably an acyl group having an alkyl group, more preferably an acyl group having 1 to 7 carbon atoms, a branched structure, and an alkyl group having 3 or less carbon atoms in the branched chain.
  • acyl group having an alkyl group having 1 to 7 carbon atoms having a branched structure, and having 2 or less carbon atoms in the branched chain, and having 1 to 7 carbon atoms and branched. It has a structure and the number of carbon atoms in the branched chain is 1 And particularly preferably an acyl group having an alkyl group is lower.
  • the acyl group having an organic group having 1 to 7 carbon atoms means that the organic group has 1 to 7 carbon atoms
  • the acyl group having an alkyl group having 1 to 7 carbon atoms is , Which means that the alkyl group has 1 to 7 carbon atoms.
  • R 1 in the above formula (1) is an organic group having 1 to 8 carbon atoms
  • the compatibility with the binder resin is further improved, so the organic group having 1 to 8 carbon atoms is 8 alkyl groups are preferred.
  • the preferable lower limit of the carbon number in the organic group having 1 to 8 carbon atoms representing R 1 in the above formula (1) is 2, and the preferable upper limit is 7.
  • the carbon number is 2 or more, the durability of the electrolyte layer is improved, and when it is 7 or less, the time from application of voltage to completion of change in light transmittance is shorter. Is obtained.
  • the more preferable lower limit of the carbon number is 3, a more preferable upper limit is 6, a further preferable lower limit is 4, and a more preferable upper limit is 5.
  • the organic group having 1 to 8 carbon atoms may be an organic group having a linear structure or an organic group having a branched structure, and may be an alkyl group having a linear structure or an alkyl group having a branched structure. Preferably there is.
  • the organic group or the branched chain of the alkyl group preferably has 3 or less carbon atoms, more preferably 2 or less, and more preferably 1 or less. Is more preferable.
  • the organic group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms and having a linear structure.
  • the organic group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms and having a branched structure, having 1 to 8 carbon atoms, having a branched structure, and having a branched chain Is more preferably an alkyl group having 3 or less carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, a branched structure, and a branched chain having 2 or less carbon atoms.
  • An alkyl group having 1 to 8 carbon atoms, having a branched structure, and having 1 or less carbon atoms in the branched chain is particularly preferable.
  • R 2 represents an ethylene group or a propylene group.
  • the propylene group may be an n-propylene group or an isopropylene group.
  • R 2 is preferably an ethylene group because an interlayer film for laminated glass having a shorter time from application of voltage to completion of change in light transmittance can be obtained.
  • R 3 represents a hydrogen atom, an acyl group having an organic group having 1 to 7 carbon atoms, or an organic group having 1 to 8 carbon atoms.
  • R 3 is preferably an acyl group having an organic group having 1 to 7 carbon atoms or an organic group having 1 to 8 carbon atoms, in order to further improve the compatibility with the binder resin.
  • An acyl group having an organic group of ⁇ 7 is more preferred, and an acyl group having an alkyl group having 1 to 7 carbon atoms is more preferred.
  • the preferable lower limit of the carbon number of the organic group is 2, and the preferable upper limit is 6.
  • the carbon number is 2 or more, the durability of the electrolyte layer is improved, and when it is 6 or less, the time from application of voltage to completion of change in light transmittance is shorter. Is obtained.
  • the more preferable lower limit of the carbon number is 3, a more preferable upper limit is 5, and a more preferable upper limit is 4.
  • the organic group having 1 to 7 carbon atoms may be an organic group having a linear structure or an organic group having a branched structure, and may be an alkyl group having a linear structure or an alkyl group having a branched structure. Preferably there is.
  • the organic group or the branched chain of the alkyl group preferably has 3 or less carbon atoms, more preferably 2 or less, and more preferably 1 or less. Is more preferable.
  • the acyl group having an organic group having 1 to 7 carbon atoms is an acyl group having 1 to 7 carbon atoms and an organic group having a linear structure, or 1 to 7 carbon atoms, and An acyl group having an alkyl group having a chain structure is preferred.
  • the acyl group having an organic group having 1 to 7 carbon atoms is an acyl group having 1 to 7 carbon atoms and an organic group having a branched structure, or has 1 to 7 carbon atoms, and has a branched structure. It is preferably an acyl group having an alkyl group, more preferably an acyl group having 1 to 7 carbon atoms, a branched structure, and an alkyl group having 3 or less carbon atoms in the branched chain.
  • acyl group having an alkyl group having 1 to 7 carbon atoms having a branched structure, and having 2 or less carbon atoms in the branched chain, and having 1 to 7 carbon atoms and branched. It has a structure and the number of carbon atoms in the branched chain is 1 And particularly preferably an acyl group having an alkyl group is lower.
  • the acyl group having an organic group having 1 to 7 carbon atoms means that the organic group has 1 to 7 carbon atoms
  • the acyl group having an alkyl group having 1 to 7 carbon atoms is , Which means that the alkyl group has 1 to 7 carbon atoms.
  • R 3 in the above formula (1) is an organic group having 1 to 8 carbon atoms
  • the compatibility with the binder resin is further improved. Therefore, the organic group having 1 to 8 carbon atoms is 8 alkyl groups are preferred.
  • the preferable lower limit of the carbon number in the organic group having 1 to 8 carbon atoms representing R 3 in the above formula (1) is 2, and the preferable upper limit is 7.
  • the carbon number is 2 or more, the durability of the electrolyte layer is improved, and when it is 7 or less, the time from application of voltage to completion of change in light transmittance is shorter. Is obtained.
  • the more preferable lower limit of the carbon number is 3, a more preferable upper limit is 6, a further preferable lower limit is 4, and a more preferable upper limit is 5.
  • the organic group having 1 to 8 carbon atoms may be an organic group having a linear structure or an organic group having a branched structure, and may be an alkyl group having a linear structure or an alkyl group having a branched structure. Preferably there is.
  • the organic group or the branched chain of the alkyl group preferably has 3 or less carbon atoms, more preferably 2 or less, and more preferably 1 or less. Is more preferable.
  • the organic group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms and having a linear structure.
  • the organic group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms and having a branched structure, having 1 to 8 carbon atoms, having a branched structure, and having a branched chain
  • the alkyl group is more preferably an alkyl group having 3 or less carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, a branched structure, and a branched chain having 2 or less carbon atoms.
  • An alkyl group having 1 to 8 carbon atoms, a branched structure, and a branched chain having 1 or less carbon atoms is particularly preferable.
  • R 1 and R 3 has an acyl group.
  • R 1 represents an acyl group having an alkyl group having 1 to 7 carbon atoms
  • R 2 represents an ethylene group or a propylene group
  • R 3 represents an acyl group having an alkyl group having 1 to 7 carbon atoms. Is more preferable.
  • R 4 represents an organic group having 2 to 8 carbon atoms and having an oxygen atom.
  • a carbon number of 2-8 representing the R 4 in the formula (2), the preferable lower limit of the carbon number of the organic group having an oxygen atom 3, and the upper limit thereof is preferably 7.
  • the carbon number is 3 or more, the durability of the electrolyte layer is improved, and when it is 7 or less, the time from application of voltage to completion of change in light transmittance is shorter. Is obtained.
  • the more preferable lower limit of the carbon number is 4, and the more preferable upper limit is 6.
  • R 5 represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 12 carbon atoms.
  • R 5 is preferably an alkylene group having 2 to 8 carbon atoms, since the compatibility with the binder resin is further improved.
  • the preferable lower limit of the carbon number of the alkylene group having 2 to 8 carbon atoms representing R 5 in the above formula (2) is 3, and the preferable upper limit is 7.
  • the carbon number is 3 to 7
  • an interlayer film for laminated glass having a shorter time from application of voltage to completion of change in light transmittance can be obtained.
  • the more preferable lower limit of the carbon number is 4, and the more preferable upper limit is 6.
  • the preferred upper limit of the carbon number of the arylene group having 6 to 12 carbon atoms representing R 5 in the above formula (2) is 10.
  • the carbon number is 10 or less, an interlayer film for laminated glass having a shorter time from application of voltage to completion of change in light transmittance can be obtained.
  • a more preferable upper limit of the carbon number is 8.
  • R 6 represents an organic group having 2 to 8 carbon atoms and having an oxygen atom.
  • a carbon number of 2-8 that represents the R 6 in the formula (2), the preferable lower limit of the carbon number of the organic group having an oxygen atom 3, and the upper limit thereof is preferably 7.
  • the carbon number is 3 or more, the durability of the electrolyte layer is improved, and when it is 7 or less, the time from application of voltage to completion of change in light transmittance is shorter. Is obtained.
  • the more preferable lower limit of the carbon number is 4, and the more preferable upper limit is 6.
  • the compounding amount of the compound represented by the formula (1) and the compound represented by the formula (2) in the electrolyte layer is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the binder resin is 15 parts by weight, preferably.
  • the upper limit is 200 parts by weight.
  • the compounding amount of the compound represented by the above formula (1) and the compound represented by the above formula (2) is 15 parts by weight or more, the time from when the voltage is applied until the change of the light transmittance is completed Becomes even shorter.
  • the compounding amount of the compound represented by the above formula (1) and the compound represented by the above formula (2) is 200 parts by weight or less, the penetration resistance of the laminated glass becomes high.
  • the more preferable lower limit of the compounding amount of the compound represented by the above formula (1) and the compound represented by the above formula (2) is 30 parts by weight, the still more preferable lower limit is 50 parts by weight, and the particularly preferable lower limit is 60 parts by weight.
  • a more preferred upper limit is 150 parts by weight, a still more preferred upper limit is 120 parts by weight, and a particularly preferred upper limit is 100 parts by weight.
  • the supporting electrolyte salt is not particularly limited, and is preferably an alkali metal salt such as a lithium salt, a potassium salt, or a sodium salt.
  • the alkali metal salt is preferably an inorganic acid and alkali metal salt or an organic acid and alkali metal salt.
  • the inorganic acid and alkali metal salt include an inorganic acid anion lithium salt, an inorganic acid anion potassium salt, or an inorganic acid anion sodium salt
  • the organic acid and alkali metal salt include an organic acid anion lithium. Examples thereof include a salt, an organic acid anion potassium salt, and an organic acid anion sodium salt.
  • the supporting electrolyte salt is preferably a lithium salt, and is an inorganic acid anion lithium salt such as lithium perchlorate, lithium borofluoride, or lithium phosphofluoride, or lithium trifluoromethanesulfonate, bistrifluoromethanesulfonate imide.
  • An organic acid anion lithium salt such as lithium is more preferable.
  • the supporting electrolyte salt may be a salt of an ammonium cation and an anion.
  • the ammonium cation is not particularly limited, and examples thereof include alkylammonium cations such as tetraethylammonium, trimethylethylammonium, methylpropylpyrrolidinium, methylbutylpyrrolidinium, methylpropylpiperidinium, methylbutylpiperidinium, and ethylmethyl Examples include imidazolium, dimethylethylimidazolium, methylpyridinium, ethylpyridinium, propylpyridinium, and butylpyridinium.
  • the anion is not particularly limited, and examples thereof include perchlorate anion, borofluoride anion, phosphofluoride anion, trifluoromethanesulfonate anion, and bistrifluoromethanesulfonate imide anion.
  • the blending amount of the supporting electrolyte salt in the electrolyte layer is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the binder resin is 3 parts by weight, and a preferable upper limit is 60 parts by weight.
  • a preferable lower limit with respect to 100 parts by weight of the binder resin is 3 parts by weight
  • a preferable upper limit is 60 parts by weight.
  • a more preferred lower limit of the amount of the supporting electrolyte salt is 10 parts by weight, a still more preferred lower limit is 20 parts by weight, a more preferred upper limit is 50 parts by weight, and a still more preferred upper limit is 40 parts by weight.
  • the electrolyte layer may contain a solvent.
  • the solvent is not particularly limited, and examples thereof include ester compounds such as acetonitrile, nitromethane, propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, and ⁇ -butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, and the like.
  • Substituted tetrahydrofuran compounds such as 1,3-dioxolane, 4,4-dimethyl-1,3-dioxolane, t-butyl ether, isobutyl ether, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, Organic solvents such as ethylene glycol, polyethylene glycol sulfolane, 3-methylsulfolane, methyl formate, methyl acetate, N-methylpyrrolidone, dimethylformamide, etc. It is.
  • the binder resin is not particularly limited, but is preferably a thermoplastic resin.
  • the binder resin include polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, polytrifluoride ethylene, acrylonitrile-butadiene-styrene copolymer, polyester, polyether, polyamide, Examples include polycarbonate, polyacrylate, polymethacrylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl acetal resin, and ethylene-vinyl acetate copolymer.
  • polyvinyl acetal resin and ethylene-vinyl acetate copolymer are preferable, and polyvinyl acetal resin is more preferable. Since an electrolyte layer with high transparency is obtained, a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde having 4 or 5 carbon atoms is more preferable.
  • the polyvinyl acetal resin is preferably a polyvinyl butyral resin.
  • the polyvinyl acetal resin preferably has an acetyl group content of 15 mol% or less. When the amount of acetyl groups in the polyvinyl acetal resin exceeds 15 mol%, the interlayer film for laminated glass may be whitened.
  • the polyvinyl acetal resin preferably has a hydroxyl group content of 30 mol% or less. When the amount of hydroxyl groups in the polyvinyl acetal resin exceeds 30 mol%, the compatibility with the solvent may be lowered, and the transparency of the electrolyte layer may be lowered.
  • the acetyl group amount and the hydroxyl group amount can be determined by a titration method according to JIS K 6728.
  • the said acetyl group amount is 5 mol% or more in the said polyvinyl acetal resin.
  • a polyvinyl acetal resin hereinafter also referred to as “polyvinyl acetal resin A”
  • a polyvinyl acetal resin having an acetalization degree of 70 to 85 mol% hereinafter also referred to as “polyvinyl acetal resin B”
  • a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde having a number of 6 or more (hereinafter also referred to as “polyvinyl acetal resin C”) is preferable.
  • the amount of acetyl group and the degree of acetalization can be determined by a titration method in accordance with JIS K 6728.
  • the minimum with the preferable amount of acetyl groups of the said polyvinyl acetal resin A is 6 mol%, and a preferable upper limit is 30 mol%. It can further prevent that the compound represented by the said Formula (1) and the compound represented by the said Formula (2) precipitate from the said electrolyte layer as the said acetyl group amount is 6 mol% or more. .
  • the manufacturing efficiency of the said polyvinyl acetal resin A can be improved as the said acetyl group amount is 30 mol% or less.
  • the more preferable lower limit of the acetyl group amount is 8 mol%, the more preferable upper limit is 28 mol%, the still more preferable lower limit is 10 mol%, the still more preferable upper limit is 25 mol%, and the particularly preferable lower limit is 12 mol%, especially A preferable upper limit is 23 mol%.
  • the polyvinyl acetal resin A has a preferable lower limit of the degree of acetalization of 50 mol% and a preferable upper limit of 80 mol%.
  • the degree of acetalization is 50 mol% or more, the compound represented by the above formula (1) and the compound represented by the above formula (2) can be further prevented from being precipitated from the electrolyte layer. .
  • the degree of acetalization is 80 mol% or less, the production efficiency of the polyvinyl acetal resin A can be increased.
  • the more preferable lower limit of the degree of acetalization is 55 mol%, the more preferable upper limit is 78 mol%, the still more preferable lower limit is 60 mol%, the still more preferable upper limit is 76 mol%, and the particularly preferable lower limit is 65 mol%.
  • a preferable upper limit is 74 mol%.
  • the polyvinyl acetal resin A is preferably a polyvinyl butyral resin.
  • the minimum with a preferable acetalization degree of the said polyvinyl acetal resin B is 71 mol%, and a preferable upper limit is 84 mol%.
  • a preferable upper limit is 84 mol%.
  • the more preferable lower limit of the degree of acetalization is 72 mol%, the more preferable upper limit is 83 mol%, the still more preferable lower limit is 73 mol%, the still more preferable upper limit is 82 mol%, and the particularly preferable lower limit is 74 mol%.
  • a preferable upper limit is 81 mol%.
  • a preferable lower limit of the amount of acetyl groups is 0.1 mol%, and a preferable upper limit is 20 mol%.
  • the amount of the acetyl group is 0.1 mol% or more, the compound represented by the formula (1) and the compound represented by the formula (2) are further prevented from being precipitated from the electrolyte layer. Can do.
  • the manufacturing efficiency of the said polyvinyl acetal resin B can be improved as the said acetyl group amount is 20 mol% or less.
  • the more preferable lower limit of the acetyl group amount is 0.5 mol%, the more preferable upper limit is 15 mol%, the still more preferable lower limit is 0.8 mol%, the still more preferable upper limit is 8 mol%, and the particularly preferable lower limit is 1.
  • the mol%, particularly preferred upper limit is 7 mol%.
  • the polyvinyl acetal resin B is preferably a polyvinyl butyral resin.
  • the polyvinyl acetal resin A and the polyvinyl acetal resin B are obtained by acetalizing polyvinyl alcohol with an aldehyde.
  • the aldehyde is preferably an aldehyde having 1 to 10 carbon atoms, and more preferably an aldehyde having 4 or 5 carbon atoms.
  • the polyvinyl acetal resin C is obtained by acetalizing polyvinyl alcohol using an aldehyde having 6 or more carbon atoms.
  • the aldehyde having 6 or more carbon atoms is not particularly limited, and examples thereof include n-hexyl aldehyde, n-octyl aldehyde, n-nonyl aldehyde, and n-decyl aldehyde.
  • the polyvinyl acetal resin C has a preferable lower limit of the degree of acetalization of 50 mol% and a preferable upper limit of 80 mol%.
  • the degree of acetalization is 50 mol% or more, the compound represented by the above formula (1) and the compound represented by the above formula (2) can be further prevented from being precipitated from the electrolyte layer. .
  • the degree of acetalization is 80 mol% or less, the production efficiency of the polyvinyl acetal resin C can be increased.
  • the more preferable lower limit of the degree of acetalization is 55 mol%, the more preferable upper limit is 78 mol%, the still more preferable lower limit is 60 mol%, the still more preferable upper limit is 76 mol%, and the particularly preferable lower limit is 65 mol%.
  • a preferable upper limit is 74 mol%.
  • the polyvinyl alcohol used as the raw material for the polyvinyl acetal resin has a preferable lower limit of the average degree of polymerization of 200 and a preferable upper limit of 5000.
  • the average degree of polymerization of the polyvinyl alcohol is 200 or more, the penetration resistance of the laminated glass is increased.
  • the average degree of polymerization of the polyvinyl alcohol is 5000 or less, the time from the application of voltage to the completion of the change in light transmittance is further shortened.
  • the more preferable lower limit of the average degree of polymerization is 500, and the more preferable upper limit is 4000.
  • the average degree of polymerization of the polyvinyl alcohol is obtained by dividing the weight average molecular weight of the polyvinyl alcohol obtained by polystyrene conversion by GPC (gel permeation chromatography) method by the molecular weight per segment of the polyvinyl alcohol.
  • GPC gel permeation chromatography
  • Examples of the column for measuring the weight average molecular weight in terms of polystyrene by the GPC method include Shodex LF-804 (manufactured by Showa Denko KK).
  • the electrolyte layer may contain a heat ray absorbent.
  • the heat ray absorber is not particularly limited as long as it has the ability to shield infrared rays, but tin-doped indium oxide particles, antimony-doped tin oxide particles, zinc oxide particles doped with elements other than zinc, lanthanum hexaboride particles, At least one selected from the group consisting of zinc antimonate particles and an infrared absorber having a phthalocyanine structure is preferred.
  • the electrolyte layer may contain an adhesion adjusting agent.
  • the adhesion adjusting agent include alkali metal salts, alkaline earth metal salts, and magnesium salts. Of these, alkali metal salts, alkaline earth metal salts and magnesium salts of carboxylic acids having 2 to 16 carbon atoms are preferred. Specific examples thereof include bis (acetic acid) magnesium, potassium acetate and bis (propionic acid) magnesium. And potassium propionate, magnesium bis (2-ethylbutanoate), potassium 2-ethylbutanoate, magnesium bis (2-ethylhexanoate), potassium 2-ethylhexanoate and the like. These adhesive force regulators may be used alone or in combination. In the case where the electrolyte layer contains a polyvinyl acetal resin as a binder resin, the electrolyte layer preferably contains an adhesive strength modifier.
  • the electrolyte layer may have a single layer structure or a multilayer structure.
  • the electrolyte layer having a multilayer structure means a structure in which two or more electrolyte layers are laminated.
  • the electrolyte layer is composed of the supporting electrolyte salt, the compound represented by the above formula (1) or the compound represented by the above formula (2), and the binder resin. It is preferable to contain a plastic resin.
  • the compound represented by the above formula (1) or the above formula (2) include triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH).
  • liquid plasticizers such as tetraethylene glycol di-2-ethylhexanoate (4GO) and dihexyl adipate (DHA).
  • 4GO tetraethylene glycol di-2-ethylhexanoate
  • DHA dihexyl adipate
  • a preferable minimum is 0.01 mm and a preferable upper limit is 3.0 mm.
  • the thickness of the electrolyte layer is 0.01 to 3.0 mm, the time from the application of voltage to the completion of the change in light transmittance is further shortened.
  • the more preferable lower limit of the thickness of the electrolyte layer is 0.1 mm, the more preferable upper limit is 2.0 mm, the still more preferable lower limit is 0.3 mm, and the still more preferable upper limit is 1.0 mm.
  • the method for forming the electrolyte layer is not particularly limited.
  • a solution in which the supporting electrolyte salt is dissolved in the compound represented by the formula (1) or the compound represented by the formula (2) is prepared and obtained.
  • Examples thereof include a method of forming an electrolyte layer by a method such as hot pressing with a mixture obtained by mixing the obtained solution with the binder resin, a method of forming the electrolyte layer by extruding the mixture with an extruder.
  • the electrolyte membrane containing the supporting electrolyte salt, the binder resin, and the compound represented by the above formula (1) or the compound represented by the above formula (2) is also one aspect of the present invention.
  • the electrolyte membrane of the present invention it is possible to obtain an interlayer film for laminated glass in which the time from application of voltage to completion of the change in light transmittance is extremely short.
  • the electrochromic layer contains an electrochromic compound.
  • the electrochromic compound contained in the electrochromic layer is not particularly limited as long as it is a compound having electrochromic properties, and may be an inorganic compound or an organic compound. Note that having an electrochromic property means having a property of changing light transmittance by applying a voltage.
  • Examples of the inorganic compound having electrochromic properties include metal oxides such as Mo 2 O 3 , Ir 2 O 3 , NiO, V 2 O 5 , WO 3 and TiO 2 , and mixed valence complexes such as Prussian blue. Can be mentioned.
  • Examples of the organic compounds having electrochromic properties include polypyrrole compounds, polyacetylene compounds, polythiophene compounds, polyparaphenylene vinylene compounds, polyaniline compounds, polyethylene dioxythiophene compounds, metal phthalocyanine compounds, viologen compounds, viologen salt compounds, ferrocene compounds, Examples thereof include dimethyl terephthalate compounds. Among these, a polyacetylene compound is preferable, and a polyacetylene compound having an aromatic side chain is more preferable.
  • the polyacetylene compound having an aromatic side chain has electrochromic properties and electrical conductivity, and can easily form an electrochromic layer. Therefore, if a polyacetylene compound having an aromatic side chain is used, an electrochromic layer having excellent light control performance can be easily formed. Moreover, the polyacetylene compound which has an aromatic side chain shows a change in an absorption characteristic, when a structure changes. As a result, since the absorption spectrum extends to the near infrared wavelength region, the electrochromic layer has excellent light control performance over a wide wavelength region.
  • the polyacetylene compound having an aromatic side chain is not particularly limited, and for example, a polyacetylene compound having a mono- or di-substituted aromatic in the side chain is suitable.
  • the substituent constituting the aromatic side chain is not particularly limited.
  • the substituent constituting the aromatic side chain has at least one substituent selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a naphthalene group, an anthracene group, a phenanthrene group, a fluorene group, and a perylene group. It is preferable. Among them, since the time from application of voltage to completion of the change in light transmittance is further shortened, the substituents constituting the aromatic side chain are naphthyl group, naphthalene group, anthracene group, phenanthrene.
  • fluorene group or perylene group is more preferable, anthracene group, phenanthrene group, fluorene group or perylene group is further preferable, and phenanthrene group is particularly preferable.
  • some hydrogen atoms of the substituents constituting the aromatic side chain may be substituted with atoms or atomic groups other than hydrogen atoms.
  • the electrochromic layer may contain a heat ray absorbent or an adhesive strength modifier.
  • the said heat ray absorber can use the heat ray absorber similar to the heat ray absorber contained in the said electrolyte layer.
  • the adhesive force adjusting agent the same adhesive force adjusting agent as the adhesive force adjusting agent contained in the electrolyte layer can be used.
  • a preferable minimum is 0.05 micrometer and a preferable upper limit is 5 micrometers.
  • the thickness of the electrochromic layer is 0.05 to 5 ⁇ m, the time from when a voltage is applied until the change of the light transmittance is completed is further shortened.
  • the more preferable lower limit of the thickness of the electrochromic layer is 0.1 ⁇ m, the more preferable upper limit is 2 ⁇ m, the still more preferable lower limit is 0.2 ⁇ m, and the still more preferable upper limit is 1 ⁇ m.
  • the interlayer film for laminated glass of the present invention has, in addition to the electrolyte layer and the electrochromic layer, an ultraviolet absorbing layer containing an ultraviolet absorber, an infrared absorbing layer containing a heat ray absorber, and the like as necessary. May be.
  • the interlayer film for laminated glass of the present invention preferably has an embossed surface.
  • the embossing roughness is not particularly limited, but the preferred lower limit of the 10-point average roughness defined by JIS B 0601 is 20 ⁇ m, and the preferred upper limit is 50 ⁇ m.
  • the emboss is preferably formed on the electrolyte layer or the electrolyte membrane, and more preferably, the emboss is formed on the surface in contact with the conductive film.
  • a laminated glass in which the interlayer film for laminated glass of the present invention is sandwiched between a pair of glass plates on which a conductive film is formed is also one aspect of the present invention.
  • the said glass plate can use the transparent plate glass generally used. Examples thereof include inorganic glass such as float plate glass, polished plate glass, template glass, netted glass, wire-containing plate glass, colored plate glass, heat ray absorbing glass, heat ray reflecting glass, and green glass.
  • organic plastics plates such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polyacrylate can also be used. Two or more types of glass plates may be used as the glass plate.
  • interposed the intermediate film for laminated glasses of this invention with the transparent float plate glass and the colored glass plate like green glass is mentioned.
  • the glass plate has a conductive film formed on at least one surface.
  • the interlayer film for laminated glass of the present invention is sandwiched between two glass plates so as to be in contact with the surface of the glass plate on which the conductive film is formed.
  • the conductive film is preferably a transparent conductive film containing tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), gallium-doped zinc oxide (GZO), or the like.
  • the surface density of the laminated glass of the present invention is not particularly limited, but is preferably 12 kg / m 2 or less.
  • the laminated glass of the present invention can be used as a side glass, a rear glass, or a roof glass when used as an automotive glass.
  • the present invention it is possible to provide an interlayer film for laminated glass in which the time from application of voltage to completion of change in light transmittance is extremely short. Moreover, the laminated glass which uses this intermediate film for laminated glasses can be provided.
  • Example 1 Preparation of electrolyte layer Triethylene glycol diacetate (a compound represented by the above formula (1-1)) as a compound represented by the above formula (1) was added to 6.5 parts by weight as a supporting electrolyte salt. An electrolyte solution was prepared by dissolving 3 parts by weight of (trifluoromethanesulfonyl) imidolithium (LiTFSI).
  • the total amount of the obtained electrolyte solution and a polyvinyl butyral resin having an acetyl group content of 13 mol% and a hydroxyl group content of 22 mol% as a thermoplastic resin obtained by butyralizing polyvinyl alcohol having an average polymerization degree of 2300 with n-butyraldehyde.
  • the polyvinyl butyral resin was mixed with 10 parts by weight to obtain a resin composition.
  • the obtained resin composition was sandwiched between polytetrafluoroethylene (PTFE) sheets, pressed through a spacer having a thickness of 400 ⁇ m with a hot press at 150 ° C. and 100 kg / cm 2 for 5 minutes, and having a thickness of 400 ⁇ m. An electrolyte layer was obtained.
  • PTFE polytetrafluoroethylene
  • the obtained 9-ethynyl-10-n-octadecylphenanthrene (3.5 parts by weight) was polymerized using 0.17 parts by weight of WCl 6 catalyst to obtain poly (9-ethynyl-10-n-octadecylphenanthrene). .
  • the molecular weight of the obtained poly (9-ethynyl-10-n-octadecylphenanthrene) was measured by gel permeation chromatography (GPC method).
  • GPC method gel permeation chromatography
  • a liquid chromatograph manufactured by Waters Waters 2695, RI Waters 2410, UV Waters 2996
  • LF-804 manufactured by Shodex was used as the column.
  • Example 2 to 29 An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 1 except that an electrolyte layer was prepared using the compounds shown in Table 1 instead of triethylene glycol diacetate.
  • Example 30 As a compound represented by the above formula (1), 6.5 parts by weight of triethylene glycol dibutyrate (a compound represented by the above formula (1-3)) and bis (trifluoromethanesulfonyl) imide lithium (as a supporting electrolyte salt) LiTFSI) 3 parts by weight was dissolved to prepare an electrolyte solution. The total amount of the obtained electrolyte solution and a polyvinyl butyral resin having an acetyl group content of 18 mol% and a hydroxyl group content of 15 mol% as a thermoplastic resin (obtained by butyralizing polyvinyl alcohol having an average polymerization degree of 2300 with n-butyraldehyde.
  • the polyvinyl butyral resin was mixed with 10 parts by weight to obtain a resin composition.
  • the obtained resin composition was sandwiched between polytetrafluoroethylene (PTFE) sheets, pressed through a spacer having a thickness of 400 ⁇ m with a hot press at 150 ° C. and 100 kg / cm 2 for 5 minutes, and having a thickness of 400 ⁇ m.
  • An electrolyte layer was obtained.
  • a laminated glass interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the obtained electrolyte layer was used.
  • thermoplastic resin As a thermoplastic resin, an electrolyte using a polyvinyl butyral resin having an acetyl group content of 6 mol% and a hydroxyl group content of 18 mol% (polyvinyl butyral resin obtained by butyralizing polyvinyl alcohol having an average polymerization degree of 2300 with n-butyraldehyde).
  • a laminated glass interlayer film and a laminated glass were produced in the same manner as in Example 30 except that the layer was prepared.
  • thermoplastic resin a polyvinyl hexyl resin having an acetyl group content of 18 mol% and a hydroxyl group content of 11 mol% (polyvinylhexyl resin obtained by acetalizing polyvinyl alcohol having an average polymerization degree of 2300 with n-hexylaldehyde)
  • a laminated glass interlayer film and a laminated glass were produced in the same manner as in Example 30 except that the electrolyte layer was prepared using the above.
  • thermoplastic resin As a thermoplastic resin, an electrolyte using a polyvinyl butyral resin having an acetyl group content of 22 mol% and a hydroxyl group content of 22 mol% (polyvinyl butyral resin obtained by butyralizing polyvinyl alcohol having an average polymerization degree of 2300 with n-butyraldehyde).
  • a laminated glass interlayer film and a laminated glass were produced in the same manner as in Example 30 except that the layer was prepared.
  • Example 34 In the same manner as in Example 3, except that the compounding amount of triethylene glycol dibutyrate (compound represented by the above formula (1-3)) was changed to 12 parts by weight as the compound represented by the above formula (1). A glass interlayer and laminated glass were produced.
  • Example 35 In the same manner as in Example 3, except that the compounding amount of triethylene glycol dibutyrate (compound represented by the above formula (1-3)) was changed to 5 parts by weight as the compound represented by the above formula (1). A glass interlayer and laminated glass were produced.
  • TC the transmittance of light at a wavelength of 640 nm of a laminated glass in a completely colored state
  • TB the transmittance of light at a wavelength of 640 nm of the laminated glass in a completely decolored state.
  • the time required for the measurement was measured, and this was defined as the decoloring time t1.
  • the time required to change up to was measured, and this was defined as the coloring time t2.
  • the transmittance was measured using a spectrophotometer “V-670” manufactured by JASCO Corporation.
  • the present invention it is possible to provide an interlayer film for laminated glass in which the time from application of voltage to completion of change in light transmittance is extremely short. Moreover, the laminated glass which uses this intermediate film for laminated glasses can be provided.

Landscapes

  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

L'invention concerne un film intermédiaire pour verre feuilleté, nécessitant un temps extrêmement court entre l'application d'une tension et la fin du changement de perméabilité à la lumière. L'invention concerne en particulier un film intermédiaire pour verre feuilleté, comprenant une couche électrolytique et une couche électrochromique formée sur au moins une surface de la couche électrolytique, cette dernière contenant un sel d'électrolyte support, une résine de liaison et un composé de formule (1) ou (2). Dans la formule (1), n représente un entier compris entre 2 et 4 ; R1 représente un atome d'hydrogène, un groupe acyle contenant un groupe organique C1-7 ou un groupe organique C1-8 ; R2 représente un groupe éthylène ou un groupe propylène ; et R3 représente un atome d'hydrogène, un groupe acyle contenant un groupe organique C1-7 ou un groupe organique C1-8 ; au moins R1 ou R3 contenant un groupe acyle. Dans la formule (2), R4 représente un groupe organique C2-8 contenant un atome d'oxygène ; R5 représente un groupe alkylène C2-8 ou un groupe arylène C6-12 ; et R6 représente un groupe organique C2-8 contenant un atome d'oxygène ; R4 et R6 pouvant être identiques ou différents.
PCT/JP2010/072672 2009-12-16 2010-12-16 Film intermédiaire pour verre feuilleté et verre feuilleté associé WO2011074639A1 (fr)

Priority Applications (1)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003091021A (ja) * 2001-09-18 2003-03-28 Nippon Oil Corp エレクトロクロミック調光ガラスの製造方法
JP2007529036A (ja) * 2004-03-12 2007-10-18 ザ・ボーイング・カンパニー 多色システム、低蒸気圧溶媒、およびエレクトロクロミック装置のためのアレイ調光制御装置
JP2009508148A (ja) * 2005-08-19 2009-02-26 エルジー・ケム・リミテッド 共融混合物を含む電解質及び前記電解質を用いた電気化学素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003091021A (ja) * 2001-09-18 2003-03-28 Nippon Oil Corp エレクトロクロミック調光ガラスの製造方法
JP2007529036A (ja) * 2004-03-12 2007-10-18 ザ・ボーイング・カンパニー 多色システム、低蒸気圧溶媒、およびエレクトロクロミック装置のためのアレイ調光制御装置
JP2009508148A (ja) * 2005-08-19 2009-02-26 エルジー・ケム・リミテッド 共融混合物を含む電解質及び前記電解質を用いた電気化学素子

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