WO2011074639A1 - Intermediate film for laminated glass, and laminated glass - Google Patents

Intermediate film for laminated glass, and laminated glass 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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Prior art keywords
group
carbon atoms
laminated glass
alkyl group
formula
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PCT/JP2010/072672
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French (fr)
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/en
Publication of WO2011074639A1 publication Critical patent/WO2011074639A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered 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
    • B32B17/10Layered 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
    • B32B17/10005Layered 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
    • B32B17/10165Functional features of the laminated safety glass or glazing
    • B32B17/10174Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered 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
    • B32B17/10Layered 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
    • B32B17/10005Layered 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
    • B32B17/1055Layered 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
    • B32B17/10761Layered 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.

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

Abstract

Disclosed is an intermediate film for a laminated glass, which requires an extremely short time between the application of a voltage and the completion of the change in light permeability. Specifically disclosed is an intermediate film for a laminated glass, which comprises an electrolyte layer and an electrochromic layer formed on at least one surface of the electrolyte layer, wherein the electrolyte layer comprises a supporting electrolyte salt, a binder resin, and a compound represented by formula (1) or (2). In formula (1), n represents an integer of 2 to 4; R1 represents a hydrogen atom, an acyl group having a C1-7 organic group, or a C1-8 organic group; R2 represents an ethylene group, or a propylene group; and R3 represents a hydrogen atom, an acyl group having a C1-7 organic group, or a C1-8 organic group; wherein at least one of R1 and R3 has an acyl group. In formula (2), R4 represents a C2-8 organic group having an oxygen atom; R5 represents a C2-8 alkylene group, or a C6-12 arylene group; and R6 represents a C2-8 organic group having an oxygen atom; wherein R4 and R6 may be the same as or different from each other.

Description

合わせガラス用中間膜及び合わせガラスLaminated glass interlayer film and laminated glass
本発明は、電圧を印加してから光透過率の変化が完了するまでの時間が極めて短い合わせガラス用中間膜に関する。また、該合わせガラス用中間膜を用いてなる合わせガラスに関する。 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.
電圧を印加することにより光の透過率が変化する調光フィルムを備える調光体は、広く用いられている。この調光体を建築物等や、電光板等の表示装置に応用することを目的とする検討が重ねられてきた。近年、自動車等の車内の温度を制御するために、調光フィルムを合わせガラス用中間膜として用いた合わせガラスが提案されている。このような合わせガラス用中間膜を用いることにより、合わせガラスの光線透過率を制御することができると考えられている。 2. Description of the Related Art 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. In recent years, 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.
上記調光体は、液晶材料を用いた調光体と、エレクトロクロミック化合物を用いた調光体とに大別される。なかでも、エレクトロクロミック化合物を用いた調光体は、液晶材料を用いた調光体に比べて光散乱が少なく、偏光の影響を受けない等の優れた性質を有している。 The dimmer is roughly classified into a dimmer using a liquid crystal material and a dimmer using an electrochromic compound. Among them, 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.
エレクトロクロミック化合物として、無機エレクトロクロミック化合物と、有機エレクトロクロミック化合物とが知られている。また、有機エレクトロクロミック化合物として、低分子量の有機エレクトロクロミック化合物と、エレクトロクロミック性を示す高分子化合物とが検討されている。 As 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.
エレクトロクロミック化合物を用いた調光体として、対向する一対の電極基板の間に、エレクトロクロミック層と電解質層とが挟み込まれている調光体が提案されている。例えば、特許文献1及び特許文献2には、無機酸化物を含有するエレクトロクロミック層、イオン伝導層、無機酸化物を含有するエレクトロクロミック層の3層が順次積層された積層体が、2枚の導電性基板間に挟み込まれている調光体が開示されている。また、特許文献3及び特許文献4には、対向する一対の電極基板の間に、有機エレクトロクロミック化合物を含有するエレクトロクロミック層と電解質層とが挟み込まれている調光体が開示されている。
しかしながら、従来の調光体は、応答性が劣るため、電圧を印加しても光の透過率の変化が完了するまでに時間を要するという問題点があった。
As a light control body using an electrochromic compound, a light control body in which an electrochromic layer and an electrolyte layer are sandwiched between a pair of opposing electrode substrates has been proposed. For example, 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.
However, 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.
特開2004-062030号公報JP 2004-062030 A 特開2005-062772号公報Japanese Patent Laying-Open No. 2005-062772 特表2002-526801号公報Special Table 2002-526801 特表2004-531770号公報JP-T-2004-53770
本発明は、電圧を印加してから光透過率の変化が完了するまでの時間が極めて短い合わせガラス用中間膜を提供することを目的とする。また、該合わせガラス用中間膜を用いてなる合わせガラスを提供することを目的とする。 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.
本発明は、電解質層と、上記電解質層の少なくとも片面に形成されたエレクトロクロミック層とを有する合わせガラス用中間膜であって、上記電解質層は、支持電解質塩、バインダー樹脂、並びに、下記式(1)で表される化合物又は下記式(2)で表される化合物を含有する合わせガラス用中間膜である。 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).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
式(1)中、n=2~4の整数を表し、Rは水素原子、炭素数1~7の有機基を有するアシル基又は炭素数1~8の有機基を表し、Rはエチレン基又はプロピレン基を表し、Rは水素原子、炭素数1~7の有機基を有するアシル基又は炭素数1~8の有機基を表し、少なくともR又はRの何れかはアシル基を有する。 In the formula (1), 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, and 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, and at least one of R 1 and R 3 represents an acyl group. Have.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
式(2)中、Rは炭素数2~8であり、酸素原子を有する有機基を表し、Rは炭素数2~8のアルキレン基又は炭素数6~12のアリーレン基を表し、Rは炭素数2~8であり、酸素原子を有する有機基を表す。R及びRは同一であってもよく、異なっていてもよい。
以下に本発明を詳述する。
In the formula (2), 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.
本発明者らは、エレクトロクロミック層と電解質層との積層体において、電解質層に特定の構造を有する化合物を添加することにより、著しく応答性が高く、電圧を印加してから光の透過率の変化が完了するまでの時間が極めて短い合わせガラス用中間膜が得られることを見出し、本発明を完成するに至った。 In the laminate of the electrochromic layer and the electrolyte layer, 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.
本発明の合わせガラス用中間膜は、電解質層とエレクトロクロミック層との積層体である。
上記電解質層は、イオンを伝導することにより上記エレクトロクロミック層に電圧を印加し、エレクトロクロミック層の光の透過率を変化させる役割を有する。
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.
上記電解質層は、支持電解質塩、バインダー樹脂、並びに、上記式(1)で表される化合物又は上記式(2)で表される化合物を含有する。上記式(1)で表される化合物又は上記式(2)で表される化合物を含有する電解質層をエレクトロクロミック層に積層することにより、電圧を印加してから光透過率の変化が完了するまでの時間が極めて短い合わせガラス用中間膜を得ることができる。
上記式(1)で表される化合物又は上記式(2)で表される化合物は、単独で用いてもよく、併用してもよい。なかでも、耐久性が向上し、かつ、電圧を印加してから光透過率の変化が完了するまでの時間がより短い合わせガラス用中間膜が得られることから、上記式(1)で表される化合物を含有することが好ましい。
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). 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. In particular, 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.
上記式(1)中、Rは水素原子、炭素数1~7の有機基を有するアシル基又は炭素数1~8の有機基を表す。なかでも、上記バインダー樹脂との相溶性がより向上することから、Rは炭素数1~7の有機基を有するアシル基又は炭素数1~8の有機基であることが好ましく、炭素数1~7の有機基を有するアシル基であることがより好ましく、炭素数1~7のアルキル基を有するアシル基であることが更に好ましい。 In the above formula (1), 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. Among these, 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.
上記式(1)中のRを表す炭素数1~7の有機基を有するアシル基における、有機基の炭素数の好ましい下限は2、好ましい上限は6である。上記炭素数が2以上であると、電解質層の耐久性が向上し、6以下であると、電圧を印加してから光透過率の変化が完了するまでの時間がより短い合わせガラス用中間膜が得られる。上記炭素数のより好ましい下限は3、より好ましい上限は5であり、更に好ましい上限は4である。 In the acyl group having an organic group having 1 to 7 carbon atoms representing R 1 in the above formula (1), the preferable lower limit of the carbon number of the organic group is 2, and the preferable upper limit is 6. When 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.
上記炭素数1~7の有機基は、直鎖構造を有する有機基、又は、分岐構造を有する有機基であってもよく、直鎖構造を有するアルキル基、又は、分岐構造を有するアルキル基であることが好ましい。上記分岐構造を有する有機基又は分岐構造を有するアルキル基において、有機基又はアルキル基の分岐鎖の炭素数は3以下であることが好ましく、2以下であることがより好ましく、1以下であることが更に好ましい。 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. In the organic group having a branched structure or the alkyl group having a branched structure, 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.
電圧を印加してから光透過率の変化が完了するまでの時間が更に一層短い合わせガラス用中間膜が得られることから、上記炭素数1~7の有機基が直鎖構造を有する場合は、上記炭素数1~7の有機基を有するアシル基は、炭素数1~7であり、かつ、直鎖構造を有する有機基を有するアシル基、又は、炭素数1~7であり、かつ、直鎖構造を有するアルキル基を有するアシル基であることが好ましい。 Since an interlayer film for laminated glass having a much shorter time from application of voltage to completion of change in light transmittance is obtained, when the organic group having 1 to 7 carbon atoms has a linear structure, 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.
電圧を印加してから光透過率の変化が完了するまでの時間が更に一層短い合わせガラス用中間膜が得られることから、上記炭素数1~7の有機基が分岐構造を有する場合は、上記炭素数1~7の有機基を有するアシル基は、炭素数1~7であり、かつ、分岐構造を有する有機基を有するアシル基、又は、炭素数1~7であり、かつ、分岐構造を有するアルキル基を有するアシル基であることが好ましく、炭素数1~7であり、分岐構造を有し、かつ、分岐鎖の炭素数が3以下であるアルキル基を有するアシル基であることがより好ましく、炭素数1~7であり、分岐構造を有し、かつ、分岐鎖の炭素数が2以下であるアルキル基を有するアシル基であることが更に好ましく、炭素数1~7であり、分岐構造を有し、かつ、分岐鎖の炭素数が1以下であるアルキル基を有するアシル基であることが特に好ましい。
なお、上記炭素数1~7の有機基を有するアシル基とは、該有機基の炭素数が1~7であることを意味し、上記炭素数1~7のアルキル基を有するアシル基とは、該アルキル基の炭素数が1~7であることを意味する。
Since an interlayer film for laminated glass having a shorter time from application of voltage to completion of change in light transmittance can be obtained, when the organic group having 1 to 7 carbon atoms has a branched structure, 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. More preferably, it is an 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, and 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.
上記式(1)中のRが炭素数1~8の有機基である場合、上記バインダー樹脂との相溶性がより向上することから、上記炭素数1~8の有機基は炭素数1~8のアルキル基であることが好ましい。
上記式(1)中のRを表す炭素数1~8の有機基における炭素数の好ましい下限は2、好ましい上限は7である。上記炭素数が2以上であると、電解質層の耐久性が向上し、7以下であると、電圧を印加してから光透過率の変化が完了するまでの時間がより短い合わせガラス用中間膜が得られる。上記炭素数のより好ましい下限は3、より好ましい上限は6であり、更に好ましい下限は4、更に好ましい上限は5である。
When 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. When 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.
上記炭素数1~8の有機基は、直鎖構造を有する有機基、又は、分岐構造を有する有機基であってもよく、直鎖構造を有するアルキル基、又は、分岐構造を有するアルキル基であることが好ましい。上記分岐構造を有する有機基又は分岐構造を有するアルキル基において、有機基又はアルキル基の分岐鎖の炭素数は3以下であることが好ましく、2以下であることがより好ましく、1以下であることが更に好ましい。 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. In the organic group having a branched structure or the alkyl group having a branched structure, 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.
電圧を印加してから光透過率の変化が完了するまでの時間が更に一層短い合わせガラス用中間膜が得られることから、上記炭素数1~8の有機基が直鎖構造を有する場合は、上記炭素数1~8の有機基は、炭素数1~8であり、かつ、直鎖構造を有するアルキル基であることが好ましい。 Since an interlayer film for laminated glass having a much shorter time from application of voltage to completion of change in light transmittance is obtained, when the organic group having 1 to 8 carbon atoms has 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 linear structure.
電圧を印加してから光透過率の変化が完了するまでの時間が更に一層短い合わせガラス用中間膜が得られることから、上記炭素数1~8の有機基が分岐構造を有する場合は、上記炭素数1~8の有機基は、炭素数1~8であり、かつ、分岐構造を有するアルキル基であることが好ましく、炭素数1~8であり、分岐構造を有し、かつ、分岐鎖の炭素数が3以下であるアルキル基であることがより好ましく、炭素数1~8であり、分岐構造を有し、かつ分岐鎖の炭素数が2以下であるアルキル基であることが更に好ましく、炭素数1~8であり、分岐構造を有し、かつ、分岐鎖の炭素数が1以下であるアルキル基であることが特に好ましい。 Since an intermediate film for laminated glass having a shorter time from application of voltage to completion of change in light transmittance is obtained, when the organic group having 1 to 8 carbon atoms has a branched 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.
上記式(1)中、Rはエチレン基又はプロピレン基を表す。上記プロピレン基はn-プロピレン基であってもよく、イソプロピレン基であってもよい。電圧を印加してから光透過率の変化が完了するまでの時間がより短い合わせガラス用中間膜が得られることから、Rはエチレン基であることが好ましい。 In the formula (1), 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.
上記式(1)中、Rは水素原子、炭素数1~7の有機基を有するアシル基又は炭素数1~8の有機基を表す。なかでも、上記バインダー樹脂との相溶性がより向上することから、Rは炭素数1~7の有機基を有するアシル基又は炭素数1~8の有機基であることが好ましく、炭素数1~7の有機基を有するアシル基であることがより好ましく、炭素数1~7のアルキル基を有するアシル基であることが更に好ましい。 In the above formula (1), 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. Among these, 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.
上記式(1)中のRを表す炭素数1~7の有機基を有するアシル基における、有機基の炭素数の好ましい下限は2、好ましい上限は6である。上記炭素数が2以上であると、電解質層の耐久性が向上し、6以下であると、電圧を印加してから光透過率の変化が完了するまでの時間がより短い合わせガラス用中間膜が得られる。上記炭素数のより好ましい下限は3、より好ましい上限は5であり、更に好ましい上限は4である。 In the acyl group having an organic group having 1 to 7 carbon atoms representing R 3 in the above formula (1), the preferable lower limit of the carbon number of the organic group is 2, and the preferable upper limit is 6. When 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.
上記炭素数1~7の有機基は、直鎖構造を有する有機基、又は、分岐構造を有する有機基であってもよく、直鎖構造を有するアルキル基、又は、分岐構造を有するアルキル基であることが好ましい。上記分岐構造を有する有機基又は分岐構造を有するアルキル基において、有機基又はアルキル基の分岐鎖の炭素数は3以下であることが好ましく、2以下であることがより好ましく、1以下であることが更に好ましい。 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. In the organic group having a branched structure or the alkyl group having a branched structure, 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.
電圧を印加してから光透過率の変化が完了するまでの時間が更に一層短い合わせガラス用中間膜が得られることから、上記炭素数1~7の有機基が直鎖構造を有する場合は、上記炭素数1~7の有機基を有するアシル基は、炭素数1~7であり、かつ、直鎖構造を有する有機基を有するアシル基、又は、炭素数1~7であり、かつ、直鎖構造を有するアルキル基を有するアシル基であることが好ましい。 Since an interlayer film for laminated glass having a much shorter time from application of voltage to completion of change in light transmittance is obtained, when the organic group having 1 to 7 carbon atoms has a linear structure, 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.
電圧を印加してから光透過率の変化が完了するまでの時間が更に一層短い合わせガラス用中間膜が得られることから、上記炭素数1~7の有機基が分岐構造を有する場合は、上記炭素数1~7の有機基を有するアシル基は、炭素数1~7であり、かつ、分岐構造を有する有機基を有するアシル基、又は、炭素数1~7であり、かつ、分岐構造を有するアルキル基を有するアシル基であることが好ましく、炭素数1~7であり、分岐構造を有し、かつ、分岐鎖の炭素数が3以下であるアルキル基を有するアシル基であることがより好ましく、炭素数1~7であり、分岐構造を有し、かつ、分岐鎖の炭素数が2以下であるアルキル基を有するアシル基であることが更に好ましく、炭素数1~7であり、分岐構造を有し、かつ、分岐鎖の炭素数が1以下であるアルキル基を有するアシル基であることが特に好ましい。
なお、上記炭素数1~7の有機基を有するアシル基とは、該有機基の炭素数が1~7であることを意味し、上記炭素数1~7のアルキル基を有するアシル基とは、該アルキル基の炭素数が1~7であることを意味する。
Since an interlayer film for laminated glass having a shorter time from application of voltage to completion of change in light transmittance can be obtained, when the organic group having 1 to 7 carbon atoms has a branched structure, 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. More preferably, it is an 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, and 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.
上記式(1)中のRが炭素数1~8の有機基である場合、上記バインダー樹脂との相溶性がより向上することから、上記炭素数1~8の有機基は炭素数1~8のアルキル基であることが好ましい。
上記式(1)中のRを表す炭素数1~8の有機基における炭素数の好ましい下限は2、好ましい上限は7である。上記炭素数が2以上であると、電解質層の耐久性が向上し、7以下であると、電圧を印加してから光透過率の変化が完了するまでの時間がより短い合わせガラス用中間膜が得られる。上記炭素数のより好ましい下限は3、より好ましい上限は6であり、更に好ましい下限は4、更に好ましい上限は5である。
When 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. When 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.
上記炭素数1~8の有機基は、直鎖構造を有する有機基、又は、分岐構造を有する有機基であってもよく、直鎖構造を有するアルキル基、又は、分岐構造を有するアルキル基であることが好ましい。上記分岐構造を有する有機基又は分岐構造を有するアルキル基において、有機基又はアルキル基の分岐鎖の炭素数は3以下であることが好ましく、2以下であることがより好ましく、1以下であることが更に好ましい。 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. In the organic group having a branched structure or the alkyl group having a branched structure, 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.
電圧を印加してから光透過率の変化が完了するまでの時間が更に一層短い合わせガラス用中間膜が得られることから、上記炭素数1~8の有機基が直鎖構造を有する場合は、上記炭素数1~8の有機基は、炭素数1~8であり、かつ、直鎖構造を有するアルキル基であることが好ましい。 Since an interlayer film for laminated glass having a much shorter time from application of voltage to completion of change in light transmittance is obtained, when the organic group having 1 to 8 carbon atoms has 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 linear structure.
電圧を印加してから光透過率の変化が完了するまでの時間が更に一層短い合わせガラス用中間膜が得られることから、上記炭素数1~8の有機基が分岐構造を有する場合は、上記炭素数1~8の有機基は、炭素数1~8であり、かつ、分岐構造を有するアルキル基であることが好ましく、炭素数1~8であり、分岐構造を有し、かつ、分岐鎖の炭素数が3以下であるアルキル基であることがより好ましく、炭素数1~8であり、分岐構造を有し、かつ、分岐鎖の炭素数が2以下であるアルキル基であることが更に好ましく、炭素数1~8であり、分岐構造を有し、かつ、分岐鎖の炭素数が1以下であるアルキル基であることが特に好ましい。 Since an interlayer film for laminated glass having a shorter time from application of voltage to completion of change in light transmittance is obtained, when the organic group having 1 to 8 carbon atoms has a branched 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.
上記式(1)において、少なくともR又はRの何れかはアシル基を有する。これにより、上記バインダー樹脂との高い相溶性が得られる。なかでも、Rは炭素数1~7のアルキル基を有するアシル基を表し、Rはエチレン基又はプロピレン基を表し、Rは炭素数1~7のアルキル基を有するアシル基を表すことがより好ましい。 In the above formula (1), at least one of R 1 and R 3 has an acyl group. Thereby, high compatibility with the binder resin is obtained. Among them, 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, and R 3 represents an acyl group having an alkyl group having 1 to 7 carbon atoms. Is more preferable.
上記式(1)で表される化合物の具体例を下記式(1-1)~(1-28)に示す。 Specific examples of the compound represented by the above formula (1) are shown in the following formulas (1-1) to (1-28).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000009
上記式(2)中、Rは炭素数2~8であり、酸素原子を有する有機基を表す。
上記式(2)中のRを表す炭素数2~8であり、酸素原子を有する有機基の炭素数の好ましい下限は3、好ましい上限は7である。上記炭素数が3以上であると、電解質層の耐久性が向上し、7以下であると、電圧を印加してから光透過率の変化が完了するまでの時間がより短い合わせガラス用中間膜が得られる。上記炭素数のより好ましい下限は4、より好ましい上限は6である。
In the above formula (2), 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. When 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.
上記式(2)中、Rは炭素数2~8のアルキレン基又は炭素数6~12のアリーレン基を表す。なかでも、上記バインダー樹脂との相溶性が更に向上することから、Rは炭素数2~8のアルキレン基であることが好ましい。 In the above formula (2), R 5 represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 12 carbon atoms. Among these, R 5 is preferably an alkylene group having 2 to 8 carbon atoms, since the compatibility with the binder resin is further improved.
上記式(2)中のRを表す炭素数2~8のアルキレン基の炭素数の好ましい下限は3、好ましい上限は7である。上記炭素数が3~7であると、電圧を印加してから光透過率の変化が完了するまでの時間がより短い合わせガラス用中間膜が得られる。上記炭素数のより好ましい下限は4、より好ましい上限は6である。 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. When 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.
上記式(2)中のRを表す炭素数6~12のアリーレン基の炭素数の好ましい上限は10である。上記炭素数が10以下であると、電圧を印加してから光透過率の変化が完了するまでの時間がより短い合わせガラス用中間膜が得られる。上記炭素数のより好ましい上限は8である。 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. When 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.
式(2)中、Rは炭素数2~8であり、酸素原子を有する有機基を表す。
上記式(2)中のRを表す炭素数2~8であり、酸素原子を有する有機基の炭素数の好ましい下限は3、好ましい上限は7である。上記炭素数が3以上であると、電解質層の耐久性が向上し、7以下であると、電圧を印加してから光透過率の変化が完了するまでの時間がより短い合わせガラス用中間膜が得られる。上記炭素数のより好ましい下限は4、より好ましい上限は6である。
In the formula (2), 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. When 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.
上記式(2)で表される化合物の具体例を下記式(2-1)に示す。 Specific examples of the compound represented by the above formula (2) are shown in the following formula (2-1).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
上記電解質層中における上記式(1)で表される化合物及び上記式(2)で表される化合物の配合量は特に限定されないが、上記バインダー樹脂100重量部に対する好ましい下限は15重量部、好ましい上限は200重量部である。上記式(1)で表される化合物及び上記式(2)で表される化合物の配合量が15重量部以上であると、電圧を印加してから光透過率の変化が完了するまでの時間がより一層短くなる。上記式(1)で表される化合物及び上記式(2)で表される化合物の配合量が200重量部以下であると、合わせガラスの耐貫通性が高くなる。上記式(1)で表される化合物及び上記式(2)で表される化合物の配合量のより好ましい下限は30重量部、更に好ましい下限は50重量部、特に好ましい下限は60重量部であり、より好ましい上限は150重量部、更に好ましい上限は120重量部、特に好ましい上限は100重量部である。 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. When 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. When 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.
上記支持電解質塩は特に限定されず、リチウム塩、カリウム塩又はナトリウム塩等のアルカリ金属塩であることが好ましい。上記アルカリ金属塩は、無機酸とアルカリ金属の塩又は有機酸とアルカリ金属の塩であることが好ましい。例えば、上記無機酸とアルカリ金属の塩として、無機酸アニオンリチウム塩、無機酸アニオンカリウム塩、又は、無機酸アニオンナトリウム塩等が挙げられ、上記有機酸とアルカリ金属の塩として、有機酸アニオンリチウム塩、有機酸アニオンカリウム塩、又は、有機酸アニオンナトリウム塩等が挙げられる。
なかでも、上記支持電解質塩はリチウム塩であることが好ましく、過塩素酸リチウム、ホウフッ化リチウム、リンフッ化リチウム等の無機酸アニオンリチウム塩、又は、トリフルオロメタンスルホン酸リチウム、ビストリフルオロメタンスルホン酸イミドリチウム等の有機酸アニオンリチウム塩であることがより好ましい。
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. Examples of 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, and 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.
Among them, 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.
上記支持電解質塩は、アンモニウムカチオンと、アニオンとの塩であってもよい。
上記アンモニウムカチオンは特に限定されず、例えば、テトラエチルアンモニウム、トリメチルエチルアンモニウム、メチルプロピルピロリジニウム、メチルブチルピロリジニウム、メチルプロピルピペリジニウム、メチルブチルピペリジニウム等のアルキルアンモニウムカチオンや、エチルメチルイミダゾリウム、ジメチルエチルイミダゾリウム、メチルピリジニウム、エチルピリジニウム、プロピルピリジニウム、ブチルピリジニウム等が挙げられる。
上記アニオンは特に限定されず、過塩素酸アニオン、ホウフッ化アニオン、リンフッ化アニオン、トリフルオロメタンスルホン酸アニオン、ビストリフルオロメタンスルホン酸イミドアニオン等が挙げられる。
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.
上記電解質層中における上記支持電解質塩の配合量は特に限定されないが、上記バインダー樹脂100重量部に対する好ましい下限は3重量部、好ましい上限は60重量部である。上記支持電解質塩の配合量が3~60重量部であると、電圧を印加してから光透過率の変化が完了するまでの時間がより一層短くなる。上記支持電解質塩の配合量のより好ましい下限は10重量部、更に好ましい下限は20重量部であり、より好ましい上限は50重量部、更に好ましい上限は40重量部である。 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. When the amount of the supporting electrolyte salt is 3 to 60 parts by weight, the time from when the voltage is applied until the change of the light transmittance is completed is further shortened. 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.
上記電解質層は溶媒を含有してもよい。上記溶媒は特に限定されず、例えば、アセトニトリル、ニトロメタン、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、メチルエチルカーボネート、γ-ブチロラクトン等のエステル化合物や、テトラヒドロフラン、2-メチルテトラヒドロフラン等の置換テトラヒドロフラン化合物や、1,3-ジオキソラン、4,4-ジメチル-1,3-ジオキソラン、t-ブチルエーテル、イソブチルエーテル、1,2-ジメトキシエタン、1,2-エトキシメトキシエタン等のエーテル化合物や、エチレングリコール、ポリエチレングリコールスルホラン、3-メチルスルホラン、蟻酸メチル、酢酸メチル、N-メチルピロリドン、ジメチルホルムアミド等の有機溶媒が挙げられる。 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 γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, and the like. Substituted tetrahydrofuran compounds, ether 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.
上記バインダー樹脂は特に限定されないが、熱可塑性樹脂であることが好ましい。
上記バインダー樹脂は、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、フッ化ビニリデン-六フッ化プロピレン共重合体、ポリ三フッ化エチレン、アクリロニトリル-ブタジエン-スチレン共重合体、ポリエステル、ポリエーテル、ポリアミド、ポリカーボネート、ポリアクリレート、ポリメタクリレート、ポリ塩化ビニル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリビニルアセタール樹脂、エチレン-酢酸ビニル共重合体等が挙げられる。なかでも、ポリビニルアセタール樹脂、エチレン-酢酸ビニル共重合体が好ましく、ポリビニルアセタール樹脂がより好ましい。透明性が高い電解質層が得られることから、炭素数が4又は5のアルデヒドによりポリビニルアルコールをアセタール化して得られたポリビニルアセタール樹脂が更に好適である。特に、上記ポリビニルアセタール樹脂はポリビニルブチラール樹脂であることが好適である。
The binder resin is not particularly limited, but is preferably a thermoplastic resin.
Examples of 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. Of these, 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. In particular, the polyvinyl acetal resin is preferably a polyvinyl butyral resin.
上記ポリビニルアセタール樹脂は、アセチル基量が15mol%以下であることが好ましい。上記ポリビニルアセタール樹脂のアセチル基量が15mol%を超えると、合わせガラス用中間膜が白化することがある。
上記ポリビニルアセタール樹脂は、水酸基量が30mol%以下であることが好ましい。上記ポリビニルアセタール樹脂の水酸基量が30mol%を超えると、上記溶媒との相溶性が低下し、電解質層の透明性が低下することがある。
なお、上記アセチル基量及び上記水酸基量はJIS K 6728に準拠して、滴定法により求めることができる。
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.
また、上記式(1)で表される化合物及び上記式(2)で表される化合物が上記電解質層から析出することを防止できることから、上記ポリビニルアセタール樹脂は、アセチル基量が5モル%以上であるポリビニルアセタール樹脂(以下、「ポリビニルアセタール樹脂A」ともいう。)、アセタール化度が70~85モル%であるポリビニルアセタール樹脂(以下、「ポリビニルアセタール樹脂B」ともいう。)、又は、炭素数が6以上のアルデヒドを用いてポリビニルアルコールをアセタール化することにより得られるポリビニルアセタール樹脂(以下、「ポリビニルアセタール樹脂C」ともいう。)であることが好ましい。
なお、上記アセチル基量及び上記アセタール化度はJIS K 6728に準拠して、滴定法により求めることができる。
Moreover, since it can 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, 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”), or carbon. 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.
上記ポリビニルアセタール樹脂Aのアセチル基量の好ましい下限は6モル%、好ましい上限は30モル%である。上記アセチル基量が6モル%以上であると、上記式(1)で表される化合物及び上記式(2)で表される化合物が上記電解質層から析出することをより一層防止することができる。上記アセチル基量が30モル%以下であると、上記ポリビニルアセタール樹脂Aの製造効率を高めることができる。上記アセチル基量のより好ましい下限は8モル%、より好ましい上限は28モル%であり、更に好ましい下限は10モル%、更に好ましい上限は25モル%であり、特に好ましい下限は12モル%、特に好ましい上限は23モル%である。 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%.
上記ポリビニルアセタール樹脂Aは、アセタール化度の好ましい下限が50モル%、好ましい上限が80モル%である。上記アセタール化度が50モル%以上であると、上記式(1)で表される化合物及び上記式(2)で表される化合物が上記電解質層から析出することを更に一層防止することができる。上記アセタール化度が80モル%以下であると、上記ポリビニルアセタール樹脂Aの製造効率を高めることができる。上記アセタール化度のより好ましい下限は55モル%、より好ましい上限は78モル%であり、更に好ましい下限は60モル%、更に好ましい上限は76モル%であり、特に好ましい下限は65モル%、特に好ましい上限は74モル%である。
上記ポリビニルアセタール樹脂Aは、ポリビニルブチラール樹脂であることが好ましい。
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%. When 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. . When 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.
上記ポリビニルアセタール樹脂Bのアセタール化度の好ましい下限は71モル%、好ましい上限は84モル%である。上記アセタール化度が71モル%以上であると、上記式(1)で表される化合物及び上記式(2)で表される化合物が上記電解質層から析出することを更に一層防止することができる。上記アセタール化度が84モル%以下であると、上記ポリビニルアセタール樹脂Bの製造効率を高めることができる。上記アセタール化度のより好ましい下限は72モル%、より好ましい上限は83モル%であり、更に好ましい下限は73モル%、更に好ましい上限は82モル%であり、特に好ましい下限は74モル%、特に好ましい上限は81モル%である。 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%. When the degree of acetalization is 71 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. . When the degree of acetalization is 84 mol% or less, the production efficiency of the polyvinyl acetal resin B can be increased. 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%.
上記ポリビニルアセタール樹脂Bは、アセチル基量の好ましい下限が0.1モル%、好ましい上限が20モル%である。上記アセチル基量が0.1モル%以上であると、上記式(1)で表される化合物及び上記式(2)で表される化合物が上記電解質層から析出することを更に一層防止することができる。上記アセチル基量が20モル%以下であると、上記ポリビニルアセタール樹脂Bの製造効率を高めることができる。上記アセチル基量のより好ましい下限は0.5モル%、より好ましい上限は15モル%であり、更に好ましい下限は0.8モル%、更に好ましい上限は8モル%であり、特に好ましい下限は1モル%、特に好ましい上限は7モル%である。
上記ポリビニルアセタール樹脂Bは、ポリビニルブチラール樹脂であることが好ましい。
In the polyvinyl acetal resin B, a preferable lower limit of the amount of acetyl groups is 0.1 mol%, and a preferable upper limit is 20 mol%. When 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.
上記ポリビニルアセタール樹脂A及びポリビニルアセタール樹脂Bは、ポリビニルアルコールをアルデヒドによりアセタール化することで得られる。上記アルデヒドは炭素数1~10のアルデヒドであることが好ましく、炭素数4又は5のアルデヒドであることがより好ましい。 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.
上記ポリビニルアセタール樹脂Cは、炭素数が6以上のアルデヒドを用いてポリビニルアルコールをアセタール化することにより得られる。上記炭素数が6以上のアルデヒドは特に限定されないが、例えば、n-ヘキシルアルデヒド、n-オクチルアルデヒド、n-ノニルアルデヒド、又は、n-デシルアルデヒド等が挙げられる。 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.
上記ポリビニルアセタール樹脂Cは、アセタール化度の好ましい下限が50モル%、好ましい上限が80モル%である。上記アセタール化度が50モル%以上であると、上記式(1)で表される化合物及び上記式(2)で表される化合物が上記電解質層から析出することを更に一層防止することができる。上記アセタール化度が80モル%以下であると、上記ポリビニルアセタール樹脂Cの製造効率を高めることができる。上記アセタール化度のより好ましい下限は55モル%、より好ましい上限が78モル%であり、更に好ましい下限は60モル%、更に好ましい上限は76モル%であり、特に好ましい下限は65モル%、特に好ましい上限は74モル%である。 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%. When 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. . When 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%.
上記ポリビニルアセタール樹脂の原料となる上記ポリビニルアルコールは、平均重合度の好ましい下限が200、好ましい上限が5000である。上記ポリビニルアルコールの平均重合度が200以上であると、合わせガラスの耐貫通性が高くなる。上記ポリビニルアルコールの平均重合度が5000以下であると、電圧を印加してから光透過率の変化が完了するまでの時間がより一層短くなる。上記平均重合度のより好ましい下限は500、より好ましい上限は4000である。
上記ポリビニルアルコールの平均重合度は、GPC(ゲルパーミエーションクロマトグラフィー)法によるポリスチレン換算により求めた上記ポリビニルアルコールの重量平均分子量をポリビニルアルコール1セグメント当りの分子量で除して求められる。GPC法によってポリスチレン換算による重量平均分子量を測定する際のカラムとしては、例えば、Shodex LF-804(昭和電工社製)等が挙げられる。
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. When the average degree of polymerization of the polyvinyl alcohol is 200 or more, the penetration resistance of the laminated glass is increased. When 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. 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).
上記電解質層は熱線吸収剤を含有してもよい。
上記熱線吸収剤は、赤外線を遮蔽する性能を有すれば特に限定されないが、錫ドープ酸化インジウム粒子、アンチモンドープ酸化錫粒子、亜鉛以外の元素がドープされた酸化亜鉛粒子、六ホウ化ランタン粒子、アンチモン酸亜鉛粒子、及び、フタロシアニン構造を有する赤外線吸収剤からなる群より選択される少なくとも1種が好適である。
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.
上記電解質層は接着力調整剤を含有してもよい。
上記接着力調整剤は、例えば、アルカリ金属塩、アルカリ土類金属塩、マグネシウム塩等が挙げられる。なかでも、炭素数2~16のカルボン酸のアルカリ金属塩、アルカリ土類金属塩及びマグネシウム塩が好適であり、具体的には例えば、ビス(酢酸)マグネシウム、酢酸カリウム、ビス(プロピオン酸)マグネシウム、プロピオン酸カリウム、ビス(2-エチルブタン酸)マグネシウム、2-エチルブタン酸カリウム、ビス(2-エチルヘキサン酸)マグネシウム、2-エチルヘキサン酸カリウム等が挙げられる。これらの接着力調整剤は単独で用いられてもよく、併用されてもよい。上記電解質層にバインダー樹脂としてポリビニルアセタール樹脂を含有する場合、上記電解質層は接着力調整剤を含有することが好ましい。
The electrolyte layer may contain an adhesion adjusting agent.
Examples of 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.
上記電解質層は単層構造であってもよく、多層構造であってもよい。上記電解質層が多層構造であるとは、上記電解質層が2層以上積層された構造であることを意味する。
上記電解質層が多層構造である場合、上記電解質層は、上記支持電解質塩と、上記式(1)で表される化合物又は上記式(2)で表される化合物と、上記バインダー樹脂として、熱可塑性樹脂とを含有することが好ましい。上記式(1)で表される化合物又は上記式(2)で表される化合物としてトリエチレングリコールジ-2-エチルヘキサノエート(3GO)、トリエチレングリコールジ-2-エチルブチレート(3GH)、テトラエチレングリコールジ-2-エチルヘキサノエート(4GO)、ジヘキシルアジペート(DHA)等の液状可塑剤が挙げられる。
例えば、上記液状可塑剤の含有量の異なる電解質層を積層したり、上記バインダー樹脂として水酸基量の異なるポリビニルアセタール樹脂を含有する電解質層を積層したりすることにより、得られる合わせガラスの遮音性を向上させることができる。
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.
When the electrolyte layer has a multilayer structure, 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. Examples of 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). And liquid plasticizers such as tetraethylene glycol di-2-ethylhexanoate (4GO) and dihexyl adipate (DHA).
For example, by laminating electrolyte layers having different contents of the liquid plasticizer, or by laminating electrolyte layers containing polyvinyl acetal resins having different amounts of hydroxyl groups as the binder resin, the sound insulation of the obtained laminated glass can be improved. Can be improved.
上記電解質層の厚さは特に限定されないが、好ましい下限は0.01mm、好ましい上限は3.0mmである。上記電解質層の厚さが0.01~3.0mmであると、電圧を印加してから光透過率の変化が完了するまでの時間がより一層短くなる。上記電解質層の厚さのより好ましい下限は0.1mm、より好ましい上限は2.0mm、更に好ましい下限は0.3mm、更に好ましい上限は1.0mmである。 Although the thickness of the said electrolyte layer is not specifically limited, A preferable minimum is 0.01 mm and a preferable upper limit is 3.0 mm. When 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.
上記電解質層を形成する方法は特に限定されず、例えば、上記式(1)で表される化合物又は上記式(2)で表される化合物に上記支持電解質塩を溶解した溶液を調製し、得られた溶液を上記バインダー樹脂と混合した混合物を熱プレス等の方法により電解質層を形成する方法や、該混合物を押出機により押出成形し電解質層を形成する方法等が挙げられる。 The method for forming the electrolyte layer is not particularly limited. For example, 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.
上記支持電解質塩、上記バインダー樹脂、並びに、上記式(1)で表される化合物又は上記式(2)で表される化合物を含有する電解質膜もまた、本発明の1つである。
本発明の電解質膜を用いることにより、電圧を印加してから光透過率の変化が完了するまでの時間が極めて短い合わせガラス用中間膜を得ることができる。
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.
By using 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.
上記エレクトロクロミック層は、エレクトロクロミック化合物を含有する。
上記エレクトロクロミック層に含有されるエレクトロクロミック化合物は、エレクトロクロミック性を有する化合物であれば特に限定されず、無機化合物であってもよく、有機化合物であってもよい。
なお、エレクトロクロミック性を有するとは、電圧を印加することにより光の透過率が変化する性質を有することを意味する。
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.
上記エレクトロクロミック性を有する無機化合物は、例えば、Mo、Ir、NiO、V、WO、TiO等の金属酸化物や、プルシアンブルー等の混合原子価錯体が挙げられる。
上記エレクトロクロミック性を有する有機化合物は、例えば、ポリピロール化合物、ポリアセチレン化合物、ポリチオフェン化合物、ポリパラフェニレンビニレン化合物、ポリアニリン化合物、ポリエチレンジオキシチオフェン化合物、金属フタロシアニン化合物、ビオロゲン化合物、ビオロゲン塩化合物、フェロセン化合物、テレフタル酸ジメチル化合物等が挙げられる。なかでも、ポリアセチレン化合物が好ましく、芳香族側鎖を有するポリアセチレン化合物がより好ましい。
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.
上記芳香族側鎖を有するポリアセチレン化合物は、エレクトロクロミック性と導電性とを有し、かつ、エレクトロクロミック層の形成が容易である。従って、芳香族側鎖を有するポリアセチレン化合物を用いれば、優れた調光性能を有するエレクトロクロミック層を容易に形成できる。また、芳香族側鎖を有するポリアセチレン化合物は、構造が変化することにより、吸収特性に変化を示す。その結果、吸収スペクトルが近赤外線の波長領域に及ぶため、エレクトロクロミック層は広い波長領域について優れた調光性能を有する。 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.
上記芳香族側鎖を有するポリアセチレン化合物は特に限定されないが、例えば、一置換又は二置換の芳香族を側鎖に有するポリアセチレン化合物等が好適である。 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.
上記芳香族側鎖を構成する置換基は特に限定されないが、例えば、フェニル、p-フルオロフェニル、p-クロロフェニル、p-ブロモフェニル、p-ヨードフェニル、p-ヘキシルフェニル、p-オクチルフェニル、p-シアノフェニル、p-アセトキシフェニル、p-アセトフェニル、ビフェニル、o-(ジメチルフェニルシリル)フェニル、p-(ジメチルフェニルシリル)フェニル、o-(ジフェニルメチルシリル)フェニル、p-(ジフェニルメチルシリル)フェニル、o-(トリフェニルシリル)フェニル、p-(トリフェニルシリル)フェニル、o-(トリルジメチルシリル)フェニル、p-(トリルジメチルシリル)フェニル、o-(ベンジルジメチルシリル)フェニル、p-(ベンジルジメチルシリル)フェニル、o-(フェネチルジメチルシリル)フェニル、p-(フェネチルジメチルシリル)フェニル等のフェニル基や、ビフェニル基や、1-ナフチル、2-ナフチル、1-(4-フルオロ)ナフチル、1-(4-クロロ)ナフチル、1-(4-ブロモ)ナフチル、1-(4-ヘキシル)ナフチル、1-(4-オクチル)ナフチル等のナフチル基や、ナフタレン基や、1-アントラセン、1-(4-クロロ)アントラセン、1-(4-オクチル)アントラセン等のアントラセン基や、1-フェナントレン等のフェナントレン基や、1-フルオレン等のフルオレン基や、1-ペリレン等のペリレン基等が挙げられる。
上記芳香族側鎖を構成する置換基として、フェニル基、ビフェニル基、ナフチル基、ナフタレン基、アントラセン基、フェナントレン基、フルオレン基及びペリレン基からなる群より選択される少なくとも1種の置換基を有することが好ましい。なかでも、電圧を印加してから光透過率の変化が完了するまでの時間がより一層短くなることから、上記芳香族側鎖を構成する置換基は、ナフチル基、ナフタレン基、アントラセン基、フェナントレン基、フルオレン基又はペリレン基であることがより好ましく、アントラセン基、フェナントレン基、フルオレン基又はペリレン基であることが更に好ましく、フェナントレン基であることが特に好ましい。
なお、上記芳香族側鎖を構成する置換基の一部の水素原子は、水素原子以外の原子又は原子団に置換されていてもよい。 
The substituent constituting the aromatic side chain is not particularly limited. For example, phenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-iodophenyl, p-hexylphenyl, p-octylphenyl, p -Cyanophenyl, p-acetoxyphenyl, p-acetophenyl, biphenyl, o- (dimethylphenylsilyl) phenyl, p- (dimethylphenylsilyl) phenyl, o- (diphenylmethylsilyl) phenyl, p- (diphenylmethylsilyl) Phenyl, o- (triphenylsilyl) phenyl, p- (triphenylsilyl) phenyl, o- (tolyldimethylsilyl) phenyl, p- (tolyldimethylsilyl) phenyl, o- (benzyldimethylsilyl) phenyl, p- ( Benzyldimethylsilyl) phenyl, o- ( Phenyl groups such as ethenyldimethylsilyl) phenyl and p- (phenethyldimethylsilyl) phenyl, biphenyl groups, 1-naphthyl, 2-naphthyl, 1- (4-fluoro) naphthyl, 1- (4-chloro) Naphtyl groups such as naphthyl, 1- (4-bromo) naphthyl, 1- (4-hexyl) naphthyl, 1- (4-octyl) naphthyl, naphthalene groups, 1-anthracene, 1- (4-chloro) anthracene And anthracene groups such as 1- (4-octyl) anthracene, phenanthrene groups such as 1-phenanthrene, fluorene groups such as 1-fluorene, and perylene groups such as 1-perylene.
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. Group, 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.
In addition, some hydrogen atoms of the substituents constituting the aromatic side chain may be substituted with atoms or atomic groups other than hydrogen atoms.
上記エレクトロクロミック層は、熱線吸収剤や接着力調整剤を含有してもよい。
上記熱線吸収剤は、上記電解質層に含有される熱線吸収剤と同様の熱線吸収剤を用いることができる。上記接着力調整剤は、上記電解質層に含有される接着力調整剤と同様の接着力調整剤を用いることができる。
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. As 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.
上記エレクトロクロミック層の厚さは特に限定されないが、好ましい下限は0.05μm、好ましい上限は5μmである。上記エレクトロクロミック層の厚さが0.05~5μmであると、電圧を印加してから光透過率の変化が完了するまでの時間がより一層短くなる。上記エレクトロクロミック層の厚さのより好ましい下限は0.1μm、より好ましい上限は2μmであり、更に好ましい下限は0.2μm、更に好ましい上限は1μmである。 Although the thickness of the said electrochromic layer is not specifically limited, A preferable minimum is 0.05 micrometer and a preferable upper limit is 5 micrometers. When the thickness of the electrochromic layer is 0.05 to 5 μm, 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 μm, the more preferable upper limit is 2 μm, the still more preferable lower limit is 0.2 μm, and the still more preferable upper limit is 1 μm.
本発明の合わせガラス用中間膜は、上記電解質層、上記エレクトロクロミック層以外に、必要に応じて、紫外線吸収剤を含有する紫外線吸収層や、熱線吸収剤を含有する赤外線吸収層等を有してもよい。 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.
本発明の合わせガラス用中間膜は、表面にエンボスが形成されていることが好ましい。
上記エンボスの粗さは特に限定されないが、JIS B 0601で定義される10点平均粗さの好ましい下限は20μm、好ましい上限は50μmである。
上記エンボスは電解質層又は電解質膜に形成されていることが好ましく、なかでも、導電膜と接する面の表面にエンボスが形成されていることがより好ましい。
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 μm, and the preferred upper limit is 50 μm.
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.
本発明の合わせガラス用中間膜が、導電膜が形成されている一対のガラス板の間に挟み込まれている合わせガラスもまた、本発明の1つである。
上記ガラス板は、一般に使用されている透明板ガラスを使用することができる。例えば、フロート板ガラス、磨き板ガラス、型板ガラス、網入りガラス、線入り板ガラス、着色された板ガラス、熱線吸収ガラス、熱線反射ガラス、グリーンガラス等の無機ガラスが挙げられる。また、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、ポリアクリレート等の有機プラスチックス板を用いることもできる。
上記ガラス板として、2種類以上のガラス板を用いてもよい。例えば、透明フロート板ガラスと、グリーンガラスのような着色されたガラス板とで、本発明の合わせガラス用中間膜を挟持した合わせガラスが挙げられる。また、上記ガラス板として、2種以上の厚さの異なるガラス板を用いてもよい。
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. In addition, 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. For example, the laminated glass which pinched | 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. Moreover, you may use the glass plate from which 2 or more types of thickness differs as said glass plate.
上記ガラス板は、少なくとも一方の面に導電膜が形成されている。本発明の合わせガラスにおいて本発明の合わせガラス用中間膜は、上記ガラス板の導電膜が形成された面に接するように2枚のガラス板の間に挟持される。
上記導電膜は、スズドープ酸化インジウム(ITO)、フッ素ドープ酸化スズ(FTO)、ガリウムドープ酸化亜鉛(GZO)等を含む透明導電膜が好ましい。
The glass plate has a conductive film formed on at least one surface. In the laminated glass of the present invention, 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.
本発明の合わせガラスの面密度は特に限定されないが、12kg/m以下であることが好ましい。
本発明の合わせガラスは、自動車用ガラスとして使用する場合は、サイドガラス、リアガラス、ルーフガラスとして用いることができる。
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.
本発明によれば、電圧を印加してから光透過率の変化が完了するまでの時間が極めて短い合わせガラス用中間膜を提供することができる。また、該合わせガラス用中間膜を用いてなる合わせガラスを提供することができる。 According to 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.
以下に実施例を挙げて本発明の態様を更に詳しく説明するが、本発明は実施例にのみ限定されない。 Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.
(実施例1)
(1)電解質層の調製
上記式(1)で表される化合物としてトリエチレングリコールジアセタート(上記式(1-1)で表される化合物)6.5重量部に、支持電解質塩としてビス(トリフルオロメタンスルホニル)イミドリチウム(LiTFSI)3重量部を溶解して電解質溶液を調製した。得られた電解質溶液の全量と、熱可塑性樹脂として、アセチル基量13mol%、水酸基量22mol%のポリビニルブチラール樹脂(平均重合度が2300のポリビニルアルコールをn-ブチルアルデヒドでブチラール化することにより得られたポリビニルブチラール樹脂)10重量部とを混合して樹脂組成物を得た。得られた樹脂組成物をポリテトラフルオロエチレン(PTFE)シートに挟み、厚さ400μmのスペーサを介して、熱プレスにて150℃、100kg/cmの条件で5分間加圧し、厚さ400μmの電解質層を得た。
Example 1
(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 μm with a hot press at 150 ° C. and 100 kg / cm 2 for 5 minutes, and having a thickness of 400 μm. An electrolyte layer was obtained.
(2)エレクトロクロミック化合物の調製
窒素雰囲気下-50℃で9-エチニルフェナントレン3重量部を溶解させたテトラヒドロフラン溶液26.7重量部に30重量%のノルマルブチルリチウムのヘキサン溶液13.4重量部を添加した。次いで、-90℃に冷却後、カリウムターシャリーブトキシド1.8重量部を溶解させたテトラヒドロフラン溶液13.3重量部を添加し、-80℃で1時間撹拌し、5℃まで昇温した。次いで、-70℃で1-ヨードオクタデカン5.6重量部を滴下し、-30℃で12時間撹拌した。0℃で水100重量部を滴下し、ヘキサン300重量部を加え、生成した化合物を抽出した。このヘキサン層を蒸留水300重量部で3回洗浄後、無水硫酸マグネシウムで1時間乾燥させ、濾過後、溶媒を留去した。カラム精製後溶媒を留去し、ヘキサンを展開溶媒としてカラム精製することにより9-エチニル-10-n-オクタデシルフェナントレンを得た。
得られた9-エチニル-10-n-オクタデシルフェナントレンについてH-NMR(270MHz、CDCl)により分析を行ったところ、δ8.7(2H)、8.5(1H)、8.1(1H)、7.7(4H)、3.7(1H)、3.5(2H)、1.7(2H)、1.6(30H)、1.0(3H)のピークが認められた。
(2) Preparation of electrochromic compound In a nitrogen atmosphere at −50 ° C., 36.7 parts by weight of 9-ethynylphenanthrene was dissolved in 26.7 parts by weight of tetrahydrofuran solution of 13.4 parts by weight of 30% by weight normal butyl lithium in hexane. Added. Next, after cooling to −90 ° C., 13.3 parts by weight of a tetrahydrofuran solution in which 1.8 parts by weight of potassium tertiary butoxide was dissolved was added, stirred at −80 ° C. for 1 hour, and heated to 5 ° C. Subsequently, 5.6 parts by weight of 1-iodooctadecane was added dropwise at −70 ° C., and the mixture was stirred at −30 ° C. for 12 hours. 100 parts by weight of water was added dropwise at 0 ° C., 300 parts by weight of hexane was added, and the resulting compound was extracted. The hexane layer was washed 3 times with 300 parts by weight of distilled water, dried over anhydrous magnesium sulfate for 1 hour, filtered, and the solvent was distilled off. After column purification, the solvent was distilled off, and 9-ethynyl-10-n-octadecylphenanthrene was obtained by column purification using hexane as a developing solvent.
The obtained 9-ethynyl-10-n-octadecylphenanthrene was analyzed by 1 H-NMR (270 MHz, CDCl 3 ). As a result, δ8.7 (2H), 8.5 (1H), 8.1 (1H ), 7.7 (4H), 3.7 (1H), 3.5 (2H), 1.7 (2H), 1.6 (30H), and 1.0 (3H).
得られた9-エチニル-10-n-オクタデシルフェナントレン3.5重量部を、WCl触媒0.17重量部を用いて重合させ、ポリ(9-エチニル-10-n-オクタデシルフェナントレン)を得た。
得られたポリ(9-エチニル-10-n-オクタデシルフェナントレン)の分子量をゲルパーミエーションクロマトグラフ法(GPC法)により測定した。Waters社製の液体クロマトグラフ装置(Waters2695、RI Waters2410、UV Waters2996)を用い、カラムはShodex社製LF-804を使用した。0.2重量%となるようにクロロホルムに溶解したポリ(9-エチニル-10-n-オクタデシルフェナントレン)を100μL注入し、カラム温度40℃で移動相をクロロホルムとして測定を行った。ポリスチレン換算分子量は、数平均分子量14万7千、重量平均分子量31万5千であった。
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). A liquid chromatograph manufactured by Waters (Waters 2695, RI Waters 2410, UV Waters 2996) was used, and LF-804 manufactured by Shodex was used as the column. 100 μL of poly (9-ethynyl-10-n-octadecylphenanthrene) dissolved in chloroform so as to be 0.2% by weight was injected, and measurement was carried out at a column temperature of 40 ° C. and using a mobile phase as chloroform. The molecular weight in terms of polystyrene was a number average molecular weight of 147,000 and a weight average molecular weight of 315,000.
(3)エレクトロクロミック層の調製
得られたポリ(9-エチニル-10-n-オクタデシルフェナントレン)0.039重量部を1.3重量部のトルエンに溶解して溶液を調製した。この溶液を、得られた電解質層上に、トルエンが揮発した後の厚さが0.3μmになるようにバーコーターを用いて塗布し、乾燥して厚さ0.3μmのエレクトロクロミック層を形成させて、合わせガラス用中間膜を得た。
(3) Preparation of electrochromic layer A solution was prepared by dissolving 0.039 parts by weight of the obtained poly (9-ethynyl-10-n-octadecylphenanthrene) in 1.3 parts by weight of toluene. This solution is applied on the obtained electrolyte layer using a bar coater so that the thickness after evaporation of toluene is 0.3 μm, and dried to form an electrochromic layer having a thickness of 0.3 μm. Thus, an interlayer film for laminated glass was obtained.
(4)合わせガラスの製造
85℃に加熱した合わせガラス用中間膜(縦5×横5cm)を、2枚のITO電極が形成されたガラス(縦5×横5cm、10Ω/cm)の間に挟み込むことにより、合わせガラスを作製した。
(4) Manufacture of laminated glass An intermediate film for laminated glass (vertical 5 × 5 cm) heated to 85 ° C. between the glass (vertical 5 × horizontal 5 cm, 10 Ω / cm 2 ) on which two ITO electrodes are formed A laminated glass was produced by sandwiching the glass.
(実施例2~29)
トリエチレングリコールジアセタートの代わりに表1に示した化合物を用いて電解質層を調製した以外は実施例1と同様にして合わせガラス用中間膜及び合わせガラスを作製した。
(Examples 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.
(実施例30)
上記式(1)で表される化合物としてトリエチレングリコールジブチラート(上記式(1-3)で表される化合物)6.5重量部に、支持電解質塩としてビス(トリフルオロメタンスルホニル)イミドリチウム(LiTFSI)3重量部を溶解して電解質溶液を調製した。得られた電解質溶液の全量と、熱可塑性樹脂として、アセチル基量18mol%、水酸基量15mol%のポリビニルブチラール樹脂(平均重合度が2300のポリビニルアルコールをn-ブチルアルデヒドでブチラール化することにより得られたポリビニルブチラール樹脂)10重量部とを混合して樹脂組成物を得た。
得られた樹脂組成物をポリテトラフルオロエチレン(PTFE)シートに挟み、厚さ400μmのスペーサを介して、熱プレスにて150℃、100kg/cmの条件で5分間加圧し、厚さ400μmの電解質層を得た。
得られた電解質層を用いた以外は実施例1と同様にして合わせガラス中間膜及び合わせガラスを作製した。
(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 μm with a hot press at 150 ° C. and 100 kg / cm 2 for 5 minutes, and having a thickness of 400 μm. 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.
(実施例31)
熱可塑性樹脂として、アセチル基量6mol%、水酸基量18mol%のポリビニルブチラール樹脂(平均重合度が2300のポリビニルアルコールをn-ブチルアルデヒドでブチラール化することにより得られたポリビニルブチラール樹脂)を用いて電解質層を調製した以外は実施例30と同様にして合わせガラス中間膜及び合わせガラスを作製した。
(Example 31)
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.
(実施例32)
熱可塑性樹脂として、アセチル基量18mol%、水酸基量11mol%のポリビニルヘキシラール樹脂(平均重合度が2300のポリビニルアルコールをn-ヘキシルアルデヒドでアセタール化することにより得られたポリビニルヘキシラール樹脂)を用いて電解質層を調製した以外は実施例30と同様にして合わせガラス中間膜及び合わせガラスを作製した。
(Example 32)
As a 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.
(実施例33)
熱可塑性樹脂として、アセチル基量22mol%、水酸基量22mol%のポリビニルブチラール樹脂(平均重合度が2300のポリビニルアルコールをn-ブチルアルデヒドでブチラール化することにより得られたポリビニルブチラール樹脂)を用いて電解質層を調製した以外は実施例30と同様にして合わせガラス中間膜及び合わせガラスを作製した。
(Example 33)
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.
(実施例34)
上記式(1)で表される化合物としてトリエチレングリコールジブチラート(上記式(1-3)で表される化合物)の配合量を12重量部に変更した以外は実施例3と同様にして合わせガラス中間膜及び合わせガラスを作製した。
(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.
(実施例35)
上記式(1)で表される化合物としてトリエチレングリコールジブチラート(上記式(1-3)で表される化合物)の配合量を5重量部に変更した以外は実施例3と同様にして合わせガラス中間膜及び合わせガラスを作製した。
(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.
(比較例1~3)
トリエチレングリコールジアセタートの代わりに下記式及び表1に示した化合物を用いて電解質層を調製した以外は実施例1と同様にして合わせガラス中間膜及び合わせガラスを作製した。
(Comparative Examples 1 to 3)
A laminated glass interlayer film 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 the following formula and Table 1 instead of triethylene glycol diacetate.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
(評価)
実施例及び比較例にて得られた合わせガラスについて、以下の評価を行った。
結果を表1に示した。
(Evaluation)
The following evaluation was performed about the laminated glass obtained in the Example and the comparative example.
The results are shown in Table 1.
(1)応答性評価
完全に着色した状態の合わせガラスの波長640nmの光の透過率をTC、完全に消色した状態の合わせガラスの波長640nmの光の透過率をTBとする。
完全に着色した状態の合わせガラスに+2Vの電圧を印加し、電圧を印加してから合わせガラスの波長640nmの光の透過率がTCからT1=TC+(TB-TC)×0.8まで変化するのに要した時間を測定し、これを消色時間t1とした。
完全に消色した状態の合わせガラスに-2Vの電圧を印加し、電圧を印加してから合わせガラスの波長640nmの光の透過率がTBからT2=TB-(TB-TC)×0.8まで変化するのに要した時間を測定し、これを着色時間t2とした。
なお、透過率の測定には、日本分光社製の分光光度計「V-670」を用いた。
(1) Evaluation of responsiveness Let TC be the transmittance of light at a wavelength of 640 nm of a laminated glass in a completely colored state, and let TB be the transmittance of light at a wavelength of 640 nm of the laminated glass in a completely decolored state.
A voltage of + 2V is applied to the laminated glass in a completely colored state, and after the voltage is applied, the transmittance of light of a wavelength of 640 nm of the laminated glass changes from TC to T1 = TC + (TB−TC) × 0.8. The time required for the measurement was measured, and this was defined as the decoloring time t1.
A voltage of −2 V is applied to the laminated glass in a completely decolored state, and the transmittance of light at a wavelength of 640 nm of the laminated glass is changed from TB to T2 = TB− (TB−TC) × 0.8 after the voltage is applied. 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.
(2)繰返し耐久性
完全に着色した状態の合わせガラスに、上記応答性評価により得られた消色時間t1だけ+2Vの電圧を印加して消色させた。次いで、消色させた合わせガラスに上記応答性評価より得られた着色時間t2だけ-2Vの電圧を印加して着色させた。この消色から着色までを一周期として、5000周期消色と着色とを繰り返した。
5000周期消色と着色とを繰り返した後に、完全に着色した状態の合わせガラスに+2Vの電圧を印加し、電圧を印加してから合わせガラスの波長640nmの光の透過率がTCからT1=TC+(TB-TC)×0.8まで変化するのに要した時間を測定し、これを消色時間t3とした。
繰返し耐久性について、t3≦2×t1の場合を「○」と、2×t1<t3≦5×t1の場合を「△」と、t3>5×t1の場合「×」と評価した。
(2) Repeatability The laminated glass in a completely colored state was erased by applying a voltage of +2 V for the decoloring time t1 obtained by the above responsiveness evaluation. Next, the decolored laminated glass was colored by applying a voltage of −2 V for the coloring time t2 obtained from the above responsiveness evaluation. From this erasing to coloring, one cycle was repeated 5000 times erasing and coloring.
After repeating 5000 period erasing and coloring, a voltage of +2 V is applied to the laminated glass in a completely colored state, and after the voltage is applied, the transmittance of light at a wavelength of 640 nm of the laminated glass is from TC to T1 = TC + The time required for the change to (TB−TC) × 0.8 was measured, and this was defined as the decoloring time t3.
Regarding the repeated durability, a case where t3 ≦ 2 × t1 was evaluated as “◯”, a case where 2 × t1 <t3 ≦ 5 × t1 was evaluated as “Δ”, and a case where t3> 5 × t1 was evaluated as “×”.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
本発明によれば、電圧を印加してから光透過率の変化が完了するまでの時間が極めて短い合わせガラス用中間膜を提供することができる。また、該合わせガラス用中間膜を用いてなる合わせガラスを提供することができる。
 
According to 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.

Claims (19)

  1. 電解質層と、前記電解質層の少なくとも片面に形成されたエレクトロクロミック層とを有する合わせガラス用中間膜であって、
    前記電解質層は、支持電解質塩、バインダー樹脂、並びに、下記式(1)で表される化合物又は下記式(2)で表される化合物を含有する
    ことを特徴とする合わせガラス用中間膜。
    Figure JPOXMLDOC01-appb-C000001
    式(1)中、n=2~4の整数を表し、Rは水素原子、炭素数1~7の有機基を有するアシル基又は炭素数1~8の有機基を表し、Rはエチレン基又はプロピレン基を表し、Rは水素原子、炭素数1~7の有機基を有するアシル基又は炭素数1~8の有機基を表し、少なくともR又はRの何れかはアシル基を有する。
    Figure JPOXMLDOC01-appb-C000002
    式(2)中、Rは炭素数2~8であり、酸素原子を有する有機基を表し、Rは炭素数2~8のアルキレン基又は炭素数6~12のアリーレン基を表し、Rは炭素数2~8であり、酸素原子を有する有機基を表す。R及びRは同一であってもよく、異なっていてもよい。
    An interlayer film for laminated glass having an electrolyte layer and an electrochromic layer formed on at least one side of the electrolyte layer,
    The said electrolyte layer contains support electrolyte salt, binder resin, the compound represented by following formula (1), or the compound represented by following formula (2), The interlayer film for laminated glasses characterized by the above-mentioned.
    Figure JPOXMLDOC01-appb-C000001
    In the formula (1), 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, and 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, and at least one of R 1 and R 3 represents an acyl group. Have.
    Figure JPOXMLDOC01-appb-C000002
    In the formula (2), 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.
  2. 式(1)中、Rは水素原子、炭素数1~7のアルキル基を有するアシル基又は炭素数1~8のアルキル基を表し、Rはエチレン基又はプロピレン基を表し、Rは水素原子、炭素数1~7のアルキル基を有するアシル基又は炭素数1~8のアルキル基を表し、少なくともR又はRの何れかはアシル基を有することを特徴とする請求項1記載の合わせガラス用中間膜。 In the formula (1), R 1 represents a hydrogen atom, an acyl group having an alkyl group having 1 to 7 carbon atoms or an alkyl group having 1 to 8 carbon atoms, R 2 represents an ethylene group or a propylene group, and R 3 represents 2. A hydrogen atom, an acyl group having an alkyl group having 1 to 7 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, wherein at least one of R 1 and R 3 has an acyl group. Interlayer film for laminated glass.
  3. 式(1)中、Rは炭素数1~7のアルキル基を有するアシル基を表し、Rはエチレン基又はプロピレン基を表し、Rは炭素数1~7のアルキル基を有するアシル基を表すことを特徴とする請求項1記載の合わせガラス用中間膜。 In the formula (1), 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, and R 3 represents an acyl group having an alkyl group having 1 to 7 carbon atoms. The interlayer film for laminated glass according to claim 1, wherein
  4. 式(1)中、Rは炭素数1~6のアルキル基を有するアシル基を表し、Rはエチレン基又はプロピレン基を表し、Rは炭素数1~6のアルキル基を有するアシル基を表すことを特徴とする請求項1記載の合わせガラス用中間膜。 In the formula (1), R 1 represents an acyl group having an alkyl group having 1 to 6 carbon atoms, R 2 represents an ethylene group or a propylene group, and R 3 represents an acyl group having an alkyl group having 1 to 6 carbon atoms. The interlayer film for laminated glass according to claim 1, wherein
  5. 式(1)中、Rは炭素数1~7であり、かつ、直鎖構造を有するアルキル基を有するアシル基を表し、Rはエチレン基又はプロピレン基を表し、Rは炭素数1~7であり、かつ、直鎖構造を有するアルキル基を有するアシル基を表すことを特徴とする請求項1記載の合わせガラス用中間膜。 In formula (1), R 1 represents an acyl group having 1 to 7 carbon atoms and having an alkyl group having a linear structure, R 2 represents an ethylene group or a propylene group, and R 3 represents 1 carbon atom. The interlayer film for laminated glass according to claim 1, which represents an acyl group having an alkyl group having a linear structure of 1 to 7.
  6. 式(1)中、Rは炭素数1~7であり、分岐構造を有し、かつ、分岐鎖の炭素数が1以下であるアルキル基を有するアシル基を表し、Rはエチレン基又はプロピレン基を表し、Rは炭素数1~7であり、分岐構造を有し、かつ、分岐鎖の炭素数が1以下であるアルキル基を有するアシル基を表すことを特徴とする請求項1記載の合わせガラス用中間膜。 In the formula (1), R 1 represents an acyl group having 1 to 7 carbon atoms, a branched structure, and an alkyl group having 1 or less carbon atoms in the branched chain, and R 2 represents an ethylene group or 2. The propylene group, wherein R 3 represents an acyl group having 1 to 7 carbon atoms, a branched structure, and an alkyl group having a branched chain carbon number of 1 or less. The interlayer film for laminated glass described.
  7. バインダー樹脂は、熱可塑性樹脂であることを特徴とする請求項1記載の合わせガラス用中間膜。 The interlayer film for laminated glass according to claim 1, wherein the binder resin is a thermoplastic resin.
  8. 熱可塑性樹脂は、ポリビニルアセタール樹脂であることを特徴とする請求項7記載の合わせガラス用中間膜。 The interlayer film for laminated glass according to claim 7, wherein the thermoplastic resin is a polyvinyl acetal resin.
  9. ポリビニルアセタール樹脂は、アセチル基量が15モル%以下であり、かつ、水酸基量が30モル%以下であることを特徴とする請求項8記載の合わせガラス用中間膜。 The interlayer film for laminated glass according to claim 8, wherein the polyvinyl acetal resin has an acetyl group content of 15 mol% or less and a hydroxyl group content of 30 mol% or less.
  10. ポリビニルアセタール樹脂は、アセチル基量が5モル%以上であることを特徴とする請求項8記載の合わせガラス用中間膜。 The interlayer film for laminated glass according to claim 8, wherein the polyvinyl acetal resin has an acetyl group amount of 5 mol% or more.
  11. ポリビニルアセタール樹脂は、アセタール化度が70~85モル%であることを特徴とする請求項8記載の合わせガラス用中間膜。 9. The interlayer film for laminated glass according to claim 8, wherein the polyvinyl acetal resin has an acetalization degree of 70 to 85 mol%.
  12. エレクトロクロミック層は、芳香族側鎖を有するポリアセチレン化合物を含むことを特徴とする請求項1記載の合わせガラス用中間膜。 The interlayer film for laminated glass according to claim 1, wherein the electrochromic layer contains a polyacetylene compound having an aromatic side chain.
  13. 請求項1、2、3、4、5、6、7、8、9、10、11又は12記載の合わせガラス用中間膜が、導電膜が形成されている一対のガラス板の間に挟み込まれていることを特徴とする合わせガラス。 The interlayer film for laminated glass according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 is sandwiched between a pair of glass plates on which a conductive film is formed. Laminated glass characterized by that.
  14. 支持電解質塩、バインダー樹脂、並びに、下記式(1)で表される化合物又は下記式(2)で表される化合物を含有することを特徴とする電解質膜。
    Figure JPOXMLDOC01-appb-C000003
    式(1)中、n=2~4の整数を表し、Rは水素原子、炭素数1~7の有機基を有するアシル基又は炭素数1~8の有機基を表し、Rはエチレン基又はプロピレン基を表し、Rは水素原子、炭素数1~7の有機基を有するアシル基又は炭素数1~8の有機基を表し、少なくともR又はRの何れかはアシル基を有する。
    Figure JPOXMLDOC01-appb-C000004
    式(2)中、Rは炭素数2~8であり、酸素原子を有する有機基を表し、Rは炭素数2~8のアルキレン基又は炭素数6~12のアリーレン基を表し、Rは炭素数2~8であり、酸素原子を有する有機基を表す。R及びRは同一であってもよく、異なっていてもよい。
    An electrolyte membrane comprising a supporting electrolyte salt, a binder resin, and a compound represented by the following formula (1) or a compound represented by the following formula (2).
    Figure JPOXMLDOC01-appb-C000003
    In the formula (1), 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, and 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, and at least one of R 1 and R 3 represents an acyl group. Have.
    Figure JPOXMLDOC01-appb-C000004
    In the formula (2), 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.
  15. 式(1)中、Rは水素原子、炭素数1~7のアルキル基を有するアシル基又は炭素数1~8のアルキル基を表し、Rはエチレン基又はプロピレン基を表し、Rは水素原子、炭素数1~7のアルキル基を有するアシル基又は炭素数1~8のアルキル基を表し、少なくともR又はRの何れかはアシル基を有することを特徴とする請求項14記載の電解質膜。 In the formula (1), R 1 represents a hydrogen atom, an acyl group having an alkyl group having 1 to 7 carbon atoms or an alkyl group having 1 to 8 carbon atoms, R 2 represents an ethylene group or a propylene group, and R 3 represents 15. A hydrogen atom, an acyl group having an alkyl group having 1 to 7 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, wherein at least one of R 1 and R 3 has an acyl group. Electrolyte membrane.
  16. 式(1)中、Rは炭素数1~7のアルキル基を有するアシル基を表し、Rはエチレン基又はプロピレン基を表し、Rは炭素数1~7のアルキル基を有するアシル基を表すことを特徴とする請求項14記載の電解質膜。 In the formula (1), 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, and R 3 represents an acyl group having an alkyl group having 1 to 7 carbon atoms. The electrolyte membrane according to claim 14, wherein
  17. 式(1)中、Rは炭素数1~6のアルキル基を有するアシル基を表し、Rはエチレン基又はプロピレン基を表し、Rは炭素数1~6のアルキル基を有するアシル基を表すことを特徴とする請求項14記載の電解質膜。 In the formula (1), R 1 represents an acyl group having an alkyl group having 1 to 6 carbon atoms, R 2 represents an ethylene group or a propylene group, and R 3 represents an acyl group having an alkyl group having 1 to 6 carbon atoms. The electrolyte membrane according to claim 14, wherein
  18. 式(1)中、Rは炭素数1~7であり、かつ、直鎖構造を有するアルキル基を有するアシル基を表し、Rはエチレン基又はプロピレン基を表し、Rは炭素数1~7であり、かつ、直鎖構造を有するアルキル基を有するアシル基を表すことを特徴とする請求項14に記載の電解質膜。 In formula (1), R 1 represents an acyl group having 1 to 7 carbon atoms and having an alkyl group having a linear structure, R 2 represents an ethylene group or a propylene group, and R 3 represents 1 carbon atom. 15. The electrolyte membrane according to claim 14, wherein the electrolyte membrane represents an acyl group having an alkyl group having a linear structure of ˜7.
  19. 式(1)中、Rは炭素数1~7であり、分岐構造を有し、かつ、分岐鎖の炭素数が1以下であるアルキル基を有するアシル基を表し、Rはエチレン基又はプロピレン基を表し、Rは炭素数1~7であり、分岐構造を有し、かつ、分岐鎖の炭素数が1以下であるアルキル基を有するアシル基を表すことを特徴とする請求項14に記載の電解質膜。 In the formula (1), R 1 represents an acyl group having 1 to 7 carbon atoms, a branched structure, and an alkyl group having 1 or less carbon atoms in the branched chain, and R 2 represents an ethylene group or 15. The propylene group, wherein R 3 represents an acyl group having 1 to 7 carbon atoms, a branched structure, and an alkyl group having a branched chain carbon number of 1 or less. The electrolyte membrane described in 1.
PCT/JP2010/072672 2009-12-16 2010-12-16 Intermediate film for laminated glass, and laminated glass WO2011074639A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003091021A (en) * 2001-09-18 2003-03-28 Nippon Oil Corp Method for manufacturing electrochromic light control glass
JP2007529036A (en) * 2004-03-12 2007-10-18 ザ・ボーイング・カンパニー Array dimming controller for multicolor systems, low vapor pressure solvents, and electrochromic devices
JP2009508148A (en) * 2005-08-19 2009-02-26 エルジー・ケム・リミテッド Electrolyte containing eutectic mixture and electrochemical device using said electrolyte

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003091021A (en) * 2001-09-18 2003-03-28 Nippon Oil Corp Method for manufacturing electrochromic light control glass
JP2007529036A (en) * 2004-03-12 2007-10-18 ザ・ボーイング・カンパニー Array dimming controller for multicolor systems, low vapor pressure solvents, and electrochromic devices
JP2009508148A (en) * 2005-08-19 2009-02-26 エルジー・ケム・リミテッド Electrolyte containing eutectic mixture and electrochemical device using said electrolyte

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