WO1999035102A1 - Plaque transparente ignifuge et resistant au feu, absorbant les ultraviolets - Google Patents

Plaque transparente ignifuge et resistant au feu, absorbant les ultraviolets Download PDF

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Publication number
WO1999035102A1
WO1999035102A1 PCT/JP1999/000042 JP9900042W WO9935102A1 WO 1999035102 A1 WO1999035102 A1 WO 1999035102A1 JP 9900042 W JP9900042 W JP 9900042W WO 9935102 A1 WO9935102 A1 WO 9935102A1
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Prior art keywords
group
ultraviolet
absorbing
carbon atoms
fire
Prior art date
Application number
PCT/JP1999/000042
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English (en)
Japanese (ja)
Inventor
Tsuyoshi Asano
Junichiro Tanimoto
Noboru Takaesu
Yoshinori Nishikitani
Original Assignee
Nippon Mitsubishi Oil Corporation
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Filing date
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Publication of WO1999035102A1 publication Critical patent/WO1999035102A1/fr

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/92—Protection against other undesired influences or dangers
    • E04B1/94—Protection against other undesired influences or dangers against fire
    • E04B1/941—Building elements specially adapted therefor
    • E04B1/942—Building elements specially adapted therefor slab-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B32B17/10045—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets with at least one intermediate layer consisting of a glass sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10311—Intumescent layers for fire protection
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00

Definitions

  • the present invention relates to a transparent laminated fireproof plate provided with an ultraviolet absorbing ability.
  • the method (1) of treating with an ultraviolet-absorbing substance is roughly classified into a method using an inorganic ultraviolet absorber and a method using an organic ultraviolet absorber.
  • the inorganic ultraviolet absorbers described in Although it has excellent weather resistance, heat resistance, and the like, the degree of freedom is small because the absorption wavelength is determined by the band gap of the compound, and the ultraviolet region near 400 nm cannot be clearly cut. In addition, many inorganic UV absorbers capable of cutting the long wavelength region are accompanied by coloring.
  • organic UV absorbers have a wide range of absorption bands, so that various types of absorption wavelengths can be obtained by selecting the type, concentration, and film thickness of the absorber.
  • systems using various organic UV absorbers have been studied.If the power is to be applied to the long wavelength region, use one having a maximum absorption wavelength in the long wavelength region or use a concentration or concentration.
  • those having a maximum absorption wavelength in a long wavelength region see, for example, Japanese Patent Application Laid-Open No. H6-1458787) have poor light resistance, and the absorption capacity decreases with time.
  • Japanese Patent Application Laid-Open No. 6-145,887 there is also a problem in that the use of a fluorescent whitening agent deteriorates the visibility due to fluorescence.
  • benzophenone-based and benzotriazole-based UV absorbers have relatively good light fastness, and can be cut relatively clearly up to the long wavelength region by increasing their concentration and film thickness.
  • the thickness of the coating film is limited to several m.
  • the concentration of the UV absorber in the coating film must be considerably increased, in which case the UV absorber precipitates and bleed out due to long-term use There is.
  • the present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide an ultraviolet absorber that is excellent in weather resistance and heat resistance, and that does not lead out even during long-term use. It is an object of the present invention to provide a UV-absorbing fire-resistant transparent plate that can be pumped to a long-wavelength region of UV light without lowering transmittance.
  • the ultraviolet-absorbing fire-resistant transparent plate according to the present invention is a laminated fire-resistant fire-resistant transparent plate provided with a foam layer containing a heat-sensitive foaming agent between a plurality of transparent substrates juxtaposed at intervals in the thickness direction.
  • the transparent substrates used for the laminated fireproof transparent plate has an ultraviolet absorbing layer on its surface, and the ultraviolet absorbing layer has
  • component A an aminosilane compound represented by the following general formula (1) or a derivative thereof (hereinafter referred to as component A):
  • component B A reaction product obtained by reacting an ultraviolet absorbing compound having a carboxyl group in the molecule (hereinafter referred to as component B) to form an amide bond derived from component A is placed on a transparent substrate. It is characterized by being manufactured by coating and curing.
  • R 1 is an alkylene group having 1 to 10 carbon atoms, or a divalent group represented by the general formula 1 (CH 2 ) m- NH-[m is an integer of l ⁇ m ⁇ 4]
  • each R 2 is the same or different, and represents a hydrogen atom, a hydroxyl group, a halogen atom,
  • the ultraviolet-absorbing fire-resistant transparent plate of the present invention has a structure in which a foam layer containing a heat-sensitive foaming agent is provided between a plurality of transparent substrates juxtaposed at an interval in the plate thickness direction. At least one of the transparent substrates used is provided with an ultraviolet absorbing layer between the transparent substrate and the foamed layer.
  • any plate having a transmittance of 10% to 100% in a visible light region and having a smooth surface at room temperature can be used. It may be deformed by stress.
  • colorless or colored glass, frosted glass, inorganic glass such as meshed glass can be used, and also colorless or colored synthetic resin, specifically, polyethylene terephthalate, polyimide Plates such as polysulfone, polysulfone, polyethersulfone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, and polystyrene can be used.
  • inorganic glass is suitable for the transparent substrate used in the present invention because of its excellent fire and fire resistance.
  • the ultraviolet absorbing layer provided on the transparent substrate is obtained by applying the reaction product of the component A and the component B on the transparent substrate and curing the component.
  • R 1 is an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or a general formula — (CH 2 ) m — NH— [m is an integer of l ⁇ m ⁇ 4] Represents a divalent group represented by Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group.
  • R 2 are the same or different groups A hydrogen atom, a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl or alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. Represents an aryl group. However, at least one, preferably 2 to 5, of all R 2 is an alkoxy group. Examples of the alkyl group for R 2 include a methyl group, an ethyl group, a propyl group, and an i-propyl group. Examples of the aryl group include a phenyl group and a tolyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and an i-propoxy group. n represents n 0, preferably an integer of 0 ⁇ n ⁇ 3.
  • aminosilane compound represented by the general formula (1) are as follows: 3-aminopropyltriethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropylmethyljetoxysilane, -Aminopropyl trichlorosilane, 3-aminopropylpolydimethylsiloxane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltris (methoxetoxyhetoxy) silane, and the like. Any of them can be synthesized by a known method.
  • a derivative of the aminosilane compound represented by the general formula (1) can be used.
  • a hydrolyzate of the aminosilane compound represented by the general formula (1) is preferably used.
  • an ultraviolet absorbing compound having at least one carboxyl group in the molecule is used as the component B used together with the component A for forming the ultraviolet absorbing layer.
  • One of the ultraviolet absorbing compounds that can be suitably used as Component B is a compound having a benzotriazole skeleton represented by the following general formula (2).
  • R 3 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10, preferably 1 to 6 carbon atoms.
  • the halogen atom may be any of fluorine, chlorine, bromine or iodine
  • the alkyl group may be a methyl group, an ethyl group, Any of a propyl group, an i-propyl group, a butyl group, a t-butyl group, a cyclohexyl group and the like may be used.
  • the substitution position of R 3 is at the 4- or 5-position of the benzotriazole skeleton, but the halogen atom and the alkyl group are usually located at the 4-position.
  • R 4 in the general formula (2) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group.
  • R 5 in the general formula (2) represents an alkylene group or an alkylidene group having 1 to 10, preferably 1 to 3 carbon atoms.
  • alkylene group examples include a methylene group, an ethylene group, a trimethylene group, and a propylene group
  • alkylidene group examples include an ethylidene group and a propylidene group.
  • Specific examples of the compound represented by the general formula (2) include the following: 3- (5-chloro-2H-benzotriazole-2-yl) -15- (1,1-dimethylethyl) -14 Hydroxy-1-benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -1-4-hydroxybenzenebenzoic acid, 3- (5-methyl-1H-benzotriazo-2-yl-2-yl) C) 1-4- (1-methylethyl) -14-hydroxybenzenepropanoic acid.
  • Another one of the ultraviolet absorbing compounds which can be suitably used as the component B is a compound having a benzophenone skeleton, which is represented by the following general formulas (3) to (6).
  • R 6 represents an alkylene group or an alkylidene group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms.
  • alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group.
  • alkylidene group include an ethylidene group and a propylidene group.
  • R 7 and R 8 in the general formulas (3) to (6) are the same or different and represent a hydroxyl group, an alkyl group or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
  • Alkyl groups include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, cyclohexyl, etc.
  • Alkoxy groups include methoxy, ethoxy, propoxy, i -Specific examples include a propoxy group and a butoxy group.
  • n and m indicate integers in the range of 0 ⁇ m ⁇ 3 and 0 ⁇ n ⁇ 3.
  • Preferred specific examples of the compound having a benzophenone skeleton include 2-hydroxy-4-methoxybenzophenone-15-carboxylic acid, 2,2, dihydroxy-4-methoxybenzophenone-15-carboxylic acid, — (2-Hydroxybenzoyl) 1-3-Hydroxybenzenepropanoic acid.
  • Any of the compounds having a benzotriazole skeleton or a benzophenone skeleton used as the component B of the present invention can be produced by a known method.
  • Component A and Component B are mixed in a suitable solvent at room temperature to 350 ° C .; preferably at a temperature of 60 to 250 ° C., usually for 5 minutes to 50 hours, preferably 10 to 50 hours.
  • the reaction can be carried out by bringing both components into contact for a period of minutes to 15 hours, and this reaction is mainly a dehydration reaction.
  • the proportion of component A and component B used in the reaction is determined by the amount of component B used.
  • the amount is usually selected in the range of 5 to 90% by mass, preferably 10 to 80% by mass, based on the total amount of the component B, whereby 10 mol% or more of the aminosilane compound (or a hydrolyzed derivative thereof) is obtained.
  • amide bonds can be formed at 50 mol% or more.
  • the reaction product thus obtained may be one in which 100 mol% of the aminosilane compound (or a hydrolyzed derivative thereof) used as a raw material forms an amide bond.
  • reaction solvent any solvent can be used as long as the above dehydration reaction is not hindered.
  • aromatic solvents such as toluene and xylene, ketone solvents such as cyclohexane, and mixtures thereof are appropriately used.
  • ketone solvents such as cyclohexane, and mixtures thereof are appropriately used.
  • an optional component can be added as necessary.
  • One of the optional components is a silicone resin (hereinafter referred to as “Component C”).
  • Component C alkoxysilyl group moiety reactive (usually dehydration reaction and / or dealcoholization reaction, etc.) which may be functional groups of component A, for example, an alkoxysilyl group Ya reactive silicone resin having a silanol group and the like c as this
  • a reactive silicone resin can be easily synthesized by a partial hydrolysis reaction of an alkoxysilane or chlorosilane and a subsequent condensation reaction.
  • silicone varnish for example, trade name “X ⁇ 7931—Clear”: manufactured by Okitsumo Co., Ltd.
  • silicone resin for example, trade name “SR2410”: Toray's Daukoichi Nylon Silicone Co., Ltd.
  • acrylic-modified silicone resin for example, trade name "Silacoat 100": manufactured by Chidso Corp.
  • the silicone resin can be used in the form of a solution using various solvents as long as the object of the present invention is not impaired.
  • the solvent include, but are not particularly limited to, various hydrocarbon solvents, ketones, ethers, esters, ethers and esters.
  • a silicone resin modified in various ways may be used.
  • component C can be added to the reaction product of component A and component B, it is particularly preferable that both components coexist in the reaction system when reacting both components.
  • the amount of the silicone resin used is generally selected in the range of 5 to 300 parts by mass, preferably 20 to 150 parts by mass, based on the total amount of the components A and B.
  • component D Another one of the optional components is various epoxysilanes (hereinafter referred to as “component D”). And preferred are epoxysilanes represented by the following general formulas (7) and (8).
  • R 9 and R 11 are the same or different groups and have an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or a compound of the formula R-0-R ' (Wherein, R and R, each represent an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms).
  • each R 10 is the same or different and is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or It represents an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.
  • at least one of all R 0 is an alkoxy group, preferably 1 to 5 is an alkoxy group.
  • n is an integer of n ⁇ 0, preferably 0 ⁇ n ⁇ 3.
  • Preferred examples of the alkylene group include a methylene group, a trimethylene group, and a tetramethylene group.
  • Preferred examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group, a pentyloxy group, and a hexyloxy group.
  • aryl group examples include a phenyl group and a tril group. No.
  • epoxysilanes include 3-glycidoxyprovirt trimethoxysilane, dimethoxy-3-glycidoxypropylmethylsilane, 2- (3: 4-epoxycyclohexylethyl) trimethoxysilane, dimethylethoxy-3- Glycidoxypropyl silane, 1,3-bis (3-glycidoxypropyl) — 1,3-dimethyl-11,3-dimethoxydisiloxane or a mixture thereof is preferred.
  • the amount of the epoxysilane to be used is generally selected in the range of 100 to 500 parts by mass, preferably 100 to 400 parts by mass, based on the total amount of the components A and B.
  • the epoxysilanes of Component D may be used after being hydrolyzed in advance.
  • the epoxy group may be previously subjected to ring polymerization with an appropriate polymerization catalyst and used.
  • a Lewis acid catalyst such as boron trifluoride getyl ether complex, aluminum chloride, and getyl zinc is preferable.
  • the polymerization conditions for the cyclic polymerization of the epoxy group are not particularly limited, but are usually about -80 ° C to 130 ° C, preferably about -20 ° C to 80 ° C.
  • the time can be appropriately selected depending on the reaction conditions, reaction mode, and the like, and is usually about 10 minutes to 10 hours, preferably about 1 hour to 6 hours.
  • the solvent used at this time is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, and various ketones and esters.
  • Component D can be present in the reaction system of component A and component B, but is preferably added to the reaction product of both components. However, when the component D is obtained by preliminarily ring-opening polymerizing the epoxy group, it is preferably added during the reaction of the components A and B. Still another optional component is a polyether-modified polysiloxane (hereinafter referred to as “component E”), preferably a polyester-modified polysiloxane represented by the following general formula (9). It is.
  • component E polyether-modified polysiloxane
  • R 1 2, R 1 3 and R 1 4 are the same or different groups, 1 to carbon atoms 1 0, preferably an alkylene group of 1 to 5, R 1 3 are the same Or a different group, such as a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms,
  • n and p are each an integer m ⁇ 0, preferably 0 m ⁇ 100, n ⁇ 0, preferably 0 ⁇ n ⁇ 10, p ⁇ 0, preferably 0 ⁇ p ⁇ 10 Is shown.
  • Preferable examples of the alkylene group include a methylene group, a trimethylene group, and a tetramethylene group.
  • Preferred examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group, a pentyloxy group, and a hexyloxy group.
  • Examples of the aryl group include a phenyl group and a tolyl group.
  • the amount of the polyether-modified polysiloxane to be used is generally selected in the range of 100 to 500 parts by mass, preferably 100 to 400 parts by mass, based on the total amount of the components A and B. .
  • polyether-modified polysiloxane represented by the above general formula (9) examples include tetraethylene glycol-bis (triethoxysilylethyl) ether and polyethylene glycol-bis (triethoxysilylethyl) A. And polypropylene glycol-bis (triethoxysilylethyl) ether or a mixture thereof.
  • the polyether-modified polysiloxane may be used after being hydrolyzed in advance.
  • component E can be added to the reaction product of component A and component B, it is preferable that component A and component B coexist in the reaction system when reacting.
  • component F an inorganic fine particle dispersion
  • component F includes, for example, silica, alumina, titanium oxide, and antimony oxide. And the like.
  • Fine particle size is 1 ⁇ It is about 100 nm, and examples of the dispersion medium include water, methanol, xylene, and methyl ethyl ketone.
  • Commercially available products include LUDOXLS (manufactured by DuPont) and XBA-ST (manufactured by Nissan Chemical Industries).
  • the amount used is generally selected from the range of 5 to 400 parts by mass, preferably 10 to 200 parts by mass, based on the total amount of the components A and B. .
  • Component F can coexist during the reaction of component A and component B, but is preferably added to the reaction product of component A and component B.
  • Component F has the effect of improving the surface hardness of the ultraviolet absorbing layer formed on the transparent substrate and improving the abrasion resistance, chemical resistance, and the like.
  • Each of the above-mentioned optional components can be manufactured by a known method.
  • the ultraviolet absorbing layer provided on the laminated fireproof plate of the present invention is obtained by reacting component A and component B in a reaction system in which one or more of the above-mentioned optional components coexist as necessary.
  • the obtained reaction product is used as a paint, or a composition obtained by adding one or more of the above-mentioned optional components to the reaction product of component A and component B as necessary is used as a paint, and this is made transparent. It can be formed by coating and curing the surface of the substrate. In this case, the reaction solvent contained in the paint can be partially or entirely removed prior to application.
  • Additives can be added to the above-mentioned paints as needed.
  • additives include antioxidants, quencher or radical scavengers, or hydrochloric acid, sulfuric acid, acetic acid, and the like.
  • the above-mentioned paint is usually in a liquid state, and when applying it to a transparent substrate, for example, a spin coat, a spray coat, a dip coat, a cast coat, a blade coat, a flow coat, etc. can be arbitrarily adopted. is there.
  • the curing of the coating film usually proceeds at room temperature to 250 ° C., preferably about 40 ° C. to 200 ° C. Further, even when no catalyst is contained, the reaction usually proceeds at room temperature to 350 ° C, preferably at about 60 ° C to 250 ° C.
  • the time required for curing is generally about 10 minutes to 5 hours in each case.
  • the thickness of the ultraviolet absorbing layer formed on the transparent substrate can be arbitrarily selected, but is usually selected within a range of about 0.5 to 50 zm. When the thickness is less than 0.5 m, it may be difficult to provide the cured coating film with a sufficient ultraviolet blocking ability, and when the thickness is more than 50 / m, cracks may occur in the cured coating film.
  • the UV-absorbing fireproof plate of the present invention can cut most or all of the transmitted light in the UV region of 300 to 40 O nm, specifically 95% or more, in a preferred embodiment.
  • the transmitted light in the ultraviolet region of 98% or more, more preferably 99% or more can be cut in a more preferred embodiment.
  • the ultraviolet absorbing layer formed on the transparent substrate of the present invention is substantially transparent, hardly or at all reduces the transmittance of the substrate in the visible region, and is transparent as a final ultraviolet absorbing fireproof plate. It is something.
  • the visible light transmittance of the UV-absorbing fireproof plate according to the present invention is in the range of 10 to 100%.
  • overcoating agents can be used, and among them, a silicon-based overcoating agent is most suitable.
  • silicone-based overcoating agent include silicone resin-based materials in which inorganic fine particles such as colloidal silica are dispersed, and products of partial hydrolysis and partial polycondensation of silanes such as alkoxysilane and chlorosilane.
  • commercially available products include Tosgard 510 (made by Toshiba Silicone), APZ7703, and APZ7705 (made by Nippon Tunicar).
  • the partial hydrolysis products of epoxy silane are abrasion resistant as overcoating agents. 51
  • the overcoat layer a known method can be appropriately adopted, and for example, a spin coat, a spray coat, a cast coat, a blade coat, a dip coat and the like can be arbitrarily selected.
  • the same method as in the case of the ultraviolet absorbing layer can be applied to the curing of the coating film.
  • the UV-absorbing layer is subjected to a light surface modification and primer treatment to improve the coatability of the overcoat material and the adhesion of the overcoat layer to the UV-absorbing layer. Can be improved.
  • a thin film of a metal oxide or the like having a heat ray reflecting function or a heat insulating function can be further formed on the surface thereof by a method such as vacuum evaporation, sputtering, or a sol-gel method.
  • a heat ray reflecting function and a heat insulating function can be provided.
  • the ultraviolet-absorbing fireproof fire-resistant plate of the present invention comprises a single-layer or two-layer laminate having a foam layer containing a heat-sensitive foaming agent between transparent substrates juxtaposed at intervals in the thickness direction. It consists of two or more layers, usually about 2 to 5 layers, and has an amide bond obtained by reacting component A and component B on at least one of the transparent substrates used. Except for providing a cured coating film of the reaction product, it can be produced by a known method.
  • the heat-sensitive foaming agent is not particularly limited as long as the object of the present invention is achieved, but is usually 30 ° ((800 ° C., preferably 100 ° C. to 600 ° C.).
  • Preferred are compounds that foam in response to heat in the temperature range of:
  • Examples include hydrated alkali metal salts such as aluminum potassium, sodium borate, potassium borate, and sodium orthophosphate; hydrated alkali metal silicates such as sodium silicate; and mixtures of two or more of these.
  • the foamed layer contains a heat-sensitive foaming agent, and is typically made of a heat-sensitive foaming agent, but may be composed of a composition of a heat-sensitive foaming agent and another compound. .
  • the thickness of the layer is not particularly limited as long as the object of the present invention is achieved, but is usually 0.1 to 50 mm, preferably 0.8 to 10 mm.
  • the light foam layer preferably has a light-transmitting property, and more preferably has transparency.
  • the method for forming the foamed layer is not particularly limited, but a method of applying and drying various solutions (typically, an aqueous solution) of the heat-sensitive foaming agent is mentioned as a suitable method.
  • FIG. 1 is a cross-sectional view of a UV-absorbing fireproof plate according to the present invention having a single foam layer.
  • FIG. 2 is a cross-sectional view of a UV-absorbing fireproof plate according to the present invention having a plurality of foam layers.
  • FIG. 3 is a graph showing an ultraviolet-visible absorption spectrum of the ultraviolet absorbing transparent plate produced in Example 1.
  • FIG. 4 is a graph showing an ultraviolet-visible absorption spectrum of the ultraviolet absorbing transparent plate produced in Example 3.
  • FIG. 5 is a graph showing an ultraviolet-visible absorption spectrum of the ultraviolet absorbing transparent plate produced in Example 4.
  • FIG. 6 is a graph showing an ultraviolet-visible absorption spectrum of the ultraviolet absorbing transparent plate produced in Example 5.
  • FIG. 7 is a graph showing an ultraviolet-visible absorption spectrum of the ultraviolet absorbing transparent plate produced in Example 6.
  • FIG. 8 is a graph showing an ultraviolet-visible absorption spectrum of the ultraviolet absorbing transparent plate produced in Example 7. Next, a typical structure of the ultraviolet-absorbing fire-resistant transparent plate according to the present invention will be described with reference to FIGS. 1 and 2.
  • FIG. 8 is a graph showing an ultraviolet-visible absorption spectrum of the ultraviolet absorbing transparent plate produced in Example 7.
  • the basic structure of the UV-absorbing fireproof plate of the present invention is such that a foamed layer 3 is provided between a transparent substrate 1 a having an ultraviolet-absorbing layer 2 and a transparent substrate 1 b opposed thereto. There is in the structure sandwiched.
  • the ultraviolet absorbing layer 2 provided on the transparent substrate may be located on the outside world side, but is preferably located on the foam layer side as shown in view of durability.
  • Fig. 2 shows a cross section of an ultraviolet-absorbing fire-resistant transparent plate obtained by laminating two foam layers on the basic structure shown in Fig. 1 with a transparent substrate interposed therebetween.
  • the number of foam layers may be one, or may be three or more.
  • the ultraviolet absorbing layer 2 is provided on the transparent substrate 1a located on the outdoor side, but the ultraviolet absorbing layer 2 is also provided on one or more of the transparent substrates lb, lc, 1d. Can be provided.
  • the ultraviolet-absorbing fire-resistant transparent plate of the present invention can be manufactured by any method. Taking the specific example shown in FIG. 1 as an example, a solution of a heat-sensitive foaming agent is applied on the ultraviolet absorbing layer formed on the transparent substrate la (that is, on the ultraviolet absorbing transparent plate) or on the transparent substrate 1b. After drying and forming a solid layer of a heat-sensitive foaming agent directly on the transparent substrate, the transparent substrate 1b or the transparent substrate 1a with an ultraviolet / ultraviolet absorbing layer can be produced by a method of combining. Also, a separately formed foam layer (film-like material) is applied on the ultraviolet absorbing layer formed on the transparent substrate 1a (that is, on the ultraviolet absorbing transparent plate) or on the transparent substrate 1b.
  • a fireproof plate having the structure shown in Fig. 2 can be manufactured by repeating the same procedure as above.
  • Preferred embodiments of the ultraviolet-absorbing fireproof plate of the present invention include the following embodiments.
  • the UV-absorbing layer-forming paint is reacted with at least (a) the aminosilane compound represented by the general formula (1) or a derivative thereof, and (b) the UV-absorbing compound having a carboxylic acid residue in the molecule.
  • the fireproof plate for absorbing ultraviolet light according to the present invention is obtained by performing the treatment in the presence of the silicone resin.
  • the ultraviolet-absorbing layer-forming paint is reacted with at least (a) an aminosilane compound or a derivative thereof represented by the general formula (1), and (b) an ultraviolet-absorbing compound having a carboxylic acid residue in the molecule;
  • the ultraviolet-absorbing fireproof plate according to the present invention which is obtained by forming an amide bond derived from the aminosilane and then further adding the epoxysilane.
  • the UV-absorbing layer forming paint is at least (a) represented by the general formula (1) An aminosilane compound or a derivative thereof, and (b) reacting an ultraviolet absorbing compound having a carboxylic acid residue in the molecule to form an amide bond derived from the aminosilane, and further adding colloidal silica.
  • An ultraviolet-absorbing fire-resistant plate according to the present invention which is obtained.
  • the UV-absorbing fireproof plate of the present invention maintains good durability even when a high concentration of the absorbing compound is contained, by bonding the UV-absorbing compound to the silicone resin as a base material through an amide bond. However, it is possible to cut clearly into the long wavelength region with almost no decrease in transmittance in the visible region.
  • the above-mentioned paint for forming an ultraviolet absorbing layer was spray-coated on a glass substrate, left at room temperature for 20 minutes, and then heated at 200 ° C for 20 minutes to produce an ultraviolet absorbing glass having an ultraviolet absorbing film having a thickness of about 1 am. .
  • FIG. 3 shows the ultraviolet-visible absorption spectrum of this ultraviolet absorbing glass. As shown in the spectrum, a glass substrate completely blocking ultraviolet light of 40 Onm or less was obtained.
  • the obtained UV-absorbing fire-resistant glass had transparency and had the same UV-blocking ability as the above-mentioned UV-absorbing transparent plate.
  • a fire prevention test of JIS-R 3204 was conducted using this UV-absorbing fireproof glass, good results were obtained.
  • the coating solution was spray-coated on a glass substrate, allowed to stand at room temperature for 20 minutes, and then heated at 130 ° C. for 30 minutes to produce an ultraviolet absorbing glass having an ultraviolet absorbing film having a thickness of about 10 / m.
  • Example 1 When the UV-visible absorption spectrum of this UV-absorbing glass was measured, Example 1 was obtained. In the same manner as described above, a glass substrate capable of completely blocking ultraviolet rays was obtained.
  • an ultraviolet absorbing fireproof glass was produced in the same manner as in Example 1.
  • the obtained UV-absorbing fire-resistant glass had transparency and had the same UV-blocking ability as the above-mentioned UV-absorbing transparent plate. Using this UV absorbing fireproof glass
  • Silicone varnish (XO-793 1-clear, manufactured by OKITSUMO) 17.7 g and 3 g of 3-aminopropyltriethoxysilane were dissolved in xylene 35, and compound I was heated at 80 ° C while heating. Was gradually added. After the addition was completed, the temperature was raised to 130 ° C., and the mixture was refluxed for 3 hours to obtain a solution-type ultraviolet absorbing coating solution.
  • the above-mentioned coating material for forming an ultraviolet absorbing layer is spray-coated on a glass substrate, left at room temperature for 20 minutes, and then heated at 200 ° C. for 20 minutes to obtain an ultraviolet ray having an ultraviolet absorbing film having a thickness of about 17 zm. An absorption glass was produced. When a cross-cut test was performed on this ultraviolet absorbing glass, 50% peeling was observed.
  • FIG. 4 shows the ultraviolet-visible absorption spectrum of this ultraviolet absorbing glass. As shown in the spectrum, a glass substrate that completely blocks ultraviolet light of 40 O nm or less was obtained. The pencil hardness was 2H.
  • an ultraviolet absorbing fireproof glass was produced in the same manner as in Example 1.
  • the obtained UV-absorbing fireproof glass has transparency, and the UV-absorbing transparent glass described above. It had the same ultraviolet blocking ability as a bright plate. Using this UV absorbing fireproof glass
  • the ultraviolet-absorbing layer forming paint is spray-coated on a glass substrate, left at room temperature for 20 minutes, and then heated at 200 ° C for 20 minutes to produce an ultraviolet-absorbing glass having an ultraviolet-absorbing coating having a thickness of about 17 / m. did.
  • FIG. 5 shows the UV-visible absorption spectrum of this glass substrate. Further, as in Example 3, no peeling was observed in the cross-cut test.
  • an ultraviolet absorbing fireproof glass was produced in the same manner as in Example 1.
  • the obtained UV-absorbing fire-resistant glass had transparency and had the same UV-blocking ability as the above-mentioned UV-absorbing transparent plate.
  • a fire prevention test of JIS-R 3204 was conducted using this UV-absorbing fireproof glass, good results were obtained.
  • Silicone varnish (X-1 7931—clear, manufactured by Okitsumo) 17.7 g and 3 g of 3-aminopropyltriethoxysilane are dissolved in 35 g of xylene, and 5 g of compound I is gradually added while heating to 80 ° C. did. After the addition was completed, the temperature was raised to 130 ° C and refluxed for 3 hours. After cooling, add 16 g of 3-glycidoxyprovirt rimethoxysilane and 8 g of colloidal silica dispersion (Nissan Chemical Industries, MIBK-ST) and add purple. A paint for forming an external line absorbing layer was obtained.
  • the above-mentioned coating material for forming an ultraviolet absorbing layer was spray-coated on a glass substrate, allowed to stand at room temperature for 20 minutes, and then heated at 200 ° C. for 20 minutes to produce an ultraviolet absorbing glass having an ultraviolet absorbing film having a thickness of about 17 m. .
  • the pencil hardness was 4H.
  • FIG. 6 shows the UV-visible absorption spectrum of this glass substrate.
  • an ultraviolet absorbing fireproof glass was produced in the same manner as in Example 1.
  • the obtained UV-absorbing fire-resistant glass had transparency and had the same UV-blocking ability as the above-mentioned UV-absorbing transparent plate.
  • a fire prevention test of JIS-R3204 was performed using this UV-absorbing fireproof glass, good results were obtained.
  • Silicone varnish (XO-7931—clear, manufactured by OKIMO) 17.7 g and 3 g of 3-aminopropyltriethoxysilane were dissolved in 29 g of xylene, and 5 g of compound I was gradually added while heating to 80 ° C. . After the addition was completed, the temperature was raised to 130 ° C and refluxed for 3 hours. After cooling, 22 g of the above epoxysilane polymer solution was added to obtain a coating for forming an ultraviolet absorbing layer.
  • the coating solution for forming the UV absorbing layer in the form of a solution was applied as a coating solution on a glass substrate by spraying, left at room temperature for 20 minutes, and then heated at 150 ° C for 30 minutes to obtain a UV light having a thickness of about 15 / m.
  • a glass substrate having an absorption layer was produced. Pencil hardness is 6H Was.
  • FIG. 8 shows the UV-visible absorption spectrum of this glass substrate.
  • an ultraviolet absorbing fireproof glass was produced in the same manner as in Example 1.
  • the obtained UV-absorbing fire-resistant glass had transparency and had the same UV-blocking ability as the above-mentioned UV-absorbing transparent plate. Using this UV-absorbing fire-resistant glass, a fire prevention test of JIS-R320 was performed, and good results were obtained.
  • the coating solution for forming the ultraviolet absorbing layer in the form of a solution was coated as a coating solution on a glass substrate by spraying, left at room temperature for 20 minutes, and then heated at 150 ° C. for 30 minutes to obtain a thickness of about 1
  • a glass substrate provided with a 5 ⁇ m ultraviolet absorbing layer was produced.
  • the pencil hardness was 5H.
  • FIG. 8 shows the UV-visible absorption spectrum of this glass substrate.
  • an ultraviolet absorbing fireproof glass was produced in the same manner as in Example 1.
  • the obtained UV-absorbing fireproof glass had transparency and had the same UV-blocking ability as the above-mentioned UV-absorbing transparent plate. Using this UV-absorbing fireproof glass, a fireproof test of JIS-R320 was performed, and good results were obtained.

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Silicon Polymers (AREA)

Abstract

Cette invention se rapporte à une plaque transparente ignifuge et résistant au feu, absorbant les ultraviolets, qui est constituée par plusieurs feuilles de base transparentes espacées dans le sens de l'épaisseur de la plaque, une ou plusieurs couches extensibles qui sont situées entre (ou parmi) les feuilles de base et qui contiennent un agent d'expansion thermosensible, et une couche absorbant les ultraviolets qui possède des liaisons amide d'un composé aminosilane et qui est située sur au moins l'une des feuilles de base.
PCT/JP1999/000042 1998-01-09 1999-01-08 Plaque transparente ignifuge et resistant au feu, absorbant les ultraviolets WO1999035102A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/14943 1998-01-09
JP1494398A JPH11199278A (ja) 1998-01-09 1998-01-09 紫外線吸収防耐火透明板

Publications (1)

Publication Number Publication Date
WO1999035102A1 true WO1999035102A1 (fr) 1999-07-15

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PCT/JP1999/000042 WO1999035102A1 (fr) 1998-01-09 1999-01-08 Plaque transparente ignifuge et resistant au feu, absorbant les ultraviolets

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JP (1) JPH11199278A (fr)
WO (1) WO1999035102A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1398147A1 (fr) 2002-09-13 2004-03-17 Scheuten Glasgroep Unité de vitrage pare-feu

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4730886B2 (ja) * 2005-06-01 2011-07-20 信越化学工業株式会社 紫外線吸収性基含有オルガノポリシロキサン、該ポリシロキサンの製造方法、及び該ポリシロキサンを配合してなる処理剤
WO2007099784A1 (fr) * 2006-02-24 2007-09-07 Idemitsu Kosan Co., Ltd. Composition de revetement, film durci et lamine de resine
TW201204820A (en) * 2010-07-16 2012-02-01 Sequoia Radcure Co Ltd Heat dissipation formulation
JP6557075B2 (ja) * 2015-07-06 2019-08-07 株式会社日本触媒 シロキサン化合物の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0340944A (ja) * 1989-07-06 1991-02-21 Fujita Corp 多機能ガラス
JPH05238785A (ja) * 1992-03-02 1993-09-17 Sekisui Chem Co Ltd フォトクロミックガラスおよびフォトクロミック合わせガラス
JPH08210041A (ja) * 1994-10-07 1996-08-13 Flachglas Ag 耐火グレイジングユニット

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0340944A (ja) * 1989-07-06 1991-02-21 Fujita Corp 多機能ガラス
JPH05238785A (ja) * 1992-03-02 1993-09-17 Sekisui Chem Co Ltd フォトクロミックガラスおよびフォトクロミック合わせガラス
JPH08210041A (ja) * 1994-10-07 1996-08-13 Flachglas Ag 耐火グレイジングユニット

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1398147A1 (fr) 2002-09-13 2004-03-17 Scheuten Glasgroep Unité de vitrage pare-feu
WO2004024441A1 (fr) * 2002-09-13 2004-03-25 Scheuten Glasgroep Unite de vitrage coupe-feu
JP2006506302A (ja) * 2002-09-13 2006-02-23 ショイテン グラースグループ 耐火窓ガラスユニット
US7340869B2 (en) 2002-09-13 2008-03-11 Scheuten Glagroep Bv Fireproof glazing unit
JP4707392B2 (ja) * 2002-09-13 2011-06-22 ショイテン グラースグループ 耐火窓ガラスユニット

Also Published As

Publication number Publication date
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