WO1999035102A1 - Ultraviolet-absorbing fire-proof and -resistant transparent plate - Google Patents

Abstract

An ultraviolet-absorbing fire-proof and -resistant transparent plate consituted of a plurality of transparent base sheets spaced in the direction of plate thickness, one or more expandable layers which lie between (or among) the base sheets and contain a heat-sensitive expanding agent, and an ultraviolet-absorbing layer which has amide linkages of an aminosilane compound and lies on at least one of the base sheets.

Description

 Description Ultraviolet absorbing fireproof transparent board

 〔Technical field〕

 The present invention relates to a transparent laminated fireproof plate provided with an ultraviolet absorbing ability.

 [Conventional technology]

 There are two methods for imparting UV-absorbing property to a transparent substrate such as a glass plate: (1) a method of treating a transparent substrate with an ultraviolet-absorbing substance, and (2) a method of using multiple reflection by a multilayer film. Generally known. The multi-reflection by the multilayer film (2) is excellent in that the cutoff wavelength can be freely adjusted and the clear cut is possible, but the formation of the multilayer film requires many work steps and is costly. is there. 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.

 JP-A-5-339033, JP-A-5-345639, JP-A-6-56464, etc.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.

 On the other hand, 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. To date, 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. There are two ways to increase the film thickness. However, 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. In addition, in the technique described in 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.

Among organic UV absorbers, 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. However, when these UV absorbers are mixed with resin and applied, the thickness of the coating film is limited to several m. To cut to the long wavelength region with this film thickness, 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.

 Therefore, many attempts have been made to react the ultraviolet absorber with the resin to avoid the above-mentioned disadvantages. One example is the copolymerization of an acrylic resin or the like with an ultraviolet absorber (see Japanese Patent Application Laid-Open Nos. 2-248412 and 6-88064), but the acrylic resin itself. However, due to poor weather resistance and heat resistance, it is not possible to obtain an ultraviolet absorbing layer that can withstand very long-term use. In addition, various studies have been made on ultraviolet absorbers that can react with silicone resins having excellent weather resistance and heat resistance.

1 _ 5480 0, No. 2-1 1 7 9 28, No. 3-4 5 0 9 4) _c However, the synthesis of this type of UV absorber is industrial In practice, it is difficult to combine them, and there is a problem in durability even if they can be synthesized.

 [Detailed Description of the Invention]

 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.

 That is, 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. Wherein at least one of the transparent substrates used for the laminated fireproof transparent plate has an ultraviolet absorbing layer on its surface, and the ultraviolet absorbing layer has

 (a) an aminosilane compound represented by the following general formula (1) or a derivative thereof (hereinafter referred to as component A):

(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.

(Wherein, 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] And each R ² is the same or different, and represents a hydrogen atom, a hydroxyl group, a halogen atom,

And represents an alkyl group having 0 or an alkoxy group having 1 to 10 carbon atoms. However, at least one of all R ² represents an alkoxy group. n represents an integer of n≥0. 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.

 As the transparent substrate, 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. Specifically, for example, 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. However, inorganic glass is suitable for the transparent substrate used in the present invention because of its excellent fire and fire resistance.

 As described above, 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. 1) An aminosilane compound represented by the formula or a derivative thereof.

In the general formula (1), 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.

 Preferable specific examples of the 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.

 As the component A, a derivative of the aminosilane compound represented by the general formula (1) can be used. As the derivative, a hydrolyzate of the aminosilane compound represented by the general formula (1) is preferably used.

 As the component B used together with the component A for forming the ultraviolet absorbing layer, an ultraviolet absorbing compound having at least one carboxyl group in the molecule is used. 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).

In the 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, and 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. 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, 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. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and examples of the alkylidene group 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).

OH 0

(Four) W / 351

一般式 （ 3 ) 〜 （ 6 ) において、 R ⁶は炭素数 1〜 1 0、 好ましくは 1〜 3 のアルキレン基又はアルキリデン基を示す。アルキレン基としては、 メチレン基、 エチレン基、 トリメチレン基、 プロピレン基等が、 アルキリデン基としてはェチ リデン基、 プロピリデン基等が挙げられる。

In the 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. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Examples of the 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. Preferably, amide bonds can be formed at 50 mol% or more. Needless to say, 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.

 As the reaction solvent, any solvent can be used as long as the above dehydration reaction is not hindered.For example, aromatic solvents such as toluene and xylene, ketone solvents such as cyclohexane, and mixtures thereof are appropriately used. Can be used.

Upon the reaction between the component A and the component B, or to the reaction product, an optional component can be added as necessary. One of the optional components is a silicone resin (hereinafter referred to as “Component C”). Of these, 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 In general, a reactive silicone resin can be easily synthesized by a partial hydrolysis reaction of an alkoxysilane or chlorosilane and a subsequent condensation reaction. Commercially available products include pure silicone varnish (for example, trade name “X〇7931—Clear”: manufactured by Okitsumo Co., Ltd.) and silicone resin (for example, trade name “SR2410”: Toray's Daukoichi Nylon Silicone Co., Ltd.), and 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. Examples of the solvent include, but are not particularly limited to, various hydrocarbon solvents, ketones, ethers, esters, ethers and esters. Further, a silicone resin modified in various ways may be used. Although 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.

一般式 （ 7 ) 〜 （ 8 ) において、 R ⁹および R ^{1 1}は同一若しくは異なる基 であって、 炭素数 1〜 1 0、 好ましくは 1〜 5のアルキレン基又は式一 R— 0— R ' 一 （但し、 R及び R， は各々炭素数 1〜 1 0、 好ましくは 1〜 5のアルキ レン基を示す） で示される 2価の基を示す。 また、 各々の R ^{1 0}は、 同一若し くは異なる基であって、 水素原子、 水酸基、 ハロゲン原子、 炭素数 1〜 1 0、 好 ましくは 1〜 5のアルキル基若しくはアルコキシ基、 または炭素数 6〜 1 0好ま しくは 6〜 8のァリール基を示す。 但し、 全ての R 0のうち少なく とも 1つ はアルコキシ基、 好ましくは 1〜 5個はアルコキシ基である。 nは n≥0、 好ま しくは 0≤n≤ 3の整数を示す。 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).

In the general formulas (7) to (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). Further, 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. However, 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. 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 tril group. No.

Specific examples of 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. Further, the epoxy group may be previously subjected to ring polymerization with an appropriate polymerization catalyst and used. As the polymerization catalyst, 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.

一般式 （ 9 ) において、 R ^{1 2}、 R ^{1 3}および R ^{1 4}は同一若しくは異なる 基であって、 炭素数 1〜 1 0、 好ましくは 1〜 5のアルキレン基を示し、 R ^{1 3}は同一若しくは異なる基であって、 水素原子、 水酸基、 ハロゲン原子、 炭素 数 1〜 1 0、 好ましくは 1〜 5のアルキル基若しくはアルコキシ基または炭素数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. (9)

In the general formula ^{(9), 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,

6 to 10, preferably 6 to 8 aryl groups, at least ^one of R ¹³ One, preferably 2 to 10, is an alkoxy group. m, 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. .

 Specific examples of the polyether-modified polysiloxane represented by the above general formula (9) include tetraethylene glycol-bis (triethoxysilylethyl) ether and polyethylene glycol-bis (triethoxysilylethyl) A. And polypropylene glycol-bis (triethoxysilylethyl) ether or a mixture thereof. As the component E, the polyether-modified polysiloxane may be used after being hydrolyzed in advance.

 Although 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.

Among the above optional components, particularly the epoxysilanes of component D and the polyether-modified polysiloxanes of component E are transparent to the ultraviolet absorbing layer formed on the transparent substrate without impairing the heat resistance. It has excellent effects such as improving the adhesion to the substrate and suppressing the occurrence of cracks in the ultraviolet absorbing layer. Still another optional component that can be used in the present invention is an inorganic fine particle dispersion (hereinafter, referred to as “component F”), which 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).

 When colloidal silica is used as the component F, 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. Examples of such additives include antioxidants, quencher or radical scavengers, or hydrochloric acid, sulfuric acid, acetic acid, and the like. Inorganic acids, organic acids, boron trifluoride / ethyl ester complex, Lewis acids such as sodium antimonate hexafluoride, bases such as potassium hydroxide, sodium hydroxide, triethylamine, aniline, dibutyltin dilaurate, titanium tetra A catalyst having a curing promoting action as exemplified by an organic metal such as isopropoxide (the amount used is usually preferably 0.1 to 5.0% by mass based on the ultraviolet absorbing material); Toluene, xylene, ethanol, isopropanol, dimethylformamide, cyclohexanone, 1-methoxy 2-a Tokishipuropan like, a solvent such as various thinners may be exemplified. 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.

 When a catalyst having a curing promoting action is contained in the coating film, 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.

 Further, 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. Incidentally, the visible light transmittance of the UV-absorbing fireproof plate according to the present invention is in the range of 10 to 100%.

 By providing an overcoat layer on the ultraviolet absorbing layer provided on the transparent substrate, functions such as abrasion resistance and chemical resistance can be imparted.

Various commonly known overcoating agents can be used, and among them, a silicon-based overcoating agent is most suitable. Examples of the 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. Specifically, commercially available products include Tosgard 510 (made by Toshiba Silicone), APZ7703, and APZ7705 (made by Nippon Tunicar). Also, the partial hydrolysis products of epoxy silane are abrasion resistant as overcoating agents. 51

It is known that they are superior. For forming 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. In addition, before the overcoat is produced, 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.

 In the overcoat layer, 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. Thus, a heat ray reflecting function and a heat insulating function can be provided.

 [0 0 1 5]

 As described above, 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: For example, potassium aluminate, potassium plumbate, sodium stannate, potassium stannate, sodium aluminum sulfate, sulfuric acid 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. In addition, 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.

 [Brief description of drawings]

 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.

As shown in FIG. 1, 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. In the example shown in the figure, 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. Alternatively, it is manufactured by a method of applying the transparent substrate 1a with an ultraviolet-ultraviolet absorbing layer on a foam layer. It goes without saying that a fireproof plate having the structure shown in Fig. 2 can be manufactured by repeating the same procedure as above.

 As described above, the present invention has been described in detail. Preferred embodiments of the ultraviolet-absorbing fireproof plate of the present invention include the following embodiments.

 (1) 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. In this case, 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.

 (2) 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.

(3) 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.

 Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to the examples.

 [Example 1]

Synthesis of UV absorbing compounds containing carboxylic acid residues

 225 g (0.46 mol) of 3- (5-chloro-2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoate Cutyl ester (TINUVIN 109, trade name, manufactured by Ciba-Geigy) was dissolved in 700 ml of acetone, 600 ml of a 2N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 24 hours. After adding 650 ml of 2N hydrochloric acid to make it acidic, the insolubilized product was separated by filtration and washed with distilled water until the filtrate became neutral. The product is vacuum dried and recrystallized from toluene to give 3- (5-chloro-2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl)- 4-Hydroxy-benzenepropanoic acid [Compound I] was obtained.

Manufacture of paint for forming UV absorbing layer

 3 g of 3-aminopropyl ethoxysilane was dissolved in 35 g of xylene, and 5 g of the 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 standing to cool, 16 g of 3-glycidoxypropyltrimethoxysilane was added to the mixture, and this was used as a coating for forming an ultraviolet absorbing layer.

When the obtained paint was analyzed by ^lciC- NMR, a carbonyl peak (about 173 ppm) derived from an amide bond was observed. 99/351

It was confirmed that there was an amide bond derived therefrom.

Formation of UV absorbing layer on transparent substrate

 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.

Preparation of UV absorbing fireproof glass

 Using an aqueous solution of sodium silicate as the foaming material, combining the above-mentioned ultraviolet absorbing glass and commercially available soda lime glass into a glass, and having a sodium silicate hydrate layer as the foaming layer. Glass was prepared.

 The obtained UV-absorbing fire-resistant glass had transparency and had the same UV-blocking ability as the above-mentioned UV-absorbing transparent plate. When a fire prevention test of JIS-R 3204 was conducted using this UV-absorbing fireproof glass, good results were obtained.

[Example 2]

Manufacture of paint for forming UV absorbing layer

3 g of 3-aminopropyltriethoxysilane was dissolved in 40 g of xylene, and while heating to 60 ° C., 5 g of the compound I obtained in Example 1 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-like coating for forming an ultraviolet absorbing layer. When the obtained coating solution was analyzed by ¹³ C-NMR, a carbonyl peak (about 173 ppm) derived from amide bonds was observed, and amide bonds derived from the raw material aminosilanes were present. It was confirmed.

Formation of UV absorbing layer on transparent substrate

 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.

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.

Preparation of UV absorbing fireproof glass

 Using the above-mentioned ultraviolet absorbing glass and commercially available soda lime glass, 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

When a fire prevention test was performed on JIS-R 3204, good results were obtained. [Example 3]

Manufacture of paint for forming UV absorbing layer

 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.

Formation of UV absorbing layer on transparent substrate

 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.

 Extraction of this UV-absorbing transparent substrate with boiling acetone for 24 hours showed almost no weight loss. From this, it was found that the ultraviolet absorbing compound was bonded to the resin via aminosilane.

Preparation of UV absorbing fireproof glass

 Using the above ultraviolet absorbing glass and commercially available soda lime glass, 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

When a fire prevention test was performed on JIS-R 3204, good results were obtained. [Example 4]

Manufacture of paint for forming UV absorbing layer

 17.7 g of silicone varnish (XO-7931-Clear, manufactured by Okitsumo) and 3 g of 3-aminopropyl ethoxysilane were dissolved in xylene 35, 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 standing to cool, 16 g of 3-glycidoxypropyltrimethoxysilane was added to obtain a coating for forming an ultraviolet absorbing layer.

Formation of UV absorbing layer on transparent substrate

 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.

Preparation of UV absorbing fireproof glass

 Using the above-mentioned ultraviolet absorbing glass and commercially available soda lime glass, 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. When a fire prevention test of JIS-R 3204 was conducted using this UV-absorbing fireproof glass, good results were obtained.

[Example 5]

Manufacture of paint for forming UV absorbing layer

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.

Formation of UV absorbing layer on transparent substrate

 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.

Preparation of UV absorbing double glazing

 Using the above-mentioned ultraviolet absorbing glass and commercially available soda lime glass, 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. When a fire prevention test of JIS-R3204 was performed using this UV-absorbing fireproof glass, good results were obtained.

[Example 6]

Epoxysilane polymerization

 Dissolve 200 g of 3-glycidoxyprovirtrimethoxysilane in 75 g of xylene, slowly add 4 ml of boron trifluoride / getyl ether complex at room temperature, and stir for 4 hours to allow polymerization of epoxy groups. went. The molecular weight of the obtained polymer was Mw = 3300 (in terms of polystyrene).

Manufacture of paint for forming UV absorbing layer

 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.

Formation of UV absorbing layer on transparent substrate

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.

Preparation of UV absorbing fireproof glass

 Using the above-mentioned ultraviolet absorbing glass and commercially available soda-lime glass, 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.

[Example 7]

Manufacture of paint for forming UV absorbing layer

 3 g of 3-aminopropyltriethoxysilane and 1 lg of the epoxysilane polymer solution of Example 6 were dissolved in 32 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 to obtain an ultraviolet ray absorbing material.

Formation of UV absorbing layer on transparent substrate

 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 μm ultraviolet absorbing layer was produced. The pencil hardness was 5H. FIG. 8 shows the UV-visible absorption spectrum of this glass substrate.

Preparation of UV absorbing fireproof glass

 Using the above-mentioned ultraviolet absorbing glass and commercially available soda lime glass, 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.

Claims

The scope of the claims 1. 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 an interval in the thickness direction of the fire-resistant transparent plate. At least one of the transparent substrates to be provided has an ultraviolet absorbing layer on its surface, and the ultraviolet absorbing layer  (a) an aminosilane compound represented by the following general formula (1) or a derivative thereof, R ² R ² H ₂ N-R ¹ -Si- † 0— Si--R ² (1) R ² R ² No ⁿ (Wherein, R ¹ represents an alkylene group having 1 to 10 carbon atoms, or a divalent group represented by the general formula — (CH ₂ ) _m -NH- [m is an integer of l≤m≤4], Each R ² is the same or different, and includes a hydrogen atom, a hydroxyl group, a halogen atom, And represents an alkyl group having 0 or an alkoxy group having 1 to 10 carbon atoms. However, at least one of all; ² represents an alkoxy group. n represents an integer of n≥0. ) (b) UV absorbing compound having a carboxyl group in the molecule A UV-absorbing fire-resistant fire-resistant transparent plate characterized by being formed by applying and curing a reaction product, which is obtained by reacting with an aminosilane compound or a derivative thereof to form an amide bond derived from an aminosilane compound, on the surface of a transparent substrate. . 2. The above-mentioned aminosilane compound or a derivative thereof is 3-aminopropyl ethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropylmethyljetoxysilane, 3-aminopropyl trichlorosilane, The ultraviolet absorption according to claim 1, wherein the ultraviolet absorption is selected from -aminopropylpolydimethylsiloxane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltris (methoxetoxyhetoxy) silane, and a hydrolyzate thereof. Fireproof transparent board. 3. The ultraviolet-absorbing fire-resistant transparent plate according to claim 1, wherein the ultraviolet-absorbing compound having a carboxyl group in the molecule is a benzotriazole compound represented by the following general formula (2).

(Wherein, R ³ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an alkylene group or an alkylidene group having 1 to 10 carbon atoms. ) Four. The UV-absorbing fire-resistant transparent plate according to claim 1, wherein the UV-absorbing compound having a carboxyl group in the molecule is any one of benzophenone compounds represented by the following general formulas (3) to (6).

OH 0 HO R ⁶ — COOH (Five) 6 OH O HO  HOOC- R (6) (In the formula, R ⁶ represents an alkylene group or an alkylidene group having 1 to 10 carbon atoms; 'And R ⁸ are the same or different and represent a hydroxyl group, an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and n and m are in the range of 0≤m≤3, 0 ^ η≤3. Indicates an integer. ) 5. The reaction product obtained by reacting the component (a) with the component (b) in the presence of a reactive silicone resin having an alkoxysilyl group or a silanol group in the ultraviolet absorbing layer is transparent. 3. The ultraviolet-absorbing fire-resistant transparent plate according to claim 1, which is formed by applying and curing the surface of the substrate. 6. 2. The ultraviolet absorbing and fireproof transparent plate according to claim 1, wherein the reaction product applied to the surface of the transparent substrate further contains an epoxysilane represented by the general formula (7) and / or (8).

(Wherein, R ⁹ and R ¹¹ are the same or different groups, and are an alkylene group having 1 to 10 carbon atoms or a group represented by the formula: R—0—R,-(where R and R are To 10 and preferably 1 to 5 alkylene groups). ¹⁰ are the same or different groups, and each represents a hydrogen atom, a hydroxyl group, a halogen atom, And represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. However, at least ^{one of} all R ¹⁰ is an alkoxy group, and n represents n 0, preferably an integer of 0 ≦ n ≦ 3. ) 7. The ultraviolet-absorbing fire-resistant transparent plate according to claim 1, wherein the reaction product applied to the surface of the transparent substrate further contains colloidal silica.