JPH06157080A - Smoky fireproof glass and its production - Google Patents

Abstract

(57) [Summary] [Constitution] The space of the double-layered glass-like structure is filled with an aqueous gel composition containing a polymer of the specified (meth) acrylamide derivative, a particulate metal oxide, an aqueous medium, etc., and is transparent. Smoke-shaped fireproof glass with a haze value of 10% or more by freezing and / or heating a special fireproof glass in a unique cycle. In addition, a manufacturing method such as freezing only at a specified temperature and time or repeating freezing and heating, and each treatment of only heating. [Effect] In addition to excellent fire protection performance, it is semi-transparent and opaque and has a lot of privacy. It also has anti-glare properties, heat insulation properties, and sound insulation properties. Obtained, stable over a long period of time, resistant to deterioration and deterioration, useful for construction, especially indoor walls or partitions.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a smoke-like fireproof glass obtained by filling a space of a multi-layer glass-like structure with a hydrogel and making the hydrogel look translucent to opaque, and a method for producing the same. Can be used for openings, doors, wall materials or interior materials in various high-rise buildings such as office buildings, hotels or department stores, and even when unfortunately a fire occurs, the flame is suppressed as much as possible to prevent the spread of fire. As well as becoming a fire wall to prevent, it is semi-transparent to opaque with moderately controlled transparency rather than conventional transparency, so for example there is a soft feeling and privacy can be secured, and also sound insulation, It is intended to provide a useful smoke-like fireproof glass having an antiglare property or a heat ray absorbing performance and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventional fireproof glass is a single plate glass of low thermal expansion glass, heat resistant glass or transparent crystallized glass, or double-layer glass in which water glass or aqueous gel is present in a double-layered space. Usually, most of them are transparent at room temperature and have high transparency, or they are aimed at high transparency.

Among them, examples of the above-mentioned double-layered glass-like fireproof glass include, for example, in a fire-resistant pane described in Japanese Patent Publication No. 60-24063, at least one acrylic acid is used in a space formed by two or more glass sheets. A substance containing a derivative and having a high heat of vaporization, for example, 65 to 95% by weight, and 1 to 20% by weight of a substance which is miscible and capable of forming a foam of a heat insulating property such as an alkali metal salt or an ammonium salt under a heat ray. It is disclosed that a gel containing and is filled.

Further, for example, in the light-transmitting flame blocking panel described in Japanese Patent Publication No. 61-24181, at least one glass and urea, polyhydric alcohol, monosaccharide,
At least one layer of a foamable flameproof material comprising a hydrated alkali metal silicate containing one or more auxiliary agents selected from polysaccharite, sodium phosphate, sodium aluminate, aluminum phosphate and colloidal silica Is disclosed.

Further, for example, in the heat insulating translucent combination glass disclosed in Japanese Patent Publication No. 47-1304, a solid water-containing alkali silicate is provided between at least two glass plates arranged in an overlapping manner. An intermediate layer comprising:
It is disclosed that it has a thickness of to 10 mm, it is also possible to start from a suspension consisting of alkaline silicate particles containing solid still water suspended in an aqueous alkali silicate solution, It is also described that a milky, yet translucent combination glass is obtained.

[0006]

[Problems to be Solved by the Invention] As described above, for example, the fire-resistant pane described in Japanese Patent Publication No. 60-24063 is
Not only is it transparent, but the soluble and effervescent salts contained in the gel itself are strongly alkaline, so there is a danger that it must be handled carefully and it is not environmentally friendly. It lacks high-temperature stability, is likely to be solubilized when exposed to a flame, and is likely to cause alteration of the acrylic acid derivative constituting the gel, and may cause corrosion depending on the holding material.

Further, for example, the light-transmissive flame blocking panel described in Japanese Patent Publication No. 61-24181 is basically transparent, and the period during which the temperature during foaming is substantially constant is extended to complete the foaming. To reduce the slope of the subsequent time / temperature curve,
When the layer is further modified at a constant temperature for a period of time and an auxiliary agent for lowering the foaming initiation temperature is used in an amount of, for example, 20% by weight or more, it becomes difficult to maintain transparency.

Further, for example, the heat insulating translucent combination glass described in Japanese Patent Publication No. 47-1304 has basically transparency, but it is a test for weather resistance or under high temperature and high humidity. After a period of time, it becomes cloudy,
It is hard to say that it is stable and has excellent light-transmitting properties for a long period of time.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and it is a specified polymer of (meth) acrylamide or a (meth) acrylamide derivative and a particulate metal oxide. A transparent gel of a more basic aqueous gel composition, by having at least translucent-like to opaque-like made by freezing treatment, has a suitable optimal smoke-like and privacy property, It has excellent fire resistance such as prevention of flame penetration, has high elasticity and sound insulation performance, and is also useful for anti-glare property and shielding of heat rays or cold radiation. Stable use for a long time at room temperature The present invention provides a smoke-like fireproof glass and a method for producing the smoke-like fireproof glass, which can be sufficiently adopted as, for example, so-called Class B fireproof doors as well as Class A fireproof doors.

That is, the present invention provides a fireproof glass in which a water-containing gel is filled in the space of a multi-layer glass-like structure,
General formula (I) or general formula (II)

[0011]

[Chemical 5]

[0012]

[0013]

[Chemical 6]

A haze value of 10 is obtained by at least freezing and / or heating the above-mentioned hydrogel consisting of a polymer of (meth) acrylamide or a (meth) acrylamide derivative represented by and a metal oxide fine particle.
Smoke-shaped fireproof glass characterized by having a content of at least%.

Further, in the method for producing a fireproof glass containing a hydrous gel, in which the hydrous gel is filled in the space of the multi-layered glass-like structure, the general formula (I) or the general formula (II) is used.

[0016]

[Chemical 7]

[0017]

[0018]

[Chemical 8]

The haze value of the above-mentioned hydrogel consisting of a polymer of (meth) acrylamide or a (meth) acrylamide derivative represented by
A method for producing smoke-like fireproof glass, which is characterized by at least freezing and / or heating so that the content of the smoked fireproof glass is at least 100%.

Alternatively, the freeze treatment is carried out sequentially from room temperature.
A method for producing a smoke-like fireproof glass, which comprises lowering the temperature to 10 ° C. or lower, maintaining the temperature for 1 hour or more in response to the low temperature, and then performing a low temperature treatment of successively returning to room temperature for at least one cycle.

Further, the heating treatment is sequentially performed from room temperature +
A method for producing a smoke-like fireproof glass, which comprises heating at 50 ° C. or higher, holding it for 1 hour or more in response to the heating, and then performing at least one cycle of a heating treatment for successively returning to room temperature.

Furthermore, the freeze treatment and the heating treatment are carried out by lowering the temperature from room temperature to a low temperature of -10 ° C or lower, holding the temperature for 1 hour or more, and then returning the temperature to room temperature. One cycle consists of heating to a temperature of + 50 ° C. or higher, holding the temperature for 1 hour or longer, and then returning it to room temperature one cycle. One cycle takes 2.5 hours or more, and at least 1 The present invention provides a method for producing a smoke-like fireproof glass, which is characterized in that the treatment is carried out for more than one cycle.

Here, as described above, the specific (meth) acrylamide derivative used in the present invention is represented by the above general formula (I) or (II), and specifically, for example, acrylamide and meta. Acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide,
N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloyl Examples thereof include piperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine and N-methacryloylmorpholine.

Among the above-mentioned monomers, those in which the polymer of the monomer exhibits temperature sensitivity in an aqueous solution, that is, those which are hydrophilic at low temperature and change to hydrophobic when heated. As, for example, N-ethyl acrylamide, N-methyl-N-ethyl acrylamide, N, N-diethyl acrylamide, N-
Methylmethacrylamide, Nn-propylacrylamide, N-methyl-N-ethylmethacrylamide, Nn-propylmethacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine,
Examples thereof include N-methacryloylpiperidine and the like, which are useful as raw materials for aqueous gel compositions for temperature-sensitive glass.

Further, as a water-based gel composition for producing fireproof glass, a monomer containing at least one of the above-mentioned monomers having a temperature sensitivity in an aqueous solution is useful as a raw material. is there.

The monomer constituting the composition of the present invention preferably contains at least one of the above-mentioned monomers. One or more monomers selected from the following crosslinkable monomers, hydrophilic monomers, ionic monomers and lipophilic monomers can be used together with the monomers. .

As the crosslinkable monomer, for example, a monomer having two or more unsaturated bonds in the molecule and an N-alkoxymethyl (meth) acrylamide derivative are crosslinked by post-treatment such as heating after polymerization. Monomers that form can also be used.

Specific examples of the crosslinkable monomer corresponding to the former include N, N'-methylenebisacrylamide and N, N-.
Diallyl acrylamide, triacrylic formal, N,
N-diacryloylimide, N, N-dimethacryloylimide, ethylene glycol acrylate, ethylene glycol dimethacrylate, various polyethylene glycol diacrylate, various polyethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, various polypropylene glycol diacrylate , Various polypropylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate,
1,4-butylene glycol dimethacrylate, glycerol dimethacrylate, neobenzyl glycol dimethacrylate, trimethylolpropane triacrylate,
Trimethylolpropane trimethacrylate, trimethylolethane triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane triacrylate, divinylbenzene, diallyl phthalate,
Urethane (meth) acrylate, polyester (meth)
Examples thereof include acrylate and epoxy acrylate.

The latter N-alkoxymethyl (meth) acrylamide derivative is N-hydroxymethyl (meth)
Other than acrylamide, for example, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-tert-butoxymethyl (meth) acrylamide and the like can be mentioned.

Examples of hydrophilic monomers include acrylamide, methacrylamide, N-methylacrylamide, N-
Methyl methacrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, diacetone acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, various methoxy polyethylene glycol (meth) acrylates, N -Vinyl-2-pyrrolidone and the like can be mentioned, and it is also possible to introduce vinyl acetate, glycidyl methacrylate and the like by copolymerization and hydrolyze them to impart hydrophilicity.

Examples of the ionic monomer include acrylic acid, methacrylic acid, itaconic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, 2 -Acrylamido-2-methyl-propanesulfonic acid, ethylene oxide-modified phosphoric acid (meth) acrylate and other acids and salts thereof, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethyl Examples thereof include amines such as aminoethyl acrylate, N, N-dimethylaminopropyl methacrylamide, N, N-dimethylaminopropyl acrylamide and salts thereof. Also various acrylates,
Methacrylate, acrylamide, methacrylamide,
It is also possible to introduce acrylonitrile or the like by copolymerization and hydrolyze it to impart ionicity.

Examples of the lipophilic monomer include N, N-di-n-
Propyl acrylamide, Nn-butyl acrylamide,
Nt-butyl acrylamide, Nn-hexyl acrylamide, Nn-hexyl methacrylamide, Nn-octyl acrylamide, Nn-octyl methacrylamide, N-tert-
Octyl acrylamide, N-dodecyl acrylamide,
N-alkyl (meth) such as Nn-dodecyl methacrylamide
Acrylamide derivative, N, N-diglycidyl acrylamide, N, N-diglycidyl methacrylamide, N- (4-Glyxidoxybutyl) acrylamide, N- (4-Glyxidoxybutyl) methacrylamide, N- (5- Glyxidoxypentyl) acrylamide, N- (6-glycidoxyhexyl) acrylamide and other N- (ω-glyxidoxylalkyl) (meth) acrylamide derivatives, ethyl acrylate, methyl methacrylate, butyl methacrylate, butyl acrylate, lauryl acrylate , 2-ethylhexyl methacrylate, glycidyl methacrylate, etc.
(Meth) acrylate derivative, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, olefins such as ethylene, propylene, butene, styrene, divinylbenzene, α-methylstyrene, butadiene, isoprene, etc. .

The quantitative ratio of the (meth) acrylamide derivative to the above-mentioned monomer varies depending on the selected combination of the monomers and cannot be said to be unequivocal. The amount is preferably 10 wt% or less, preferably 5 wt% or less, more preferably 3 wt% or less, and if present in an excessive amount, gel hardness increases but becomes brittle. Hydrophilic or ionic monomers are both 90 wt% or less, preferably 80 wt% in the total amount of monomers.
% Or less, more preferably 70 wt% or less, and if present in an excessive amount, the whitening temperature becomes high or whitening becomes difficult. The lipophilic monomer content is 40 wt% or less, preferably 20 wt% or less, and more preferably 10 wt% or less based on the total amount of the monomers.

As the fine particle metal oxide which is another component constituting the aqueous gel composition, various kinds can be used as long as it is water-insoluble. Specific examples thereof include silicon dioxide, aluminum oxide, antimony oxide, titanium oxide, tin oxide, zirconium oxide, lead oxide, calcium oxide, magnesium oxide, and composite oxides thereof. Among them, silicon dioxide, aluminum oxide, antimony oxide and their composite oxides are preferable.

The particulate metal oxide does not melt even after the gel composition comes into contact with the flame and the water and the organic components burn or volatilize, and remains in a porous form to prevent penetration of the flame and to have a porous structure. This has the effect of effectively insulating heat.

As a method for producing silicon dioxide, a dry method by thermal decomposition of silicon tetrachloride, a wet method based on precipitation formation by complex decomposition of sodium silicate acid, carbon dioxide, ammonium salt, etc., organic liquid such as alcohol and silica gel The airgel method etc. which heat and manufacture in an autoclave can be employ | adopted.

The product may be used either in a state of being suspended in an aqueous medium or the like, or in the form of a dry powder. Various manufacturing methods can be adopted also in the production of aluminum oxide, specifically, heating dehydration of hydroxide, reaction of sodium aluminate with carbon dioxide or sulfur dioxide, alumina obtained by adding an alkaline substance to an aluminum salt aqueous solution. Examples thereof include dehydration of hydrate, high temperature roasting of aluminum salt, hydrolysis of aluminum alkoxide, hydrolysis of alkylaluminum, and the like, and those produced by any of the production methods can also be used.

As the antimony oxide, for example, antimony trioxide is suitable, and the production method thereof is diantimony trioxide which is oxidized and volatilized by feeding air into molten pyroxene or molten metal antimony or by burning pyroxene. It is possible to employ a method such as rapidly cooling to obtain fine powder.

The composite oxide is, for example, aluminum silicate, which can be obtained by the reaction of an aqueous solution of sodium silicate and an aqueous solution of aluminum salt. Further, these metal oxide fine particles can be used alone or in combination of two or more kinds. If the particle size of the fine particles is too large, the compounding effect when combined with a polymer of a specific (meth) acrylamide derivative will be small, so fine particles, for example, about 20 μm or less, preferably
It is 10 μm or less, more preferably 5 μm or less, and for example, 0.001 μm or more. Further, in order to obtain transparency of the aqueous gel, it is 1 μm or less, preferably 0.5 μm or less, more preferably 0.1 μm or less, and 0.001 μm or more.

In general, a suspension of a particulate metal oxide has transparency when the particle diameter is made small, but has a problem that it exhibits a transparent opalescence even if it becomes too small. By mixing with the specific (meth) acrylamide derivative in (1), the effect of exhibiting transparency with suppressed opalescence is exhibited.

The medium of the aqueous gel composition is water, and any of ion-exchanged water, distilled water, ground water, tap water, industrial water and the like can be suitably used, and a freezing control agent miscible with water, for example, lower alcohol. , Ethylene glycols, ketones, amides, sugars, urea and the like can be used in combination. The freezing control agent controls freezing at extremely low temperatures and imparts weather resistance. In some cases, depending on the environment such as location or climate, the freezing treatment can be performed at a higher temperature without the antifreezing agent. However, even if an antifreeze agent is used, the heating treatment is hardly affected.

The lower alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, etc., and the ethylene glycols include ethylene glycol, propylene glycol, glycerin, diethylene glycol,
Dipropylene glycol, further higher polyethylene glycol, polypropylene glycol, polyglycerin, copolymers thereof, etc., acetone as the ketones, methyl ethyl ketone, etc., formamide as the amides, N, N-dimethylformamide, N, N-dimethylacetamide and the like, as sugars glyceraldehyde, erythritol, xylose, repose, arabitose, galactose, glucose, sorbose, mannose sugar monosaccharide, saccharose, maltose, lactose sugar disaccharide, cyclodextrin, raffinose, agarose,
Polysaccharides such as glycogen and dextrin sugar can be mentioned.
The proportion of the freezing control agent in these aqueous medium and freezing control agent is 70 wt% or less, preferably 50 wt% or less, more preferably 30 wt% or less.

The proportion of the polymer of the specific (meth) acrylamide derivative in the aqueous gel composition is 1 to 40 wt%,
It is preferably 2 to 35 wt%, more preferably 3 to 30 wt%, and the ratio of metal oxide particles is 1 to 45 wt%, preferably 4
.About.40 wt%, more preferably 8 to 35 wt%, with the remaining components being an aqueous medium. In this range, the transparency of the gel at room temperature is not impaired, the weather resistance is good, and the penetration of the flame is blocked under the high temperature in contact with the flame, the heat insulation is maintained, and the water-soluble gel excellent in fireproofness is obtained. Can be obtained.

Further, in order to stabilize the dispersion of the above particulate metal oxide, various kinds of surfactants can be used together. As the surfactant, any of anionic, nonionic, cationic and amphoteric surfactants can be appropriately selected and used, and among them, anionic and nonionic surfactants are preferable.

In the method for producing the aqueous gel composition, the specific (meth) acrylamide derivative may be polymerized while suspending the particulate metal oxide, and an aqueous solution of the polymer and a suspension of the metal oxide are mixed. You may. The former has the advantage that the suspension of the metal oxide can be made uniform and easy.

Polymerization of the aqueous gel is preferably carried out by filling a solution of the aqueous gel into an assembly in which a spacer is circumferentially integrated with a peripheral portion between a pair of glass plates as described later. The polymerization can also be carried out in the presence of a polymerization initiator such as an inorganic peroxide, an organic peroxide, a combination of those oxides and a reducing agent, or an azo compound, but high energy rays such as ultraviolet rays and electron beams. Among them, it is preferable to use photopolymerization, and as a specific method thereof, there is a method of starting by ultraviolet irradiation, a method of starting by ultraviolet irradiation in the presence of a polymerization initiator, and the like. Originally, the method of irradiating with ultraviolet rays is preferable.

Examples of the photopolymerization initiator include, but are not limited to, alkyl ester derivatives of dimethylaminobenzoic acid such as dimethylaminobenzoic acid and methyl dimethylaminobenzoate, and acetophenone derivatives such as 2,2-diethoxyacetophenone. , Ketal and acetal derivatives such as benzene dimethyl ketal, diazide derivatives such as 4,4′-diazidostilbene-2,2′-disulfonic acid,
Pyrene derivatives such as 3,3-dimethyl-4-methoxy-benzophenone azidopyrene, naphthoquinone (1,2) diazide (2)-
Naphthoquinone (1,2) diazide (2) derivatives such as sodium 4-sulfonate, triphenylpyrylium perchlorate and its derivatives, benzophenone derivatives such as 4,4'-bisdimethylaminobenzophenone, benzyl, benzoin and its derivatives Alkyl ether derivatives, derivatives such as 2-hydroxy-2-methyl-propiophenone and 2,4-diethylthioxanthone, nuclear-substituted derivatives of azite groups such as p-azitobenzoic acid, thioxanthone and 2,4-diethylthioxanthone, etc. Examples thereof include derivatives, dibenzosuberone, 5-nitroacenaphthene, 1-hydroxycyclohexyl phenyl ketone and the like. The photopolymerization initiator may be used in combination of two or more, and in addition, aromatic amines, aliphatic amines, and photosensitizers such as amine derivatives such as p-dimethylaminobenzoic acid isoamyl ester are used, You may make it accelerate a hardening speed.

The amount of the photopolymerization initiator added is usually 0.05 to 10 wt% with respect to the specific (meth) acrylamide derivative,
Preferably 0.07 to 6 wt%, more preferably 0.1 to 4 wt%
As described above, the action is exhibited, and two or more kinds may be used in combination.

Further, at least a pair of glass plates which are separated from each other are, for example, preliminarily subjected to a silane coupling treatment on the opposing surfaces, and the peripheral edges of the plates are adhered with an adhesive and water-impermeable adhesive. A spacer is provided around the spacer, and a sealing agent is applied to the outer peripheral portion of the spacer to form a space inside to form a multi-layer glass-like structure, and the internal space is filled with the above-mentioned aqueous gel composition.

To fill the above-mentioned aqueous gel stock solution, a spacer is appropriately provided with injection holes and deaeration holes, and the atmosphere in the fireproof glass assembly is kept as an air atmosphere, preferably a nitrogen-rich atmosphere or an inert atmosphere such as nitrogen gas. Do it below. The stock solution of gel is also preferably subjected to a treatment such as deaeration in advance to remove dissolved oxygen, and the presence of the oxygen has a harmful effect of delaying the polymerization. After the injection is completed, the hole is sealed with a suitable sealing means.

The above-mentioned polymerization is carried out by irradiating ultraviolet rays from one side of the fireproof glass assembly, preferably from both sides. The UV irradiation lamp is not specified, and it uses a normal mercury lamp, a high-pressure mercury lamp, and an ultra-high-pressure mercury lamp.Various types of lamps such as standard type, ozoneless type, metal halide type, water cooling type can be used, Lamp output is 0.1 ~ 500w
/ cm ² is sufficient. The accumulated irradiation light amount (energy amount) is 10
The range is preferably up to 10000 mJ / cm ² , and more preferably 1000 to 9000 mJ / cm ² . The UV irradiation time varies depending on the aqueous gel composition and the UV intensity and may be set appropriately in consideration of the degree of polymerization, but it is preferably in the range of several seconds to several tens of minutes.

The glassy plate is made of polycarbonate,
(Meth) Acrylic-based organic glass may be used,
From the viewpoint of fire protection, inorganic glass is recommended. As the inorganic glass, not only ordinary soda lime glass, borosilicate glass, various transparent colored such as aluminosilicate glass, uncolored glass, tempered glass thereof,
It may be a semi-tempered glass, a partially tempered glass, a wire-containing glass, a laminated glass, a crystallized glass, or the like, in addition to a glass surface on which various functional films such as a heat ray reflective film are attached, and a combination of these various glasses. Further, the shape is not specified, and the plate thickness can be appropriately selected such as about 1 mm to several tens of mm, and bent plate glass or the like can be adopted.

The vitreous plate-like body has a plurality of layers of two or more layers, and the layer interval is several mm to several tens of mm, for example 3 mm to 60 mm, and the like, and the aqueous gel composition is placed between the plate-like objects. It may be filled or may be combined with a so-called multi-layer glass having an air or gas space.

The surface of the vitreous plate which contacts the aqueous gel is preferably treated with a silane coupling agent in advance in order to improve the adhesion with the gel. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N -β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc. Among them, those having an unsaturated bond in the molecule are preferable, and vinyltrimethoxysilane, vinyltriethoxysilane, γ- (methacryloxypropyl) trimethoxysilane and the like are preferable.

The spacer that separates the plate-like bodies is basically of a cross-section (dimple type) in cross section, but the above-mentioned aqueous gel composition can be filled up to the peripheral edge of the vitreous plate-like body as much as possible. The structure and shape are preferred. The material may be metal such as aluminum, lead, steel, etc. or ceramic, FRP, etc., as long as it can support the aqueous gel in the normal temperature range, but metal is preferable in view of ease of processing and thermal stability. is there.

The spacer and the vitreous plate-like body are preferably bonded with a synthetic rubber-based water-impermeable and tacky adhesive agent such as polyisobutylene, polyisobutylene-butyl, and butyl. It should be noted that silica, white carbon, titanium oxide, magnesium silicate, aluminum silicate, etc. are usually used as reinforcing fillers in adhesives, unsaturated hydrocarbon resins, chroman resins, terpene resins, rosin derivatives, etc. are used as tackifiers, and others are dried. Agents and the like can be added as appropriate. The adhesive can hold the vitreous plate in a wide temperature range with an adhesive force even if the vitreous plate is bent due to fluctuations in atmospheric pressure or expansion / contraction of the aqueous gel, and prevents escape of the aqueous medium in the aqueous gel. However, it maintains stability over a long period of time.

Further, the outer peripheral portion of the spacer is sealed with a similar synthetic rubber type sealing agent such as silicone type, polysulfide rubber type, polyurethane type, polybutadiene-polystyrene type sealing agent. A filler such as heat-resistant inorganic material powder and other additives can be appropriately mixed in the sealing agent. Of course, the sealing agent also has tackiness, but it is an important component particularly for firmly holding the vitreous plate-like body and the spacer and for more completely blocking the aqueous gel from the outside.

Next, the fireproof glass, which is a multilayer glass-like structure filled with the above-mentioned specific aqueous gel, is frozen or / and
By heating and heating, the haze value was set to 10% or more. The reason is that a haze value of about 10% or more is required to change from transparent and highly transparent to translucent to opaque. It has properties such as softness, environmental friendliness, and good design. It is used not only for window and door openings, but also for interior materials such as wall materials and partitions, and in some cases even exterior materials. This is because it will be possible. A preferable haze value is about 10 to 70%, and a more preferable haze value is about 20 to 60%. Needless to say, the easiness of generation of haze is adjusted in consideration of other physical properties, depending on the type and ratio of each compound contained.

Regarding the above-mentioned freezing and / or warming treatment, the freezing treatment is a low-temperature treatment, and in particular, the temperature is gradually lowered from room temperature to a low temperature of about -10 ° C or less, and at least about 1 hour or more corresponding to the low temperature. After being kept, it is a low temperature treatment in which the temperature is successively raised to room temperature for 1 cycle or more, preferably 2 cycles or more. This is because it is hard to say that it is not practical because it is difficult to be sufficient. Although it may be possible to make it in a considerably shorter time than about 1 hour at an extremely low temperature, for example, a temperature lower than about -50 ° C, it is expected. It is difficult to say that it is necessarily economical and of high quality because it is difficult to control and obtain adverse effects on other components. The temperature is preferably about -10 to -30 ° C, more preferably about -15 to -25 ° C.

Further, the heating treatment is carried out sequentially from room temperature +50.
The temperature was raised to a temperature of about ℃ or more over about 30 minutes, and the temperature was maintained for about 1 hour or longer, preferably for about 2 hours or longer, and more preferably for about 3 hours or longer, in accordance with the raised temperature. After that, it is a heating process that returns to room temperature for about 30 minutes or more, and if it is less than + 50 ° C, for example, about + 30 ° C,
This is because even if it takes about 1 hour or more, even if it takes a long time, it is difficult to obtain the desired result. For example, if it is about + 100 ° C, it may be possible to do it in a considerably shorter time than about 1 hour, It is difficult to say that the desired product is economical and of high quality because it is difficult to obtain the desired product and it is easy to adversely affect other components.
Preferably about +50 to + 80 ° C, more preferably +50 to +
It is about 70 ℃.

Further, the freeze treatment and the heating treatment are performed in series, and one cycle is performed for 2.5 hours or more, and the treatment for at least one cycle is performed. When performing the above-mentioned heating treatment, the time for returning from room temperature to low temperature or returning from low temperature to room temperature is about 15 minutes or more, preferably about 20 minutes or more, so that one cycle is about 2.5 hours or more, preferably about 2.5 hours or more. Is about 3 hours or more.

Furthermore, after the above-mentioned treatments, a haze value (%) (cloudiness) was measured by a haze meter (manufactured by Suga Test Instruments Co., Ltd.) and evaluated as semitransparent or opaque.

The mechanism of the above-mentioned translucent to opaque appearance is not known in detail, but rather than the above-mentioned aqueous gel being whitened and made porous, the above-mentioned fine particle metal oxide is probably used. Acts as a nucleating agent,
It is assumed that some of the various compositions containing the polymer in the aqueous gel are aggregated in the aqueous gel. Moreover, the fireproof glass that is stable in the normal temperature range for a long period of time and is in a transparent state that can be said to be a precursor and fireproof performance are unchanged, and when it comes into contact with a flame, the plate-shaped body on the contact side is damaged, and then the flame is gelled. Water evaporates in contact with the surface, the temperature rise is prevented by the heat of evaporation, and the gel becomes white and becomes porous to block the heat. When further heated, organic components are decomposed and volatilized to form a metal oxide-only porous body, which itself has a heat insulating property.
It exhibits excellent fire protection performance, such as heat resistance stability of more than 2000 ° C for 00 ° C and 2000 ° C for alumina.

[0064]

EXAMPLES The present invention will be described below based on examples. However, the present invention is not limited to the embodiment.

Example 1 Approximately 8 aqueous suspensions of alkaline colloidal silica having a particle size of colloidal silica of about 7 to 9 mμ and a silica content of about 30 wt%.
8.73 g to N-acryloylpyrrolidine about 10.11 g, acrylamide about 1.00 g, methylenebisacrylamide about 0.05
The mixture was gradually added with stirring at a rate of g to completely dissolve it. The PH at this time was 10.3.

2-hydroxy-2-methyl-1- was added to this aqueous solution.
Phenylpropan-1-one was added at a rate of 0.03 g to dissolve it, and degassed under reduced pressure to prepare an aqueous gel stock solution. In the form as shown in Fig. 1, thickness about 6mm, glass size about 300mm ×
300mm pair of soda-lime float glass sheets 2,2 '
The opposite surface is treated with a silane coupling agent consisting of γ- (methacryloxypropyl) trimethoxysilane in advance, and the aluminum spacer 3 is inserted through the sealing material 5 made of butyl rubber adhesive with a plate interval of about 18 mm. A multi-layer glass-like structure which is a fireproof glass assembly is provided around the spacer and a sealant 6 which is a silicone-based sealing agent is attached to the outer periphery of the spacer, and the multi-layer glass-like structure is degassed under reduced pressure. The above-mentioned aqueous gel stock solution was injected into the space of 1 through the injection port, and after filling, the space was sealed. The multi-layer glass-like structure containing the aqueous gel stock solution is irradiated with ultraviolet rays by an ultraviolet curing device equipped with a mercury lamp having an output of 120 w / cm ² , for example, and is passed about 3 times at a transfer speed of about 2 m / min to cure by gel polymerization. By doing so, a transparent fireproof glass containing the hydrogel 4 was obtained.

Then, the transparent fireproof glass was put in a temperature cycle tank and only the following freezing treatment was performed. That is, the temperature is gradually lowered from room temperature (about 25 ° C) to -10 ° C to -12 ° C over about 1 hour, and kept at -10 ° C to -12 ° C for about 1 hour, and then from the low temperature to room temperature for about 1 hour. Smoke-shaped fireproof glass 1 was obtained by performing a freezing treatment for 2 cycles of about 8 hours, in which one cycle was a total of about 4 hours in which the temperature was sequentially raised and the room temperature was maintained for about 1 hour. The haze value (cloudiness) of the obtained smoke-like fireproof glass was 20%.

The fire protection glass is notified by the Ministry of Construction, No. 1125, 1990.
In accordance with the fire door test method of No. 3, a predetermined test furnace opening (not shown) was set as shown in FIG. 2 and heated according to a prescribed heating curve to test the fire prevention performance. The setting includes, for example, a setting block 7 made of calcium silicate, a steel supporting member 8, a heat insulating member 9 made of a ceramic wool or glass wool sheet, a silicone sealing material 10 and a ceramic wool or glass wool sheet arranged inside the furnace. It is made of a coated heat insulating material 11 etc. and is arranged and fixed at the open end of the test furnace.

In the heating test, 20 minutes after the start of heating, 795
Even if the crack does not reach the back side even at ℃, it does not penetrate the flame, and it does not deform or drop even if shocked with a 3 kg sand bag under the specified conditions If there are no cracks, penetration of flames, deformation due to impact, etc. even after heating for 60 minutes at 925 ° C for 60 minutes after heating, it can be applied as a type A fire door (fireproof section of the building). It can be applied as an opening). The possibility of application to these Class B fire doors (simply called Oto) and Class A fire doors (simply called Kobo) was observed and tested.

Further, the fireproof glass was measured with a sunshine weather meter (model WEL-SUN-HMC light source carbon arc) manufactured by Suga Test Instruments Co., Ltd. to obtain a black panel temperature of 63 ± 3.
A weathering test was conducted at a temperature of 12 ° C. for 12 minutes / 60 minutes for up to about 1000 hours. After a predetermined time, the fireproof glass was taken out and returned to room temperature, and the appearance was observed.

As a result, it has a fireproof property that can be sufficiently applied as a fire extinguisher or a class A fire door, and has good weather resistance and durability. Further, if it is used for windows of buildings, for example, it protects privacy, and It was also excellent in that it had a sound-insulating property and had the effect of scattering it against the direct sunlight and blocking the heat to insulate it from the outside of the room.

Example 2 In the same manner as in Example 1, about 87.68 g of a colloidal silica suspension aqueous solution (the particle size of the colloidal silica was about 7 to
9 mμ, silica content about 30 wt%), N, N-diethylacrylamide about 5.21 g, N, N-dimethylacrylamide about 4.38
g, about 0.08 g of methylenebisacrylamide, 0.03 g of 2-hydroxy-2-methyl-1-phenylpropan-1-one and about 2.62 g of ethylene glycol, respectively, to prepare an aqueous gel stock solution.

Using the aqueous gel stock solution, a transparent fireproof glass was prepared in the same manner as in Example 1, and as a freezing treatment, the temperature was successively lowered from room temperature to -20 ° C to -22 ° C over about 1 hour. Only one cycle was carried out by maintaining the temperature at 20 ° C to -22 ° C for about 10 hours, then successively raising the temperature over about 1 hour and returning to room temperature. The smoke-like fireproof glass obtained has a haze value of about 15%.
It was about.

The smoked fireproof glass obtained was used in Example 1.
It was subjected to various tests in the same manner as. As a result, similar to Example 1, it has sufficient fireproofness that it can be applied as a type B fire door, and has good weather resistance and durability. Furthermore, for example, privacy when adopted for windows of buildings. Although it is slightly inferior in the heat resistance and the direct light of sunlight, it is excellent in that it has a sound-insulating property and has the effect of blocking the heat and insulating the indoors and outdoors.

Example 3 In the same manner as in Example 1, about 44.66 g of an aqueous colloidal silica suspension solution (the particle size of the colloidal silica was about 7 to
9 mμ, silica content about 30 wt%, colloidal silica suspension aqueous solution about 44.66 g (colloidal silica particle size is about 10 ~
20 mμ, silica content about 30 wt%), N-acryloylpyrrolidine about 8.21 g, N-acryloylpiperidine about 2.41 g, methylenebisacrylamide about 0.02 g and 2-hydroxy
-2-Methyl-1-phenylpropan-1-one 0.04 g of each was used to prepare an aqueous gel stock solution.

Using the aqueous gel stock solution, a transparent fireproof glass was prepared in the same manner as in Example 1. As a freezing treatment, the temperature was gradually lowered from room temperature to -15 ° C to -17 ° C over about 1 hour. Hold at 15 ℃ to -17 ℃ for about 1 hour, and then gradually raise the temperature from room temperature to about +50 ℃,
The temperature is kept at about + 50 ° C for about 1 hour, and then kept at room temperature for about 0.
Two cycles were carried out for about 9 hours, with one cycle consisting of successively lowering the temperature over 5 hours. The haze value of the obtained smoke-like fireproof glass was about 25%.

The smoked fireproof glass obtained was used in Example 1.
It was subjected to various tests in the same manner as. As a result, similar to Example 1, it has sufficient fireproofness that it can be applied as a type B fire door, and has good weather resistance and durability. Furthermore, for example, privacy when adopted for windows of buildings. And excellent directivity of sunlight and sound insulation, and has the function of further blocking the heat and providing high heat insulation indoors and outdoors, which is excellent for the intended purpose. Met.

Example 4 In the same manner as in Example 1, about 75.17 g of an aqueous colloidal silica suspension solution (the particle diameter of the colloidal silica was about 7 to 7).
9 mμ, silica content about 30 wt%), N-acryloylpyrrolidine about 6.70 g, N-acryloylmorpholine about 7.84 g, methylenebisacrylamide about 0.02 g, propylene glycol about 5.08 g, urea about 5.08 g, saccharose about 5.08 g and 2 -Hydroxy-2-methyl-1-phenylpropane-1-
An aqueous gel stock solution was prepared by using 0.03 g of each on.

Using the aqueous gel stock solution, a transparent fireproof glass was prepared in the same manner as in Example 1, and as freezing treatment, the temperature was gradually raised from room temperature to about + 70 ° C. over about 1 hour, and the temperature was increased to about + 70 ° C. The temperature was maintained for about 8 hours, and then the temperature was gradually lowered over about 1 hour to return to room temperature, so that only one cycle was performed.
The smoked fireproof glass obtained was ground glass-like and had a slightly uniform color and a haze value of about 30%.

The smoked fireproof glass obtained was used in Example 1.
It was subjected to various tests in the same manner as. As a result, it has sufficient fireproofness that it can be applied as a type B or type A fire door, and has good weather resistance and durability. Furthermore, for example, it has privacy when used in windows of buildings and scattering of direct sunlight. The performance was further excellent, and it was excellent in that it had a desired effect, such as having a sound insulating property, and having the effect of further blocking the heat and providing high heat insulation indoors and outdoors.

In Examples 1 to 4, when the adhesive was changed to an isobutylene type adhesive and butyl rubber or isobutylene-butyl type rubber was adopted, the sealing agent was changed to a silicone type rubber, a polysulfide rubber type, Even when polyurethane type rubber and polybutadiene-polystyrene type rubber were adopted, results comparable to those of the above examples were obtained. Furthermore, in the above-mentioned Examples 1 to 4, the plate interval is changed to about 18 mm,
For example, even when the thickness is set to about 16 mm or about 12 mm, good results similar to those in the above-described examples can be obtained in the fireproof test, the weathering test and the like.

[0082]

EFFECTS OF THE INVENTION The smoke-like fireproof glass according to the present invention is excellent in fireproof performance, and is rich in privacy and has antiglare property, heat insulation property or sound insulation property, becomes soft and environment-friendly, and is simple and specific. It is possible to provide a fireproof glass which is stable for a long period of time by treatment without deterioration and is unlikely to deteriorate and deteriorate, and which is useful for various purposes such as construction, particularly indoor walls or partitions, and translucent or opaque.

[Brief description of drawings]

FIG. 1 is a side sectional view showing an example of the configuration of a smoke-like fireproof glass of the present invention.

FIG. 2 is a side cross-sectional view in which the attachment portion is partially enlarged when the smoke-like fireproof glass of the present invention is attached to an opening of a heating furnace for a fire door test.

[Explanation of symbols] 1 Smoked fireproof glass 2, 2'Plate glass 3 Spacer 4 Water-containing gel 5 Sealing material 6 Sealing material

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location E06B 5/16 (72) Inventor Kouji Azumaya 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Technical Center (72) Inventor Masanori Kurahashi 4-39-3-201 Hayamiya, Nerima-ku, Tokyo (72) Inventor Hiroshi Ito 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor, Takashi Abe Kanagawa Mitsui Toatsu Chemical Co., Ltd. 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Japan (72) Inventor Hitoshi Yamashita 1190 Kasama-cho Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. 1190 Kasama Town Mitsui Toatsu Chemical Co., Ltd.

Claims (5)

[Claims] 1. A fireproof glass in which a water-containing gel is filled in a space of a multi-layer glass-like structure, wherein the general formula (I) or the general formula (II): [Chemical 2] Represented by (meth) acrylamide or (meth)
A smoke-like fireproof glass, which is obtained by at least freezing and / or heating treatment of the water-containing gel comprising a polymer of an acrylamide derivative and a particulate metal oxide, and has a haze value of 10% or more. 2. A method for producing a fireproof glass containing a hydrous gel, wherein a hydrous gel is filled in the space of a multi-layer glass-like structure, wherein the general formula (I) or the general formula (II): [Chemical 4] Represented by (meth) acrylamide or (meth)
A method for producing a smoke-like fireproof glass, characterized in that the hydrogel comprising a polymer of an acrylamide derivative and a particulate metal oxide is at least frozen and / or heated so that a haze value is 10% or more. 3. The freezing treatment is sequentially lowered from room temperature to a low temperature of −10 ° C. or lower, and after being kept for 1 hour or more in correspondence with the low temperature,
A method for producing a smoke-like fireproof glass, characterized in that at least one cycle of low-temperature treatment of returning to room temperature is performed. 4. The heating treatment is performed by successively heating from room temperature to + 50 ° C. or more, holding for 1 hour or more in response to the heating, and then performing at least one cycle of heating treatment that is sequentially returned to room temperature. A method for producing smoke-like fireproof glass, characterized by: 5. The low-temperature treatment in which the freezing and warming treatments are sequentially lowered from room temperature to a low temperature of −10 ° C. or lower, and the temperature is kept at room temperature for 1 hour or more, and then sequentially returned to room temperature; One cycle consists of heating to a temperature of ℃ or more, holding for 1 hour or more in accordance with the temperature raised, and then sequentially returning to room temperature, one cycle, and taking one cycle for 2.5 hours or more. A method for producing smoke-like fireproof glass, characterized by performing a treatment for one cycle or more.