JPH09227179A - Laminated molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated molded product enabling to simplify its production process, excellent transparency and having a fireproof function by placing an interlayer containing a hydrophilic resin and water glass between two substrates. SOLUTION: This laminated molded product has an interlayer containing a hydrophilic resin and water glass between two substrates. Water is preferably added to the interlayer. The water content of the interlayer is preferably 30-98wt.%. The hydrophilic resin is preferably a polysaccharide or a hydroxyl group-containing polymer. The water glass especially preferably contains sodium silicate or potassium silicate. A solubilizing agent and a flame retardant are preferably added to the interlayer in order to improving the functions of the molded product.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated molded article, and particularly to transparency, flame retardancy, heat resistance, fire resistance, fire resistance,
Excellent in flame resistance, smoke resistance, safety, crime prevention, soundproofing, durability, light resistance, weather resistance, impact resistance, penetration resistance, boiling water resistance, glass shatterproof property and chemical resistance. The present invention relates to a laminated molded body that is suitably used for laminated glass and the like.

[0002]

2. Description of the Related Art Generally, plastic materials are lightweight, have excellent impact resistance, workability and mass productivity, and are used as substitute materials for inorganic materials such as metal and glass in various fields, and their demand is expanding. It's just one. In addition, by combining a plastic material with an inorganic material to form a composite material with each other, not only the performances of the organic material and the inorganic material are complemented with each other, but also new characteristics that cannot be obtained individually are obtained. Such an organic
It is expected that the product manufactured using the inorganic composite material will have significantly higher performance than the product manufactured using either the organic material or the inorganic material alone.

Currently, the most widely used inorganic material is glass. Glass has SiO ₂ as a main component and is excellent in transparency, durability, weather resistance, heat resistance, nonflammability, low wavelength dispersibility, etc., and is used for applications requiring transparency.
For example, it is widely used in optical fields such as eyeglass lenses, contact lenses, and optical filters, in the field of building materials such as window glasses, and daily household products. Glass is made from silica sand, which is inexhaustible on the earth,
It is noteworthy that it has excellent recyclability and the cost of raw materials is extremely low. However, glass has drawbacks such as large specific gravity and poor flexibility and impact resistance, so various organic materials improved in these respects are used as substitute materials for glass, such as eyeglass lenses, contact lenses, and Widely used in optical products such as optical filters. As optical products, organic transparent resins such as polymethylmethacrylate, polystyrene, polycarbonate, amorphous polyolefin, and polydiethylene glycol bisallyl carbonate are used, and have impact resistance, moldability, low specific gravity, high refractive index, etc. It is superior to glass in that respect.

Products such as laminated glass for construction and laminated glass for automobiles, which are used in combination with an organic material and have properties which cannot be obtained by glass alone, are also widely used.
The laminated glass is a glass in which an intermediate film made of an organic film is present between two plate glasses, and a transparent resin such as polyvinyl butyral, polyvinyl chloride or polyvinyl alcohol is used as the intermediate film. The transparent resin, which is an intermediate film of laminated glass, imparts impact resistance, penetration resistance, and shatterproofness to ordinary plate glass. Although the transparency of the transparent resin is similar to that of glass, the current transparent resin is inferior to glass in heat resistance, weather resistance, light resistance, abrasion resistance and surface hardness. In particular, in laminated glass for construction, the current transparent resin is strongly demanded to make buildings incombustible in order to minimize damage due to fire.
Incombustibility and flame retardancy were extremely insufficient, and it was difficult to use as a laminated glass interlayer film for construction in view of noncombustibility and flame retardancy.

Fireproof glass is one of the building materials developed for making buildings incombustible. Ordinary float glass is very vulnerable to thermal shock due to flame, and JIS A 13
11 "Fire protection test method for building fire doors" and DIN standard (D
It does not conform to the fire protection glass standards specified in IN 412). To solve this problem, a net-cored glass was developed by embedding a metal net in the glass plate so that it will not fall even if the glass is damaged by the thermal shock of a flame. is occupying. However, the screened glass has a low heat insulating property and has a problem that the translucency is lowered.

On the other hand, it is a kind of laminated glass, and in the case of a fire or the like, even if the glass plate is cracked by thermal shock, the glass adheres to the intermediate layer forming the heat insulating layer by heating and the glass falls. Do not use fireproof glass
No. 04 etc. have been proposed. The intermediate layer of this fireproof glass is hydrous sodium silicate, so-called water glass.
Water glass having a melting point of 500 to 600 ° C. is softened by heating, then the water contained in the water glass is vaporized and foams to swell to a volume several times that before heating, forming a heat insulating layer, and flame. It has the effect of closing the cracks generated in the glass on the side and firmly adhering to the broken glass to prevent the glass from falling off. However, since this intermediate layer is obtained by applying water glass to a glass plate, each manufacturing step of coating, drying and laminating is required, and the manufacturing cost of laminated glass is significantly high. Laminated glass coated with such water glass is considerably more expensive than ordinary laminated glass using polyvinyl butyral, and is also expensive for meshed glass, so it is hardly accepted in the market. .

If the water glass can be formed into a film, the manufacturing process of the laminated glass can be simplified. As one of them, there is a method in which water glass and an organic transparent resin are composited and a film containing water glass as a main component is used as an intermediate layer due to the film forming ability of the transparent resin. However, as an organic resin that can be combined with water glass, carboxymethyl cellulose as disclosed in JP-A-51-95479 is known. However, carboxymethyl cellulose has poor transparency when formed into a film, and is transparent mainly composed of water glass. No film was obtained.

[0008]

As described above, no inexpensive and transparent fireproof laminated glass has been obtained so far, and the manufacturing process can be simplified and the fireproofness is excellent. There has been a strong demand for a laminated molded product that can be used as a laminated glass having a function.

[0009]

Means for Solving the Problems Accordingly, the present inventors have:
The present invention has been achieved as a result of earnestly studying a laminated molded body that can simplify the manufacturing process, is excellent in transparency, and has a fireproof function.

The present invention provides a hydrophilic resin between two substrates,
And a laminated molded article characterized by the presence of an intermediate layer containing water glass.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrophilic resin of the present invention is not particularly limited as long as it is a resin that can be stably dispersed or dissolved in the presence of water glass. The hydrophilic resin in the present invention is preferably a resin which can coexist with water glass and can be stably dispersed or dissolved without agglomerating in the precursor composition solution or the intermediate layer of the laminated molded body.

The hydrophilic resin in the present invention is more preferably a water-soluble resin. Examples of such water-soluble resins include natural polymer-based water-soluble resins, semi-synthetic polymer-based water-soluble resins, synthetic polymer-based water-soluble resins, and inorganic polymer-based water-soluble resins.

Examples of the natural polymer water-soluble resin include starches such as corn starch, wheat starch, kansho starch, potato starch, tapioca starch, rice starch, seaweeds such as funari, agar and sodium alginate, gum arabic, Examples include plant mucilages such as tragacanth gum, totorooi and konjac, animal proteins such as glue, casein, gelatin, egg white and plasma protein, and fermented mucilages such as pullulan and textran.

Examples of the semi-synthetic polymer water-soluble resin include soluble starch, carboxyl starch, predish gum, starches such as dialdehyde starch, dextrin and cationic starch, and hydroxylalkyl-substituted derivatives such as viscose. Can be mentioned.

Examples of the synthetic polymer water-soluble resin include completely or partially saponified polyvinyl acetate such as polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyacrylamide, polyacrylic acid and metal salts thereof, poly (meth). Acrylic acid and its metal salts, polyhydroxyalkyl (meth) acrylate or its copolymer, alkylpolyalkylene oxide (meth) acrylate polymer or its copolymer, hydrophilic urethane resin, polyvinylpyrrolidone, water-soluble alkyd, polyvinyl ether, Examples thereof include polymaleic acid copolymer and polyethyleneimine.

Examples of the inorganic polymer water-soluble resin include sodium polyphosphate and water glass.

Further, as the hydrophilic resin of the present invention, a resin obtained by introducing a reactive functional group into the above hydrophilic resin is also preferably used. The introduced functional group is not particularly limited and can be cationic, anionic or nonionic, but in order to make it more hydrophilic or to improve the compatibility with the inorganic fine particles, a hydroxyl group, an alkoxy group, or a phenoxy group. Group, carboxyl group, carboxyalkyl ester group, carboxyphenyl ester group, silanol group,
Reactive functional groups such as alkoxy silanol groups, phenoxy silanol groups, thiol groups, thioalkyl ester groups, thiophenyl ester groups, epoxy groups, sulfone groups, and amino groups are preferably introduced, and particularly hydrophilic resins containing hydroxyl groups are used. preferable. Further, these functional groups are anionized or cationized to give K ⁺ , Na ⁺ , Li ⁺ ,
NH ₄ ⁺ , Ca ²⁺ , Mg ²⁺ , F ⁻ , Cl ⁻ , Br ⁻ , I ^−.
It is also possible to use a resin that is ionically bonded to ions such as. Further, it is also possible to use a resin containing an alkoxy group or a phenoxy group by reacting the above-mentioned functional group with, for example, esterification. As such an alkoxy group or phenoxy group, one having 1 to 10 carbon atoms is more preferably used.

The hydrophilic resin used in the present invention includes
Particularly preferred are those having excellent compatibility with water glass, crosslinkability, and formation of a gel containing water glass and water, and a hydroxy group-containing polymer such as polyhydroxy (meth) acrylate or a copolymer thereof, and Examples include polysaccharides. Further, as the polysaccharide, color-guinan, agar, alginic acid, wafers, gum arabic, arabinogalactan, pectin, tamarind seed gum, guar gum, locust bingham, tara gum, silum gum, cellulose, plant-based natural polysaccharides such as starch, chitin, Animal-based natural polysaccharides such as chitosan, xantham, and vullan, semi-synthetic natural polysaccharides such as polydextrose, and among them, wafers, carrageenan, alginic acid,
Agar and the like have excellent film forming ability and are preferably used.

Further, in the hydrophilic resin of the present invention, the hydrophilic resin described above in which a substituent is introduced to such an extent that the compatibility with water glass, the crosslinkability, and the formation of a gel containing water glass and water are not impaired. It can also be used. In this case, the content of the functional group to be introduced is not particularly limited, but a range of less than 50% in weight ratio with respect to the weight of the resin before introduction is preferably used. If it is 50% or more, the reaction / crosslinking in the molecule of the hydrophilic resin proceeds to make the hydrophilic resin hydrophobic and impair its hydrophilicity. Further, the hydrophilic resin may be a composite system with an inorganic substance or the like as long as the transparency is not impaired, and may further contain an inorganic bond such as a siloxane bond or a phosphazene bond. Further, these hydrophilic resins can be used alone or in combination of two or more kinds, and can be three-dimensionally crosslinked by using various curing agents, crosslinking agents and the like.

The transparency of the hydrophilic resin is preferably 60% or more, more preferably 80% or more, when the total light transmittance when uncolored is used as an index. For applications requiring optical isotropy, for example, substrates for liquid crystal displays, optical disc substrates, etc., the birefringence is preferably 30 nm or less, more preferably 15 nm or less.

Further, the water glass in the present invention is not particularly limited as long as it does not impair the transparency as an intermediate layer of the laminated molded body. From the viewpoint of improving workability and imparting transparency, sodium silicate-based water glass, potassium silicate-based water glass,
Lithium silicate-based water glass or the like is preferable, and particularly, water glass containing sodium silicate or potassium silicate is preferable. Further, when the laminated molded product of the present invention is used as a laminated glass for fire protection, it improves fire resistance. In order to have a melting point of 1
It is preferable that the temperature is 000 ° C or lower, and Na in silicate is
SiO ₂ for alkali metal oxides such as ₂ O and K ₂ O
Sodium silicate or potassium silicate having a weight ratio of 0.8 to 5 is preferably used.

Water is preferably added to the intermediate layer of the laminated molded article of the present invention. Water is a composition that is particularly important as an improvement in the compatibility between the hydrophilic resin and water glass, and as a heat insulating component when the laminated molded body is used as fireproof glass. The water content in the intermediate layer is preferably 30 to 98% by weight, and more preferably 50 to 95% by weight in terms of both the heat insulating effect and the strength of the laminated molded body. Water content is 30%
If it is less than 100%, the heat insulating effect is poor, and if it is more than 98%, the supporting strength as a laminated molded article becomes small. Further, even if an organic substance or an inorganic substance is dissolved in the added water, it can be used in the present invention as long as the properties such as transparency and fireproofness are not impaired.

In addition, it is preferable to add a compatibilizing agent to the intermediate layer of the laminated molded article of the present invention in order to impart transparency and improve the compatibility of the hydrophilic resin, water glass and water. As the compatibilizing agent, for example, anionic / cationic / nonionic surfactants and polyhydric alcohols such as glycerin, ethylene glycol and diethylene glycol are preferably used.

Further, in order to improve flame retardancy, heat resistance, fire resistance, fire resistance, flame resistance and smoke resistance, it is preferable to add a flame retardant to the intermediate layer of the laminated molding of the present invention. The flame retardant that can be added is not particularly limited as long as it does not impair the transparency of the obtained laminated molded body, but a halogen compound, a phosphorus compound, a phosphoric acid compound, an antimony compound, an aluminum compound, a flame retardant resin or the like is preferable. Used. More preferably, a flame retardant hydrophilic compound is used, and for example, a highly water-soluble phosphoric acid compound such as a phosphonic acid compound is particularly preferably used. Examples of the highly water-soluble phosphoric acid compound include, for example, ethyl diethylphosphonoacetate, ethyl diacid phosphate, butyl acid phosphate, butyl pyrophosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, euler acid phosphate, tetracosyl acid phosphate. Phosphate, di (2-ethylhexyl)
Examples thereof include phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl) methacrylate acid phosphate, nitrile tris (methylene) phosphate, 1-hydroxyethylidene-1,1'-diphosphate and the like. In addition, organic salts such as metal salts or melamine salts of these phosphonic acid compounds can also be used. Further, the above flame retardants can be added alone or as a mixture of two or more kinds.

Further, in the intermediate layer of the present invention, in addition to hydrophilic resin, water glass, water, a compatibilizer, a flame retardant, other additives such as inorganic substances are added as long as the performance such as transparency is not impaired. It is also possible to add.

The intermediate layer of the present invention can improve various properties such as adhesion to a substrate, chemical resistance, surface hardness, durability and dyeability by using an additive such as an inorganic substance.
Examples of inorganic substances that can be added include inorganic oxides such as metal alkoxides represented by M (OR) _m , chelate compounds, and / or hydrolysates thereof. Here, M is a metal such as silicon, titanium, zircon, antimony, tantalum, germanium, and aluminum, R is an alkyl group, an acyl group, an alkoxyalkyl group, and m is the number of charges of the metal M.

Further, for the purpose of improving weather resistance, light resistance, heat deterioration resistance and antistatic property, it is also useful to add an ultraviolet absorber, an antioxidant and an antistatic agent. In particular, in order to improve weather resistance, light resistance, heat deterioration resistance, antistatic property, etc. without lowering chemical resistance or heat resistance, a monomer having ultraviolet absorption property or antioxidant property is copolymerized. It is preferable. Preferred examples of such a monomer include a benzophenone-based UV absorber having an unsaturated double bond, a phenylbenzoate-based UV absorber having an unsaturated double bond, and a (meth) acryl having a hindered amino group as a substituent. Monomers and so on. These copolymerization monomers are preferably used in the range of 0.5 to 20% by weight. If it is less than 0.5% by weight, the effect of addition is not observed, and if it exceeds 20% by weight,
Heat resistance and mechanical strength tend to decrease.

Further, if necessary, the intermediate layer of the laminated molded article of the present invention may contain various additives such as surfactants for improving the surface smoothness. As such an additive, for example, a silicon-based compound, a fluorine-based surfactant, an organic surfactant or the like can be used. Furthermore, hydrophilic polymers such as alcohol-soluble nylon and organic polymers having good compatibility with organosilicon compounds, and further ethyl silicate, n-propyl silicate, i-
Propyl silicate, n-butyl silicate, sec-
It is also possible to add a tetrafunctional silane compound such as butyl silicate or t-butyl silicate. Further, various epoxy resins, melamine resins, amide resins and the like are also suitable.

Further, various curing agents may be used in combination for the purpose of accelerating curing and low temperature curing. As such a curing agent, various epoxy resin curing agents or various organic silicon resin curing agents are used. Specific examples of these curing agents include various organic acids and acid anhydrides thereof, nitrogen-containing organic compounds, various metal complex compounds, or metal alkoxides, and organic carboxylates of alkali metals,
Examples thereof include various salts such as carbonates, and radical polymerization initiators such as peroxides and azobisisobutyronitrile. These curing agents can be used as a mixture of two or more kinds. Among these curing agents, the aluminum chelate compound is particularly useful from the viewpoint of stability of the precursor composition solution and transparency of the intermediate layer of the laminated molded body. Further, it is also possible to add various surfactants to the precursor composition solution for the purpose of improving the flow at the time of coating and improving the smoothness of the surface of the intermediate layer to reduce the friction coefficient of the surface, Particularly, a block or graft copolymer of dimethylpolysiloxane and alkylene oxide, and a fluorine-based surfactant are effective.

The hydrophilic resin, water glass, and additive components other than water are applicable to the present invention such as heat resistance, weather resistance, adhesiveness or chemical resistance with respect to the intermediate layer of the laminated molded article of the present invention. In order to improve various practical properties depending on the intended use, not only one kind but also a plurality of kinds may be added.

The method for producing the intermediate layer of the laminated molded article of the present invention is not particularly limited, but it is preferable that the composition components be a solvent in order to uniformly disperse the hydrophilic resin, water glass and water. A method is used in which the precursor composition solution is dispersed in the solution and then the solvent is removed by a method such as evaporation, evaporation, or membrane separation. More preferably, a method of manufacturing by cast molding is used. In this case, when removing the solvent, heating and / or depressurization can be performed to the extent that transparency and dispersibility of the composition components are not impaired. Furthermore, for the purpose of promoting the curing of the composition components, 2
It is preferable to heat in the range of 5 to 120 ° C, more preferably 40 to 95 ° C.

The solvent for dissolving and dispersing the hydrophilic resin is not particularly limited, but due to the solubility of the hydrophilic resin, water, alcohols such as methanol, ethanol, isopropyl alcohol, acetone, diacetone alcohol, DMF, DMSO, dimethylimidazolidinone and the like are preferably used, and each is preferably used alone or as a mixed solvent of a plurality of types. In particular, in order to obtain an intermediate layer of a laminated molded article having good flame retardancy and fire resistance, a nonflammable solvent system containing mainly water as a solvent is particularly preferable.

As a method for adjusting the precursor composition solution for the intermediate layer of the laminated molded body, for example, a method of simply mixing the respective additive components, or a component which has been subjected to a treatment such as hydrolysis in advance depending on the component, and further other components are used. And the like, all of which are useful methods for producing the intermediate layer of the laminated molded body of the present invention.

Further, the mechanical strength of the intermediate layer of the laminated molded article
For the purpose of improving heat resistance, heat treatment may be performed to the extent that transparency is not impaired.

In the present invention, glass, film, wall material, plastic plate and the like are used as the substrate, but it is preferable that at least one substrate is glass. Further, when used as a laminated glass, one of the substrates is glass, and the other substrate is not particularly limited, but glass, a transparent resin plate made of polycarbonate, polymethacrylate, or the like is preferably used. . Also,
There is no problem whether these substrates are flat or curved.

The method for producing the laminated molded body is not particularly limited, but it is a method of sandwiching the intermediate layer between two substrates and performing pressure bonding, forming an intermediate film on one substrate, and thereafter A method of laminating one sheet and a method of laminating two plates by providing a space corresponding to the intermediate layer portion and injecting the precursor composition solution as it is or by condensing it as a fluid gel-like material is preferably used. To be

The intermediate layer of such a laminated molded product may be used not only as a single intermediate layer itself but also as a coating on a glass plate or other plate constituting laminated glass without any problem. In this case, the precursor composition solution can be used as it is as a coating composition, or can be used by diluting it with a solvent. In this case, what is applied as a usable solvent is not particularly limited, but it is required not to impair the surface properties of the object to be coated, and further stability of the coating composition, wettability to a substrate, volatility, When applying, it is selected in consideration of workability, adjustment of coating thickness, and the like. Further, the solvent can be used not only as one kind but also as a mixture of two or more kinds. Examples of these solvents include water, various alcohols, esters, ethers, ketones, dimethylformamide, dimethylsulfoxide, dimethylimidazolidinone, and halogenated hydrocarbons. Examples of the coating means include brush coating, dip coating, roll coating, spray coating, spin coating, and flow coating. In addition, a mixed solvent can be used if necessary.

In applying the coating composition,
It is also an effective means to improve cleaning, adhesion, water resistance and the like by subjecting a substrate such as a glass plate forming a laminated molded body to various pretreatments. Particularly preferably used methods include activation gas treatment, chemical treatment, and ultraviolet treatment. These pretreatments can be carried out continuously or stepwise in combination.

The above-mentioned activated gas treatment is a treatment with ions, electrons or excited gas produced under normal pressure or reduced pressure. As a method of generating these activated gases, for example, corona discharge, direct current under reduced pressure, low frequency, high frequency, or high voltage discharge by microwave or the like is used.

The gas used here is not particularly limited, but specific examples are oxygen, nitrogen, hydrogen, carbon dioxide, sulfur dioxide, helium, neon, argon, freon, water vapor, ammonia, carbon monoxide. , Chlorine, nitric oxide, and nitrogen dioxide. These can be used not only as one type but also as a mixture of two or more types. Among the above, preferable gases include those containing oxygen such as air. More preferably, pure oxygen gas is effective for improving the adhesion. Furthermore, for the same purpose, the temperature of the substrate to be treated can be raised in the treatment.

Specific examples of the chemical treatment include alkali treatment of caustic soda and the like, acid treatment of hydrochloric acid, sulfuric acid, potassium permanganate, potassium dichromate and the like, organic solvent treatment, and the pretreatment is continuous or It is sufficiently possible to carry out the steps in combination.

The transparency of the intermediate layer of the laminated molding of the present invention is
When the total light transmittance when uncolored is used as an index, it is 60
% Or more, more preferably 80% or more.
Further, the transparency of the obtained laminated glass is preferably 60% or more, and more preferably 80% or more, when the total light transmittance when uncolored is used as an index.

The laminated glass of the present invention is transparent, flame retardant, heat resistant, fire resistant, fire proof, flame proof, smoke proof, safety, crime proof, sound proof, durable, light fast and weather resistant. It is preferably used as a safety glass, a security glass, a soundproof glass and a fireproof glass because it has excellent properties, impact resistance, penetration resistance, boiling water resistance, splash resistance of adhered glass and chemical resistance. In particular, architectural laminated glass (JIS R 320
5 laminated glass, safety glass, crime prevention glass, soundproof glass, fireproof glass) or an interlayer film for laminated glass for automobiles. Moreover, since it is excellent in optical isotropy, it is also applied to optical disk substrates and substrate materials for various displays.

Since it has excellent adhesiveness, surface hardness, and abrasion resistance with organic or inorganic materials, it can be used as various coatings, and also with glass, adhesiveness, flame retardancy, penetration resistance, and impact resistance. The laminated glass for construction (laminated glass according to JIS R 3205, safety glass, crime prevention glass, soundproof glass,
It is preferably used as an interlayer film for fireproof glass) applications or automotive laminated glass applications.

[0045]

EXAMPLES The present invention will be described more specifically below based on examples.

Example 1 In a container equipped with a rotor, 45 g of water, 5 g of color Guinan (trade name "Soafil" manufactured by Mitsubishi Rayon Co., Ltd., which is a product of Mitsubishi Rayon Co., Ltd.), which is a polysaccharide as a hydrophilic resin, and 5 g of glycerin were completely put. Dissolved in water. JIS K was added to the obtained aqueous solution.
No. 3 sodium silicate stipulated in 1408 (manufactured by Osaka Silica Soda Co., Ltd., SiO ₂ content 28 to 30 wt%, Na
A solution of 12.5 g of ₂ O content (9 to 10%) dissolved in 27.5 g of water was gradually added while stirring with a magnetics stirrer. The precursor composition solution thus obtained is poured onto an aluminum vat having a bottom area of 1000 cm ² , and 1
After leaving at room temperature for an hour, a plate-shaped transparent molded body having a thickness of 1 mm was obtained. The obtained plate-shaped transparent molded body is 100 cm on a side and has a thickness of 5
It is sandwiched between 2 mm square float glass plates, 12
The laminated glass was obtained by pressure bonding at 0 ° C. and 15 kg / cm ² .

The light transmittance between glasses of the obtained laminated glass was measured by using an SM computer manufactured by Suga Test Instruments Co., Ltd., and the light transmittance was 89%. Moreover, the obtained laminated glass is JIS R 3205.
The laminated glass passed the prescribed impact test and shotback test. Furthermore, when a heating test was carried out according to the heating curve prescribed in JIS R 1311, "Fire protection test method for building fire doors", the glass did not fall off during the heating test for 60 minutes, and no flame or smoke harmful to the back surface of the heating was fired. There was no leakage and the fire resistance was good. Also, in the impact resistance test with steel balls after 60 minutes of the heating test, there was no major damage.

Example 2 The precursor composition solution obtained by the same method as in Example 1 was applied to the surface of a square float plate glass having a side of 100 cm and a thickness of 5 mm to form a gel-like coating on the float plate glass. Further, another glass was bonded to the obtained gel-coated float glass plate to obtain a laminated glass.

The light transmittance between the glasses of the obtained laminated glass was measured in the same manner as in Example 1, and it was 88%. Further, the obtained laminated glass was subjected to an impact test and a shotback test in the same manner as in Example 1,
Passed each test. Furthermore, when a heating test was performed in the same manner as in Example 1, no glass fell off during the heating test for 60 minutes, and no harmful flame or smoke leaked to the back surface of the heating for fire prevention. Also, in the impact resistance test with steel balls after 60 minutes of the heating test, there was no major damage.

Comparative Example 1 In Example 1, methyl silicate (molecular weight of about 1000) was used in place of No. 3 sodium silicate.
A plate-shaped molded body was obtained in the same manner as.

The inter-glass transmittance of the obtained laminated glass was 88%. However, when a heating test was conducted according to a heating curve prescribed by JISR 1311 “Fireproof Test Method for Architectural Fire Doors”, the glass cracked and ignited within 5 minutes of the heating test. Furthermore, after 7 minutes, the glass fell off, flames and smoke penetrated through the heating back surface, and fire resistance was poor.

[0052]

Industrial Applicability According to the present invention, it can be manufactured at low cost and is transparent, flame-retardant, heat-resistant, fire-resistant, fire-proof, flame-proof, smoke-proof, safety, crime-proof, sound-proof, and durable. It is possible to provide a laminated glass having excellent light resistance, weather resistance, impact resistance, penetration resistance, boiling water resistance, glass scattering prevention property, and chemical resistance.

Claims (9)

[Claims] 1. A hydrophilic resin between two substrates, and
A laminated molded article, characterized in that an intermediate layer containing water glass is present. 2. The laminated molded article according to claim 1, wherein the intermediate layer contains water. 3. The laminated molded body according to claim 1, wherein the hydrophilic resin is a polysaccharide. 4. The laminated molded article according to claim 1, wherein a hydrophilic resin having a hydroxyl group is used. 5. A laminated molded article comprising water glass containing sodium silicate or potassium silicate. 6. The laminated molded body according to claim 1, wherein at least one of the substrates is glass. 7. The laminated molded article according to claim 1, wherein the intermediate layer contains a compatibilizing agent. 8. The laminated molded article according to claim 1, wherein the intermediate layer contains a flame retardant. 9. The laminated molded article according to claim 2, wherein the water content of the intermediate layer is 30 to 98% by weight.