JPH0146475B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an inorganic fiber heat insulating material used in architecture, civil engineering, and various industrial fields. [Conventional technology] Conventionally, felt-like,
BACKGROUND OF THE INVENTION Inorganic or organic heat insulating materials such as pine, board, and cylindrical glass fibers, rock wool, asbestos fibers, polystyrene foam, and polyurethane are used in architecture, civil engineering, and various industrial fields. Among these insulation materials, organic foams are lightweight and have good insulation properties, but they are flammable and have extremely poor heat resistance. It is used only in fields where it is not. On the other hand, inorganic fiber insulation materials such as glass fiber and rock wool are nonflammable and more heat resistant than organic foams, so they are widely used in housing and industrial fields. However, even with these inorganic fiber insulation materials, temperatures up to 400℃
If it is used at high temperatures of ~700℃ for a long time, or if it is exposed to high temperatures for an even shorter period of time as a fireproof plate, the fibers will soften and shrink in size, so it is not used as a heat insulator in high temperature ranges. However, there are natural usage temperature limits (300-400℃ for glass fiber insulation, 600℃ for rock wool insulation).
~700℃). Furthermore, these inorganic fiber insulation materials have low resistance to chemicals such as acids and alkalis, and are not used as insulation materials in fields that require chemical resistance, or if they are used in this field, Construction methods are used that take into account protection using materials with excellent chemical resistance, and as a result, there are problems such as the construction becoming complicated and the construction work becoming more extensive. [Problems to be Solved by the Invention] In view of the above-mentioned problems, the present invention combines an inorganic fibrous body with an inorganic material having excellent fire resistance and chemical resistance, thereby making it nonflammable and resistant to chemicals. However, the aim is to obtain a material that can withstand a high temperature range of 1000 to 1500°C for a long time. [Means for solving the problems] The present invention includes 15 to 70 wt% of a synthetic resin binder,
A composition containing 30 to 85 wt% of at least one of colloidal silicic anhydride-blended silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina (all of the above on a solid basis) contains a small amount of lead oxide and tin oxide. By bonding a material containing at least one of the following to an inorganic fibrous body, a heat-resistant and chemical-resistant carbide is formed on the surface of the inorganic fibrous body when exposed to fire heat. be. In addition, the synthetic resin binder is 15 to 70 wt%, and at least one of silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina is 30 to 85 wt%,
The range is such that the binding strength of the synthetic resin binder is not reduced and the formation of carbides is not insufficient. Furthermore, 10 wt% or less of carbon black is blended into the synthetic resin binder so that even if the synthetic resin binder is used in a relatively small amount and the carbon produced is insufficient, there will be no shortage of carbide formation. [Function] The present invention combines an inorganic material with an inorganic fibrous body using a synthetic resin binder as a binder, and when exposed to fire heat, the synthetic resin binder carbonizes and becomes a carbon source, and silicon oxide, zirconium oxide, titanium oxide, etc. Lead oxide and tin oxide are used as vitrification forming aids and are fused to form a carbide together with carbon black on the surface of the inorganic fibrous material. [Constitution of the Invention] Colloidal silicic anhydride silicon oxide, zirconium oxide, titanium oxide, colloidal alumina, which are nonflammable and impart fire resistance and chemical resistance, constitute the present invention.
The inorganic materials made of lead chloride and tin oxide, the synthetic resin binder, and the inorganic fibrous material will be explained in detail. Titanium oxide, zirconium oxide, and silicon oxide as inorganic materials are each produced by a drying temperature of 200 to 300°C or thermal decomposition during the manufacturing process of the heat insulating material of the present invention. It also includes things that are. In the case of titanium compounds, oxides such as titanium oxide, titanic acid, titanium sulfate, titanium chloride, titanium oxyacetylacetonate, titanium alkoxide, acids, inorganic salts, chlorides, organic titanium compounds, and zirconium Compounds include oxides, acids, such as zirconium oxide, zirconic acid, zirconium sulfate, zirconyl nitrate, zirconyl acetate, zirconyl oxychloride, zirconyl oxynitrate, zirconyl ammonium carbonate, zirconyl chloride, zirconium acetylacetonate, zirconium alkoxide, Inorganic salts, chlorides, organic zirconium compounds, colloidal zirconium compounds, and silicic acid compounds include oxides, acids, inorganic salts, chlorides, and organic silicon compounds such as silicon oxide, colloidal silicic anhydride, silicon tetrachloride, and organic silicon ammonium. can be given. Furthermore, lead oxide and tin oxide, which are inorganic materials, are mixed with lead compounds and tin compounds during the manufacturing process.
It also includes those produced by drying temperatures of 200 to 300°C or thermal decomposition. Specific examples of lead oxides include lead acetate, lead benzoate, lead oxalate, lead citrate, lead nitrate, lead chromate, lead carbonate, red lead tetraoxide, lead dioxide, lead oxide, lead metaborate, and water. For lead oxide, lead molybdate, lead silicate, and tin oxide,
Examples include tin oxide, tin hydroxide, stannous oxide, stannous sulfate, stannous acetate, and tin oxalate. In addition to the above, it is effective to add colloidal alumina to the inorganic material to improve heat resistance. In addition, in order to reduce costs, inorganic fillers such as clay, mica, talc, glass powder, rock wool fine fibers, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, ammonium bromide, phosphoric acid, etc. There is no problem in adding organic or inorganic flame retardants such as guanidine, phosphoric acid silica, and antimony trioxide to the extent that fire resistance and chemical resistance are not impaired. Furthermore, carbon black as an inorganic material is a black fine powder and is usually produced by the furnace method such as furnace black, acetylene black, thermal black, channel black produced by the impact method, disk black, German naphthalene black, etc. Commercially available products such as Black can be used, and inorganic fibers can be heated in a high-temperature reducing atmosphere.
It is also possible to use a type in which carbon black treated with carbon is fixed and integrated on the surface of inorganic fibers. Examples of this type include carbon black-bound potassium titanate fibers, and also fine carbon fibers such as carbon fibers. Further, part or all of the carbon black may be replaced with a flame retardant that promotes carbonization of pulp, resin, etc. contained in the inorganic fibrous material by heating during the manufacturing process. Examples of synthetic resin binders include vinyl acetate resin, ethylene/vinyl acetate resin, acrylic resin,
Synthetic rubber such as SBR and NBR, emulsion type such as polyvinyl alcohol, starch, polyamide resin, polyimide resin, aqueous solution type, solution type dissolved in organic solvent, thermoplastic resin, melamine resin, phenol resin, epoxy Thermosetting resins such as emulsion type resins, polyester resins, furan resins, aqueous solution types, and solution types dissolved in organic solvents can be used as binders alone or in the form of mixtures, but there is a risk of fire. It is preferable to use a water-soluble type or emulsion type binder due to its properties. Examples of the inorganic fibrous material include glass fibrous material, rock wool fibrous material, and composite inorganic fibrous material made by combining these inorganic fibers. Glass fibrous bodies are usually long fibers with a fiber diameter of about 5 to 15 μm, or cut fibers made by cutting long fibers, or fibers made by using centrifugal force or the like. It has a sheet-like, cross-like, felt-like, mat-like, board-like, or cylindrical shape made of so-called short fibers, and the fibers are bonded chemically using a small amount of resin binder, or by needling. It is an inorganic fibrous material made mechanically by methods such as rings and looms. Rotsuk wool insulation material is made by melting a raw material composition containing basalt, peridotite, iron ore slag, silica, dolomite, lime, etc.
It is obtained by making fibers using centrifugal force using a multi-rotor system, etc., and is an inorganic fibrous body whose shape and fiber bonding method are similar to those of the above-mentioned glass fiber type. Furthermore, inorganic fibrous bodies made of composite fibers of glass fibers and rock wool fibers having the same shape and bonding method as above, and these glass fiber-based, rock wool-based, and glass fiber/rock wool composite inorganic fibrous bodies have combustibility. It also includes organic materials such as pulp, as well as inorganic fibrous materials that are partially blended with inorganic fillers, flame retardants, etc., to the extent that they do not impair the quality of the materials. A typical example is rock wool sheathing board. Note that it is effective to use these fibrous bodies having a bulk specific gravity of 0.5 or less, preferably 0.3 or less in terms of their heat insulating performance. During production, the above-mentioned inorganic material is dispersed and diluted in the above-mentioned synthetic resin liquid, and this dispersion liquid is absorbed into the above-mentioned inorganic fibrous material by a method such as impregnation, spraying, or coating, and then dried. The inorganic material is bonded to the inorganic fibrous body by heat curing under no pressure and further heat treatment if necessary. The mechanism of action of treating an inorganic fibrous body with the composition of the present invention to impart fire resistance and chemical resistance is presumed to be due to the following reasons. First, the resin binder of the fibrous body functions to maintain the shape of the fibrous body in a temperature range of about 200℃ or less, and then the inorganic material acts as a vitrification formation aid in a temperature range of 200℃ to 600℃. It is fused to the inorganic fibrous body by the action of lead oxide, tin oxide, or a mixture thereof, and then at high temperatures, carbon black made of synthetic resin thermal decomposition products or carbon black from the original combination and inorganic materials titanium oxide, oxidized Zirconium and silicon oxide react with carbon to form carbides on the fiber surface (the higher the temperature, the more carbides are formed), and when colloidal alumina is added, in addition to the formation of these carbides, As a result of the formation of a highly fire-resistant mullite composition (3Al ₂ O ₃・2SiO ₂ ), the fibrous body has non-combustible, fire-resistant, It is presumed that this makes it possible to impart chemical resistance. The blending ratio of the constituent components of the composition that imparts nonflammability, fire resistance, and chemical resistance of the present invention is such that the total of carbon black and synthetic resin binder is 15 to 15% in terms of solid content.
70wt% (However, the amount of carbon black
(10wt% or less) colloidal silicic anhydride blended silicon oxide as an essential component, and zirconium oxide,
Total amount of titanium oxide and colloidal alumina: 85~
0.05 to 15 parts by weight of lead oxide, tin oxide, or a mixture thereof is added to 100 parts by weight of the composition in a proportion of 30 wt%.
Parts by weight range. Total of carbon black and synthetic resin binder (however, the blending amount of carbon black is 10wt% or less)
If the solid content is less than 15 wt%, the amount of synthetic resin binder in the composition will be small, the force that binds the inorganic material to the inorganic fibrous body will be small, and it will be easy to fall off due to external force such as impact, and it will be difficult to process. When the inorganic fibrous material is exposed to high temperatures, the amount of carbon black formed as a whole decreases when the initially added carbon black or the synthetic resin binder is heated to high temperatures, resulting in carbides of silicon oxide, zirconium oxide, and titanium oxide. Formation is insufficient,
It does not provide satisfactory fire resistance, and
At 70wt% or more, the adhesion strength described above is fully satisfied, but the content of the synthetic resin binder also becomes 60wt% or more, and as a result, the proportion of inorganic materials decreases, resulting in a decrease in fire resistance and chemical resistance, and furthermore, the Ministry of Construction In order to pass the noncombustible grade listed in Public Notice No. 1828, there are restrictions on the composite ratio that imparts fire resistance and chemical resistance (in this case, fire resistance is also sacrificed), and as a result, It becomes difficult to impart satisfactory fire resistance to the inorganic fibrous body. If the synthetic binder content is increased within the above range, carbon is formed by high-temperature pyrolysis, so the carbon black content can be reduced, and as a limit, the carbon content can be reduced to zero. The upper limit of the amount of carbon black added was set at 10wt%,
Even if the amount added is increased further, no improvement in the effect is observed, so taking into account the combination of other ingredients, 10 wt% or less is sufficient. The components of the inorganic material are silicon oxide containing colloidal silicic anhydride, zirconium oxide, titanium oxide, and colloidal alumina, with a total solid content of 85 ~
The reason why it is 30wt% is due to the above reason. Its composition includes silicon oxide as an essential component, and titanium oxide, zirconium oxide, and colloidal alumina are blended singly or in a mixture as necessary depending on the level of fire resistance and chemical resistance. In particular, adding liquid colloidal silicic anhydride to silicon oxide improves the bonding properties with inorganic fibrous bodies.
It is also effective because it has better fire resistance than powdered silicon oxide. Titanium oxide and zirconium oxide also have a positive effect on fire resistance, but they also play an important role in terms of chemical resistance. As for colloidal alumina, it has a slight negative effect on chemical resistance, so it is not preferable to mix it in large amounts, but this material reacts with inorganic fibrous materials or silicon oxide at high temperatures, and has a mullite composition (with excellent fire resistance). 3Al ₂ O ₃ .2SiO ₂ ), it is effective to blend colloidal alumina as necessary. It is important to further add 0.05 to 15 parts by weight of lead oxide, tin oxide alone or a mixture thereof to 100 parts by weight of the composition having the above blending ratio, preferably 0.5 to 10 parts by weight (both calculated as solid content). be. Adding a small amount of vitrification forming aids such as lead oxide and tin oxide gives fire resistance and chemical resistance to the inorganic fibrous material, even if the composite ratio is small, the inorganic fibrous material can be exposed to high temperatures for a long time. It is possible to impart durable performance. The reason is as mentioned above, but
The effect becomes noticeable when the amount is 0.05 part by weight or more, preferably 0.5 part by weight or more, and the effect increases when the amount is more than 0.05 part by weight. On the other hand, since these vitrification forming aids have a slightly negative effect on resistance to chemicals such as acids and alkalis, they must be avoided in amounts of 15 parts by weight or more. The preferred blending ratio of these components is 3 to 8 wt%. A treatment liquid consisting of a composition having the above-mentioned preferred blending ratio is composited into an inorganic fibrous body by a method such as impregnation or coating, but the composite ratio that imparts fire resistance and chemical resistance is not particularly limited. but,
In terms of solid content, per 100 parts by weight of inorganic fibrous material,
A sufficient effect can be obtained even if the amount of the material that imparts fire resistance and chemical resistance is preferably 100 parts by weight or less, preferably 50 parts by weight or less. The inorganic fibrous material obtained by processing in this way depends on the resin binder, but is usually
In the case of resin binders that require drying at 60 to 110°C and subsequent curing, the inorganic fibrous material is cured at 150 to 200°C under pressure or no pressure, and then partially baked as necessary. By performing heat treatment at a temperature below the softening temperature (usually 250 to 800°C), it is possible to produce an inorganic fibrous insulation material that is nonflammable, fire resistant, and chemical resistant. [Effect of the invention] According to the invention, the synthetic resin binder is 15 to 70wt.
% and at least one of colloidal silicic anhydride-blended silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina (all of the above in terms of solid matter), a small amount of lead oxide, Because the material containing at least one type of tin oxide is bonded to the inorganic fibrous material, when exposed to fire heat, lead oxide and tin oxide fuse to the inorganic fibrous material at low temperatures, and when the temperature rises further, The synthetic resin binder carbonizes and reacts with titanium oxide, zirconium oxide, and silicon oxide to form carbide on the surface of the inorganic fibrous material.This carbide has a high melting point and high chemical resistance, making it nonflammable. fire resistant,
Chemical resistance can be imparted. In addition, since the synthetic resin binder was 15 to 70 wt% and at least one of silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina was 30 to 85 wt%,
If the synthetic resin binder is less than 15%, the bond with the inorganic fibrous body will be low, and the amount of carbon will be insufficient when carbonized, so that sufficient fire resistance cannot be expected. Moreover, if it exceeds 70%, the relative amounts of silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina to be blended will be insufficient, resulting in a decrease in fire resistance and chemical resistance. Furthermore, since the material does not contain carbon black, when it is bonded to an inorganic fibrous material, it becomes white or pale in color and can be colored in any desired color. Furthermore, the adhesion of silicon oxide, zirconium oxide, and titanium oxide to the inorganic fibrous body is aided by the vitrification formation aids of lead oxide and tin oxide, which are added in small amounts, so the amount of these oxides added can be reduced. It can provide fire resistance and chemical resistance. In addition, carbon black is added to the synthetic resin binder.
When blended in an amount of 10wt% or less, it is possible to supplement carbon that is insufficient when the amount of synthetic resin binder blended is small. It should be noted that even if the amount of carbon black added is increased to 10% or more, the effect will not be improved, and the amount of other ingredients will be reduced, which is inconvenient. [Example] Examples of the present invention will be explained with reference to the attached table along with comparative examples. Sample Material concentration of composition (solid content equivalent) shown in the attached table: 6 to 8 wt
% of the aqueous dispersion shown in the same table was impregnated into the inorganic fibrous body shown in the same table, and test specimens No. 1 to No. 17 were prepared using the composite ratio (adhesion rate) shown in the same table and the drying and curing conditions shown in the same table. Test specimen No.1
- No. 3 are comparative examples, and test specimens No. 4 to No. 17 are examples of the present invention. Test Method Fire Resistance A test specimen (any size) is subjected to a flame test for 30 minutes using an acetylene torch burner at 900 to 1200°C at a distance of 10 cm from the surface of the specimen, until the flame penetrates the specimen and a hole appears. It was evaluated as the time of Chemical Resistance Approximately 10 gr of the above test specimen was placed in 500 c.c. of each of IN's NaOH and IN's HCl aqueous solutions, placed in a closed plastic container (No. 1), and immersed in a constant temperature bath at 80°C ± 1°C for 2 hours, with no change in shape. A rating was given for those that did not occur, a rating of B for those that caused slight deformation but no practical problem, and a rating of C for those that caused deformation and required improvement. Nonflammability test for inorganic fibrous materials Base material test stipulated in Ministry of Construction Notification No. 1828 using a size of 40 mm (length) x 40 mm (width) x 49 mm (height).
(Pass is 800℃) Test results No. 1 to No. 6 show cases where the blending ratio of the binder and inorganic material was changed, and comparative examples No. 1 and No. 2 show cases where the blending ratio of the binder and the inorganic material was changed. The blending ratio with the raw material is outside the blending ratio of the present invention, and both have poor fire resistance. In addition, Comparative Example No. 3 does not contain either lead compounds or tin compounds, but for this reason, in order to impart sufficient fire resistance and chemical resistance comparable to the products of the present invention, it is necessary to The blending amount has increased to 31%. No. 7 to No. 13 show the relationship between the amount of binder blended and carbon. When the amount of binder increases, the resin thermally decomposes at high temperatures and becomes carbon, so carbon may not be added, and colloidal silicic anhydride and alumina This shows that it is possible to eliminate carbon black by adding . In No. 10 and No. 11, the material of the inorganic fibrous body was changed. No. 14 to No. 17 show cases where the type and amount of vitrification forming aids (lead oxide, tin oxide, etc.) were changed,
This shows that the effect increases as the amount added increases. Next, the inorganic fibrous bodies and other materials used in the above-mentioned comparative examples and examples will be explained. Glass fiber felt Fuji Jushi Kako Co., Ltd./Product number Fuji Glass Matsuto
RM (bulk specific gravity 80Kg/m ³ , thickness 5mm) resin (solid content 55%). Rock wool board Nitto Boseki Co., Ltd./Insal boat (bulk specific gravity
80Kg/ ^m3 , thickness 25mm). Rock wool sheathing board, general commercial product, made of rock wool pulp, inorganic filler, and organic binder, bulk specific gravity 400Kg/ ^m3 ,
10mm thick, non-combustible grade product. Melamine resin Nippon Carbide Co., Ltd. Product number S-260 (100%)
solid content). Phenol resin Showa Union Gosei Co., Ltd. Product number BRL-141 Water-soluble resol type phenolic resin. Colloidal silicic anhydride Nippon Shokubai Chemical Co., Ltd. Cataloid SI
45P (solid content 40-40%). Titanium oxide Fuji Titanium Industries Co., Ltd. Rutile type titanium oxide powder. Silicon dioxide powder 200 mesh pass General commercial product Zirconium oxide powder Nippon Metal Chemical Co., Ltd. Zirconia Powder Carbon Black Asahi Carbon Co., Ltd. Positive Furness Black Colloidal Alumina Nissan Chemical Industries Co., Ltd. Product number Alumina sol
200 (concentration approx. 10%) Mica Manufactured by Kuraray Co., Ltd., product name Tin Olite Mica G-325 Modified acrylic resin Kureha Chemical Industry Co., Ltd., product number VATR-106 Acrylic/vinylidene chloride copolymer resin emulsion Lead acetate, lead oxide, tin oxide Uses first grade reagent (commercially available)

【table】

Claims (1)

[Scope of Claims] 1 15 to 70 wt% of a synthetic resin binder, and 30 to 85 wt% of at least one of colloidal silicic anhydride compounded silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina (all of the above) 1. An inorganic fibrous heat insulating material, characterized in that it is made by bonding a material containing a small amount of at least one of lead oxide and tin oxide to an inorganic fibrous body. 2 15 to 70 wt% of a synthetic resin binder containing 10 wt% or less of carbon black, and 30 to 85 wt% of at least one of colloidal silicic anhydride compounded silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina. All are converted to solid matter)
1. An inorganic fibrous heat insulating material, characterized in that it is made by combining a composition consisting of the above with a small amount of at least one of lead oxide and tin oxide and bonding it to an inorganic fibrous body. 3. The inorganic fiber insulation according to claim 1 or 2, characterized in that 0.05 to 15 parts by weight of at least one of lead oxide and tin oxide is blended with respect to 100 parts by weight of the composition. Material.