JPS6131336A - Inorganic fiber heat insulating material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention applies to inorganic sulfur used in architecture, civil engineering, and various industrial fields.
IA miscellaneous miscellaneous insulation material.

[Conventional technology]

Traditionally, inorganic or organic insulation materials such as felt, mat, board, and cylindrical glass am, rock wool, asbestos fiber, polystyrene foam, and polyurethane have been used in architecture, civil engineering, and various industries for the purpose of saving energy. used in the field.

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 areas where it is not necessary. On the other hand, inorganic fiber insulation materials such as glass am and rock wool are nonflammable and compared to organic foams,
Due to its heat resistance, it is widely used in residential and industrial fields.

However, even with these non-trade insulation materials, temperatures of 400℃~
If it is used for a long time at a high temperature of 700℃, 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 should not be used as a heat insulator in high temperature ranges. However, the current situation is that there are naturally usage temperature restrictions (300 to 400°C for glass fiber insulation and 600 to 700°C for rock wool insulation). Furthermore, these inorganic IN insulation materials have low resistance to chemicals such as acids and alkalis, and are either 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 time being increased considerably.

(Problems to be Solved by the Invention) In view of the above-mentioned problems, the present invention has been developed by combining an inorganic fiber corpus luteum with an inorganic material having excellent fire resistance and chemical resistance. , 1000-150
The objective is to obtain a product that has the ability to withstand a high temperature range of 0° C. for a long time.

(Means for solving the problems) According to the present invention, 15 to 7 wt% of a synthetic resin binder,
A composition consisting of 30 to 55 wt% (all of the above in terms of solid matter) of at least one of colloidal silicic anhydride-blended silicon oxide, zirconium oxide, titanium oxide, and [0oidal alumina], and a minimum amount of lead oxide. By bonding a material containing at least one of tin oxide and tin oxide to an inorganic fibrous material, a heat-resistant and chemical-resistant carbide is formed on the surface of the unsharpened mmH material that is exposed to fire heat. This is what I did.

In addition, the synthetic resin binder should be 15 to 70 w (%), and at least one of silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina should be 30 to 85 wt % to avoid reducing the binding strength of the synthetic resin binder and forming carbides. The scope is set so as not to be insufficient.

Furthermore, carbon black of iQwt% or less is blended with the synthetic resin binder so that even when the synthetic resin binder is in a relatively small amount and the carbon produced is insufficient, the formation of carbide is not insufficient.

[Effect]

The present invention combines an inorganic material with an inorganic fiber corpus luteum using a synthetic resin binder as a binder, and when exposed to fire heat, the synthetic resin binder carbonizes and becomes a carbon source.Silicon oxide, zirconium oxide, titanium oxide, etc. are made of lead oxide, tin oxide, etc. is fused as a vitrification forming aid and forms a carbide on the surface of the inorganic fiber corpus luteum together with carbon black.

(Structure of the Invention) An inorganic material comprising colloidal silicic anhydride type silicon oxide, zirconium oxide, titanium oxide, colloidal alumina, lead oxide, and tin oxide, which is nonflammable and imparts fire resistance and chemical resistance, constituting the present invention. , synthetic resin binder, and inorganic 1M substance will be explained in detail.

Titanium oxide, zirconium oxide, and silicon oxide as inorganic materials are used as titanium compounds, zirconium compounds, and silicon compounds, respectively, during the manufacturing process of the heat insulating material of the present invention.
It also includes those produced by dry water temperature of 0 to 300°C or thermal decomposition. In the case of titanium compounds, oxides, acids, inorganic salts, chlorides, and organic titanium compounds such as titanium oxide, butanoic acid, di-titanium chloride, di-titanium chloride, ditanium oxyacetylacetonate, titanium alkoxide, etc. , Zirconium oxide, zirconic acid, lilliM zirconium,
Zirconyl nitrate, zirconyl acetate, Δxyzirconyl chloride, zirconyl oxynitrate, zirconyl ammonium carbonate, zirconyl chloride, zirconium ■ Oxides, acids, inorganic salts, chlorides, organic zirconium compounds such as acetylacetonate, zirconium alkoxide, Colloidal zirconium compounds, silicon oxide in silicon compounds,
Examples include oxides, acids, inorganic salts, chlorides, and organosilicon compounds such as Ooid-like anhydrous silicon tetrachloride and organosilicon ammonium.

Further, lead oxide and tin oxide as inorganic materials include lead compounds and tin compounds produced by drying at a temperature of 200 to 300° C. or thermal decomposition during the manufacturing process. Specific examples of lead oxides include lead acetate, lead benzoate, lead oxalate, lead citrate, lead nitrate, lead chromate, lead carbonate,
Kyuuda (trilead tetroxide) lead dioxide, lead oxide, lead metaborate,
For lead hydroxide, lead molybdate, lead silicate, and tin oxide,
tin oxide, tin hydroxide, stannous oxide, stannous sulfate,
Examples include 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, microscopic rock wool, maznesium hydroxide, aluminum hydroxide, ammonium polyphosphate, ammonium bromide, phosphoric acid, etc. It is permissible to add organic and S-type 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 fine black powder and is usually commercially available such as furnace black, acetylene black, and thermal black manufactured by the furnace method, channel black, disk black, and German naphthalene black manufactured by the impact method. Carbon black made by treating FjAmH-free with carbon in a high-temperature reducing atmosphere is S
A type that is fixed and integrated with the surface of the machine fiber can also be used. An example of this type is potassium titanate I, which has the same name as carbon black! Carbon fibers such as carbon fibers can also be used. Furthermore, part or all of the carbon black may be replaced with a flame retardant that promotes carbonization of valves, resins, etc. contained in the free mass by heating during the manufacturing process.

Synthetic resin binders include vinyl acetate resin, ethylene/vinyl acetate resin, acrylic resin, synthetic rubbers such as SBR and NBR, emulsion types such as polyvinyl alcohol, starch, polyamide resins, and polyimide resins, aqueous solution types, and those dissolved in organic solvents. Thermosetting resins such as solution types such as thermoplastic resins, melamine resins, phenol resins, epoxy resins, polyester resins, furan resins, etc., aqueous solution types, and solution types such as solution types dissolved in organic solvents. Alternatively, it can be used as a binder in the form of a mixture, but it is preferable to use a water-soluble type or emulsion type binder due to the risk of fire.

Examples of the inorganic fibrous material include a glass lI&H material, a rock wool fibrous material, and a composite wireless fibrous material made by combining these inorganic fibers. Glassy! The fibrous body usually has a so-called E-glass composition to a C-glass composition, and has a fiber diameter of 5.
Sheet-like, felt-like, mat-like fibers made of short fibers made into fibers using centrifugal force, etc.
It has a board-like or cylindrical shape, and is an inorganic fibrous body in which the lI and miscellaneous bonds are made chemically using a small amount of resin binder or mechanically by methods such as needling. be. Rock wool insulation material is obtained by melting a raw material composition containing basalt, peridotite, iron ore slag, silica, dolomite, lime, etc., and turning it into fibers using centrifugal force, such as with a multi-rotor. It is an inorganic fibrous body made of the same shape and fiber bonding method as the glass m1. Further, an inorganic fibrous body made of composite fibers of glass fibers and rock wool fibers having the same shape and bonding method as above, and an inorganic fibrous body based on glass fibers, rock wool, and glass fiber/rock wool composites. It also includes inorganic fibrous materials partially blended with organic substances such as valves, inorganic fillers, flame retardants, etc., within the range that does not impair combustibility.The composition is rock wool, valves, inorganic fillers, In the binder system,
A typical example is rock wool sheathing board. Note that it is effective to use these IIaN masses having a bulk specific gravity of 0.5 or less, preferably 0.3 or less, in terms of their heat insulation performance.

During production, the above-mentioned inorganic material is dispersed and diluted in the above-mentioned synthetic resin liquid, this dispersion is absorbed into the above-mentioned inorganic fibrous material by impregnation or coating, and then dried, and then under pressure or no pressure. The inorganic material is bonded to the inorganic fibrous body by heat curing 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 fibrous resin binder has approximately 200%
It functions to maintain the shape of the m fibrous body in the 4 degree range below ℃,
Subsequently, in the temperature range of 200°C to 60°C, the inorganic material is fused to the inorganic fibrous material by the action of lead oxide, tin oxide, or a mixture thereof as a vitrification forming aid, and the synthetic resin is thermally decomposed at a further high temperature. Carbon black from the product or carbon black from the original blend and inorganic materials such as titanium oxide, zirconium oxide, 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 further blended, in addition to the formation of these carbides, a highly refractory Murai 1 composition (3A1z 03
・2SiDz) is formed, resulting in the properties of these carbides l! (High melting point, chemical resistance) etc., it is presumed that it has become possible to impart nonflammability, fire resistance, and chemical resistance to the IIH mass.

The blending ratio of the constituent components of the composition of the present invention, which is nonflammable and imparts fire resistance and chemical resistance, is that the total of carbon black and synthetic resin binder is 15 to 70 wt% in terms of solid content (however,
The amount of carbon black is 10 wt% or less) A composition consisting of colloidal silicic anhydride blended silicon oxide as an essential component and zirconium oxide, titanium oxide, and colloidal alumina in a total ratio of 85 to 30 wt%. 0.05 lead, tin oxide or a mixture of these
~15 parts by weight.

If the total amount of carbon black and synthetic resin binder (however, the amount of carbon black is 10 wt% or less) is less than 15 wt% in terms of solid content, the amount of synthetic resin binder in the composition will be small, and the inorganic material will become an inorganic IIN substance. The bonding force is small, and it is easy to fall off due to external edges such as impact, and when the treated inorganic fibrous material is exposed to high temperatures, it may be formed during high temperature heating of initially added carbon black or synthetic resin binder. As a result of the overall decrease in carbon black ω, the formation of carbides of silicon oxide, zirconium oxide, and titanium oxide becomes insufficient, and satisfactory fire resistance is not imparted. Although this is fully satisfied, the content of the synthetic resin binder is 60w% or more, and as a result, the blending ratio of inorganic materials is reduced, resulting in a decrease in fire resistance and chemical resistance. In order to pass the test, there are restrictions on the composite ratio that imparts fire resistance and chemical resistance (in this case, fire resistance is also sacrificed).As a result, the fire resistance that should be added to the inorganic fibrous material It becomes difficult to give gender. Note that when 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 carbon black addition amount is 10wt
%, but since no improvement in the effect is seen even if the amount added is increased further, it is sufficient to use less than 10 wt %, considering the combination of other ingredients. The reason why the inorganic material is composed of silicon oxide containing colloidal silicic anhydride, zirconium oxide, titanium oxide, and colloidal alumina is 85 to 30 wt % in terms of solid content. In addition, its composition includes silicon oxide as an essential component, titanium oxide, zirconium oxide,
Colloidal alumina is added alone or in the form of a mixture as necessary depending on the level of fire resistance and chemical resistance. In particular, it is effective to contain liquid colloidal silicic anhydride in silicon oxide because it improves the bonding properties with the inorganic fibrous body and has better fire resistance than powdered silicon oxide. Titanium oxide and zirconylum oxide also have a positive effect on fire resistance, but they also play an important role in terms of chemical resistance. Regarding colloidal alumina, it is not preferable to mix it in a large amount because it has a slight negative effect on chemical resistance, but this material has a mullite composition that reacts with inorganic fibers or silicon oxide at high temperatures and has excellent fire resistance. (
3^1203.2SiOz), it is effective to blend colloidal alumina as necessary.

Further, 0.05 of lead oxide, tin oxide alone or a mixture thereof is added to the mouth of the composition consisting of the above 2 compounding ratios.
It is important to include ~15 parts by weight, preferably 0.5 to 10 parts by weight (all calculated in terms of solid content). Adding a small amount of vitrification forming aids such as lead oxide and tin oxide improves fire resistance.
Even if the ratio of the material imparting chemical resistance to the inorganic fiber III body is small, it is possible to impart the ability of the inorganic fibrous material to withstand high temperatures for a long time. The reason is as described above, but the effect is noticeable when the amount is 0.05 parts by weight or more, preferably 0.5 parts by weight or more, and the effect increases with more than 0.5 parts by weight. On the other hand, these vitrification forming aids are acid,
Since it has a slightly negative effect on resistance to chemicals such as alkali, it is necessary to avoid adding more than 15 parts by weight. The preferred blending ratio of these components is 3 to Bwt%.

A treatment liquid consisting of a composition having the above-mentioned preferred blending ratio is composited into an inorganic fibrous body by impregnation or coating, but the composite ratio that reduces fire resistance and chemical resistance is not particularly limited. However, in terms of solid content, it is preferable to use less than 100 parts by weight of the inorganic #HN mass 100 parts by weight to impart fire resistance and chemical resistance, and even less than 50 parts by weight can have a sufficient effect. can get. The inorganic fibrous material obtained by processing in this way is usually dried at 60 to 110°C, depending on the resin binder, and then, in the case of a resin binder that requires curing, at 150 to 200°C under pressure. Alternatively, in order to harden under no pressure and further to partially bake if necessary, the temperature is below the softening temperature of the inorganic fibrous material (
By performing heat treatment at a temperature (usually 250 to 800°C), it is possible to produce a non-flammable heat insulating material that is nonflammable, fire resistant, and chemical resistant.

(Effects of the Invention) According to the present invention, 15 to 70 wt% of the 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 (any of the above) (solid equivalent)
A composition consisting of a small amount of at least one of lead oxide and tin oxide is combined with an inorganic fibrous material, so that when exposed to fire heat, lead oxide and tin oxide will dissolve in the inorganic fiber at low temperatures. When the synthetic resin binder is fused to the atomized material and heated to a higher temperature, the synthetic resin binder carbonizes and reacts with titanium oxide, zirconium oxide, and silicon oxide to form carbide on the surface of the atomized material. Since it has high chemical resistance, it can impart nonflammability, fire resistance, and chemical resistance to inorganic fibrous materials. In addition, 15 to 70 wt% of synthetic resin binder
, 30 to 85 wt% of at least one of silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina.
Therefore, if the synthetic resin binder is 15% or less, there is no am
The bond with foreign matter is low, and when carbonized, the amount of carbon is insufficient, so sufficient fire resistance cannot be expected.

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 combined with an inorganic fibrous material, it becomes white or pale and can be colored in any desired color.Furthermore, lead oxide and tin oxide are added in small amounts. Since the vitrification forming aid assists in the adhesion of silicon oxide, zirconium oxide, and titanium oxide to the inorganic fibrous material, it is possible to increase the fire and chemical resistance effects by reducing the amount of these oxides. .

In addition, synthetic resin binder (iQwt carbon black)
% or less, it is possible to supplement carbon that is insufficient when the amount of synthetic resin binder is small.

Even if the amount of Naori-Bon black is increased to 10% or more, the effect will not improve and the amount of other components will be reduced, which is disadvantageous.

(Example) Examples of the present invention will be explained with reference to the attached table along with comparative examples.

An aqueous dispersion with a material concentration of 6 to 8 wt% having the composition (solid content equivalent) shown in the sample table was impregnated into the inorganic Il fibrous body shown in the same table, and the composite ratio (applied rate) shown in the same table and the dry hardening rate shown in the same table were obtained. Test specimen 11 under conditions
G1 to Nc17 were created. Test specimen N.

Test specimens NQ4 to Nci17 are comparative examples, and test specimens NQ4 to Nci17 are examples of the present invention.

Test method A fire resistance test specimen (any size) was heated with an acetylene torch burner at 900 to 1200°C for 3 seconds at a distance of 10 seconds from the surface of the specimen.
A 0-minute flame test was conducted, and the time required for the flame to penetrate the test piece and for a hole to appear was evaluated.

Chemical resistant IN Mail, IN lC1 aqueous solution 500c each
Place the above test specimen in C for about 10 or, put it in a sealed plastic container of No. 11, and immerse it in a constant temperature bath at 80°C ± 1°C for 2) 1rs. Those with no practical problems were evaluated as B, and those that caused deformation and required improvement were evaluated as C.

Non-combustibility test of inorganic fibrous material A test of inorganic fibrous material specified in Ministry of Construction Notification No. 1828 using a size of 40 m5 + (length) x 40 m (width) x 49 a (height). (Pass: 800°C) Test results NQ 1 to NQ6 show cases where the blending ratio of binder and S-based material was changed, Comparative example) io, "l, 1
In m2, the blending ratio of the binder containing carbon black and other materials is outside the blending ratio of the present invention, and both have poor fire resistance.

Furthermore, Comparative Example No. 3 does not contain either a lead compound or a tin compound. Therefore, in order to impart sufficient fire resistance and chemical resistance comparable to the product of the present invention, it is necessary to mix the material with respect to the inorganic fibrous body. The amount has increased by 31%.

7 to Nα13 indicate the relationship between the blending amount of binder and carbon; as binder m increases, the resin thermally decomposes at high temperatures and becomes carbon, so carbon may not be added, and colloidal silicic anhydride or alumina may be added. This also shows that it is possible to eliminate the addition of carbon black.

NQIO and NQll are obtained by changing the material of the inorganic fiber 11.

NQ14 to NQ17 indicate cases where the type and amount of vitrification forming aids (lead oxide, tin oxide, etc.) were changed, and the formulation m
This shows that the effect is greater when the value is increased.

Next, the inorganic fibrous bodies and other materials used in the above-mentioned comparative examples and examples will be explained.

Glass fiber felt Hatakeshi Resin Processing Co., Ltd. Product number Fujigerasmat RM (
Bulk specific gravity Bogy/condition, thickness 5 m > resin (solid content 5
5%).

Rock wool board Nittobo Co., Ltd./Insal boat (bulk specific gravity Bob/
rd, thickness 25#).

Rock wool sheathing board, general commercial product, rock wool valve, inorganic filler, organic binder, bulk specific gravity 400; T/bottom, thickness 10I
a. Nonflammable grade product.

Melamine resin Nippon Carbide Co., Ltd. product number S-260 (100% solids).

Phenolic 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 Sl~45P (
solids content 40-40%).

titanium oxide Fuji Titanium Industries Co., Ltd. Rutile type titanium oxide powder.

Silicon dioxide powder 200 mesh bath general commercial product Zirconium oxide powder Shin Nippon Metal Chemical Co., Ltd. Zirconia powder carbon black Asahi Carbon Co., Ltd. Positive furnace black colloidal alumina Nissan Chemical Industries, Ltd. Product number Alumina Sol-200 (temperature approx. 10%) Mica stock Company manufactured by Kuraray, product name: tin olide mica modified acrylic resin Kureha Chemical Industry Co., Ltd., product number: VATR-106 Acrylic/vinylidene chloride copolymer resin emulsion lead, lead oxide, tin oxide reagent grade (commercial product) Amendment of Usage Procedures (Mutsu) 1.Indication of Incident 1982 Patent Application No. 153477
No. 2, Title of the invention Inorganic fiber insulation material 3, Relationship with the case of the person making the amendment Patent applicant Sadao Suzuki 4, Attorney 5, Date of amendment order None Specification 1, Name of the invention Inorganic fiber Insulating material 2, claims (1) 15 to 70 wt% of synthetic resin binder, colloidal silicic anhydride compounded silicon oxide, zirconium oxide,
An inorganic material is made by blending a small amount of at least one of lead oxide and tin oxide into a composition consisting of 30 to 85 wt% of at least one of titanium oxide and colloidal alumina (both on a solid basis). An inorganic fibrous heat insulating material characterized by being bonded to a fibrous body.

(2) 15 to 70 wt % of a synthetic resin binder containing 1 Q wt % or less of carbon black, and 30 to 70 wt % of at least one of colloidal silicic anhydride compounded silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina.
An inorganic material comprising a composition consisting of 55 wt% (all of the above in terms of solid matter) and a small amount of at least one of lead oxide and tin oxide combined with an inorganic woven material. 188 quality insulation material.

(3) The composition 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. Inorganic fiber insulation material.

3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an inorganic fiber heat insulating material used in architecture, civil engineering, and various industrial fields.

[Conventional technology]

Traditionally, inorganic or organic insulation materials such as felt, mat, board, and cylindrical glass fibers, rock wool, asbestos fibers, polystyrene foam, and polyurethane have been used in architecture, civil engineering, and various industrial fields for the purpose of saving energy. It's being used.

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 areas where it is not necessary. On the other hand, inorganic fiber insulation materials such as glass fiber and rock wool are nonflammable, and compared to organic foams,
Due to its heat resistance, it is widely used in residential and industrial fields.

However, even with these inorganic fiber insulation materials, temperatures ranging from 400℃ to 700℃
If it is used for a long time at high temperatures of ℃, or if it is exposed to dark and high temperatures for a short period of time as a fireproof board, the fibers may soften.
Although it is used as a heat insulating material in high temperature ranges due to dimensional shrinkage, it naturally has a usage temperature limit (300 to 400 °C for glass fiber insulation and 600 to 700 °C for rock wool insulation). That is the current situation. Moreover, these are inorganic! /aH 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. Construction methods are adopted that take into account protection using materials that are excellent in quality, and as a result, there are problems such as the construction becoming complicated and the construction work being completed over a long period of time.

[Problem that the invention seeks to solve]

In view of the above-mentioned problems, the present invention provides fire resistance and
By combining inorganic materials with excellent chemical resistance,
Nonflammable and resistant to chemicals, 1000-15
The objective is to obtain a product that has the ability to withstand a high temperature range of 00°C for a long time.

[Means for solving problems]

The present invention comprises 15 to 70 wt% of a synthetic resin binder, colloidal silicic anhydride compounded silicon oxide, zirconium oxide,
An inorganic material is made by blending a small amount of at least one of lead oxide and tin oxide into a composition consisting of 30 to 55 wt% (all of the above on a solid basis) of at least one of titanium oxide and colloidal alumina. By bonding to the fibrous body, there is no resistance when exposed to fire heat! Heat-resistant and chemical-resistant carbide is formed on the surface of the illumination body.

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%, so that the binding strength of the synthetic resin binder is not reduced and carbide formation is prevented. The amount is set within a range that is not insufficient.

Furthermore, 10 wt % or less of carbon black is blended with 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, the formation of carbides will not be insufficient.

[Function] The present invention uses a synthetic resin binder as a binder to bind an inorganic material to a HAH-free material, and when exposed to fire heat, the synthetic resin binder carbonizes and becomes a carbon source, and silicon oxide, zirconium oxide, titanium oxide, etc. are oxidized. Lead and tin oxide are fused together as vitrification forming aids to form carbide on the surface of the inorganic fibrous body together with carbon black.

[Structure of the invention]

An inorganic material consisting of colloidal silicic anhydride silicon oxide, zirconium oxide, titanium oxide, colloidal alumina, lead oxide, and tin oxide, which is nonflammable and imparts fire resistance and chemical resistance, which constitutes the present invention, and a synthetic resin binder; The inorganic fibrous body will be explained in detail.

Titanium oxide, zirconium oxide, and silicon oxide as inorganic materials are used as titanium compounds, zirconium compounds, and silicon compounds, respectively, during the manufacturing process of the heat insulating material of the present invention.
It also includes those produced at a drying temperature of 0 to 300°C or by thermal decomposition. 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 zirconium oxide, zirconic acid, zirconium sulfate, zirconyl nitrate, zirconyl acetate, zirconyl oxychloride, zirconyl oxynitrate, zirconyl ammonium carbonate, zirconyl chloride, zirconium acetylacetonate, and zirconium alkoxide. , oxides, acids, inorganic salts,
Chlorides, organic zirconium compounds, colloidal zirconium compounds, and silicon compounds include oxides, acids, inorganic salts, chlorides, and organic silicon compounds such as silicon oxide, colloidal silicic anhydride, silicon tetrachloride, and organic ammonium ammonium. be able to.

Further, lead oxide and tin oxide as inorganic materials include lead compounds and tin compounds produced by drying at a temperature of 200 to 300° C. or thermal decomposition during the manufacturing process. Specific examples of lead oxides include lead acetate, lead benzoate, lead oxalate, lead citrate, lead nitrate, lead chromate, lead carbonate,
Red lead (trilead tetraoxide), lead dioxide, lead oxide, lead metaborate,
For lead hydroxide, lead molybdate, lead silicate, and tin oxide,
tin oxide, tin hydroxide, stannous oxide, stannous sulfate,
Examples include 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, fine rock wool, maznesium hydroxide, aluminum hydroxide, ammonium polyphosphate, ammonium bromide, phosphoric acid, etc. guanidine,
There is no problem in adding organic or inorganic flame retardants such as phosphoric acid silica and antimony trioxide to the extent that fire resistance and chemical resistance are not impaired.

Furthermore, carbon blank as an inorganic material is a black fine powder and is usually commercially available such as furnace black, acetylene black, thermal black manufactured by the furnace method, channel black, disk black, and German naphthalene black manufactured by the impact method. It is also possible to use a type in which inorganic fibers are treated with carbon in a high-temperature reducing atmosphere and carbon black is fixed and integrated on the surface of the inorganic fibers. Examples of this type include potassium titanate fibers fixed to carbon black, and carbonized fine ams such as carbon fibers can also be used. Furthermore, part or all of the carbon black may be replaced with an H fuel agent that promotes carbonization of pulp, resin, etc. contained in the inorganic fibrous material by heating during the manufacturing process.

Synthetic resin binders include vinyl acetate resin, ethylene/vinyl acetate resin, acrylic resin, synthetic rubbers such as SBR and NBR, emulsion types such as polyvinyl alcohol, starch, polyamide resins, and polyimide resins, aqueous solution types, and those dissolved in organic solvents. Thermosetting resins such as solution types such as thermoplastic resins, melamine resins, phenolic resins, epoxy resins, polyester resins, furan resins, etc., aqueous solution types, and solution types dissolved in organic solvents. They can be used as a binder either alone or in the form of a mixture, but it is preferable to use water-soluble or emulsion type binders due to the risk of fire.

Inorganic! For fiber suspension, glass fibrous material, rock wool NM material, or a composite material made of these i-free fibers is used.
There are 1111 substance types. Glass fiber type usually has a so-called E glass composition to C glass composition, and has a fiber diameter of 5.
Sheet-like, cross-like, felt-like, mat-like, board-like, cylindrical shapes made of long fibers of ~15μ, cut fibers made by cutting long S fibers, or so-called short 11xH fibers made into fibers using centrifugal force, etc. has the shape of
tJAM is an inorganic fibrous material in which bonding is done chemically using a small amount of resin binder or mechanically by methods such as needling and l1m. Rock wool insulation is obtained by melting a raw material composition containing basalt, peridotite, iron ore slag, Silino J, dolomite, lime, etc., and turning it into fibers using centrifugal force, such as with a multi-rotor. It is an inorganic fibrous material having the same shape and fiber bonding method as the glass fibrous material. Furthermore, an inorganic wa fibrous body made of a composite 11 navy blue of the glass fibers and rock wool m fibers with the same shape and bonding method as above, and these glass fiber-based,
Rock wool type, glass fiber/rock wool composite type
1lIAN material includes organic materials such as pulp, as well as inorganic fibrous materials partially blended with inorganic fillers, flame retardants, etc., within the range that does not impair combustibility, and its composition is rock wool, pulp, inorganic Rock wool sheathing board is a typical example of filler and binder materials. 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.

When making an Ill, 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, followed by drying. Alternatively, the inorganic 11I can be cured by heating under no pressure and further subjected to heat treatment as necessary.
ff Bind an inorganic material to the corpus luteum.

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 fibrous resin binder has approximately 200%
It functions to maintain the shape of the fibrous body in the temperature range below ℃,
Subsequently, in the temperature range of 200°C to 600°C, the inorganic material is fused to the non-NailI heterogeneous body by the action of lead oxide, tin oxide, or a mixture thereof as a vitrification forming aid, and the synthetic resin is further bonded at a high temperature. Carbon black made from pyrolysis products or carbon black from original formulations and inorganic materials titanium oxide, zirconium oxide,
Silicon oxide reacts with carbon to form carbides on the 118 surface (the higher the temperature, the more carbides are formed), and when colloidal alumina is added, in addition to the formation of these carbides, fire resistance High mullite composition (3AJ
! As a result of the formation of 03.2SiDz), reflecting the performance of these carbides (melting point, chemical resistance), a
It is presumed that it has become possible to enhance fire resistance and chemical resistance due to the flammability of the rolling element.

The blending ratio of the constituent components of the composition of the present invention that is nonflammable and enhances fire resistance and chemical resistance is that the total of carbon black and synthetic resin binder is 15 to 70 W [%] in terms of solid content (however,
100 parts by weight of a composition consisting of colloidal silicic anhydride-blended silicon oxide as an essential component, and zirconium oxide, titanium oxide, and colloidal alumina in a total ratio of 85 to 30 wt% (carbon black content is 10 wt% or less) 0.05 lead oxide, tin oxide or a mixture thereof
~15 parts by weight.

If the total amount of carbon black and synthetic resin binder (however, the amount of carbon black is 10 wt% or less) is less than 15 wt% in terms of solid content, the amount of synthetic resin binder in the composition will be small, and the inorganic material will become inorganic fibrous material. When the treated inorganic fibrous material is exposed to high temperatures,
When initially added carbon black or synthetic resin binder is heated to high temperature, the amount of carbon black formed decreases overall, resulting in silicon oxide, zirconium oxide,
Carbide formation of titanium oxide becomes insufficient, and satisfactory fire resistance is not achieved.Also, although the above-mentioned rigidity is fully satisfied at 70wt% or more, the content of the synthetic resin binder becomes 6wt% or more, and the inorganic material Fire resistance and chemical resistance decrease as a result of a decrease in the blending ratio of
Furthermore, in order to pass the noncombustible grade listed in Ministry of Construction Notification No. 1828, there are restrictions on the composite ratio that adds fire resistance and chemical resistance (in this case, fire resistance is sacrificed as well). As a result, it is difficult to impart satisfactory fire resistance to the inorganic MS material. It should be noted that when 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, h-bond can be reduced to zero. The upper limit of the amount of carbon black added was set at 10W1%, but since no improvement in the effect was seen even if the addition layer was increased beyond this level, it is sufficient to keep the amount of carbon black below iQwt% in consideration of the other components. The reason why the total solid content of the constituent components of the inorganic material is silicon oxide mixed with colloidal silicic acid, zirconium oxide, titanium oxide, and colloidal alumina is 85 to 30 W[%] for the reason described above. Moreover, its composition includes silicon oxide as an essential component, and titanium oxide, zirconium oxide, and colloidal alumina are blended singly or in the form of a mixture as necessary depending on the level of fire resistance and chemical resistance. In particular, it is effective to contain liquid colloidal silicic anhydride in silicon oxide because it improves the bonding properties with the inorganic fibrous body and 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. Regarding 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 excellent fire resistance.・Composition (3Ah
It is effective to blend colloidal alumina as necessary to form a 2SiOz (Da.

Add 0.05 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.
It is important to incorporate up to 15 parts by weight, preferably 0.5 to 10 parts by weight (all calculated in terms of solid content). Adding a small amount of vitrification forming aids such as lead oxide and tin oxide improves fire resistance.
Even if the ratio of the compounded material to the S11 fiber material that enhances chemical resistance is small, it is possible to enhance the ability of the inorganic fibrous material to be cut open at high temperatures for a long time. The reason is as described above, but the effect is greater than 0.05 parts by weight, preferably 0.
．． It is noticeable when there are 5 layers or more, and the effect increases when more than 5 layers are added. On the other hand, since these vitrification forming aids have a slightly negative effect on resistance to chemicals such as acids and alkalis, it is necessary to avoid adding more than 15 parts by weight. The preferred blending ratio of these components is 3 to Bwt%.

A treatment solution consisting of a composition having the above-mentioned preferred mixing 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. However, in terms of solid content, material 1 imparts fire resistance and chemical resistance to 100 parts by weight of inorganic fibrous material.
It is preferable that the amount is less than 1 part by weight, and sufficient effects can be obtained even if it is less than 50 parts by weight. Inorganic products obtained by processing in this way! The fibrous body is usually dried at 60 to 110°C, depending on the resin binder, and then, in the case of a resin binder that requires curing, it is cured at 150 to 200°C under pressure or no pressure. In order to partially bake the inorganic fibrous body, the temperature is below the softening mi of the inorganic fibrous material (usually 25
By performing heat treatment at a temperature of 0 to 800°C, up to 1 inorganic fiber heat insulating material that is nonflammable, fire resistant, and chemical resistant can be produced.

(Effects of the Invention) According to the present invention, 15 to 70 wt% of the 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 (any of the above) (solid equivalent)
A composition consisting of at least one of lead oxide and tin oxide is added, and the combined materials are bonded together in a single layer, so that when exposed to fire heat, lead oxide and tin oxide will not form at low temperatures. Tin oxide fuses with the inorganic 1N corpus luteum, and when the temperature rises further, the synthetic resin binder carbonizes, and titanium oxide, acid,
Zirconium oxide and silicon oxide react to form a carbide on the surface of the inorganic fibrous material, and this carbide has a high melting point and high chemical resistance, making the inorganic fibrous material nonflammable, fire resistant, and chemical resistant. be able to. In addition, 1 synthetic resin binder
5 to 70 wt%, at least one of silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina.
Since it is set as 0 to 85w [%, the synthetic resin binder is 15%
In the following, the bond with No-1!11 quality rest is low, and the amount of carbon when carbonized is insufficient, so that sufficient fire resistance cannot be expected.

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 carbon black is not blended into the material, when it is bonded to an m5In-free substance, 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, 10wt of carbon black is added to the synthetic resin binder.
% or less, it is possible to supplement carbon that is insufficient when the amount of synthetic resin binder is small.

Even if the amount of Naori-Bon black is increased to 10% or more, the effect will not be improved and the amount of other components will be reduced, which is disadvantageous.

(Example) Examples of the present invention will be explained with reference to the attached table along with comparative examples.

An aqueous dispersion with a material concentration of 6 to 8 wt% having the composition (solid content equivalent) shown in the sample table was impregnated into the inorganic fibrous material shown in the same table, and the composite ratio (adhesion resistance) shown in the same table and the drying and curing conditions shown in the same table were applied. Test specimen NQI
~ Created ship 17. Test specimen N.

1 to IIQ3 are comparative examples, and test specimens No. 4 to Nα17 are examples of the present invention.

Test method Fire resistance test specimen (any size) is subjected to a flame test for 30 minutes with an acetylene torch burner at 900 to 1200°C at a distance of 10 cIR from the surface of the specimen, until the flame penetrates the specimen and a hole occurs. It was evaluated as the time of

Chemical resistance IN NaOH, IN HC1 aqueous solution each 500cc
Approximately 10 gr of the above test specimen was placed in a sealed plastic container and immersed in a constant temperature bath at 80°C ± 1°C for 211rs, and the specimen showed no shape change at all. Items that did not have any defects were rated 8, and items that were deformed and required improvement were rated C.

inorganic! 11fi nonflammability test Base material test stipulated in Ministry of Construction Notification No. 1828 with dimensions of 40 m (length) x 40 m (width) x 49 m (height). (
(Pass: 800℃) Test results IIQ1 to NQ6 show cases where the blending ratio of binder and inorganic material was changed, and comparative examples Nal and No. 2 show cases where the blending ratio of binder containing carbon black and other materials was changed according to the present invention. All of them have poor fire resistance because they are outside the mixing ratio of .

Furthermore, although Comparative Example 1103 does not contain any lead compounds or tin compounds, in order to impart sufficient fire resistance and chemical resistance comparable to the products of the present invention, it is necessary to The amount has increased by 31%.

Orders 7 to 13 show the relationship between the amount of binder blended and carbon, and as the amount of binder increases, the resin will thermally decompose at high temperatures and become carbonized, so carbon may not be added, and colloidal silicic anhydride or alumina may be added. This also shows that it is possible to eliminate the addition of carbon black.

Na1 o and 1kL11 are obtained by changing the material of the inorganic fibrous body.

11014 to 1ki17 show cases where the type and amount of vitrification forming aid (I! lead chloride, 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 Il Fiber Felt Fuji Resin Processing Co., Ltd. Product number Fujigerasmat RM (bulk specific gravity 80 to 9/rtt, thickness 5m) Resin (solid content 55
%).

Rock wool board Nitto Boseki Co., Ltd./Insal boat (bulk specific gravity 80Kg)
/Tl11 thickness 25 shoes).

Rock wool sheathing board, general commercial product, rock wool valve, inorganic filler, organic binding material, specific gravity 400 Ky/bottom, thickness 10 a*
, nonflammable grade product.

Melamine resin Nippon Carbide Co., Ltd. product number S-260 (100% solids).

Phenolic 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 5I-45P (
solids content 40-40%).

titanium oxide Fuji Titanium Industries Co., Ltd. Rutile type titanium oxide powder.

Silicon dioxide powder 200 mesh bath General commercial product Zirconium oxide powder Shin Nippon Metal Chemical Co., Ltd. Zirconia powder carbon black Asahi Carbon Co., Ltd. Positive furnace black Colloidal alumina Nissan Chemical Industries Co., Ltd. Product number Alumina sol-200 (l)
1 degree (approximately 10%) Mica Co., Ltd., Kuraray, product name: tin olide Mica modified acrylic resin Kureha Chemical Industry Co., Ltd., product number: VATR-106 Acrylic/vinylidene chloride copolymer resin emulsion Lead acetate, lead oxide, tin oxide reagent - grade (commercially available product) used

Claims (3)

[Claims] (1) 15 to 70 wt% of a synthetic resin binder, and 30 to 85 wt% of at least one of colloidal silicic anhydride-containing silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina (all of the above in terms of solid content) What is claimed is: 1. An inorganic fibrous heat insulating material, characterized in that it is made by combining a composition consisting of a small amount of at least one of lead oxide and tin oxide with 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 8 wt % of at least one of colloidal silicic anhydride compounded silicon oxide, zirconium oxide, titanium oxide, and colloidal alumina.
In a composition consisting of 5 wt% (all of the above in terms of solid matter),
An inorganic fibrous heat insulating material comprising a material containing a small amount of at least one of lead oxide and tin oxide combined with an inorganic fibrous body. (3) 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. Inorganic fiber insulation material.