JPS64339B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an inorganic fiber heat insulating material used in architecture, civil engineering, and various industrial fields.

[Technical background of the invention and its problems]

Currently, for the purpose of saving energy, 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 insulation properties, so they are mainly used in the residential field or have problems with combustible 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, the
If used for a long time at high temperatures between ℃ and 700℃, the fibers will soften and shrink in size, so although it is used as an insulator in high temperature ranges, there are naturally limits on the operating temperature (glass fiber insulation 300~400
℃, and 600 to 700℃ for rock wool insulation materials). 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, resulting in problems such as complicated construction and a significant increase in construction costs.

[Purpose of the invention]

In view of the above-mentioned problems, the present invention combines an inorganic fibrous material with an inorganic material that has excellent fire resistance and chemical resistance, thereby making it nonflammable and resistant to chemical products, and capable of withstanding high temperature ranges of 1000 to 1500 degrees Celsius. The aim is to obtain something with tolerable performance.

[Summary of the invention]

In the present invention, an inorganic material consisting of at least two of titanium oxide, zirconium oxide, and silicon oxide and carbon black is dispersed in a synthetic resin binder liquid and absorbed into an inorganic fibrous body. By bonding it to the inorganic fibrous material, high heat resistance and chemical resistance are imparted to the inorganic fibrous material.

[Structure of the invention]

The inorganic material, synthetic resin binder liquid, and inorganic fibrous material that are nonflammable and impart fire resistance and chemical resistance, which constitute the present invention, will be described in detail.

Titanium oxide, zirconium oxide, and silicon oxide as inorganic materials are used during the manufacturing process of titanium compounds, zirconium compounds, and silicon compounds, respectively.
It also includes those produced by drying temperatures of 200 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, titanic acid, titanium sulfate, titanium chloride, titanium ()oxyacetylacetonate, and titanium alkoxide are used. , Zirconium compounds include zirconium oxide, zirconic acid, zirconium sulfate, zirconyl nitrate, zirconyl acetate, zirconyl oxychloride, zirconyl oxynitrate, zirconyl ammonium carbonate, zirconyl chloride, zirconium ()
Oxides such as acetylacetonate and zirconium alkoxide, acids, inorganic salts, chlorides, organic zirconium compounds, silicon compound oxides such as silicon oxide, colloidal silicon anhydride, silicon tetrachloride, and organic silicon ammonium; Examples include acids, inorganic salts, chlorides, and organic silicon compounds.

In addition to the above, inorganic materials such as clay, mica, talc,
Inorganic fillers such as glass powder, magnesium hydroxide, and aluminum hydroxide, as well as organic and inorganic flame retardants such as ammonium polyphosphate, ammonium bromide, guanidine phosphate, silica phosphate, and antimony trioxide, are used to improve fire resistance and resistance. There is no problem in adding or blending it as long as it does not impair drug properties.

Furthermore, carbon black as an inorganic material is a fine black powder and is usually produced by the furnace method, such as furnace black, acetylene black, thermal black, channel black, disk black, or German naphthalene produced by the impact method. Commercially available products such as black can be used, and carbon black, which is prepared by treating inorganic fibers with carbon in a high-temperature reducing atmosphere, can be used. can. An example of this type is carbon black fixed potassium titanate 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 solution, thermoplastic resin, melamine resin, phenolic 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 a binder alone or in the form of a mixture, but there is a risk of flame. 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 15μ, or cut fibers made by cutting long fibers, or fibers made by using centrifugal force, etc. It has a sheet, felt, mat, board, or cylindrical shape made of so-called short fibers, and the fibers are bonded chemically using a small amount of a resin binder or by methods such as needling. It is an inorganic fibrous body made of mechanically produced materials. Roke 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 a multi-rotor system. It is an inorganic fibrous material whose shape and fiber bonding method are similar to those of the glass fibrous material. moreover,
An inorganic fibrous body made of composite fibers of the glass fibers and rock wool fibers having the same shape and bonding method as above, and glass fiber-based, rock wool-based,
Organic substances such as pulp,
In addition, inorganic fillers such as clay, mica, talc, glass powder, lead oxide, aluminum hydroxide, antimony trioxide, silica phosphate, boric acid, lead metaborate, sodium borate, lead acetate, alumina sol, etc. are vitrified and formed. It also includes inorganic fibrous materials partially blended with auxiliary agents or flame retardants. In addition,
From the viewpoint of heat insulation performance, it is effective to use these fibrous bodies having a bulk specific gravity of 0.5 or less, preferably 0.3 or less.

During production, the above-mentioned inorganic material is dispersed in the above-mentioned synthetic resin liquid, and this dispersion is absorbed into the above-mentioned inorganic fibrous material by impregnation or coating, followed by drying, followed by heating under pressure or no pressure. The inorganic material is bonded to the inorganic fibrous body by curing and, if necessary, heat treatment.

Although the mechanism of action of imparting fire resistance and chemical resistance to an inorganic fibrous body by treating it with the composition of the present invention is not completely clear, it is presumed to be due to the following reasons. First, the fibrous resin binder is heated to approximately 200°C.
It functions to maintain the shape of the fibrous body in the following temperature range, and in the softening temperature range of glass fiber or rock wool at 200°C or higher, carbon black and the fibers are fixed and fired, and then titanium oxide,
Zirconium oxide and silicon oxide react with carbon, and their carbides are formed on the fiber surface (the higher the temperature, the more carbides are formed).As a result, the performance (high melting point, chemical resistance) of these carbides is improved. Reflecting,
It is presumed that it has become possible to impart noncombustibility, fire resistance, and chemical resistance to the fibrous material. Although there are no particular limitations on the blending ratio of the constituent components of the composition that imparts nonflammability, fire resistance, and chemical resistance of the present invention, from the viewpoint of productivity and raw material cost, the preferred blending ratio is calculated on a solid basis. Silicon oxide + zirconium oxide + titanium oxide 35-70wt%, carbon black 5-10wt%, resin binder 10-50wt%, flame retardant/others 0-10wt%. The inorganic fibrous body is made into a composite by impregnation or coating with a treatment liquid consisting of the composition in the above-mentioned preferred blending ratio, but the composite ratio that imparts fire resistance and chemical resistance is not particularly limited. However, in terms of solid content, fire resistance, per 100 parts by weight of inorganic fibrous material
The amount of the composition imparting chemical resistance is preferably 100 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, they are cured at 150 to 200°C under pressure or no pressure, and if necessary, are partially fired to soften the inorganic fibers. By performing heat treatment at a temperature below this temperature (usually 250 to 800°C), it is possible to produce an inorganic fibrous heat insulating material that is nonflammable, fire resistant, and chemical resistant.

〔Effect of the invention〕

According to the present invention, an inorganic material made of at least two or more of titanium oxide, zirconium oxide, and silicon oxide and carbon black is dispersed in a synthetic resin binder liquid and absorbed into an inorganic fibrous body. Carbon black and two or more types of oxides are bonded to the surface of the fibers of the inorganic fibrous material, and at least three types of inorganic materials each have different chemical resistance properties, so they have a wide range of chemical resistance. can be given gender. Furthermore, even when they encounter fire heat and turn into carbides, they each have different heat resistance temperatures, so they can be imparted with heat resistance in different temperature ranges. Furthermore, since inexpensive carbon black, titanium oxide, zirconium oxide, and silicon oxide are used as inorganic materials, the material cost is reduced, and the overall cost can be reduced.

[Embodiments of the invention]

Examples of the present invention will be described, and the results of physical property tests will also be shown.

Example 1 100 parts by weight of a composition containing 46 wt% silicon dioxide powder, 14 wt% zirconium oxide powder, 11 wt% carbon black, and 29 wt% phenol resin (solid content) was added to water.
Add 10 parts by weight of the blended resin liquid to needling type glass fiber felt in solid terms.
25 parts by weight per 100 parts by weight were compounded by an impregnation method. Subsequently, the wet felt was dried at 105°C until it became completely dry, pressurized to a thickness of 3 m/m, and cured at 150°C for 5 minutes. A further heat treatment was performed at 300℃ for 15 minutes to produce the final felt. This felt was subjected to a flame test for 30 minutes at a distance of about 10 cm from the felt surface in an acetylene tiberna at 900 to 1200°C, but no external deformation was observed. In addition, accurately weigh 10 gr of the above felt test piece into 500 c.c. of each of the IN NaOH and IN HCl aqueous solutions, and place them in a closed plastic container (No. 1) for 80±
Immerse in a constant temperature bath at 1℃. After 24 hours, it was washed with clean water, dried, and examined for weight loss, but no weight loss was found. Note that no shape deformation was observed at all.

(Note) silicon dioxide powder 200 mesh pass general commercial product.

Zirconium oxide powder Nippon Metal Chemical Co., Ltd. Zirconia powder.

carbon black Furnace black manufactured by Asahi Carbon Co., Ltd.

Phenol resin Showa Union Gosei Co., Ltd. Water-soluble resol type phenolic resin, product number BOL-141 (50% concentration).

Glass fiber felt Fuji Jushi Kako Co., Ltd./Product number Fuji Glass Matsuto
RM (bulk specific gravity 80Kg/m ³ , thickness 5mm).

Example 2 30 parts by weight of water was added to 100 parts by weight of a composition containing 35 wt% silicon dioxide powder, 15 wt% zirconium oxide powder, 6 wt% titanium oxide powder, 8 wt% carbon black, 6 wt% ammonium polyphosphate, and 30 wt% melamine resin. The resulting resin liquid was applied onto a short glass fiber board and compressed to form a composite of 30 parts by weight per 100 parts by weight of the short glass fiber board in solid terms. Subsequently, it was dried at 105°C and heat-cured at 150°C for 5 minutes. The final board was prototyped by further heat treatment at 270℃ for 10 minutes.
The same fire resistance test and chemical resistance test as in Example 1 were conducted, and the same results as in Example 1 were obtained in both cases.

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

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

Short glass fiber board Nippon Glass Wool Co., Ltd. Product number GL-2425 (bulk specific gravity 24Kg/ ^m3 , thickness 25mm).

ammonium polyphosphate Use first-class commercially available reagents.

Example 3 A composition of 35 wt% colloidal silica, 15 wt% zirconium oxide powder, 8 wt% carbon black, 5 wt% black type potassium titanate fiber, and 37 wt% phenolic resin was applied to a rock wool board and compressed to form a solid rock. 20 parts by weight of the composite was added to 100 parts by weight of wool board. The final board was then dried at 105°C, cured by heating at 150°C for 20 minutes, and further heated at 500°C for 2 minutes to produce the final board. This board is 40mm (length) x 40mm (width) x 49mm (height)
When the base material test specified in the Ministry of Construction Notification No. 1828 was conducted on the size of the material, it passed the test as nonflammable at 796℃. Further, the same fire resistance test and chemical resistance test as in Example 1 were conducted, and the same results as in Example 1 were obtained in both cases.

(Note) Black type titanium potassium fiber Otsuka Chemical Co., Ltd. Chismo Black Type.

Phenol resin Showa Union Gosei Co., Ltd., product number BLD-352 Methanol-soluble resol type phenolic resin (solid content
55%).

Rock wool board Nitto Boseki Co., Ltd./Insal board (bulk specific gravity
80Kg/ ^m3 , thickness 25mm).

Colloidal Silica Nippon Shokubai Chemical Co., Ltd./Cataroid SI-
45P (solid content 40-41%).

Example 4 Silicon dioxide 34wt%, colloidal silica 8wt%,
Carbon black 8wt%, zirconyl acetate 15wt
%, 25 wt % acrylic resin emulsion, and 10 wt % antimony trioxide was applied to a glass fiber woven fabric at a solid content of 300 gr/m ² by a coating method and heated at 130°C.
A flexible glass fiber sheet was prototyped by drying and curing for 10 minutes. This prototype was tested and evaluated in accordance with the JIS draft of the 1980 Building Materials Test Information Notice - Flame retardant test method for welding and fusing sparks for sheets for construction work - and as a result, it passed Class A.

(Note) antimony trioxide Uses commercially available first grade reagent powder.

Glass fiber woven fabric Nitto Boseki Co., Ltd. WL-700A-100 (thickness 0.5
mm, basis weight 610gr/m ² ).

Acrylic resin emulsion Nippon Acrylic Co., Ltd. Primal RA-90 (solid content 46%).

Comparative Example 1 The untreated glass fiber felt of Example 1 was heated to 800°C.
When treated in an electric furnace set to In addition, this felt was prepared using IN NaOH in Example 1.
As a result of the test, the weight was reduced by 7.5wt%, and the felt strength was approximately 7.5wt% compared to the original one.
It has only 23% retention, indicating no chemical resistance.

Comparative Example 2 The rock wool board before treatment of Example 3 was 800
When it was heated in this electric furnace for 5 minutes at a temperature of 1.5°C, it showed a dimensional shrinkage of about 14%, indicating that it had no fire resistance. In addition, when this board was tested using the method of Example 1 using IN HCl, the test was stopped because flowing hydrogen gas continued to be generated immediately after immersion, and it was confirmed that there was no chemical resistance.

As seen in Examples 1 to 4 and Comparative Examples 1 to 2 above, it is understood that the inorganic fiber heat insulating material of the present invention is nonflammable and has excellent fire resistance and chemical resistance.

Claims (1)

[Claims] 1 An inorganic material consisting of at least two or more of titanium oxide, zirconium oxide, and silicon oxide and carbon black is dispersed in a synthetic resin binder liquid and absorbed into an inorganic fibrous body, and the inorganic material is absorbed into an inorganic fibrous body. An inorganic fiber insulation material characterized by being bonded together.