JPS60181400A - Inorganic sheet - 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] [Technical Field of the Invention] The present invention provides a material for use in various building materials and various industrial fields.
The present invention relates to an inorganic sheet having fire resistance and chemical resistance.

[Technical background of the invention and its problems]

Traditionally, asbestos fibers, glass fibers, and ceramic fibers have been used in industrial materials such as flame retardant, noncombustible wall materials, building materials such as Dangor paper, and backings and gaskets that require flame retardant or noncombustible heat resistance.

Rock wool fiber, steel fiber, silicon carbide fiber.

(SIC fibers), inorganic fibers such as carbon fibers, aromatic polyamides, organic fibers such as phenol fibers alone or in combination, and organic or inorganic binders, i-fuel agents,
A nonwoven fabric made with a filler.

Woven fabrics and film-like sheets are widely used.・These non-woven fabrics and woven fabrics contain inorganic fillers and inorganic fibers.

Depending on the amount of flame retardant blended, flame retardant to non-flammable properties and heat resistance are imparted, but if a high degree of heat resistance or fire resistance is required, high-purity asbestos fibers, ceramic fibers, s
It is limited to nonwoven fabrics, woven fabrics, and film-like sheets containing inorganic fibers such as IC fibers, carbon fibers, and steel fibers. Among these, nonwoven fabrics, woven fabrics, and film sheets containing asbestos fibers have been banned in some countries due to restrictions on their use in recent years as asbestos fibers have been designated as specified chemical substances and from the perspective of pollution prevention and occupational health. The current situation is that In addition, ceramic fibers, (among ceramic fibers, ceramic fibers with a high alumina content have excellent heat resistance and are expensive. On the other hand, as the silica content increases, the price becomes relatively cheap, but the heat resistance also decreases) SIC fibers. , nonwoven fabrics, woven fabrics, and film sheets containing steel fibers and carbonaceous fibers have high heat resistance and are satisfactory in this respect, but they are expensive, and ceramic fibers have low resistance to acids and alkalis. The current situation is that it is not directly linked to demand expansion.

[Purpose of the invention]

In view of the above-mentioned problems, the present invention does not use asbestos fibers or expensive inorganic fibers, but uses an inorganic material consisting of at least one kind of inorganic fiber such as inexpensive glass fiber, rock wool fine fiber, or ceramic fiber, and an inorganic filler. Titanium oxide and zolconium oxide are added to the sheet material obtained by paper-making a small amount of organic materials such as pulp, organic binder, and binding aid.

A noncombustible material made by blending at least two types of silicon oxide and carbon black into a synthetic resin binder is combined to provide noncombustibility, fire resistance, and chemical resistance, and is fire resistant from 1000°C to 1500°C. , the aim is to obtain a product that has chemical resistance.

[Summary of the invention]

The present invention comprises 50 to 90% by weight of an inorganic material such as at least one type of inorganic fiber such as glass fiber, rock wool microfiber, or ceramic fiber, and an inorganic filler, a /9 type lubricant, a combination agent, and a binding aid. Good organic materials 10-5
0% by weight, and the resulting sheet material is combined with a noncombustible material containing at least two of titanium oxide, zirconium oxide, and silicon oxide and caden black in a synthetic resin binder, It provides even higher fire resistance and chemical resistance to inorganic sheet materials.

[Structure of the invention]

Inorganic sheet material and fire resistance constituting the present invention.

A non-combustible material such as a synthetic resin containing an inorganic material and a liquid that imparts chemical resistance will be described in detail.

The inorganic sheet material which is a constituent element of the present invention is an inorganic material made of at least one kind of inorganic fiber such as glass fiber, rock wool fine fiber, and ceramic fiber and an inorganic filler. It is a flame-retardant to non-combustible sheet obtained by paper-making a mixture of 10 to 50% by weight of an organic material comprising a binder and a binding aid as a papermaking raw material composition.

As the inorganic fibers, the following glass fibers, ceramic fibers, and rock wool fine fibers can be used alone or in combination.

The composition of glass fiber is 5IO255-65/At
2030~15 Section, NazOO~15 'A, Q glare, 4
~12chi, BaO'0~5%, ZnOO~5%,
Ca01~18chi, Mg01~6chi, K2O0~4chi,
TIo, 2.

Glass fibers made of so-called E or C glass compositions containing less than 1 inch of trace components such as F. It is preferable that there be.

The fiber length can be adjusted arbitrarily from 250 to 7000 μm by, for example, changing the distance between the teeth of the roving cutter.

The composition of the ceramic fiber is 5IO25-49, A
t20.94-50%, CaOlMgO, B2O3+
Na2O.

It is possible to use ceramic fibers containing trace components such as K2O, TlO2, and FeO of 1 or less (all by weight); It is preferable to use one in the range of 7000 μm. Ceramic fibers that are suitable for this purpose include commercially available ceramic fibers that have been cut to adjust the fiber length, or Tenzo manufactured by Johnsmanville Co., Ltd., for example.

Strump eye bar Q'4 can be used.

The rock wool fine fiber has a composition of 810235~5°, A
t20310~15%, CaO20~40'It, M
g05-25%, trace components such as TlO2r, FiinO, F@O, etc. are 1% (all weight%), and the fiber length is in the range of 70-700 μm and does not substantially contain non-fiber particles. be able to.

As for pulp, Saran, non-derashi pulp, NLffi craft pulp, link pulp, recycled valve etc. have a fiber length of 500.
~2000μm, freeness (Shonno!-Rigler) 30
It is the same as in paper manufacturing that about 60 to 60 general-purpose materials can be used.

Examples of organic binders include acrylic fibers, butylene butadiene rubber, acrylonitrile butazoene rubber, vinylidene chloride fibers, emulsions such as ethylene vinyl acetate resin, thermoplastic resins such as polyamide resins, phenolic resins, epoxy resins, silicone resins, etc. However, when adding these organic binders to the papermaking raw material composition, in order to effectively fix the organic binder to the wet sheet, it is necessary to add a thermosetting resin as a binding aid. It is desirable to add a small amount of an anionic flocculant or a cationic flocculant. For example, polyacrylamide, which is an anionic flocculant, or sodium polyacrylate 0.1
When added in a range of 0.5 to 1.5 weight percent of sulfate, approximately 100% of the organic binder will adhere to the wet sheet.

Further, as a cationic flocculant, when 0.1 to 1.0% by weight of boramide polyamine epichlorohydrin resin is added, the same effect as the anionic flocculant can be obtained. Furthermore, as an organic binder, a small amount of glue, alkyl kettin dimer, rosin size, or plant size can be used to impart water repellency to the sheet material.

It is possible to use a sizing agent such as a wax emulsion.

Note that if an organic binder is not added internally, it may be applied to the sheet after paper making.

As an inorganic filler, it is effective to combine aluminum hydroxide as a component that imparts flame retardancy through dehydration of crystal water.
Others include clay, mica, talc, antimony trioxide, and calcium carbonate.

Combination use of silica, glass powder magnesium hydroxide, gypsum, etc. with aluminum hydroxide is effective in further increasing flame retardancy. Further, from the viewpoint of the appearance of the sheet material, the particle size of these particles is preferably 100 μm or less.

Next, the blending ratio of the constituent components of the inorganic sheet material will be explained.

The blending ratio of the inorganic material consisting of the inorganic fiber and the inorganic filler is 50 to 90% by weight, and if the inorganic material containing 5% by weight or less of the inorganic fiber becomes 90% by weight or more, the papermaking composition will contain particulate inorganic matter. Because the amount of paper is large, the water resistance after paper making is extremely poor, and the strength of the wet sheet is low, it is impossible to form small grains at normal paper making speeds. In addition, the inorganic material is 5
If the amount is less than 0% by weight, it becomes difficult to impart flame retardancy to the obtained sheet material. Moreover, when aluminum hydroxide as an inorganic filler is heated to 200 to 350C, 2 At(OH), → At20. +3 I(20) to dehydrate crystal water, and 1/3 weight of water of the original At(OH) is dehydrated.

In addition, since the ignition temperature of Nofrug is 260 to 280°C, the temperature decreases due to the evaporation of water in the dehydrated aluminum hydroxide in this temperature range and ignition is prevented, so the flame retardant effect is great. Preferably, aluminum hydroxide is added.
There are no particular limitations on the amount of inorganic fiber added, but the texture of the surface layer and back layer of the obtained sheet material may differ, or the specific gravity may differ in the thickness direction. Therefore, a blending ratio of 5 to 40% by weight is suitable.

For the above reasons, the total of the other components of the papermaking raw material, namely Grug, organic binder, and binding aid, is 10 to 50% by weight, but among these, the lower limit of the blending ratio of Grug is not particularly limited. However, in order to improve the retention of other papermaking raw materials, it is desirable to use a 10-weight board.

An aqueous dispersion of a papermaking raw material composition such as the above-mentioned mixture can be easily prepared by using a mixer, a beater, a knuckle/gun, etc. to prepare an aqueous dispersion containing about 3% by weight of solids. Paper making can be carried out using either a cylinder-type paper machine or a fourdrinier-type paper machine, but it is preferable to use an aqueous dispersion diluted to the extent of the sheet obtained. Off-machine (on-machine) inorganic sheet material obtained in the above papermaking process.
e) In the off-machine process, if necessary, add or coat a sizing agent such as glue, alkyl kettin dimer, rosin size, vegetable size, wax emulsion, etc. to impart total water repellency. Alternatively, it can be coated with a flame retardant material to further increase flame retardancy.

Next, a description will be given of the noncombustible material that is bonded to the sheet material obtained as described above by impregnation or coating.

The noncombustible material is made by dispersing at least one of titanium oxide, zirconium oxide, and silicon oxide and carbon black in a synthetic resin binder.

Titanium oxide, zorconium oxide, and silicon oxide include titanium compounds, zirconium compounds, and silicon compounds each produced by drying at a temperature of 200 to 300° C. or thermal decomposition during the manufacturing process. Among titanium compounds, titanium oxide, titanic acid, titanium sulfate, titanium chloride, and titanium (It) oxyacetylacetonate.

Oxides such as titanium alkoxides, acids, inorganic salts,
In the case of chlorides, organic titanium compounds, and zirconium compounds, zirconium oxide, zirconic acid, zirconium sulfate, zirconyl nitrate, zirconyl acetate, zirconyl oxychloride, zirconyl oxynitrate, zirconyl ammonium carbonate, zirconyl chloride, zirconium (n) acetylacetonate, zirconium oxides, such as alkoxides,
Acids, inorganic salts.

Chlorides, organic zirconium compounds, and silicon compounds include silicon oxide, colloidal silicic anhydride, and silicon tetrachloride.

Oxides, acids, and inorganic salts such as organosilicon ammonium.

Examples include chlorides and organic silicon compounds.

In addition to the above oxides, in order to reduce costs, inorganic fillers such as clay, mica, talc, glass powder, magnesium hydroxide, aluminum hydroxide and other rock wool fine fibers, ammonium polyphosphate, etc. , Jl ammonium, guanidine phosphate.

Organic, such as silica phosphate and antimony trioxide.

There is no problem in adding an inorganic flame retardant to the extent that it does not impair fire resistance and chemical resistance.

Carbon black is a fine black powder and commercially available products such as furnace black manufactured by the furnace method, acetylene black, channel black manufactured by the thermal plaque, disk black, and German naphthalene black can be used. 1-
1 Furthermore, it is also possible to use a type in which inorganic fibers are treated with carpin in a highly reducing atmosphere and carbon black is fixed and integrated on the surface of the inorganic fibers. Examples of this type include carpin plaque-fixed potassium titanate fibers, and carbonized fine fibers such as carpin fibers can also be used. In addition, Gurno, which is contained in the inorganic sheet material,
Part or all of the carbon black may be replaced with a flame retardant that promotes carbonization of resin etc. by heating during the manufacturing process.

Vinyl acetate resin is used as a synthetic resin binder.

Ethylene/vinyl acetate resin, acrylic resin, SBR.

NOR, etc. (D synthesis: emulsion type, aqueous solution type, solution type formed by dissolving in organic solvent, thermoplastic resin, melamine resin, phenolic resin, etc.) Thermosetting resins such as emulsion types such as epoxy resins, polyester resins, and furan resins, aqueous solution types, and solution types dissolved in organic solvents can be used alone or in the form of a mixture as a binder, but there is a risk of fire. Due to its nature, it is preferable to use water-soluble binders and emulsion type binders.

The blending ratio of noncombustible materials is not particularly limited, but from the viewpoint of productivity and raw material price, the preferred blending ratio is:
Solid equivalent: silicon oxide zirconium decaoxide + titanium oxide 3
5~7o vrt%, car? Black 5~l Q,
, wt%, resin binder lO~50wt%, flame retardant/others 0~10wt%.

The noncombustible material made of the above-mentioned preferred blending ratio is impregnated into a sheet material or composited by a method such as coating, but the composite ratio that imparts fire resistance and chemical resistance is not particularly limited. However, in terms of solid content, the sheet material is 10
10 parts by weight of noncombustible material that imparts fire resistance and chemical resistance
The amount is preferably 0 parts by weight or less. Next, the sheet material impregnated or coated with a noncombustible material is usually dried at a temperature of 60 to 110°C, depending on the synthetic resin binder, and then cured at a temperature of 150 to 200°C.
℃ under pressure or no pressure, and if necessary, heat treatment at a temperature of 200 to 600℃ for a short time to partially bake the product.) To produce products with fire resistance and chemical resistance. I can do it.

〔Effect of the invention〕

According to the invention, glass fibers, rock wool fine fibers.

50 to 90% by weight of an inorganic material such as at least one type of inorganic fiber such as ceramic fiber and an inorganic filler, pulp,
Organic materials such as organic binders and binding aids 10 to 50
A sheet material obtained by paper-molding a mixture consisting of The /4 loop and synthetic resin binder in the material work to maintain the sheet shape at temperatures below 200°C, and at temperatures above 200°C, the carburizes in the softening temperature range of glass fibers, rock wool fine fibers, or ceramic fibers. The pin black and the inorganic fibers of the sheet material are fixed and fired, and then titanium oxide, zirconium oxide, and silicon oxide react with carbon to form carbides on the surface of the sheet material. The higher it is, the more it is. As a result, the sheet material has a high melting point.

Compounded with chemically resistant and highly carbide, 1000-150
It has high temperature fire resistance and chemical resistance of 0℃.

Furthermore, the materials that make up the sheet material are StC fiber, steel fiber, glass fiber, which is cheaper than carbon fiber,
Since it is made of rock wool fine fibers and ceramic fibers, it can be provided at low cost.

[Embodiments of the invention]

The present invention will be described in detail.

Sheet material <Formulation example 1> Glass fiber 4vt Aluminum thihydroxide 75wt N-type kraft pulp 15wt Modified acrylic resin emulsion 5wt% Polyacrylamide Q, lvt% Band sulfate 0.9wt% <Formulation example 2> Rock wool fine Fiber 26wt Ticeraminok fiber 10wL% Aluminum hydroxide 35wt Nya Craft Pulg 25wt Modified acrylic resin emulsion 3wt% Polyacrylamide 0.1wt% Sulfuric acid band Q, 9vt% Blend example 3> Glass fiber Svt Aluminum hydroxide 35wtqb Mica 10wt Retaining type Kraft/Yargu 46wt4 Modified acrylic resin emulsion 3wtl The raw materials used in the above formulation examples (1 to 3) are as follows.

Light H-21 Fist Mica: Manufactured by IM Kuraray; Product Name: Tin Olide Mica
325 Snout polyamide polyamine epichlorohydrin resin: Manufactured by Arayo Kagaku Kogyo ■: Product name ARAIFUKUS 100 ・Bory acrylamide: Manufactured by Arayo Kagaku Kogyo ■; Product name -
117 Φ Modified acrylic resin emulsion: Toagosei Kagaku ■, trade name AP-5950 - Rock wool fine fiber Nikichito Boseki ■, trade name Microfiber-NIX.

e Ceramic fiber: Manufactured by Johnsman Building Co., Ltd., product name: Te
mpmtran Fib@r Q--Bandoni sulfate (commercially available product) Beated for 2 hours to obtain a beating degree of 40.

[Manufacturing method of material sheet]

The papermaking raw material compositions of the above formulation examples (1) to (3) were prepared as a final KO as a solid component, respectively, as an aqueous dispersion of 5 wt. Sheet materials (1) to (3) 1 were obtained by paper making and subsequent drying.

The characteristic values of the sheet material obtained as described above were determined as follows.

Measurement of orIIX index - Evaluated in accordance with JIS K 7201 using an oxygen index combustion tester (manufactured by Suga Test Instruments).

The strength retention rate after treatment was evaluated.

It can be seen from the above that sheet materials 1 and 2.3 exhibit flame retardancy to non-flammability, and both have heat resistance.

(B) Noncombustible material formulation example 4; Noncombustible material> Added water・・・・・・・・・・・・・・・・・・・・・
・・・－・・・・・・・・・・・・・・・・・・・・・
・・・・・・ 130 parts by weight Blending example 5: Noncombustible material 2> Added water ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...53 parts by weight The raw materials used in Formulation Examples 4 and 5' above are as follows.

・Silicon dioxide: 200 mesh/yasu General commercial product Zirconium oxide powder: Nippon Metal Chemical ■, Zirconia powder ・Cargin black: Made by Asahi Carbon ■ Furnace black Sodium alginate: Made by Fuji Chemical ■, Snow Algin l58H Resin 1 part number BRL -141゜@Titanium oxide: Manufactured by Fuji Titanium Co., Ltd. Rutile type titanium oxide colloidal silica Nippon Shokubai Chemical Co., Ltd. Cataloid 5I-45P Acrylic/vinylidene chloride copolymer resin emulsion:
Kureha Chemical Industry ■9 Product No. VATR-106 [Production method of non-combustible material] The powder components of the compositions of Formulation Examples 4 and 5 above are pulverized in a mill to a particle size of 10μ or less, and then the remaining components are added and blended. Then, water was added and stirred so that the solid content concentration was 40 wt% to the above formulation, and a synthetic resin binder liquid containing inorganic powder with a solid content concentration of 40 v + rt% was mixed. A noncombustible material 1,2fi was prepared.

(C) Sample sheet [Sample sheet 1]: A non-combustible material (20,017 m” of solid content was applied to the sheet material (1), and then heated at 105℃5
The mixture was dried by heating at 150° C. for 3 minutes.

[Sample sheet 2]: Apply 15017 m of non-combustible material (1) as a solid content to the sheet material (2), and then
After drying by heating in the same manner as above, the surface was further treated at 300° C. for 10 seconds in a propane gas burner furnace.

[Sample sheet 3]; Noncombustible material (2) on sheet material (3)
A t-solid content of 250,117 m'' was applied and dried by heating in the same manner as the sample sheet (1).

[Sample sheet 4]: A sheet material (υ) was impregnated with the nonflammable material (2) to a solid content of 45% by weight by dipping method, and then heated at 105°C for 5 minutes.

It was dried by heating at 150°C for 3 minutes.

υ) Test method and results [Fire resistance test] A flame test was conducted on the sample sheets (1), (2 bars, 3), and (4) using an acetylene torch at a distance of 106 R from each sample sheet. Sample sheet at this time (1) ~
The surface temperature of (4) was 1030°C to 1070°C, and a burner was applied for more than 5 minutes, but the surface of each sample sheet turned white, and no deformation of the external shape such as penetration or distortion was observed. Ta. In addition, when a similar test was conducted using a sheet material (υ), it penetrated in about 2 to 3 seconds and immediately showed its shape to collapse, indicating that a sheet material that does not bind noncombustible material has no fire resistance. Glass cloth (Atsumi 0
．． 5111+, weighing about 600,117 m2), the hole penetrated in about 8 seconds, and then the hole enlarged and the shape was distorted.

Based on the above results, sample sheet (1) (2) (3) (
4) were all found to have excellent fire resistance.

[Chemical resistance test]

For sample sheet (4), 10% NaOH at 80°C.

It was immersed in 10 HC1 dairy liquid for 1 hour and observed for changes in shape, and it was found that it did not change at all and had chemical resistance. For reference, a general commercially available short glass fiber board (specific gravity 24
1φ/m3. When we conducted a similar test on a small piece of Atsumi (25%), it swelled to the point that it no longer retained its original shape.
It was found that it had no acid or alkali resistance.

The above results revealed that the product of the present invention has excellent fire resistance and chemical resistance.

Claims (1)

[Scope of Claims] (1) 50 to 90% by weight of an inorganic material consisting of at least one pure inorganic fiber such as glass fiber, rock wool fine fiber, or ceramic fiber and an inorganic filler, and a matrix. An organic binder, Organic materials such as binding aids 10 to 50
Titanium oxide and zirconium oxide are added to the sheet material obtained by papermaking from a mixture with weight control. An inorganic sheet characterized by being formed by bonding a noncombustible material containing at least two types of silicon oxide and carbon black in a synthetic resin binder.