JPS5935938A - Fire-resisting heat-insulating 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 Alternatively, an inorganic core material (AJ silanol hydroxyl end-capped diorganosiloxane pine resin, (B) a crosslinking agent consisting of an alkyl silicate or a hydrolyzable silane compound, (
0) a curing catalyst and CD) a refractory heat insulating sheet ζ characterized in that it is coated with a NJfi4 material whose main component is an alkali titanate.

Traditionally, it has been used in steel factories to protect the human body from high temperatures in steelmaking T-frames and scorching hot iron powder that scatters, and to protect the human body and surrounding combustible materials and equipment from slag that scatters during welding or fusing operations. Asbestos fibers, aluminum foil, and sheets mainly made of combustible plastics are used for this purpose. However, all of these currently used heat-resistant materials have their own drawbacks, so they cannot be said to be satisfactory for their purposes. In other words, those made mainly of asbestos fiber lack durability in terms of mechanical strength and fire resistance. Also, although aluminum foil has good resistance to radiant heat, it lacks mechanical strength, making it difficult to weld. :Easy to hit by slag during melting (this allows penetration, so the protective effect is small.Furthermore, those made mainly of twist-resistant plastic are virtually ineffective against scorching iron powder and slag). However, there is a risk that the iron powder or slag may decompose due to heat and produce toxic gas.

In addition to the above-mentioned conventional sheets, composite sheets have also been proposed in which asbestos fibers or a coating layer is provided on the surface of glass fiber cloth, but the coating layer of these sheets has low heat resistance and
Moreover, it is impractical because it easily becomes perforated when high-temperature iron powder or slag collides with it.

In addition, a fireproof sheet has been proposed in which a silicone varnish layer in which a scale-like heat-resistant inorganic substance and an inorganic pigment are dispersed is provided on the surface of glass fiber cloth. However, the fire resistance was low.
fT has poor thermal properties, and because the silicone varnish uses a polysiloxane with a three-dimensional network structure obtained by hydrolyzing organochlorosilanes, it tends to have straightness, and the texture of the sheet when used in practical use as a fireproof sheet. ,
Considering workability, it is recommended to use a self-extinguishing rubber-like silicone varnish with a three-dimensional network structure. It was difficult to adjust the

As outlined above, conventional fireproof insulation materials have their own merits and demerits, and none of them are satisfactory.In recent years, asbestos fiber, which has been the most widely used material, has been the main material. It is worth noting that there is a movement to ban the use of such sheets, mainly in Western countries, due to concerns about their carcinogenicity.

Based on the above facts, the inventors endeavored to create a more excellent fire-resistant and heat-insulating material, and created an alkali titanate and silicone resin composition that already has excellent fire-resistant and heat-insulating properties and has solved health problems such as carcinogenicity. We have made proposals regarding fire-resistant and heat-insulating coating compositions, sheets, and films, and we have made strenuous efforts to improve the industrial applicability of such technologies, and have finally achieved the present invention.

An object of the present invention is to provide a sheet material that has excellent fire resistance and heat insulation, and particularly has a high reflective effect against radiant heat. Yet another object of the present invention is to provide a stable sheet material that will not decompose, burn or melt when in contact with hot materials such as slag.

Still another object of the present invention is to provide a safe sheet material that will not be perforated even when hit by flying hot slag or the like.

The features of the present invention will be explained in detail below.

Component (A) used in the present invention is a silanol-based hydroxyl-terminated diorganosiloxane resin used in condensed polysiloxane compositions, and exhibits particularly good coatability when applied to the surface of an inorganic mass, and exhibits excellent properties after curing. It provides suitability as a coating material such as film forming property, durability, mechanical strength, and texture, and has a viscosity of 100 to 20 at 25°0.
A range of 0,000 cat is preferable. If the viscosity is less than 100 cst, the durability after curing is insufficient,
Even with fire-resistant and heat-insulating sheets that do not require much elongation, a decrease in texture and flexibility is observed;
If it exceeds 0 cst, it is difficult to obtain a homogeneous composition (even if a diluting solvent is used as an auxiliary agent, a large amount of solvent is required to achieve the appropriate viscosity during coating, and inorganic fabrics It becomes difficult to form a coating layer of a desired thickness on the surface of the coating, and coating workability deteriorates.

Therefore, the preferred range is 100 to 150,000 in order to harmonize the properties of the composition before and after curing.
ast range, preferably 500 to 500
00 cst contains less of the component (A) (both 5
0% by weight and whose viscosity as a polyorganosiloxane resin is adjusted to a range of 1,000 to 100,000 cst. It also has excellent miscibility with other compounds.

Examples of organic groups directly bonded to silicon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, and hexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl; Examples include aralkyl groups such as phenylethyl groups, and monovalent substituted hydrocarbon groups such as 3,3.3-)lifluoropropyl groups, chloromethyl groups, and β-cya/ethyl groups, but they are easy to synthesize. Monovalent hydrocarbons such as methyl, vinyl or phenyl groups are generally advantageous; other organic groups impart special properties to the cured rubber-like elastomer, such as oil resistance or paintability. Recommended only when giving. Among them, methyl groups are easily obtained when raw material intermediates have them, and the viscosity when organosiloxane is polymerized is low.
Preferably, 85% or more of all organic groups are methyl groups, in order to achieve an advantageous balance between the extrusion workability of the composition before curing and the physical properties of the rubber elastic body or coating composition after curing.
It is further preferred that substantially all organic groups are methyl groups.

Component (B) used in the present invention I is a crosslinking agent (
A) It cures by reacting with the silanol hydroxyl group of the component, and currently in practical use there are acetic acid or long-chain carboxylic acid releasing type, organic amine, amide, organic hydroxylamine releasing type, oxime, alcohol, and acetone releasing type. It can also be used in combination with a crosslinking agent.

However, vinegar w, long chain carboxylic acid releasing type, organic amine,
Amide and organic hydroxylamine releasing types cause odor, corrosion of coating equipment during the crosslinking process, and pollution of the working environment.
In addition, the oxime and acetone releasing type has problems such as difficulty in synthesizing the crosslinking agent.

On the other hand, the alcohol-releasing type is cheap and easy to manufacture.
Problems related to terminal contamination are also reduced, and there is less corrosion of coating machines, etc. (This is advantageous in terms of industrial applicability.

In the present invention, the crosslinking agent is not limited (although this is limited, dealcoholization type crosslinking agents, which were conventionally considered difficult to put into practical use due to their low cost, low toxicity, and reduced adverse effects on adherends, can also be used satisfactorily). , these are general formulas: % formula %) (wherein, R1 and R2 are alkyl groups, aryl groups, etc.
substituted or unsubstituted hydrocarbon group (X is a real number of 0 to 4); alkyl silicates such as tetramethyl silicate, tetraethyl silicate, tetraalkyl silicate, tetrabutyl silicate 11, and condensates thereof; , methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane,
Dimethyldibutoxysilane, methyltriphenoxysilane, dimethyldiphenoxysilane, ethyltriphenoxysilane, etc. Alkyloxyallylsilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyl I-IJ butoxysilane, diphenyldimethoxy silane, diphenyljethoxysilane, phenylalkoxysilane, etc., and substantially has 2 or more, preferably 2.5 or more, alkoxy groups, phenoxy groups, etc. to a silicon atom.
(Which crosslinking agent is preferable in terms of economy, labor safety, and mechanical properties?

However, compared to the alkoxy group ζ, the phenoxy group has inferior reactivity with component (A), so it is advantageous to adjust the storage stability and pot life during the coating process of the product II. Tetraalkyl silicates and their condensates or methylalkoxysilanes are currently available in the market due to the fact that they require long periods of time or high temperatures or long-term heating to complete the process, and methoxy groups, ethoxy groups, etc. It is recommended to use similar types.

The crosslinking agent that is component (E) of the present invention has a general formula: % formula (%) (in the formula, R1, R2, and I are the same as above). Any commonly used material can be used as long as it reacts with hydroxyl groups to cure the composition.

These are acetic acid or long-chain carboxylic acid releasing type represented by the general formula: % formula %) (in the formula, R1 and Dimethyldiacetyloxysilane, methyltripropylcarbonyloxysilane, dimethyldipropylcarbonyloxysilane, methylacetyloxydipropylcarbonyloxysilane,
Methyltributylcarbonyloxysilane, dimethyldibutylcarbonyloxysilane, etc. alone or a mixture of two or more, oxime-releasing type represented by the general formula: (wherein R, R, x are the same as above), Methyl(trimethylcarboximinooxy)silane, Methyl(trimethylethylcarboximinooxy)silane, Dimethyl(dimethylethylcarboximinooxynosilane,
alone or as a mixture of two or more, general formula: % formula %) (wherein, R, R, and (dimethylaminofusilane, methyl tri(
Various crosslinking agents such as methylethylaminofusilane, dimethyldi(methylethylaminonesilane, methyltri(dimethylaminolasilane), dimethyldi(diethylaminofusilane) alone or in mixtures of two or more thereof).

Component (0) used in the present invention is a catalyst that cures the composition through the reaction of components (A) and (B), including iron octoate, zinc octoate, tin octoate, cobalt octoate, manganese octoate, and octane. Metal carboxylic acids such as lead acid, iron naphthenate, titanium naphthenate, zinc naphthenate, tin naphthenate, cobalt naphthenate, lead naphthenate, tin caprylate, tin oleate, zinc stearate, dibutyltin diacetate , dibutyltin diacetate, dibutyltin laurate, phenyltin diacetate, dibutyltin oxide, dibutyltin methoxide, organic tin compounds such as tetrapropyl titanate, tetrabutyl titanate, tetraoctyl titanate, diisopropoxy bis(acetyl Acetonatonotitanium, diisopropyl bis(
titanium chelate compounds such as ethylacetoacetatonotitanium, 1,6-propylenedioxybis(ethylacetoacetatonotitanium), N,N-dimethylaniline, dimethyloctadecylamine, γ-(tetramethylguanidino)propyltrimethoxysilane, etc. Examples include tertiary amines.

The component CD) of the present invention is a well-known compound represented by the general formula: % formula % (where M is an alkali metal such as Li, Na, or Krj, a is a positive real number of 8 or less, and b is a real number of O to 4). It is a compound of ILi, and more specifically, ILi
4 T i Oa, I, 12TiO3 (where 0(a(
1, b-0) Alkali titanate with a salt type structure, Na2T17015, R2T' 16013, R2
Examples include alkali titanate having a tunnel structure represented by T18o17 (wherein a<6, b=o).

Among these, potassium hexatitanate and its hydrate represented by the general formula: % (in the formula, b is the same as above) are suitable in that they greatly improve the fire resistance and heat insulation properties of the final object.

Not limited to potassium hexatitanate, alkali titanates are generally powders or fibrous microcrystals, but among these, those with a fiber length of 5 μm or more and an aspect ratio of 20 or more, especially 100
The above provides favorable results in terms of the strength of the fireproof heat insulating sheet of the present invention.

In addition, fibrous potassium titanate has a high specific heat and excellent heat insulating performance, and is particularly preferred for realizing the performance of the fireproof heat insulating sheet of the present invention.

In the present invention, ordinary heat-resistant mechanical materials can also be used, such as micas such as phlogopite, muscovite, and sericite, montmorillonites, graphite scale stainless steel, fluorine-containing synthetic micas, and others. can.

The high refractive index inorganic compound used in the present invention has a particularly excellent shielding property against radiant heat, and when the endothermic inorganic compound comes into direct contact with slag during welding or fusing, it will cause damage to the contact surface. When the slag is heated and decomposed, an endothermic reaction occurs and the temperature of the slag is lowered, thereby suppressing the collapse and slag of the refractory and heat-resistant sheet of the present invention.

A refractive index of 1.5 as a high refractive index inorganic compound in the present invention
Among the above, the combination of those with a ratio of 2.8 or higher is particularly suitable for insulation purposes: (1) Dolomite (dolomite, specific gravity 2.8-2.9)
refractive index 1.50-1.68), magnesite (rhombite, specific gravity 6.0-3.1, refractive index 1.52-1.72)
J, aragonite (specific gravity 2.9-6.0, refractive index 153
~1.68), apatite (apatite, specific gravity 3.1~6)
．． 2, refractive index 1.63-1.64), spinel (spinel, ratio ij'15-3.6, refractive index 1.72-1.73)
J, corundum (specific gravity 3.9-4.0, refractive index 1.76
~L77), zircon (specific gravity 6.9-4.1, refractive index 1.79-1.81), silicon carbide (specific gravity 3.17-6
．． 19, refractive index 2.65-2.67) and other crushed stone powders of natural or synthetic minerals.

(2) Examples include frit, high refractive index glass, molten phosphorus fertilizer obtained as a solid solution of phosphate rock and serpentinite, and other similar solid solution crushed powders, granular materials, fibrous materials, or foams.

Excellent endothermic inorganic compounds include crystalline release type such as calcined gypsum, alum, calcium carbonate, aluminum hydroxide hydrosaltite aluminum silicate, carbon dioxide release type, decomposition endothermic type, and endothermic type such as phase change type. Examples include inorganic compounds.

The mixing ratio of component (A), component (B), and component (0) of the present invention varies depending on the desired type and combination of each component, as well as the purpose of use as a fireproof heat insulating sheet, but usually (A
CB) component is 1 to 30 parts, preferably 6 to 20 parts, per 100 parts (by weight, the same applies hereinafter) of component (B), and if component (B) is less than 1 part, sufficient strength cannot be obtained when used as a composition. On the other hand, if it exceeds 60 parts, the tensile strength and bending resistance will decrease.

The curing catalyst as component (0) is in the range of 0.01 to 10 parts, preferably 0.1 to 1 part, per 100 parts of component (A). Less than 0.01 part is insufficient as a curing catalyst (
Not only does it take a long time to cure, but it is also difficult to change the desired physical properties. On the other hand, if it exceeds 10 parts, it may gel during mixing or significantly increase the apparent viscosity, resulting in decreased workability and storage stability.

When component (0) is brought into contact with the mixture of components (A) and (B) of the present invention, the reaction between components (A) and (B) proceeds due to humidity and water, resulting in a three-dimensional network structure even at room temperature.

Therefore, (A) lff1 min and CB) component and (a
) To transport the entire amount of ingredients offshore, combine them in a state that excludes moisture and store them in an airtight container, or (0)
Components (B) (1) It is appropriate to store component (1) separately and to cure it by exposing it to air before use.

Both of these reactions are accelerated by heat. Therefore, in the present invention, the preparation of a homogeneous dispersion of each component [A), (B), (a) and the alkali titanate as component (D), and a high refractive index inorganic compound and/or an endothermic inorganic compound is (A), (B), (0) and (D) [
Mix all of the ingredients in a homogeneous dispersion of (A) and (B) with (D) and (0) or (A). There is a method in which a two-component system consisting of a homogeneously dispersed component (D) and a CI component (B) is prepared by mixing the two components immediately before coating on an inorganic fabric.

The usage ratio of component (D) according to the present invention is (A) and (B)
, type of component (0), blending ratio 8, and type and particle size of component (D).In general, if there is too much component (D), the fireproof insulation properties will improve, but the strength as a fireproof insulation sheet will be insufficient. On the other hand, if the amount of component (D) is too small, the heat resistance decreases, and in severe cases, n-flame combustion may occur.

Therefore, in the present invention, the amount of component (D) to be blended is 1 to 200 parts, preferably 30 to 100 parts, per 100 liters of component FA), and furthermore, a high refractive index inorganic compound and/or ) When an endothermic inorganic compound is blended, the blending ratio thereof is 400 parts or less, preferably 10 to 300 parts, based on 100 parts of component (A). In this case, component (D) is a combination of these inorganic compounds.
It is sufficient to mix an amount reduced by one weight from the same weight as .

In addition, some or all of these high refractive index inorganic compounds and endothermic inorganic compounds can be replaced with commonly used inorganic pigments, inorganic bulking agents, T111 that imparts flame retardance (organic powders, etc.). The amount of baashi moon that is used is (
A) 400 parts or less, preferably 30 parts per 100 parts of component
0 parts or less (should be strained.

The fireproof heat insulating sheet of the present invention can be obtained, for example, as follows. That is, a crosslinking agent consisting of a diorganosiloxane resin, an alkyl silicate or a hydrolyzable compound, alkalina titanate, a mixture of a high refractive index inorganic compound and/or an endothermic inorganic compound, and optionally toluene,
An organic solvent such as xylene or trichlene, and additives such as a dispersant are added to prepare a dispersion liquid with an appropriate concentration. This dispersion with a curing catalyst added, or with all of these ingredients or organic solvents omitted, is homogeneously dispersed in a moisture-blocking state, either as it is, or with an organic solvent added just before coating. Glass fiber cloth, asbestos sheet, rock wool sheet, metal foil, ceramic wool sheet, It is applied to one side or the entire surface of an inorganic fabric such as a special inorganic fiber cloth, and is applied at room temperature or under heating, preferably at 150%
The polydiorganosiloxane is cured by heat treatment for 1 to 30 minutes at a temperature of 200 DEG 0 to 200 DEG 0, and is then integrally fixed to the base material described in i1 for practical use.

In the present invention, in addition to components (A), (I3), (0), and CD), a dispersant and a defoaming agent for homogeneous dispersion, a coloring agent for adjusting color and mechanical strength, resin powder, and Fuel and various fillers can be mixed freely.

However, metal powders such as copper powder, nickel powder, brass powder, and aluminum powder should be mixed in to improve the surface heat reflection effect and penetration suppression effect immediately before coating on the inorganic fabric from the viewpoint of storage stability. And when these metal powders are used, when the inorganic fabric is Kinhohaku (E)
As the component crosslinking agent, an alkyl silicate or alkoxysilane type crosslinking agent should be used, and other crosslinking agents should be avoided as they generally tend to corrode metal powder or metal foil.

The thickness of the fireproof insulation sheet of the present invention is preferably 0.3 m.
m or more and 5 mm, preferably within J21. This thickness is 0.1mm
If the thickness is less than 3 m, sufficient fire resistance and insulation properties cannot be achieved, and the thickness is less than 3 m.
If it exceeds m, the fire resistance and insulation properties will improve.

This increases cost and weight, making it impractical.

However, the fire-resistant heat insulating sheet of the present invention is made by simply coating components (A), (E), (0) and (D) on the surface of a single sheet of inorganic fabric. Before the adhesion or coating layer dries, other inorganic fabrics are layered, and components (A), (B), (0), and (D) are further coated on the surface and then cured, etc. It can be used in a laminated structure.

As described above, the fireproof heat insulating sheet of the present invention has extremely excellent fireproof heat insulating properties, can form a flexible coating layer, and does not come into direct contact with high 7Ai molten slag generated during welding. Even at times, the coating layer only turns white and does not burn, decompose, or melt, and can completely protect objects to be protected, such as the human body, combustible materials, and equipment. Moreover, it is lightweight and has excellent toughness and M-ray reflectivity, and is advantageous in that it can be used as a crosslinking agent with alkyl silicate, tetraethyl orthosilicate and its condensates, or alkoxysilane, and methyltrimethoxysilane. When used, these crosslinking agents are inexpensive, low in toxicity, easy to handle, and extremely chemically utilizable compared to other crosslinking agents.

The present invention will be specifically explained below with reference to Examples, but of course these are for illustrative purposes only and are not intended to define the connotation or scope of the invention.

Example 1 Potassium titanate (trade name Teismo D, Otsuka Chemical Channel #+ W
(locally made) in various proportions and stir and mix to create a uniform dispersion. This was applied to one side of asbestos paper with a thickness of 0.5 mm at various thicknesses, air-dried for 5 minutes, and then heated at 150°
0 for 5 minutes to produce a fireproof heat insulating sheet in which one side of the asbestos paper was covered with a silicone resin layer containing potassium titanate.

This sheet was cut into pieces with a diameter of 100 cm and a length of 180 cm to prepare test samples (Y1 to A9). A fire resistance and insulation test was conducted according to the "Flame Retardant Test Method", and the measurement results and comparative results using commercially available asbeth 1-(3-part grade) are shown in the first section.

Example 2 using 3 parts and 15 parts of methyltrimethoxysilane
A fireproof sheet was produced in the same manner as above, and evaluated by the above-mentioned fireproof and heat insulation test method, and found to be Class A.

Examples 4 to 16 The type and amount of the inorganic core material, the type and amount of silicone resin, the type and amount of titanium alkali, and the type and quality of other auxiliary materials were varied to achieve fire resistance I#r in the same way as rotation. A thermal sheet was manufactured, and a fire resistance and insulation test was conducted according to 1TI, and the measurement results and ratio axis vs. It ((
The results are shown in Table 2.

In Table 2, Resins 1.2 and 6 are Example 1.2, respectively.
and 6 represents the resin.

Explanation of abbreviations in Table 2 TBS: Tetraethylsilicate MTMS: Methyltrimethoxysilane DMDMS Nidimethyldimethoxysilane FTMS: Phenyltrimethoxysilane Patent applicant Otsuka Chemical Co., Ltd. 223-

Claims (1)

[Scope of Claims] 1 The inorganic core material comprises (A) a silanol hydroxyl end-blocked diorganosiloxane resin, (B) a crosslinking agent comprising an alkyl silicate and/or a hydrolyzable silane compound, and (0) a curing catalyst. , and (D) a fire-resistant heat insulating sheet, characterized in that it is covered with a coating layer mainly composed of alkali titanate. 2. The sheet according to claim 1, wherein the coating layer contains a high refractive index inorganic compound and/or an endothermic inorganic compound as an auxiliary component. 25'O) 500~500
00 cat, and contains at least 50% by weight of the total of the components (A), CB) and (0). sheet.