JPS585340A - Heat insulating material having superhigh heat resistance produced by using flame-retardant expanded binder - Google Patents

Abstract

PURPOSE:To provide the titled material which is suitable for use as a core for sandwich panels, etc. and does not suffer heat deformation at an elevated temperature, by molding a solid filler by using, as a binder, a flame-retardant expanded polymer in which a main repeating polymer unit is composed of isocyanurate. CONSTITUTION:An org. isocyanate such as tolylene or xylylene diisocyanate, a trimerization catalyst such as potassium acetate or caprylate, a blowing agent such as water or trichoromonofluoromethane, and a polyol such as polyether polyol, are reacted together to obtain a flame-retardant expanded polymer in which a main repeating polymer unit is composed of isocyanurate. A powdered and/or particulate filler such as rock wool, glass bead or activated carbon is molded by using said expanded polymer as a binder in a weight ratio of the polymer to the filler of 1 to at least 1.5.

Description

[Detailed description of the invention] It's about materials.

More specifically, the present invention relates to a super heat-resistant heat-insulating material characterized in that one or more solid fillers are molded using a flame-retardant foamed polymer in which one main repeating polymer unit is isocyanurate as a binder.

Cellular polymers in which one major repeating polymer unit is an isocyanurate are well known, and this technology is widely used.

In general, polyisocyanurate foams made according to the prior art are known in the foam art and exhibit higher flame retardant properties when subjected to various flame retardant tests compared to polyurethane foams. be discovered.

However, polyisocyanurate foams are brittle due to their polymer structure, and many efforts have been made to overcome this drawback. For example, Japanese Patent Application Publication No. 54
-98, British Patent Nos. 1223415 and 1 40482
2 issues etc. are referred to.

- Much effort has also been made regarding the problem of smoke generation during the combustion of polyisocyanurate foams.

For example, Japanese Patent Publication No. 52-7038e55-1291, Japanese Patent Publication No. 54-53198, +55-
8, 6, 8, 1, 0, etc. are referred to.

However, it cannot be denied that technology for improving brittleness and smoke-emitting properties has progressed to a considerable extent, but when used as a composite material, especially when used as a core material for sealed sandwiches and nochi panels, for example, JIS A 1311-2
Problems arise when the face material is deformed due to decomposed gas pressure when exposed to high temperatures such as heating at high temperatures, and thermal deformation of the core material itself. In particular, when the core material is a foam alone, the decomposition gas generated and the deformation of the core material greatly deform the sandwich panel, and the flame may penetrate to the back surface at the fitting portion. Therefore, many considerations must be made, such as the sandwich panel's face material, the type of frame material, and the structure of the fitting part, which may lead to an unrealistic sandwich panel structure or complicated manufacturing equipment. There is a risk that a situation may arise where this becomes necessary.

Particularly in the case of thin sand inch panels, when the foam alone is exposed to the above-mentioned JISA 1311 class 2 heating, it will completely carbonize, causing deformation of the heated backing material and even an increase in the backside temperature.

In addition, if a thin sand-inch panel whose core material is solely made of foam is exposed outdoors, there is a risk of warping due to the temperature difference between the sun-exposed and unexposed surfaces, which can cause various problems in practical engineering. come.

The present inventors have developed this type of thin panel/doinochi panel according to the JIS standard.
As a result of our intensive efforts to improve panel deformation that occurs when exposed to high temperatures such as A1311's secondary heating, and panel warping that is a practical problem, we have discovered a problem in which the main repeating polymer unit is incyanurate. We have succeeded in overcoming these problems by using a flammable foamed polymer as a binder to obtain an insulating material based on one or more solid fillers.

Namely, the present invention provides flame retardant foams in which one main repeating polymer unit is incyanurate, which consists of reacting an organic incyanate, a trimerization catalyst, and a polyol as a binder for one or more powdered and/or particulate fillers. The present invention relates to a superpolymer 1 heat-resistant heat insulating material that uses a polymer and has a weight mixing ratio of 10-material≧''-.

- Utilizing the reaction of organic isocyanate, when a polyol and organic incyanate are reacted using a blowing agent in the presence of an incyanurate-forming catalyst, the urethane-forming reaction and the incyanurate-forming reaction usually occur over time. It is well known that the formation of incyanurate polymers lags behind the progress of the main urethane reaction.

Based on this idea, by using a foaming binder that generates urethane isocyanurate groups as a foaming binder, the initial reaction is slow even when the binder is applied to the filler, and the formation of incyanurate is promoted by heating. The greatest feature of using this binder is that it can be processed without being restricted by time constraints. In addition, the polyisocyanurate structure itself is inherently brittle and it is difficult to obtain strong adhesive strength, but the adhesive strength is improved by mixing it with the urethane bond structure, and both are excellent when the ratio of urethane group/isocyanurate group is in the range of 14 to 1102. It is ideal for use as a binder as a heat-resistant material because it has both high adhesive strength and heat resistance. Furthermore, the reactivity of this foaming binder is extremely low compared to ordinary foaming stock solutions, and in particular, the foaming start time is more than five times that of the latter.
It has extremely good workability when used as a binder.

The weight mixing ratio of the filler of the heat insulating material in the present invention must be 15 or more to 1.0 of the foamed polymer. Although it is a known fact that a filler is added to a foam to improve flame retardancy, the feature of the present invention lies in the use of a flame-retardant foamed polymer as a binder for the filler. Because of this, the apparent density of the insulating material is increased, and as a result, the sound insulation effect is significantly improved. Furthermore, although the heat insulating material produced by this method has somewhat inferior performance in terms of thermal conductivity compared to the foam alone, it is still sufficient to be used as a heat insulating material.

In any case, the heat insulating material according to the present invention is characterized in that it has heat resistance that cannot be determined by the foam alone.

However, if the weight mixing ratio of the filler to the foamed polymer is less than 1.5, its characteristics cannot be fully exhibited.

The flame retardant foamed polymer used in the present invention can be obtained by reacting together an organic incyanate, a trimerization catalyst, a blowing agent and a polyol.

Examples of the organic incyanate include tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, polytunylmethane polyisocyanate obtained by a conventional method, diphenyl ether diisocyanate, methylene biscyclohexyl isocyanate, and the like.

As a trimerization catalyst, potassium acetate, potassium onacylate, N,
N', N''-tris(dimenalaminopropyl)-S
Known trimerization catalysts such as -hexahydrotriazine and 2,4.6-)lis(methylaminomethyl)phenol may be used, and it is also possible to use them in combination with general urethanization catalysts.

As a blowing agent, water, trichloromonofluoromethano,
Trichlorotrifluoroethane, methylene chloride, etc. are used.

The polyol has two or more hydroxyl groups,
In addition, common polyether polyols having a hydroxyl value of 30 or more are used.

The chemical equivalent ratio of organic isocyanate and polyol is 7:1
It is desirable that the range is from 2=1.

As solid fillers, lightweight foams containing 70% or more of silicic anhydride, rice husks, wheat husks, activated carbon, asbestos, mica, rasparoons, glass peas, aluminum hydroxide, etc. are used alone or in combination. . The filler is used in a weight mixing ratio of 15 or more with respect to the above-mentioned polymer 10, and preferably a range of 2.0 to 40 is recommended from the viewpoint of moldability and performance of the heat-resistant panel.

The surface material that can be used for sandwich panels is steel plate, 7/L.
'Mi board% asbestos board, lightweight concrete board, stainless steel board,
Any non-combustible material such as ceramic plate etc. may be used.

The sandwich panels used in the examples were preheated to about 50°C.
Above, preferably 60. It is a colored steel plate that is led into a press heated to a temperature in the range of 100°C to 100°C and heat cured, and the frame material is made of aluminum with a thickness of 1.0 m. The size of the sandwich panel is 250 x 500 x 18 m, and the two panels will be joined together for the heating test. In the heating test, two sandwich panels were firmly joined together and stood vertically, six gas burners were set so that the entire surface was exposed to flame, and the temperature was adjusted by adjusting the amount of propane gas and air. The heating temperature is 850°C and 20°C on the surface of the panel material.
so that it becomes Temperature control is performed using thermocouples. The heating time of the heating test conducted in the present invention was 30 minutes.

After the heating test, we removed the face material and observed the state of the core material, and found that in the case of the foam alone, it was completely carbonized to the back side, with cracks appearing in some parts, and in the case of Comparative Example 6, compared to the foam alone. Although he was several steps superior, he still had a small rank. In the example, uncarbonized portions of 10115 or more were left, no cracks were observed, and there was no change in thickness, shape, etc.

In addition, in the outdoor backdrop test, the backlight was exposed horizontally for 7 hours from 9:00 to 16:00 on a sunny day, and the warpage was measured. Measurements were made by measuring the deformed length at the center point of the sand inch panel by applying a water system.

The basic formulation of the flame-retardant foamed polymer used in the present invention is as follows. Units are parts by weight.

Polyol l) 12.1 1) Toluenediamine polyether OHV 400PEG-200
2) 2.2 2) Polyethylene glycol average molecular weight 200. G-4003) 3. . 3)
49zf, 7ke9y-A-average molecular weight. 0'CM-2
944) 4.5 4) 7f force rN knee f
0HV39L-5420") 2.0")
Silicone oil Catacyst manufactured by Nippon Neniker
LB6) 0.2 6-Potassium in 50% ethylene glycol solution 7, Off 11 7) 36.0
7))su,p,,7. ,O□ri.

The present invention will be further explained using Examples and Comparative Examples in Table 1, but the present invention is not limited thereto.

As is clear from the Examples and Comparative Examples, by molding one or more solid fillers with a flame-retardant foamed polymer as a binder, deformation in high temperature ranges, increase in back surface temperature,
This prevents smoke generation and warping during outdoor exposure.

Claims (1)

Claims: Flame retardant in which one unit of the main repeating polymer is incyanurate, consisting of reacting an organic incyanate, a trimerization catalyst and a polyol as a binder for one or more powdered and/or particulate fillers. A super heat-resistant heat insulating material characterized by using a foamed polymer and having a weight mixing ratio of 1.5□--ton filler.