JPS5914343B2 - non-combustible insulation panels - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a noncombustible heat insulating panel that has strong adhesion between a phenolic resin foam and a noncombustible substrate, and also has good fire protection performance of the panel, and a method for manufacturing the same.

Various technologies related to noncombustible heat insulating panels have been made public. However, the resol type phenolic resin foam used in the present invention (hereinafter referred to as resol foam) has not been put to practical use in this field. This is because resol foam has low strength, is brittle, and has poor self-adhesive properties, and furthermore, it is impossible to avoid the residual strong acid used as a curing catalyst when manufacturing resol foam, which corrodes steel plates etc. This is because there was a problem that it was easy to do. o The present inventor was able to solve the above problem by interposing a layer of a specified adhesive substance capable of reacting with the phenolic resin, which also serves as a rust prevention layer, between the resol foam and the nonflammable substrate. .

That is, the present invention provides a method for attaching a substance containing 1% by weight or more of free isocyanate groups selected from polyether urethane prepolymers and acrylic urethane prepolymers onto a nonflammable substrate at a rate of 2 to 2009/m. After the foaming agent, foam stabilizer, and hardening agent are mixed,
The solid concentration of the condensation reaction product obtained by condensing phenol and formaldehyde under alkaline conditions is 7.
This is a non-combustible heat insulating panel characterized by applying a resol type phenolic resin stock solution of 5% or more and foaming and curing.

H5: In the present invention, the free isocyanate groups selected from polyether urethane prepolymers and acrylic urethane prepolymers are contained in an amount of 1% (% refers to % by weight).

The same applies hereinafter) or more is used, particularly preferably 2% or more, and substances containing these free isocyanate groups dissolved in a solvent or mixed with other substances may also be used. It is possible. As the polyether urethane prepolymer mentioned above, for example, Hypren A manufactured by Mitsui Nisso Urethane Co., Ltd.
x-580, Hypren P-302 and Hypren P
-760, and the acrylic urethane prepolymer also includes M-35AR urethane primer.

When the content of NCO groups in the above-mentioned substances is less than 1%, the adhesion between the nonflammable substrate and the resol foam is hardly improved and there is no effect; ~2009/M2.

For impermeable substrates such as metal plates, this amount of adhesion may be small, but for transparent substrates such as gypsum boards, this amount of adhesion is required to be slightly larger.

However, when it exceeds 2009/M2, local foaming phenomenon occurs violently, making it impossible to obtain a uniform foam, and combusting easily, resulting in a decrease in fire protection performance. On the other hand, 29/M2
If it is less than that, the effect will not be obtained, the adhesiveness will be reduced, and in the case of iron plates, rust will easily occur. Substances containing these free isocyanate groups can be deposited onto a nonflammable substrate using a nozzle, roll coater, bar coater, flow coater, etc. for continuous methods, and spraying for low viscosity materials. There is also a way to use .

It can also be done using a brush, roller, spatula, etc. The resol type phenolic resin stock solution used in the present invention is a common one and is not particularly limited.

In order to effectively obtain a resol foam, it preferably has the following properties. Viscosity 100-50,000cp
s(2'C) and is mainly composed of 1 to 10 nuclear bodies. A resol type phenolic resin stock solution is obtained by a condensation reaction of phenol and formaldehyde (or paraformaldehyde) under alkaline conditions. If the condensation reaction product is used as it is, the solid concentration of the condensation reaction product is low, and foaming and curing cannot be performed effectively. Therefore, the resol type phenolic resin stock solution of the present invention is obtained by concentrating the solid matter concentration to 7570 or more. The foaming agent, foam stabilizer, curing agent, etc. to be mixed into this resin stock solution are common ones.

Specific examples are shown below. The blowing agent may be any substance that can exist as a gas or release a gas at a temperature below the temperature required to cure the resin stock solution.

The former include low-boiling organic solvents such as n-pentane and heptane, and Freon-based solvents, while the latter include metal peroxides such as calcium peroxide, lead peroxide, and magnesium peroxide, and acids such as sodium bicarbonate. There are some that release carbon dioxide gas.

As the foam stabilizer, silicone-based ones or those made by adding ethylene oxide or propylene oxide to fatty acids are used. Hardening agents are mainly strong acids and phenolic 0H.
It is a substance that reacts with groups.

These are known techniques, but the following examples include sulfuric acid,
Mineral acids such as phosphoric acid and boric acid, aromatic sulfonic acids such as phenolsulfonic acid, benzenesulfonic acid and toluenesulfonic acid, sulfonated nopolac resins, phenolsulfonic acid urea formaldehyde condensate, aminosulfonic acid formaldehyde condensate, sulfosalicylic acid formaldehyde condensate These are oligomers such as diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate. The non-combustible substrate is intended to supplement the strength of the resol foam and to be used as a building or civil engineering material or as a molding material.

Specifically, these include iron plates, galvanized iron plates, colored galvanized iron plates, copper plates, thin metal plates such as aluminum plates, gypsum plates, gypsum boards, asbestos plates, rock wool plates, concrete plates, perlite plates, and the like. As described above, the present invention allows a resol foam with particularly excellent heat insulation properties and flame retardance to be practically used as a heat insulation panel using an inexpensive manufacturing method.

This will be explained using a practical example. Examples 1 to 4 and Comparative Example 1 47% formaldehyde aqueous solution 25.5 Kf (formaldehyde 400 mol), phenol 23.5 YK9 (phenol 250 mol) and 4070 NaOH solution 1.2
5K! 9 was mixed, heated and continued stirring at 85° C. for 4 hours.

Next, the temperature was lowered to 55° C. and maintained until 55% of the water evaporated. In this way, a resol type phenolic resin stock solution (hereinafter referred to as resol stock solution) having a non-volatile content of 75% was obtained. This resol stock solution was distilled and dehydrated under reduced pressure and concentrated until the nonvolatile content reached 8570 to obtain a resol type phenolic resin foaming stock solution (hereinafter referred to as foaming stock solution).

UCC silicone L-5340 (
4 parts by weight (manufactured by Nippon Unica Co., Ltd.), 15 parts by weight of n-pentane, and 32 parts by weight of 60% sulfuric acid were added and mixed uniformly. This is called liquid A. A colored galvanized iron plate was prepared, and a substance containing free isocyanate groups, that is, polyether-based urethane polymer Hypren Ax-580, P-302, and P-760 manufactured by Mitsui Nisso Ureta 7 Co., Ltd., was prepared on this plate. Further, M-35AR urethane primer (hereinafter referred to as NCO material), which is an acrylic urethane prepolymer, was spray-coated in the amount shown in Table 1, liquid A was spread using a bar coater, and the tube was inserted into an open tube at 70°C.

I took it out from the open after 15 minutes and it was 19rr! A resol foam laminated colored galvanized iron plate [1] with a thickness of /m was obtained.

The bulk specific gravity of [1] was 0.19-0.20. The bulk specific gravity of the colored galvanized iron plate used is approximately 7.0 and the thickness is 0.4.
m/m, it is estimated that the bulk specific gravity of the resol foams of these Examples is about 0.03. Regarding [1], a vertical tensile peel test was conducted to examine the adhesive strength of the resol foam to a colored galvanized iron plate.

The results are shown in Table 1, and in the present invention, all materials were broken from resol foam, and the breaking strength was 0.5 to 1K.
It was f/M2. Next, regarding [1], JISK54
A salt spray test was conducted according to OO-70. The results are also shown in Table 1, and in the case of the present invention, no change occurred even after 500 hours. On the other hand, the breaking strength of the example shown for comparison was 0.
Less than 1K9/d could not be measured, and peeling occurred near the interface between the resol foam and the colored galvanized iron plate. Five things about the salt spray test
After 00 hours, the colored galvanized iron sheet and the resol foam were no longer adhered to each other, and the colored galvanized iron sheet was already undergoing corrosion. The thermal conductivity of the non-combustible insulation panel manufactured according to the recipe of Example 1 above is 0.038 Kcat/m-Hr・℃
It was hot.

The fire protection performance of this non-combustible heat insulating panel was measured by the method specified in JIS Al32l-1975, and Table 2 shows the results confirming that it had fire protection performance equivalent to semi-incombustible material A.

Examples 5 to 7 and Comparative Examples 2 to 3 Using liquid A from the previous example, a 9m7m nonflammable substrate was
An example using thick gypsum board (specific gravity 0.7) is shown below.

The M-35AR urethane primer used in Example 4 was used as the NCO material. A noncombustible heat insulating panel with a total thickness of 29 m/m was obtained. The average specific gravity of this panel was 0.23. Since the amount of NCO material used was varied, the results are shown in Table 3. The methods of measuring peel test, breaking strength, etc. are the same as in Examples 1-4. Examples 5 to 7 and Comparative Example 2
.about.3 shows that adhering too much NCO substance reduces the strength of the resol foam.

Claims (1)

[Claims] 1. A substance containing 1% by weight or more of free isocyanate groups selected from polyether urethane prepolymers and acrylic urethane prepolymers on a nonflammable substrate. 2.
After depositing at a rate of ~200g/m^2, blowing agent,
Apply a resol type phenol resin stock solution with a solid concentration of 75% or more of the condensation reaction product obtained by condensing phenol and formaldehyde in an alkaline environment by mixing a foam stabilizer and a curing agent. , a noncombustible insulation panel characterized by foam hardening.