JPS6158735A - Refractory composite board - 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] Industrial 1' The present invention relates to a composite board made by laminating a surface material layer on a glass fiber composite plate-shaped phenol foam, and more specifically, as a base material for heat-insulating interiors of buildings, for ceilings, etc. The present invention relates to a fire-resistant composite board with excellent fire resistance, which is suitably used as a heat-insulating interior material, various industrial heat-insulating materials, and rooftop heat-insulating material.

Prior art and part 1 Phenol foam has been known as a flame-retardant foam, but Jl5-A-13
When the test conditions are very strict, such as the fire resistance test for architectural drawings stipulated in 04, the fire resistance is insufficient and it cannot be used for architectural materials that require strong fire resistance. It was difficult. Various methods have been tried to solve this problem. For example, a method d1 has been put into practice in which a large amount of phenol foam is injected with a large amount of a liquid or solid fil fuel agent of the Japanese or non-Japanese type, but this method does not improve the fire resistance as much as expected. However, on the other hand, it had the disadvantage of increased brittleness and increased cost, and was not an effective method.

&"Sad" 1 This book was created in view of the above circumstances, and by crystallizing specific glass fibers in a specific phenol foam in an appropriate state, the fire resistance of the phenol foam is improved, and this glass The object of the present invention is to provide a composite plate with excellent fire resistance, which is a combination of a fiber composite plate-like phenol foam and a surface material layer.

That is, in order to achieve the above object, the present invention provides a glass fiber mat having an insect vinegar content of 50' or more per 11 TIl with an acid 111
A surface material layer is laminated on a glass fiber composite plate-shaped phenol foam having a phenol foam of 430 or more and dispersed in the thickness direction by 10% or more.

Hereinafter, the present invention will be explained in more detail with reference to the drawings.

As shown in the drawing, the fire-resistant composite board according to the present invention is made of a glass fiber composite plate-like phenol foam 3 in which glass fiber mat 1 is dispersed and mixed in a nord foam 2. It is formed by laminating material layers 4, and in this case, in the present invention, a glass fiber mat having a weight (area weight) per 1T1' of 50' or more is used. If the basis weight of the glass fiber mat is less than 50't, in the fire resistance evaluation test for composite boards mentioned below,
This is unfavorable in terms of fire resistance, such as deformation, destruction, or falling off of the composite plate, ignition of flames on the back side or the surrounding area (near the joiner), generation of afterflame after the completion of the fire resistance evaluation test, and rise in temperature on the back side. A phenomenon occurs. The upper limit of the basis weight is not necessarily limited, but if the basis weight is too large, the dispersibility with the phenol foam, the foamability of the phenol foam,
The insulation, handling properties, and fire resistance may deteriorate.
Normal basis weight is 2000? Preferably, the following are used:

In addition, the types of glass fiber mats include ■Several 10wm
Chopped strand mat is made by randomly and uniformly dispersing strands cut into strands and bonding them into a mat shape with a binder. ■ Continuous long glass fibers are stacked in one or more layers in a spiral shape, and this is biased. Continuous strand mats formed into a mat shape aligned in the same direction and bonded with a binder; ■Glass nonwoven fabrics in which glass fiber filaments are randomly dispersed and bonded and formed with a binder; and ■Surface mats. One or more of these can be appropriately selected and used. The above-mentioned glass fiber mats are easy to handle, disperse well with the phenol foam, and the mat itself does not fall off the phenol foam in a fire resistance test, so the fire resistance of the composite board is demonstrated well. Ru.

Furthermore, in this iN specification, phenolic foams that have an oxygen index of 3 or more layers in the combustion test method specified in JIS-7201 are used, and in particular, phenol foams that have an oxygen index of 3 or more layers are used. (preferably) is used for δ. If the oxygen index of the phenol foam is less than 30, if the composite plate is heated and deformed during the fire resistance test and breaks, the heat will concentrate in that area, causing a flame, which will significantly reduce the fire resistance. .

The fire-resistant pitch board of the present invention uses a glass fiber composite plate-like phenol foam in which the above-mentioned glass fibers are dispersed and mixed in the phenol foam. Here, the glass fiber mat is dispersed and mixed in the phenol foam. In this case, 10% or more, preferably 15 to 30%, of glass fiber mat is dispersed and mixed in the thickness direction of the phenol foam. That is, with respect to the total thickness of the phenolic foam, the dispersed portion of the glass fiber cloak is more than one layer thick.
Preferably, the glass fibers are dispersed so as to occupy 15 to 30% of the thickness. To explain this with drawings, A is a portion of only phenol foam without fibers dispersed and mixed in the glass 11, B is a portion of phenol foam with glass fibers dispersed therein, and T (%) = B layer ( 1) I'7g x1
In the thickness of 008 layers + the thickness of 8 layers, the thickness is 10% or more, preferably 15 to 30%.

By the way, when dispersing glass fibers in phenolph A-me, as shown in Figures 1 and 2,
Although it is sufficient to disperse and mix only on one side of the phenol foam 2 on the combustion prevention side, it is also possible to disperse and mix glass fibers on both sides of the phenol foam 2, respectively, as shown in FIG. In this case, the thickness a of both 88 formed on both surfaces of the phenol foam 2 is preferably 20% or more, preferably 30 to 60%, of the total thickness of the phenol foam 2.

Furthermore, as shown in Fig. 2.3, the glass fiber 1 forms a layer B in which the glass fiber 1 is dispersed in the phenolic foam 2 and a layer C in which only the glass la t-1t is slightly exposed from the 1iUB. Although it is preferable that the glass fibers 1 be dispersed in the phenol foam 2, all of the glass fibers 1 may be dispersed in the phenol foam 2 as shown in FIG. In this case, the thickness of layer C made only of glass fibers is 0.1
The thickness is preferably 0.2 to 0.4 mm, preferably 0.2 to 0.4 mm.

The method of dispersing and mixing the glass m
It is preferable and necessary to use a method for flooring in which a B layer in which a glass fiber mat and phenol foam are densely mixed and an Alm foamed as it is without the foamable phenol resin stock solution penetrating into the glass fiber mat.

Here, the above B layer! '! ! ! The degree is Alt! density of 1
．． It is preferable to set the fire resistance to 02 times or more, particularly 1.06 to 25 times, thereby further improving the fire resistance.

The composite board of the present invention is made as described above. ζ A surface material layer is laminated on the glass fiber composite plate-like phenol foam. In this case, as shown in Fig. 1.2, the surface material layer 4 is applied to at least the combustion prevention surface of the glass fiber composite plate-like phenol foam 3. Lamination is preferable, and it is also possible to laminate on both sides of the glass fiber composite plate-like phenol foam 3 as shown in FIG. 3, thereby making it possible to further improve the fire resistance. As described above, in the present invention, it is necessary that the surface material layer is laminated on the glass fiber composite plate-shaped phenolic foam, and if this surface material layer does not exist, the phenolic resin carbonized during the fire resistance test will fall off, and the fire resistance will drop significantly.

Here, as the surface material layer, it is preferable to use a VL-free coating material or one further laminated with an inorganic sheet material thereon. In this case, inorganic coating materials include water-curable substances such as Bortland Hyment, gypsum, and silica flff calcium, alkali metal silicate base adhesives, phosphate-based inorganic adhesives, colloidal silica-based inorganic adhesives, Examples include alkyl silicate-based inorganic adhesives, among which:
Alkali metal silicate-based inorganic adhesives are preferred, and in particular, water glass hardened bodies containing granular or powdery hardeners are preferably used. The granular or powder hardening agents include calcium carbonate, alumina, kaolin clay, graphite, sodium silicofluoride, magnesium oxide, titanium oxide, iron oxide, magnesium hydroxide, aluminum hydroxide, talc, mica, borax, and boric acid. Examples include substances such as sodium, barium sulfate, and barium borate, perlite particles, glass balloons, glass balloons, silica gel, pumice, vermiculite, and other non-V1 porous materials, and inorganic foams.

In addition, it is preferable that the inorganic coating material be applied to an arbitrary thickness of 0.3 mm or more, but practically 0.8 m is preferable.
It is preferable to have a thickness of up to about 100 m. Here, the coating film is the glass 4u Il exposed on the phenol foam surface.
Direct adhesion to i-mat (ie, C layer) further improves fire resistance.

Examples of inorganic sheet-like materials include items made of inorganic materials such as asbestos paper and vermiculite paper, metal plates, and UL-free boards such as six-piece boards. Asbestos paper is preferably used in terms of adhesiveness and manufacturability.

In this case, the thickness of this unborn sheet-like proboscis is 0.1-0.
It is preferably 8 mm, particularly 0°2 to 0.4 mm.

As the method for manufacturing the composite plate according to the present invention, conventionally known methods can be employed. For example, a method in which a resin composition, a blowing agent, and a curing catalyst are uniformly mixed and injected into a mold covered with a glass fiber mat and foamed and cured, or a belt covered with the above glass fiber mat is passed through continuous VT kneading and reforming. Glass fiber #l composite plate-like phenol foam is manufactured by applying a method of foaming and curing by continuous discharge on a conveyor, etc., and the surface of the glass fiber composite plate-like phenol foam manufactured in this way is The above-mentioned free coating film material is applied using a roll coater or the like, and the above-mentioned sand-free sheet material is further laminated on top of it to form a surface material layer on the glass fiber composite plate-like phenol foam. It is possible to manufacture a composite board made of

The phenol foam composite board of the present invention is a phenol foam reinforced with fire resistance, and its mechanical strength is improved several times compared to a case where no glass fiber is present.

In other words, this tendency was maintained to a considerable extent even when the composite plate was heated during the fire resistance test, although there was a decrease in the adhesive force at the glass fiber/phenolic resin interface, phenolic resin strength, and glass l1IN1 strength due to heat. There is. Also,
The carbonized phenol foam remains within the glass fiber and does not dissipate outside the phenol foam system. For this reason, the occurrence of deformation and destruction that are considered harmful in terms of fire resistance or structural strength, which are evaluation items in fire resistance tests, is suppressed, and cracks that would allow flames to pass through are also prevented. As a result, the fire on the back side of the phenol foam composite board can be suppressed. Furthermore, as described above, due to the improvement in mechanical strength, the volumetric shrinkage of the phenol foam due to thermal deterioration is suppressed, and the dimensional shrinkage of the composite plate is reduced.

Therefore, ml due to the removal of 1l111 from a part of the joiner of the phenolic foam composite board, which was the cause of the decrease in fire resistance.
Flame intrusion into the n12 part does not occur, improving fire resistance. In addition, the oxygen index of the phenol form used is 30.
Because of the above, the possibility of flaming is small, and since the surface material layer is added, it has synergistic effects such as flame shielding effect, prevention of dissipation of phenolic resin carbide, and mechanical strength of the phenol foam composite board. In addition, it is said to have excellent fire resistance.

As described in detail, the fireproof composite board of the present invention is made by laminating a surface material layer on the surface of a glass fiber composite plate-like phenol foam. Therefore, deformation, destruction, and falling off are prevented as much as possible, the temperature on the back side is low, there is no flame on the back side, and there is no ignition or afterflame, and the fire resistance performance is rated 1. It is.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples 1 to 6] Resol type 7E/-) Lt resin (A 1 ) with an oxygen index of 52 when foam-stopped (A 1 ) 100fflff
I part, acid curing agent 18 nails E part, 1,1,2-tric-O-rotrifluoroethane 9 heavy mountain parts for 3 continuous intervals! l! ! Mix uniformly by stirring, and mix this mixture until the basis weight is 50.
2/I and 100? /Tl11 glass nonwoven fabric, basis weight is 235F/I and 300? Chopped strand mat with a weight of /A, continuous strand mat with a weight of 3002/A, and continuous strand mat with a weight of 20(1/A).
The material is continuously discharged onto a belt conveyor covered with a surface mat of m and glass fiber mat, and is foamed.
Pass it through a curing oven at about 90℃ to harden it to a thickness of 2.
A glass fiber composite plate-like phenol foam of 8 ntm was obtained. On the glass fiber composite plate-like phenol foam that has been removed, 45 parts of No. 3 water glass, 50 ffl of FA calcium acid, and 5 m of sodium silicate fluoride are added to the surface on the side where the glass fibers are unevenly distributed. The homogeneous mixture was uniformly coated using a roll coater to a thickness of about 0.5 mm, and asbestos paper was laminated thereon and dried to form a composite board. The fire resistance of the obtained composite board was evaluated by the following test method according to J15-A-1304, which is a fire resistance test method for architectural grooved parts.

As shown in FIG. 2, the composite board obtained in Example 3.4.5 was formed by directly adhering the non-lacquered coating material and the glass fibers exposed on the surface of the phenol foam.

As shown in Figure 4, the test surface has a length of 120 cm.
1rll 12OCT11 test pieces 5,5
The test was carried out using a test piece having a length of 240 cm and a width of 1201 cm, which were joined through 6 wires.

Heating was carried out by substantially uniformly heating the entire surface of the test specimen so that the surface temperature of the test specimen was as shown in Table 1.

This test method is almost the same as J15-A-1304 except that the heating time is 15 minutes. Therefore, the results obtained with this test method are based on JIS-A-
This is almost the same as the 1q result obtained in the 15-minute fire resistance test of 1304.

The above results are shown in Table 2.

As is clear from the results in Table 2, the composite plate made of the glass fiber composite plate-like phenol foam prepared in the present invention and the surface material layer has very high fire resistance. .

[Comparative Examples 1 and 21 Glass fiber mats (not used or with a basis weight of 161/
Composite plates were manufactured in the same manner as in Examples 1 to 6, except that a glass nonwoven fabric of No. m was used, and a fire resistance test was conducted. The results are shown in Table 3.

As is clear from the results in the 8i￥3 table, if a glass fiber mat is not used or if a glass fiber mat is used but has a basis weight of 167/T1', the fire resistance is very poor. It is found that there are

[Example 7. Comparative Examples 3 to 5 Glass fiber mat composite plate-like phenol foams were produced in the same manner as in Examples 1 to 6 using a glass nonwoven fabric with a basis weight of ff 1100')/-m', and then the surface material layer A composite board with only a coating film (Example 7), a composite board with a glass fiber mat dispersion rate of 5% (Comparative Example 3, a glass fiber mat dispersion rate of 15%, but a surface material layer (inorganic coating film) ) and also no asbestos paper (Comparative Example 4), and a composite board laminated with only asbestos paper (Comparative Example 5). The results are shown in Table 4.

Table 4 [-1:1] As is clear from the results in Table 4, the composite board of the present invention has excellent fire resistance, but the composite boards of the comparative examples were all found to have poor fire resistance. Ru.

[Examples 8 and 9, Comparative Example 6] Three types of resol-based phenolic resins A-2 and A- each exhibiting an oxygen index of 45.37°29 when formed into foams.
3. Using a glass nonwoven fabric of D-17M and area weight fi100')/A, 1 g of a composite plate with a glass fiber mat dispersion rate of 15% was prepared in the same manner as in Examples 1 to 6. A fire resistance test was conducted on the 1q composite board. The results are shown in Table 5.

Table 5 As is clear from Table 5, when the oxygen index of the phenolic resin is greater than 30, the fire resistance of the composite board is of concern, but when the oxygen index is 30 or less, the fire resistance of the composite board is poor. be discovered.

[Brief explanation of the drawing]

1 to 3 are cross-sectional views showing one embodiment of the present invention, and FIG. 4 shows a test specimen, A is a plan view thereof, and B is a [
9i side view. 1... Glass fiber, 2... Phenol foam. 3...Glass fiber composite plate-shaped phenol foam. 4... Surface material layer, 5... Composite board, 6... Joiner-0 Figure 1 Figure 2

Claims (1)

[Claims] 1. A glass fiber composite plate in which a glass fiber mat having a weight of 50 g or more per m^2 is dispersed and mixed in a phenol foam having an oxygen index of 30 or more in an amount of 10% or more in the thickness direction thereof. A fire-resistant composite board characterized by laminating a surface material layer on phenolic foam. 2. Glass fiber mat is chopped strand mat,
The fire-resistant composite board according to claim 1, which is one or more selected from continuous strand mat, glass nonwoven fabric, and surface mat. 3. The fire-resistant composite board according to claim 1 or 2, wherein the surface material layer is laminated on the combustion prevention surface of the glass fiber composite plate-shaped phenol foam. 4. Any one of claims 1 to 3, wherein the surface material layer is an inorganic coating material layer or an inorganic sheet material laminated on the inorganic coating material layer. fire-resistant composite board.