JP2516556B2 - Sealant made of heat-expandable inorganic fiber composite material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealant made of a heat-expandable inorganic fiber composite material, which is used as, for example, a sealant for fireproof doors, a ceramic catalyst holding material, or a gap filling material for preventing the spread of fire to a cable insertion hole. It is about.

[0002]

2. Description of the Related Art As a composite material of this type, for example, a sealing material for fireproof doors, as disclosed in Japanese Patent Publication No. 58-12315, acid-treated graphite 100w as an expanding agent has hitherto been used.
t part, 24 wt% of polychloroprene as an organic binder
Parts, 20 wt parts of phenolic resin, 48 wt parts of aluminum hydroxide as an inorganic binder, 10 wt% of asbestos fibers
It is known that an extremely thin sheet-like base material made of glass fiber is coated in a layered manner with a kneaded product of 1 part by weight and 2 parts by weight of a stabilizer.

Separately from this, a glass fiber cloth as a base material, which is filled with water glass (water-containing alkali silicate), is also known.

[0004]

Among the conventional composite materials having the above-mentioned structure, the former composite material has no reinforcement when heated, and tends to lose its shape when heated to about 500 ° C. Since the sheet-like base material is simply coated with the kneaded product, the direction of expansion is random, the expandability is poor, and high sealing properties cannot be expected. Also, the latter one is superior to the former one in terms of shape retention at high temperatures, but it cannot exhibit a high expansion coefficient, so it must fully exhibit the sealing function such as fire and smoke prevention. It was something that could not be done.

The present invention has been made in view of the above-mentioned circumstances, and it is excellent in expansion performance at the time of heating, surely retains its shape at high temperature, and is capable of significantly improving the sealing function. The purpose is to provide a sealing material made of wood .

[0006]

In order to achieve the above object, a heat-expandable inorganic fiber composite sealing material according to the present invention comprises an acid-treated graphite as an expanding agent and a heat-resistant reinforcing agent. A mixture of inorganic fibers, an inorganic binder as a heat-resistant binder, and an organic binder as a shape-retaining material before heating is formed into a sheet by a papermaking method.

Further, the thermally expandable inorganic fiber composite papermaking
The blending ratio of Lumpur material, the acid-treated graphite 30-7
It is preferable to set 0 wt%, inorganic fiber 15 to 45 wt%, and inorganic binder 1 to 20 wt%.

[0008]

According to the present invention, the acid-treated graphite expands by heating, but at this time, if only the acid-treated graphite is expanded, it cannot scatter and maintain its shape.
It is necessary to expand while maintaining the original sheet shape. Therefore, a predetermined amount of inorganic fiber and inorganic binder are blended,
By uniformly dispersing these with acid-treated graphite to form a sheet, the inorganic fibers serve as a layered base material to reinforce the acid-treated graphite, and further, the inorganic binder reinforces the entire sheet. Therefore, the expansion of the acid-treated graphite is slightly suppressed, but it is possible to expand while maintaining the shape of the sheet. Therefore, since the strength of the sheet in the heated state is maintained, a high expansion pressure can be obtained and the expansion pressure can be maintained for a long time.

The mixture having the compounding ratio as set forth in claim 2 is uniformly dispersed by a papermaking method using water as a medium. In particular, according to this papermaking method, flaky (scale-like) acid-treated graphite is laminated in one direction, so that the expansion direction is aligned in a certain direction. It can be used effectively.

The acid-treated graphite is obtained by subjecting graphite to acid treatment with sulfuric acid, hydrochloric acid, fuming nitric acid or the like, and the compounding ratio thereof is preferably 30 to 70 wt%, and when it is less than 30 wt%, the expansion agent is insufficient. As a result, the desired expansion force cannot be obtained, and when it exceeds 70 wt%, it swells like a cotton when it is formed into a sheet and heated, and sufficient rigidity cannot be obtained, and anxiety remains in terms of mechanical strength. Further, as the inorganic fiber, a ceramic fiber such as SC bulk is used. The compounding ratio of this inorganic fiber is 15 to 45 wt.
%, The strength after heating is lowered when it is less than 15 wt%, and the expansion characteristics are suppressed when it exceeds 45 wt%.

Furthermore, as the inorganic binder, for example, silica sol or alumina sol is suitable, and the compounding ratio thereof is 5
It is preferably about 25 wt%. If it is less than 5 wt%, the mechanical strength after heating will be low, and 25 wt%
If it exceeds, the deterioration of the expansion property is remarkable. Furthermore, as the organic binder, rubber latex (Sumikaflex) or the like is used, and the compounding ratio thereof is preferably 1 to 20 wt%, and if it is less than 1 wt%, the effect on the initial handling property is hardly exhibited, and If it exceeds 20 wt%, it will be burnt out during heating and the mechanical strength will decrease.

[0012]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows a heat-expandable inorganic fiber composite material according to the present invention.
A part of a fireproof door incorporating a sealing material is shown in a broken view.

In FIG. 1, a fire door 1 has a heat insulating material 4 filled between exterior plates 2 and 3 on both inner and outer sides, and a heat-expandable inorganic fiber composite sealing material inside the wood cover plates 5 and 6. M is installed. The sealing material M made of the composite material expands in the event of a fire, and the expansion force causes the exterior plates 2 and 3 and the cover plate 5 to be expanded.
The adhesive plate 6 is peeled off and the covering plates 5 and 6 are brought into close contact with a door frame (not shown). This composite
The structure of the sealing material M is shown in the following examples.

Example 1 55 wt% of graphite treated with fuming nitric acid as a swelling agent,
Ceramic fiber as heat resistant reinforcement (SC Bulk 12
60-D Shin Nikka) 25 wt%, inorganic binder (alumina sol 200 Nissan Chemical) 10 wt% as a heat resistant binder, organic binder (Sumikaflex 900 Sumitomo Chemical) as a pre-heating shape retainer Mix at a compounding ratio of 10 wt%, make a paper, and have a bulk density of 0.73 g.
/ Cm ³ and a thickness of 2.54 mm.

Example 2 55 wt% graphite treated with sulfuric acid, ceramic fiber (S
25% by weight of C bulk 1260-D2 manufactured by Shin Nikka,
Inorganic binder as heat-resistant binder (alumina sol 200
10% by weight of Nissan Chemical Co., Ltd. and 10% by weight of an organic binder (Sumikaflex 900 Sumitomo Chemical Co., Ltd.) as a pre-heating morphological agent are mixed at a compounding ratio of 10% by weight, and this is made into paper to have a bulk density of 0.73 g / cm ³ , And formed into a sheet having a thickness of 2.54 mm.

Comparative Example 1 50 wt% graphite treated with fuming nitric acid, 12 wt% polychloroprene as an organic binder, 10 wt% phenol resin, 24 wt% aluminum hydroxide as an inorganic binder, and 4 wt% glass fiber. An extremely thin sheet made of glass fibers was coated in layers at a blending ratio of to obtain a bulk density of 0.91 g / cm ³ and a thickness of 2.54 mm.
Was formed into a sheet shape.

Comparative Example 2 Using a glass fiber cloth as a base material, water glass (water-containing alkali silicate) was filled, and the surface thereof was coated with an epoxy resin.

[0018] Evaluation of the Comparative Examples 1 and 2 Examples 1 and 2, the first each sample were measured in the free <br/> Rise Zhang rate when heated in an electric furnace. The results are shown in Table 1 of FIG. As is clear from Table 1 in FIG. 4, it was found that those of Examples 1 and 2 exhibited a high free expansion amount due to the reinforcement of the inorganic binder (alumina sol) and the inorganic fiber (ceramic fiber). On the other hand, in Comparative Example 1, there is nothing to reinforce at the time of heating, and the shape collapses at 500 ° C.
Further, the fuming nitric acid-treated graphite started to expand at around 150 ° C., and the sulfuric acid-treated graphite showed a larger value. Water glass begins to expand at around 125 ° C.

Next, Examples 1 and 2 and Comparative Examples 1 and 2
As the evaluation, the amount of expansion of each sample was measured when the temperature was raised at a temperature rising rate of 11 ° C./min while a surface pressure of 17 KPa was applied. FIG. 2 shows a measuring device therefor. In FIG. 2, reference numerals 21 and 22 denote a pair of upper and lower quartz rods sandwiching a sample M heated by a heater 23 of an electric furnace. When M starts to expand, the quartz rod 21
Since it is pushed up, the displacement is measured by the dial gauge 24.
The load of 4 and the quartz rod 21 applies a load of 17 KPa to the sample M. The measurement results are shown in Table 2 of FIG.

As is clear from Table 2 in FIG. 5, the products of Examples 1 and 2 expand due to the reinforcement of the inorganic binder and the inorganic fiber without impairing the sheet form, and the expansion amount is also high. It turned out to be stable at the level. On the other hand, in Comparative Example 1, the shape could not be maintained at high temperature,
The expansion amount decreases at a peak of 320 ° C. Further, in Comparative Example 2, the expansion amount is considerably low. With regard to the time that the expansion amount expands from 0 to 100%,
Graphite treated with fuming nitric acid required 100 seconds, and graphite treated with sulfuric acid and water glass required 150 seconds. From these results, the examples 1 and 2 can follow the seal of a wide gap with a large expansion amount, and the shape retention property is maintained at a high heating temperature for a long time, so that the gap is stable against the pressure of the outside air. It has become clear that they can be filled in a desired manner.

Finally, as an evaluation of Examples 1 and 2 and Comparative Examples 1 and 2, the sample M is filled in a gap corresponding to the thickness of each sample M, and the sample M is heated at a constant heating rate. The expansion pressure generated when the pressure was applied was measured. FIG. 3 shows a measuring device therefor. As shown in FIG. 3, a sample M heated by a heater 31 in an electric furnace is provided with a gap between upper and lower quartz rods 32 and 33 set to match its thickness. Filling g to a constant heating rate 1
The expansion pressure when the sample M starts expanding at 1 ° C./min is measured by the load cell 34. The measurement results are shown in Table 3 of FIG.

As is clear from Table 3 in FIG. 6, the ones of Examples 1 and 2 can generate a high expansion pressure. Therefore, when used as a seal material for a fire door as shown in FIG. Since the force to spread the plates 5 and 6 continues to be generated for a long time, an effective sealing effect can be exhibited, and since the expansion pressure does not decrease, it is also effectively used as a holding material for a ceramic catalyst, for example. be able to.

[0023]

As described above, according to the present invention, acid-treated graphite as a swelling agent, an inorganic fiber or an inorganic binder as a reinforcing agent, and an organic binder as a shape-retaining agent before heating. In addition, since these are formed into a sheet by papermaking, the direction of expansion is constant, high expansion characteristics can be obtained without fear of deformation, and a high expansion pressure in the heated state is secured by the reinforcing action. It is possible to exert an excellent sealing function for gap filling of fire doors and the like.

[Brief description of drawings]

FIG. 1 is a partially cutaway perspective view showing a fire door incorporating a sealing material made of a heat-expandable inorganic fiber composite material according to an embodiment of the present invention.

FIG. 2 is a schematic configuration diagram showing an expansion rate measuring device.

FIG. 3 is a schematic configuration diagram showing an inflation pressure measuring device.

FIG. 4 is a chart showing measurement results of free expansion coefficient.

FIG. 5 is a chart showing the measurement results of the expansion coefficient under load.

FIG. 6 is a chart showing measurement results of generated expansion pressure.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Satoshi Tanimura, Satoshi Tanimura 2-66-3 Nagatano-cho, Fukuchiyama City, Kyoto Prefecture 3 Japan Pillar Industry Co., Ltd., Fukuchiyama Factory (56) Reference JP-A-5-295351 (JP, A) )

Claims (2)

(57) [Claims] 1. Papermaking a mixture of acid-treated graphite as a swelling agent, inorganic fibers as a heat-resistant reinforcing agent, an inorganic binder as a heat-resistant binder, and an organic binder as a shape-retaining material before heating. A sealant made of a heat-expandable inorganic fiber composite material, which is formed into a sheet by the method. 2. The acid-treated graphite is 30 to 70 wt%, the inorganic fiber is 15 to 45 wt%, and the inorganic binder is 5 to 25 wt%.
%, The organic binder is set to 1 to 20 wt%, and the sealing material made of the heat-expandable inorganic fiber composite material according to claim 1.