JPS6351495A - Fire-resisting, waterproof sealing material - Google Patents

Abstract

PURPOSE:To obtain a fire-resisting, waterproof sealing material being made into ceramic in high temperature, remaining in joint parts and preventing smoke, flame and heat from transferring, containing a specific diorganopolysiloxane, a specific organosilane, etc., filler and platinum (compound) in a specific ratio. CONSTITUTION:A sealing material consisting of (A) 100pts.wt. diorganopolysiloxane which is shown by formula I [R<1> is (substituted) monofunctional hydrocarbon; a is 1.9-2.1] and has plural Si-bonded hydroxyl groups and 100-500,000 CS viscosity, (B) 0.5-30pts.wt. organosilane or organosiloxane which is shown by formula II [R<2> is (substituted) monofunctional hydrocarbon; Y is hydrolyzable group; b and c are in 0<=b<=2, 0<C<=4 and 0<b+c<=4] and contains plural Si-bonded hydrolyzable groups, (C) 30-300pts.wt. filler comprising (i) one or more of manganese carbonate, mica, black iron oxide and calcium carbonate and (ii) zinc oxide and/or crystallite and (D) 5-50ppm based on the component A of platinum (compound).

Description

[Detailed Description of the Invention] (Field of Industrial Application) The present invention focuses on fireproof and waterproof sealing materials, especially organopolysiloxanes that become ceramic at high temperatures and remain in joints to prevent the transfer of smoke, flames, and heat. The present invention relates to a fireproof and waterproof sealing material that is used as a material.

(Prior technology) Currently, the joints of concrete, sash, etc., and glass areas in various buildings are filled with sealants such as synthetic rubber. , polyurethane-based, acrylic-based, SBR-based, and butyl-based sealants are known, but silicone-based sealants are widely used in terms of adhesiveness, heat resistance, weather resistance, and durability. However, if conventional silicone sealants are exposed to high temperatures such as flames for long periods of time, they will burn without retaining their original shape and will no longer function as intended, so products containing platinum or platinum compounds, known as flame extinguishers, may also be put into practical use. However, this also has the disadvantage of becoming brittle and combustible at high temperatures of 800°C or higher, and peeling off from the treated surface. Therefore, the sealing material for movable joints in this building is made airtight and watertight using the above-mentioned sealant. At the same time, the method of fireproofing using asbestos or rock wool materials has been adopted, but since this requires a complicated construction method, improvements are desired.

Therefore, as a fireproof and waterproof sealing material of this kind, the present inventors have developed an organopolysiloxane having at least two hydroxyl groups bonded to a silicon atom in one molecule and a hydrolyzable organopolysiloxane having at least two hydroxyl groups bonded to a silicon atom in one molecule. At least 2 groups
proposed a composition in which zinc oxide and/or aluminum oxide and a platinum compound were added to a composition consisting of organosilane or organosiloxane (see Japanese Patent Application Laid-open No. 141778/1983); Standard Law Construction Order No. 107, Ministry of Construction Notification No. 29 of 1960
It was found that the fire resistance performance was still not sufficient as it corresponds to the 30 minute heating, 1 hour heating, 2 hour heating, and 3 hour heating as the fire resistance classification of JIS A1304 related to No. 99. death.

It was confirmed that there is a need to further improve its fire protection performance.

(Structure of the Invention) The present invention relates to a fireproof and waterproof sealing material with excellent fireproofing performance that can meet the above-mentioned demands, and is composed of A) average composition formula RAS i 04-a (where R1 is unsubstituted or substituted). same or different monovalent hydrocarbon groups, a is 1.
100 parts by weight of a diorganopolysiloxane having an average number of 9 to 2.1), having at least two hydroxyl groups bonded to a silicon atom in one molecule, and having a viscosity of 100 to 5o○, 0OOcS at 25°C. , B) Average composition formula RAYes iO (in the formula, R2 is an unsubstituted or substituted same or different monovalent hydrocarbon group, Y is a hydrolyzable group, b is O≦b≦2, C is 0 c≦4 but Q
(b + c≦4) and has at least two of the hydrolyzable groups bonded to a silicon atom in one molecule, organosilane or organosiloxane 0.5 to 3
0 parts by weight, c) B manganese carbonate, mica, black red iron,
At least one selected from calcium carbonate and ■)
30 to 300 parts by weight of a filler consisting of zinc oxide and/or crystallite, and D) 5 to 50 ppm of platinum or a platinum compound containing the same amount of platinum based on component A). It is something.

Namely, as a result of various studies conducted by the present inventors on ways to improve the performance of the above-mentioned fire-resistant and waterproof sealing materials, the above-mentioned known fire-resistant and waterproof sealing materials change into a strong and lightweight ceramic-like material in a high-temperature atmosphere. Although cracks and fragmentation do not occur on the surface, it was found that this sintered body has the disadvantage of peeling due to its weak strength. At least one element selected from manganese carbonate, mica, black red iron, and calcium carbonate that improves strength, and when zinc oxide and/or crystallite are added to this, this material becomes a ceramic in a high-temperature atmosphere, but the strength is strong and the oxidation Since zinc and crystallite have an expansion rate of 1.0% or more, this sintered ceramic will not shrink, and as a result will not peel off from the seal joint, resulting in excellent fire resistance. Having discovered this, the present invention was completed by conducting research on the types and amounts of the above-mentioned components A) to D) used in rowing.

Organopolysiloxane as component A) constituting the fireproof and waterproof sealing material of the present invention is conventionally known as a main ingredient of room temperature curable silicone rubber, and has the above-mentioned average compositional formula of ethyl group, propyl group, etc. Alkenyl groups such as alkyl groups, vinyl groups and allyl groups, aryl groups such as phenyl groups and naphthyl groups, aralkyl groups such as benzyl groups, and some or all of the hydrogen atoms bonded to carbon atoms of such hydrocarbon groups. Similar or different groups selected from groups substituted with halogen atoms, etc., where a is 1.9 to 2.1
This is the average number of hydroxyl groups bonded to at least two silicon atoms in one molecule. In addition, this diorganopolysiloxane does not provide a silicone rubber with excellent mechanical strength when the viscosity at 25°C is less than 100 cS;
If it is 0aS or more, the viscosity will be too high and the workability of the composition will deteriorate.
00,000cS (7) range, but 1,
It is preferable to set it as the range of 000-100.00OcS.

The organosilane and organosiloxane as component B constituting the composition of the present invention act as a crosslinking agent for curing the diorganopolysiloxane described above, and have the average composition formula R″b as described above. ,YC8
R2 is a monovalent hydrocarbon group similar to R1 described above, and Y is a hydrolyzable group exemplified by an acylamino group, an amino group, an aminoxy group, a ketoxime group, an alcohol group, and an alkenyloxy group. is a group, and b and c are 0≦b
≦2, O<c≦4.0 and b+c≦4, which must have at least two hydrolyzable groups represented by Y in one molecule.

A. ) 0.5 per 100 parts by weight of component
-30 parts by weight, preferably from 2 to 25 parts by weight.

In addition, this B) component is as follows: CH2=CH3i (NHC4H,), , SiC○N
(csns)zL, CHy S I CON (CI(z C)(3)2
)3, or the organosiloxanes shown below, but these amino groups and aminoxy groups may be substituted amino groups or substituted aminooxyl, and these organosiloxanes may be The organic silicon compound having a hydrolyzable group may be one type or a mixture of two or more types.

In addition, the filler as component C) in the composition of the present invention is (1) at least one selected from manganese carbonate, mica, black red iron, and calcium carbonate, and has an expansion rate of 1.
0% or more ) It is essential that vated subbutton and/or crystallite be added. Also,
If this amount is too small, the silicone rubber will not become ceramic due to high temperatures, and if it is too large, the composition will have a high viscosity and poor workability. 30 to 3
00 parts by weight, preferably 50 to 0.00 parts by weight.
It is said that the amount is in the range of 150 parts by weight, but the above-mentioned component I) and
The blending ratio with component I) is n) for 100 parts by weight of component I).
The content of the components may range from 10 to 300 parts by weight. In addition, since it is preferable that this component C) is uniformly dispersed in dimethylpolysiloxane, the average particle size is 50%.
- It is preferable to add the following as a fine powder.

Platinum and platinum compounds added as component D) to the composition of the present invention are useful together with fillers as flame retardants for silicone rubber, and are useful for making silicone rubber into ceramics at high temperatures. For the purpose of forming a ceramic at high temperatures, the amount of platinum is 5 to 5 with respect to dimethylorganopolysiloxane as component A).
It is necessary to add it in an amount within the range of 0.00 ppm, but
Preferably, it is used in a range of 20 to 200 ρpHl. Examples of component D) include metallic platinum such as platinum black, chloroplatinic acid, complex salts of chloroplatinic acid and alcohol, and ether 5-acetaldehyde. It may be supported, and chloroplatinic acid, complex salts thereof, etc. may be used as an alcohol solution.

The fireproof and waterproof sealing material of the present invention can be easily obtained by mixing predetermined amounts of the above-mentioned components A) to D). Saturated aliphatic carboxylic acids such as acetic acid, octylic acid, lauric acid, stearic acid, oleic acid,
Unsaturated aliphatic carboxylic acids such as linoleic acid, benzoic acid,
Lead, tin, titanium compounds, or amine compounds of aromatic carboxylic acids such as naphthoic acid may be added, and pigments, fungicides, antifouling agents, adhesion aids, etc. It may be added as long as it is not included.

The above-mentioned composition of the present invention cures at room temperature to become a silicone rubber with excellent physical properties.
When exposed to high temperatures of 00°C or higher, it sinters and becomes a ceramic, and the treated surface of this cured product will not crack or become fine powder, and this sintered product has a large hardness that will prevent it from forming during sintering. Since the volume increases by 1.1 to 1.7 times and it does not shrink or peel off from the treated surface, it is useful as a sealing material and coating material in various fields, but it is especially useful for concrete curtain wall construction methods in buildings. If the material is used as a sealing material for the joints, it will prevent the accident of combustion and peeling in the event of a fire, making it ideal as a fireproof and waterproof sealing material.

Next, examples of the present invention will be given, in which parts are parts by weight, and viscosity is a value measured at 25°C.

Examples 1 to 8, Comparative Examples 1 to 7 100 parts of dimethylpolysiloxane having a viscosity of 5,000cS and having both ends of the molecular chain blocked with hydroxyl groups were mixed with fillers of the type and amount shown in Table 1 and in terms of platinum. After adding chloroplatinic acid in an amount of 30 ppm per 100 parts of dimethylpolysiloxane and uniformly mixing using a triple roll,
Eight compositions of the present invention were prepared by mixing cyclic organopolysiloxanes represented by the following formulas (1) and (2) in the amounts shown in Table 1, and for comparison, the above I) manganese carbonate, mica, Seven compositions were prepared as comparative examples by adding only one of black red iron oxide, calcium carbonate, (1) zinc oxide, and glistalite in the amounts shown in Table 1.

Next, these compositions were formed into a sheet-like body with a thickness of 2 m, and left to cure under conditions of 20° C. and 60% RH for 7 days, and the dumbbell physical properties of this cured product were determined according to JIS-
When measured according to the method of -6301, the results were as shown in Table 1.6 Also, from these compositions 2X20X100an(A)
Make two molded bodies of 10X2010X20X10,
This was cured in the same manner as above, and then placed in an electric furnace and heat treated at 840°C for 2 hours.The hardness and appearance of the resulting sintered body were examined, as well as its volume increase rate was measured. , the results as shown in Table 1 were obtained, and all of the examples were hard, did not crack or crack even after sintering, and shrunk with a coefficient of 1 volume expansion of 1.1 to 1.7. Therefore, when used as a joint sealant for buildings, it will not peel off even if exposed to high temperature atmosphere, but the comparative example cracks or breaks into pieces when sintered. It was confirmed that when used as a joint sealant, it would peel off if exposed to a high temperature atmosphere.

Example 9 Two ALC plates with a width of 120 m were installed with a distance of 25III11, and the curable composition 1 prepared in Example 1 and the backup material 2 of expanded polystyrene rings were placed in the space between them as shown in FIG. A gasket 4 made of chloroprene rubber was filled with the cavity 3 in between, and after curing and curing at room temperature for 30 days, a heating test was conducted for 120 minutes according to JI 5-A-1304 fire resistance test method for building structural parts. As a result, the results shown in Figures 2 and 3 were obtained for this heating temperature curve (A) and the temporal change curve of joint surface temperature (B). The temperature was 90°C, and it was confirmed that there was no risk of fire spreading from outside.

[Brief explanation of the drawings] Figure 1 is the longitudinal section factor of the sample in the fire resistance test method for building structural parts of Example 9, Figure 2 is a graph of the heating temperature curve in that test, and Figure 3 is the back surface temperature curve. This is a graph of . 1... Curable composition 2... Backup material 3... Cavity portion 4... Rubber gasket. Patent applicant Shin-Etsu Chemical Co., Ltd. agent Patent attorney Ryo Yamamoto 5711th place 2? O clear cloud (na) Fig. 3 edge false (axe)

Claims (1)

[Claims] 1. A) Average composition formula▲There are mathematical formulas, chemical formulas, tables, etc.▼
(In the formula, R^1 is an unsubstituted or substituted monovalent hydrocarbon group of the same or different type, a is an average number of 1.9 to 2.1), and is bonded to a silicon atom in one molecule. Contains at least two hydroxyl groups and has a viscosity of 100 to 500,000 c at 25°C
100 parts by weight of diorganopolysiloxane that is S, B) Average composition formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^2 is an unsubstituted or substituted same or different monovalent hydrocarbon group, Y is a hydrolyzable group, b is 0≦b≦
2, c is shown as 0<c≦4, but 0<b+c≦4),
0.5 to 30 parts by weight of an organosilane or organosiloxane having at least two of the hydrolyzable groups bonded to a silicon atom in one molecule, C) I) Manganese carbonate, mica, black red iron, calcium carbonate and II) 30 to 300 parts by weight of a filler consisting of zinc oxide and/or crystallite; D) 5 to 500 ppm of platinum or a platinum compound containing the same amount of platinum based on component A). A fireproof and waterproof sealing material comprising: