JPS6392690A - Refractory and fireproof sealant composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent rubber properties and weather resistance, which comprises a polyether polymer having a hydrolyzable silicon function at its terminal, organosilane, aluminum hydroxide, and a catalyst for a silanol compd. CONSTITUTION:The title compsn. comprises, as main components, 100pts.wt. polyether polymer (A) having a hydrolyzable silicon function at its terminal and represented by formula I (wherein R<1> is a 1-12C monovalent hydrocarbon group; R<2> is a 1-6C monovalent hydrocarbon group; and n is 0-2) (e.g., methyldimethoxysilyl group-terminated polypropylene oxide), 0.5-30pts.wt. organosilane (B) of formula II (wherein R<3> and R<4> are each a 1-4C monovalent hydrocarbon group; Y is a monovalent hydrocarbon group containing a functional group; a, b and a+b are each 0-2) (e.g., methyltrimethoxysilane), 20-300 pts.wt. aluminum hydroxide and/or magnesium hydroxide (C), and 0.05-5pts.wt. catalyst for a silanol compd. (e.g., tin octylate).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to fire-resistant and fire-retardant sealant compositions;
More specifically, it is applied to the joints of the interior and exterior walls of general buildings, and has properties such as fire resistance, fire prevention, water resistance, airtightness, weather resistance, etc.
The present invention relates to a sealant composition having excellent durability.

[Prior Art/Problems] In recent years, there has been an increase in the number of gauges requiring fire resistance and fire prevention performance for members of the inner and outer walls of -i buildings.

In general, silicone-based, modified silicone-based, polysulfide-based, and polyurethane-based sealing materials are widely used to seal movable joints for the purpose of watertightness and airtightness. Most of these materials burn down when exposed to high temperatures due to a fire, which not only makes them a weak point in terms of fire protection, but also has the disadvantage that flames linger for a long time due to the combustion of the materials.

Conventionally, in order to provide joints with fireproof and fireproof properties, complicated structures such as putting noncombustible material in the bottom of the joints were used to ensure fireproof and fireproof performance.

In addition, inorganic materials such as mortar, plaster, and hydraulic lath are often used for joint parts of fire-resistant members used for interior panels, partitions, etc., for the purpose of fire resistance and sound insulation.

However, because these materials inevitably shrink during the curing process and are extremely hard after curing, they may crack or break at the interface within a short period of time due to microtremors that cannot be avoided in -m buildings. This has the disadvantage that gaps are likely to occur and the original function is not necessarily exhibited.

In addition, in high-rise buildings where interlayer displacement and followability are important, the joints are movable to absorb displacement, so the inorganic hardened material cannot be used, and fire-resistant and sound-insulating properties are ensured as a complex structure.

[Means for Solving the Problems] The present inventors have improved the above-mentioned drawbacks of conventional sealants and inorganic joint materials, and have improved fire resistance, fire resistance, moisture resistance, airtightness, weather resistance, and durability. In order to provide an excellent sealant, the present invention was achieved as a result of extensive research.

That is, the present invention is based on (A) the general formula % (wherein R1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R2 is a monovalent carbon 1 arsenic group having 1 to 6 carbon atoms). and
■ is an integer from 0 to 2. ) 100 parts by weight of a polyether heavy body having a hydrolyzable silicon functional group at the end; 1 arsenic group, Y is a monovalent hydrocarbon group containing a functional group, a and b are each an integer of O to 2, and the sum of a and b is 0 to 2.) 0.5 to 30 parts by weight of organosilane; (C)
A fire-resistant product characterized by having as main components 20 to 300 parts by weight of aluminum hydroxide and/or red sea bream sium hydroxide; and (D) 0.05 to 5 parts of a silanolized shrinkage catalyst; A fire retardant sealant composition is provided.

[Function] In the present invention, the polyether weight body (A) having a hydrolyzable silicon functional group at the end represented by the general formula % (wherein R1, R2 and n have the same meanings as above) is The main chain is essentially -R-0- (wherein R
is a divalent alkylene group having 2 to 11 carbon atoms), and has a hydrolyzable functional group represented by the above formula at at least one of the terminal ends. Polymers are preferred.

The polyether polymer used in the present invention (
A) is, for example, a reaction product of an incyanate-terminated polyether urethane prepolymer with r-aminopropyltrimethoxysilane, r-aminopropyl 1-ethoxysilane, or r-mercaptopropyltrimethoxysilane (Tokuko Showa). 46-30711), or C1+ as a terminal silyl ether group.

■ (C1130)2 Si CH2・C112・C1
120- or (CI+30): l Si C112
・CIl□・C1120- and CH.

Heat (C2+l5O)2 Si CH2・CI(2・C
H20-, C, R5 (CtlJ)z S+ Ctlz・CH2・CH,
Examples include oxypropylene heavy wood having 0-.

Orcassilane (B) in the present invention is the polyether weight body (A) having the above-mentioned hydrolyzable silicon functional group at the end.
As mentioned above, this acts as a crosslinking agent of the general formula R3b Ya-Si-(OR')4-ra+b) (wherein R3
, R'', Y, a and b have the same meanings as above).

Specific examples include dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, dimethyljethoxysilane, methyltri-oxysilane, tetraethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, and vinyltris-1 -'i disilane r-mercaptopropyltrimethoxysilane, r-chlorophyllobyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, aminomethyl 1-lye 1-xysilane, N
-β(aminoethyl)aminemethyltrimethoxysilane, aminemethyljethoxysilane, N-β(aminoethyl)methyltributoxysilane, r-aminopropyltrimethoxysilane, r-aminopropyltriethoxysilane, “-amino 10 Billmethyldiethoxysilane, r
-Aminoisobutyltri,methoxysilane,N-β(aminoethyl)r-aminopropyltrimethoxysilane,N-β(aminoethyl) −β
(aminoethyl)] "-aminopropyl 1-rimethoxysilane, r-glycidoxypropyltrimethoxysilane, r-crisitoxypropylmethyljethoxysilane,
3,4-Epoxycyclohexylethyltrimethoxysilane, r-methacryloxypropyltrimethoxysilane, -methacryloxypropylmethyldimethoxysilane, r-incyanatepropyltrimethoxysilane, r-incyanate l-propylmethyljethoxysilane These may be used alone, but it is also possible to combine several types.

This component (B) is 0.5 per 100 weight of component (A).
The amount of component (B) is preferably in the range of ~30 parts by weight, preferably 1 to 15 parts by weight. If the amount of this component (B) is too small, no effect on heat resistance will be seen, and if it is too much, the cured physical properties will become hard and brittle, making it difficult to use as a sealant. The durability of the product becomes inferior.

In the present invention, aluminum hydroxide and/or magnesyl hydroxide <C) provide fireproofing and fireproofing properties and a reinforcing effect.

Aluminum hydroxide has the chemical formula AN20.・31-120
or A1<OH)C1, and magnesila hydroxide l\ is represented by the chemical formula Mg<OH)2, and those having a particle size of 0.1 to 80 μm are generally used.

The content of component (C) is preferably 20 to 300 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of component (A). If the amount is too small, the fire resistance and fire protection characteristics will not be obtained, and if it is too large, the composition will become too viscous, resulting in difficulties in workability.

In the present invention, the silanol compound condensation catalyst (D) includes organosilicon titanates, metal salts of carboxylic acids such as tin octylate, dibutyltin diacetate, dibdel-dilaurate, dibutylamine-2-ethylhexate, etc. Known silanol condensation catalysts such as amine salts such as ate are effective.

The amount of condensation catalyst (D) used is 1 polyether polymer (A)
The amount is 0.05 to 5 parts by weight per 00 parts by weight.

Sealan 1 to the compositions of the present invention may optionally contain a metal acid of Group I of the Periodic Table, such as zinc oxide, calcium oxide, and magnesium oxide, and a cocatalyst for adjusting the curing speed. It is also possible to use organic amines such as xylylene diamine, hexamethylene diamine, and octyl amine.

Fillers, plasticizers, pigments, anti-aging agents, ultraviolet absorbers, anti-sagging agents, and the like may be added to the composition of the present invention within a range that does not impair the object of the present invention.

The fillers include fumed silica, precipitated silica,
Reinforcing fillers such as anhydrous silicic acid, hydrated silicic acid, and carbon black; calcium carbonate, Magui Shira 11 carbonate, diatom, calcined ray, clay, taryu, acid 1 hinatan, bentonite, organic bentonite, ferric oxide, Fillers such as aluminum oxide, mica and shirasu balloons;
Fibrous fillers such as asbestos, glass fibers and filaments can be used.

In addition, the plasticizers include serial number plasticizers, such as phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, and butylbenzyl phthalate; fatty acid secondary basic acid esters such as dioctyl adipate, indecyl succinate, and dibutyl cehatate. glycol esters such as diethylene glycol dibenzoate, pentaerythritol ester, etc., aliphatic esters such as butyl oleate, methyl acetyl ricinoleate, phosphoric esters such as tricresyl phosphate, triocnal phosphate, etc., chlorinated Examples include paraffin.

It is also possible to use a liquid resin having a molecular weight of about 100 to 10.0 parts as a superplasticizer.

For example, xylene resin, polybutadiene, polyoxypropylene glycol, polyoxypropylene triol,
Polyester resin, acrylic oligomer, NBR, SB
Examples include liquid materials such as R and polysulfide rubber.

[Example] The present invention will be further explained with reference to an example (hereinafter referred to as just one example unless otherwise specified). In addition, the part in these examples indicates the heavy foot part 9 polyether heavy body (A
), 100 parts of methyl dimethoxysilyl group-terminated polypropylene oxide, Kanejiri MS Polymer (manufactured by Kanegafuchi Chemical Industry Co., Ltd.) were added, 150 parts of 1-hyaluminum hydroxide as component (C), and 1 part of DoptBo as a plasticizer. ,
5 parts of non-silica was added as an anti-sagging agent, and the mixture was stirred at room temperature until it became paste-like. Next, the mixture was thoroughly mixed using three rolls to form a more uniform paste.

To this composition were added 5 parts of vinyltrimethoxysilane as an organosilane (B>), 1 part of ophthalic acid as a condensation catalyst (D), and 1 part of laurylamine, and the mixture was heated under a N2 stream for 3 minutes.
A sealant composition was obtained by stirring for 0 minutes.

11 bottles - The sealant composition prepared in Example 1 above was applied to a thickness of 3III.
Formed into a sheet of III, left to cure for 14 days under conditions of 20 ° C. and 65% RH, and about this cured product,
A No. 2 dumbbell was punched out in accordance with JIS-K-6301, and the physical properties of the rubber were measured. The results obtained are listed in Table 1 below.

A fire protection test of the sealant composition prepared in Example 1 above was conducted overnight in a small heating furnace prepared in accordance with JIS-A-1301.

The fire protection test was conducted at Kt as shown in Figures 1 and 2.
900 mI@, width 445mm, thickness 11+11111
Using two fiber-containing cement calcium silicate plates (“Kabe Ichiban J” manufactured by Ashi Asbestos Industries Co., Ltd.) (1), tomm
Arrange the joints (2) with IrX1 spacing, so that the back side of the joints is in contact with the wood stringers (40111111 width and 90 mm thickness)<3), and apply the above-mentioned sealant of the present invention to the joints. Fill the composition and then store at room temperature for 7
After 0 minutes, a flame is applied from the surface of the joint and heated for 30 minutes along the standard heating curve based on the JIS-11301 fire prevention class 2 heating test.The temperature on the back surface of the sealant composition (wood surface temperature) is This was carried out by measuring with a thermocouple (4).

In the same way, four types of compositions were prepared by adding and mixing aluminum hydroxide, magnesium hydroxide, organosilane, and wire catalyst in the amounts shown in Table 1, and the physical properties were determined in the same manner as above. and conducted fire protection tests.

For comparison, a composition was prepared in the same manner as above except that aluminum hydroxide and monomagnesium hydroxide were not added at all. As is clear from Table 1 above, the fireproof and fireproof sealant composition of the present invention has excellent rubber physical properties and fireproofing properties, and can be suitably used as a sealant for joints in the interior and exterior walls of general buildings. .

[Brief explanation of the drawing]

FIG. 1 is a top view of the structure for fire resistance testing, and FIG. 2 is a side view of the structure for fire resistance testing. In the diagram: 1...Fiber-mixed cement calcium silicate plate, 2...Joint area, 3...
・Wood, 4...Thermocouple. Patent applicant Asaguchi Asbestos Industry Co., Ltd. Same as above Cemedine Co., Ltd. Figure 1

Claims (1)

[Claims] 1. (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R^2 is (B) 100 parts by weight of a polyether polymer having a hydrolyzable silicon functional group at the end, which is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 to 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^3 and R^4 are monovalent hydrocarbon groups having 1 to 4 carbon atoms, and Y is a monovalent hydrocarbon group containing a functional group. a and b are each an integer of 0 to 2, and a and b
The sum is 0 to 2. ) 0.5 to 30 parts by weight of organosilane; (C)
Aluminum hydroxide and/or magnesium hydroxide2
0 to 300 parts by weight; and (D) 0.05 to 5 parts by weight of a silanol compound condensation catalyst.