JPH04366170A - Fire-resistant silicone composition - 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]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable silicone composition whose cured product has fire resistance.

0002

2. Description of the Related Art In recent years, sealing materials used for joints between interior and exterior walls of general buildings are required to have fire resistance and fire retardance to the extent that they can pass two-hour and three-hour fire resistance tests. In particular, sealing materials used for internal and external wall joints in high-rise buildings are required to have high fire resistance and fireproofing properties, as well as low modulus of the resulting cured product. Room temperature curable silicones have been found to be suitable. In addition, conventional compositions used as such sealing materials include (1) a rubber composition containing aluminum hydroxide (Japanese Patent Laid-Open No. 58-14
(2) modified silicone composition filled with aluminum hydroxide and/or magnesium hydroxide (see JP-A-62-43435)
etc. are publicly known.

0003

[Problem to be solved by the invention] However, in order to improve the fire resistance of a material, it is generally necessary to increase the amount of filler added, which has the contradictory problem of increasing the modulus of the cured product. . In the rubber composition of (1) above, even if the amount of aluminum hydroxide that imparts flame retardancy to the composition is kept to a minimum within the range that provides satisfactory fire resistance, the cured product has a very high modulus. becomes. The modified silicone composition (2) above has low durability of the cured product, which is an inherent drawback of modified silicone.
Furthermore, the fire resistance is inferior to that of unmodified silicone compositions, so it is not put to practical use. Therefore, an object of the present invention is to provide a fire-resistant silicone composition whose cured product has excellent fire resistance, durability, and low modulus.

0004

[Means for Solving the Problems] That is, the present invention provides (
A) The following general formula (1):

A diorganopolysiloxane represented by the following formula:
(B) The following general formula (2) bonded to a silicon atom:

[
(wherein R2 may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group), and the following general formula (3) bonded to a silicon atom:

[
N selected from the group consisting of the group represented by the following formula (wherein R3 is a substituted or unsubstituted divalent hydrocarbon group)
- an organosilicon compound having two or more substituted aminoxy groups in one molecule; Provides a fire-resistant silicone composition comprising aluminum hydroxide of 10 μm or less, (D) copper and/or a copper compound, and (E) platinum and/or a platinum compound, and a cured product obtained by curing the same. It is something to do.

(A) Diorganopolysiloxane (A)
The component diorganopolysiloxane has the above general formula (1
), both ends of the molecule are blocked with hydroxyl groups and has a group represented by R1 as a side chain organic group.

R1 is a substituted or unsubstituted monovalent hydrocarbon group. The monovalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
It is 8. Specifically, for example, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, aryl groups such as phenyl group and tolyl group, alkenyl groups such as vinyl group and allyl group, cycloalkyl groups such as cyclohexyl group, Examples include aralkyl groups such as benzyl group and phenylethyl group. Examples of substituted hydrocarbon groups include chloromethyl groups, trifluoropropyl groups, and cyanoethyl groups in which some or all of the hydrogen atoms bonded to carbon atoms of these monovalent hydrocarbon groups are substituted with halogen atoms, cyano groups, etc. Examples include. Preferred are methyl group, ethyl group, phenyl group, vinyl group, trifluoropropyl group, and the like. In addition, the plurality of R1 groups bonded to the silicon atom are
May be the same or different.

[0007] n is a number corresponding to the degree of polymerization of the diorganopolysiloxane (A), and is an integer of 1 or more. This n is preferably 50 to 2,000 in terms of viscosity and workability. More preferably 100-200
It is 0.

Specifically, the diorganopolysiloxane (A) has the following chemical formula: HO-(Si Me2 O)
i −H , (where i is an integer greater than or equal to 1) HO
−(Si Me2 O)k −(Si Ph2 O)l
-H,HO-(SiMe2O)k-[Si(
Me)(CHCF3)O]l-H,HO-(Si
Me2O)k-[Si(Me)(CH=CH2
)O] l -H (In the above formula, Me represents a methyl group,
k and l are integers of 0 or more, provided that k+l is an integer of 1 or more, which corresponds to n in formula (1) above.

Organosilicon compound (B) The organosilicon compound (B) acts as a crosslinking agent for the diorganopolysiloxane (A), and is a compound represented by the general formula (2) bonded to a silicon atom. It has two or more N-substituted alkyl groups in one molecule, which are selected from the group consisting of groups represented by the general formula (3) above and which are bonded to a group and a silicon atom.

In the general formula (2), R2 is a substituted or unsubstituted monovalent hydrocarbon group, and specific examples include the above R
The examples given for No. 1 are listed below. In addition, in general formula (2), the two R2 groups may be the same or different. On the other hand, in the general formula (3), R3 is a substituted or unsubstituted divalent hydrocarbon group. Such divalent hydrocarbon groups preferably have 2 to 8 carbon atoms. Examples of R3 include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group. The organosilicon compound (B) may have a linear or cyclic structure.

As the organosilicon compound (B), for example, the following chemical formula:

[C4]

Examples include those represented by the formula (wherein, Me represents a methyl group, Et represents an ethyl group, and Pr represents a propyl group).

[0012] The blending amount of component (B) is as follows: (A) component 1
0.5 to 30 parts by weight per 00 parts by weight is preferable, and 1 to 30 parts by weight.
10 parts by weight is more preferred. Note that component (B) may be one kind alone or two or more kinds of the above-mentioned organosilicon compounds.

(C) Aluminum hydroxide (C) The aluminum hydroxide is surface-treated with at least one selected from higher fatty acids, fatty acid soaps, resin acid soaps, silane coupling agents, and titanium-based coupling agents. It is hydrophobic.

If unsurface-treated aluminum hydroxide is used as component (C), the thixotropy of the resulting composition may gradually increase as the aluminum hydroxide is filled into the composition, or It may become impossible to incorporate a sufficient amount of aluminum hydroxide into the composition so that the cured product obtained has fire resistance, or the cured product obtained by curing the composition may have a high modulus. Relaxing.

Specific examples of the surface treatment agents include stearic acid, palmitic acid, myristic acid, lauric acid,
Capric acid, caprylic acid, caproic acid, arachidic acid, behenic acid, ribnoceric acid, zomarinic acid, oleic acid,
Higher fatty acids such as oleic acid, linoleic acid, and linolenic acid; fatty acid soaps such as sodium stearate, potassium stearate, calcium stearate, lithium stearate, sodium palmitate, and sodium arachinate; mainly abietic acid, dextropial acid, etc. resin acids or sodium salts of these resin acids,
Resin acid soaps such as potassium salts, calcium salts, and lithium salts; vinyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, cyanoethyltrimethoxysilane, trifluoropropylmethyldimethoxysilane, phenyltrimethoxysilane, or these alkoxysilanes Examples include silane coupling agents such as alkoxysilanes in which the methoxy group of is substituted with an ethoxy group, propoxy group, etc.; titanium-based coupling agents such as tetraisopropyl titanate and tetrabutyl titanate; Among these, preferred are stearic acid, sodium stearate, potassium stearate, palmitic acid, and the like. A predetermined amount of the above-mentioned surface treatment agent is mixed with untreated aluminum hydroxide in a solvent such as toluene, heated for a certain period of time, and then the solvent is removed to obtain surface-treated aluminum hydroxide.

On the other hand, the aluminum hydroxide component (C) has a particle size of 10 μm or less, preferably 0.01 to 2 μm. If the particle size exceeds 10 μm, the resulting composition will have poor reinforcing properties as a sealing material. The blending amount of component (C) is preferably 50 to 300 parts by weight, more preferably 80 parts by weight per 100 parts by weight of component (A).
~200 parts by weight. If the amount of component (C) is too small, the resulting cured product will not have fire resistance, and if it is too large, the viscosity of the composition will become high and workability will deteriorate.

(D) Copper and copper compound (D) Ingredients are:
Copper and/or copper compounds. As a copper compound,
Examples include copper metal salts such as cuprous chloride, cupric chloride, copper sulfate, and copper hydroxide, and complex salts such as copper(II) 2,4-pentanedione.

[0018] The blending amount of component (D) is (A) component 10
The amount is preferably 0.002 to 5 parts by weight, more preferably 0.05 to 1.0 parts by weight. (D)
If the amount of the component is too small, the cured product obtained by curing will not have sufficient fire resistance, and if it is too large, the obtained cured product will not have the desired hardness. Furthermore, (D)
When blending the components, one or more of them may be blended, or copper and a copper compound may be used in combination.

(E) Platinum and platinum compound Component (E) is platinum and/or a platinum compound. Examples of such platinum compounds include complex compounds such as chloroplatinic acid and olefins, chloroplatinic acid and aldehydes, chloroplatinic acid and vinylsiloxane, chloroplatinic acid, alcohol-modified chloroplatinic acid, and the like.

[0020] The blending amount of component (E) is as follows: (A) component 1
The amount is preferably 0.001 to 1 part by weight, more preferably 0.1 to 0.5 part by weight per 00 parts by weight. (E
) If the amount of the component is too small, the cured product obtained will not have sufficient fire resistance, and if it is too large, the physical properties of the cured product obtained from the composition will deteriorate. In addition, when blending component (E), one or more of them may be blended, or platinum and a platinum compound may be used in combination.

Other Compounds The composition of the present invention may contain fillers such as calcium carbonate and finely powdered silica, various pigments, dyes, adhesion promoters, thixotropic agents, and preventive agents. Rust agents, fungicides, etc. may be added as appropriate.

Cured Product The composition of the present invention cures when components (A) and (B) are mixed, so components (A) and (B) are usually placed in separate containers and mixed immediately before use. and use 2
Prepared in liquid form.

Applications The composition of the present invention is useful as a sealing material for joints between interior and exterior walls of general buildings. It is particularly useful as a sealing material for interior and exterior wall joints of high-rise buildings, which require fire resistance and low modulus.

[0024]

[Action] In the composition of the present invention, component (A) and
Component (B) contributes to lower modulus of the resulting cured product, and component (C), the surface-treated aluminum hydroxide, releases moisture when heated and turns the cured product into a ceramic, suppressing combustion. As a result, it contributes to improved flame retardancy,
Copper and copper compounds as component (D) improve the heat resistance of organopolysiloxane, but especially when used in combination with component (C), they greatly contribute to improving fire resistance.Platinum and platinum compounds as component (E) improve the heat resistance of organopolysiloxane. It is thought that it acts to promote the formation of ceramics and prevent its combustion and cleavage of siloxane bonds, and these actions combine to maintain the modulus of the cured product at a low level while increasing its fire resistance.

[0025]

【Example】

Example 1 α, ω with a viscosity of 5000 cSt at a temperature of 25°C
-100 parts by weight of dihydroxydimethylpolysiloxane, 160 parts by weight of aluminum hydroxide surface-treated with stearic acid, average particle size 0.5 μm, 0.1 part by weight of copper(II) acetylacetone, and approximately 1% by weight of platinum. A base composition was prepared by mixing 0.2 parts by weight of divinyltetramethyldisiloxane complex of chloroplatinic acid. To 100 parts by weight of this base composition, 1,3-di(diethylaminoxy-5,7-dipropyl-1,
3,5,7-tetramethylcyclotetrasiloxane and 1,3,5-tri(diethylaminoxy)-7-propyl-1,3,5,7-tetramethylcyclotetrasiloxane in a weight ratio of 95:5. A composition was obtained by blending 3 parts by weight of the curing agent obtained by mixing in the proportions.

Comparative Example 1 Instead of the aluminum hydroxide used in Example 1, (
Surface treated with fatty acid soap), average particle size 0.
A base composition was obtained in the same manner as in Example 1, except that 75 parts by weight of 1 μm calcium carbonate was blended. A curing agent was added to this in the same manner as in Example 1 to obtain a composition.

Example 2 Example 1 except that 150 parts by weight of aluminum hydroxide with an average particle size of 1.0 μm, which had been surface-treated with vinyltrimethoxysilane, was added instead of the aluminum hydroxide used in Example 1. A base composition was obtained in the same manner as above. A curing agent was added to this in the same manner as in Example 1 to obtain a composition.

Example 3 Instead of the aluminum hydroxide used in Example 1, 150 parts by weight of aluminum hydroxide having an average particle size of 1.0 μm was mixed with a surface treated using vinyltrimethoxysilane as a surface treatment agent. A base composition was obtained in the same manner as in Example 1 except for the following. To 100 parts by weight of this base composition, 3,5-di(diethylaminoxy)octamethyltetrasiloxane and 3,5,7-tri(diethylaquinoxy)nonamethylpentasiloxane were added in a weight ratio of 95:5. The curing agent obtained by mixing 2
．． A composition was obtained by blending 5 parts by weight.

Comparative Example 2 The same procedure was carried out except that in place of the aluminum hydroxide used in Example 2, 90 parts by weight of aluminum hydroxide, which had not been surface-treated and had an average particle size of 0.5 μm, was blended and no copper compound was used. A base composition was obtained in the same manner as in Example 2. A composition was obtained by blending 3 parts by weight of the curing agent used in Example 1 with 100 parts by weight of this base composition.

Comparative Example 3 A product was prepared in the same manner as in Example 2, except that 90 parts by weight of unsurface-treated crystalline silica with an average particle size of 1.5 μm was blended instead of the aluminum hydroxide used in Example 2. A base composition was obtained. A composition was obtained by adding 3 parts by weight of the same curing agent as used in Example 1 to 100 parts by weight of this base composition. Examples 1 to 3 and Comparative Example 1 above
The following measurements were performed on each of the compositions obtained in steps 3 to 3.

(Rubber Physical Properties) The composition was molded into a sheet with a thickness of 2 mm and cured at 20° C. and 55% RH for 7 days to obtain a cured product. Regarding the obtained cured product, JIS K-
Rubber physical properties were measured in accordance with 6301.

(Block physical properties and durability) JIS A
-5758, the composition was molded into an H-shaped block of float glass, and the physical properties and durability of the block were measured.

(Fire resistance) A joint 4 having a shape as shown in FIG. 1 is made from two ALC (light concrete) plates 1, a gasket 2, and a backup material 3, and the composition is filled into this joint as a sealing material 5. Then, it was cured at 20° C. and 55% RH for 7 days to obtain a cured product. Regarding this cured product, JIS
The fire resistance of the cured product was measured in accordance with A-1304. The results of the above measurements are shown in Table 1 below.

[0034]

[Table 1]

[0035]

According to the fire-resistant silicone composition of the present invention, a cured product having excellent fire resistance and durability and low modulus can be obtained.

[Brief explanation of the drawing]

FIG. 1 is a perspective view of a test specimen used in a fire resistance test in an example.

[Explanation of symbols]

1 ALC board 2 Gasket 3 Backup material 4 Sealing material

Claims (2)

[Claims] [Claim 1] (A) The following general formula (1):
] (wherein R1 may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group, and n is an integer of 1 or more), (B)
A group represented by the following general formula (2) bonded to a silicon atom: [Formula 2] (wherein R2 may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group), and N- selected from the group consisting of a group represented by the following general formula (3) bonded to a silicon atom: [Chemical formula 3] (wherein R3 is a substituted or unsubstituted divalent hydrocarbon group) an organosilicon compound having two or more substituted aminoxy groups in one molecule; (C) surface-treated with at least one selected from higher fatty acids, fatty acid soaps, resin acid soaps, silane coupling agents, and titanium-based coupling agents; Also, the particle size is 1
Aluminum hydroxide of 0 μm or less, (D) copper and/
or a copper compound, and (E) a fire-resistant silicone composition comprising platinum and/or a platinum compound. 2. A cured product obtained by curing the composition according to claim 1.