JPH0475271B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to a fire-resistant sealing material used for windproofing, dustproofing, soundproofing, waterproofing, etc. in civil engineering, architecture, vehicles, ships, containers, etc. A sealing material that provides excellent adhesion as a joint by simply applying a primer treatment to the joints, and has excellent properties such as high fire resistance, flame resistance, waterproofness, weather resistance, durability, cold resistance, and ozone resistance. It provides materials. [Prior art] Sealants such as butyl, acrylic, and silicone are used as sealants to provide windproof, dustproof, soundproof, waterproof, etc. to connection points in civil engineering, architecture, vehicles, ships, containers, etc. Oil-based caulking materials, emulsion caulking materials, etc. are used. [Problems to be Solved by the Invention] However, none of the above-mentioned conventional sealing materials can fully satisfy the fire resistance and flame resistance required in recent years, especially in high-rise buildings. is the reality. [Means for Solving the Problems] The present invention provides that, for 100 parts by weight of silicone resin,
A paste or silicone resin varnish consisting of 5 to 400 parts by weight of fibrous potassium titanate and 20 to 300 parts by weight of an endothermic decomposition type inorganic flame retardant,
In some cases, the composition may contain conventional components such as a curing agent, a curing accelerator, a coloring agent, etc., which may be added as desired. In addition, when obtaining the paste-like material or silicone resin varnish of the present invention, a solvent that allows each component to be uniformly dissolved or dispersed, for example,
Petroleum solvents such as xylene, naphtha, gasoline, or benzene are used. The silicone resin in the fire-resistant sealing material of the present invention is generally substituted with a hydrogen atom, a vinyl group, an allyl group, an aryl group, a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, an amino group, a mercapto group, etc. For example, polydimethylsiloxane-based silicone resins, polydiphenylsiloxane-based silicone resins, polymethylphenylsiloxane-based silicone resins containing at least one group, epoxy-modified silicone resins modified with other resins, and polyester-modified silicone resins. Organopolysiloxane-based silicone resins such as silicone resins, fatty acid-modified silicone resins, alkyd-modified silicone resins, and amino resin-modified silicone resins, as well as polyacryloxyalkylalkoxysilane-based silicone resins and polyvinyl-based silicone resins, are heat-curable resins and It is used as a room-temperature curing silicone resin using the catalyst described below. Further, the fibrous potassium titanate that provides the fire-resistant sealant of the present invention with sufficient heat resistance, fire-resistant properties, and reinforcing effect has a component having the general formula K ₂ O.
mTiO ₂・nH ₂ O (in the formula, m is a positive integer of 8 or less, n
is a positive integer of 0 or 4 or less) and generally has a fiber diameter of 0.1 to 0.7 μm and a fiber length of 10 to 50 μm.It is a whisker that uses titanium oxide and potassium carbonate as raw materials and can be processed by a calcination method, a hydrothermal method, or a flux method. It is manufactured by law etc. The fibrous potassium titanate can be used as is, but in order to achieve a better reinforcing effect,
The fiber surface is treated with a silane coupling agent of about 0.05 to 1.0% by weight based on the fibrous potassium titanate, such as γ-aminopropyltriethoxysilane, γ-glycidoxypropyltritomethoxysilane, etc. It is preferable to use what is available. Furthermore, the flame retardant that imparts sufficient flame retardant properties to the fire-resistant sealant of the present invention is an endothermic decomposition type inorganic flame retardant, specifically, calcined gypsum, alum, hydrotalcite aluminum silicate, etc. An inorganic flame retardant that releases water of crystallization and is endothermic by decomposition is used. In the fire-resistant sealing material of the present invention, the endothermic decomposition type inorganic flame retardant may optionally contain other flame retardants, such as organic flame retardants such as phosphate ester type, organic halogen compound type, phosphazene compound type, and antimony. It can be used in combination with inorganic flame retardants such as compounds. In addition, in the fire-resistant sealant of the present invention,
Combined with an inorganic fine powder that forms an inorganic component together with the aforementioned fibrous potassium titanate, such as a fine powder selected from titanium oxide, mica, alumina, talc, glass fiber powder, rock wool fine fiber, silica powder, and clay. can do. In this case, the above-mentioned fibrous potassium titanate and the above-mentioned inorganic fine powder are mixed at a ratio of 5 to 400 parts by weight in total with respect to 100 parts by weight of the silicone resin in the fire-resistant sealing material. , the fibrous potassium titanate in the mixture is preferably 50 to 90 parts by weight in the mixture) and provides better flame retardant properties. In the fire-resistant sealant of the present invention, curing agents and curing accelerators, which are usual components added as desired, include, for example, metal carboxylates, organotin compounds, titanium chelate compounds, peroxides, and platinum-based Such as catalysts. [Example] Hereinafter, the specific structure of the fire-resistant sealing material of the present invention will be explained based on its manufacturing example. Example 1 A mixed composition consisting of the following (1) to (5) was stirred and mixed to obtain a substantially uniform high viscosity dispersion [viscosity: 3000 Poise
(25°C)], by adding 65 parts by weight of a curing agent and curing accelerator for silicone resin consisting of a tertiary amine compound and a platinum catalyst to 1300 parts by weight of the dispersion. A silicone resin varnish, which is an example of the fire-resistant sealant of the present invention, was obtained. (1) Silicone resin...390 parts by weight (molecular weight 70,000-74,000) (2) Fibrous potassium titanate...137 parts by weight (3) Aluminum hydroxide...610 parts by weight (endothermically decomposed inorganic flame retardant) ( 4) Colorant: 26 parts by weight (5) Xylene: 137 parts by weight Example 2 A mixed composition consisting of the following (1) to (5) was stirred and mixed to form a substantially uniform, highly viscous dispersion. [Viscosity: 2500 Poise
(25°C)], by adding 65 parts by weight of a curing agent and curing accelerator for silicone resin consisting of a tertiary amine compound and a platinum catalyst to 1300 parts by weight of the dispersion. A silicone resin varnish, which is an example of the fire-resistant sealant of the present invention, was obtained. (1) Silicone resin...400 parts by weight (molecular weight 70,000-74,000) (2) Fibrous potassium titanate...400 parts by weight (3) Aluminum hydroxide...200 parts by weight (endothermically decomposed inorganic flame retardant) ( 4) Colorant: 26 parts by weight (5) Xylene: 137 parts by weight Example 3 A mixed composition consisting of the following (1) to (6) was stirred and mixed to form a substantially uniform highly viscous dispersion. [Viscosity: 3200Poise
(25°C)], by adding 65 parts by weight of a curing agent and curing accelerator for silicone resin consisting of a tertiary amine compound and a platinum catalyst to 1300 parts by weight of the dispersion. A silicone resin varnish, which is an example of the fire-resistant sealant of the present invention, was obtained. (1) Silicone resin...390 parts by weight (molecular weight 70,000-74,000) (2) Fibrous potassium titanate...290 parts by weight (3) Aluminum hydroxide...390 parts by weight (endothermically decomposed inorganic flame retardant) ( 4) Calcium carbonate...78 parts by weight (endothermically decomposed inorganic flame retardant) (5) Colorant...26 parts by weight (6) Xylene...137 parts by weight Comparative Example 1 Consists of the following (1) to (5) Stir and mix the mixed composition to obtain a substantially uniform, highly viscous dispersion [viscosity: 2400Poise]
(25°C)], by adding 65 parts by weight of a curing agent and curing accelerator for silicone resin consisting of a tertiary amine compound and a platinum catalyst to 1300 parts by weight of the dispersion. A silicone resin varnish, which is a fire-resistant sealant, was obtained for comparison. (1) Silicone resin......400 parts by weight (molecular weight 70,000-74,000) (2) Calcium carbonate......400 parts by weight (endothermic decomposition type inorganic flame retardant) (3) Aluminum hydroxide......200 parts by weight (endothermic decomposition type) (inorganic flame retardant) (4) Colorant: 26 parts by weight (5) Xylene: 137 parts by weight Experiments 1 to 9 Fire resistance of each silicone resin varnish obtained in Examples 1 to 3 and Comparative Example 1 Fire resistance tests were conducted using sealants and commercially available sealants in the combinations shown in Table 1 in a small vertical fire resistance test furnace constructed in accordance with JIS-A-1304. carried out.

【table】

[Table] As shown in Figure 1, the fire resistance test is conducted vertically.
Two fireproof asbestos cement extruded plates 1 and 2 of 1000 mm, width 500 mm, and thickness 60 mm are arranged with a gap S of 12 mm between them, and on the back side of the gap S, a vertical 100 mm,
Top with three cedar boards 3, 3, 3, 100mm wide and 10mm thick.
Contact the three points A, B, and C in the downward direction, and then press the mark 4.
After filling approximately half of the gap S with the secondary sealing material listed in the prescribed column of Table 1 at the position indicated by , Fill the primary sealant with a caulking gun at the position indicated by code 5, and after 24 hours, apply a flame to the surface of the primary sealant, as stipulated in Article 107, Item 1 of the Building Standards Act Construction Ordinance. The temperature of the back surface of the secondary sealing material 4 was measured at the contact position of the cedar board 3 when the secondary sealing material 4 was heated for 30 to 60 minutes along a heating standard curve based on . The measured temperatures obtained are shown in Table 2.

[Table] In Experiments 2, 4, 5, and 6, the secondary sealant was made by bending the glass fiber nonwoven fabric into a U-shape so that the bent part was in contact with the primary sealant. This is what I used. After the fire resistance tests in Experiments 1 to 5, all of the residue from combustion of the primary sealant remained in the form of a scab, and the joints remained sealed, preventing flames from passing through them throughout the test. The primary sealant after the fire resistance tests in Experiments 6 to 8 had small cracks in various places, some of which were scattered by the strong force of the flame during the test, and the cracks became thin. The primary sealant after the fire resistance test in Experiment 9 was:
The flames during the test directly hit the secondary sealant, causing the cedar board on the back to burn and fall, making it impossible to measure the temperature on the back. Next, for reference, the rainwater resistance of each primary sealant used in Experiments 1, 7, and 9 was calculated by 3×
Table 3 shows the results of testing the water absorption rate and water repellency of a 25 x 100 (mm) sample. The water absorption rate (%) was calculated using the following formula by keeping the sample stationary for 24 hours at a position 100 mm below the water surface, pressing it lightly onto a filter paper, and quickly wiping off the water adhering to the surface. It is something. Water absorption rate (wt.%) = W ₂ - W ₁ / W ₁ × 100 W ₂ : Weight of sample after slight dehydration W ₁ : Weight of sample before putting it in the water tank In addition, water repellency (degree) is This is the contact angle between the surface of a square sample and water, measured using a contact angle meter CA-D manufactured by Kagaku Co., Ltd.

[Operation and effect of the invention]

The fire-resistant sealing material of the present invention is a paste-like material or a paste-like material in which 5 to 400 parts by weight of fibrous potassium titanate and 20 to 300 parts by weight of an endothermic decomposition type flame retardant are added to 100 parts by weight of a silicone resin. It is made of silicone resin varnish. However, the fire-resistant sealant of the present invention having the above structure has good adhesion as a joint,
By simply applying a primer treatment to the surface to which the sealant is applied, extremely excellent adhesion to the treated surface can be obtained. In addition, the fire-resistant sealant of the present invention has a high degree of fire resistance and heat resistance, and furthermore, has waterproofness, weather resistance,
It also exhibits excellent properties such as durability, cold resistance, and ozone resistance.

[Brief explanation of the drawing]

FIG. 1 is a plan view of the fire resistance tests conducted in Experiments 1 to 9, and FIG. 2 is a reduced rear view thereof. 1, 2... Fireproof asbestos cement extruded board, 3...
Cedar board, 4...secondary sealing material, 5...primary sealing material, A, B, C...backside temperature measurement position.

Claims (1)

[Claims] 1. It is a paste or silicone resin varnish in which 5 to 400 parts by weight of fibrous potassium titanate and 20 to 300 parts by weight of an endothermic decomposition type inorganic flame retardant are added to 100 parts by weight of silicone resin. A fire-resistant sealant with special features.