JPS5910397B2 - foam fire retardant putty - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has excellent fire retardant properties due to its foaming action, and has excellent properties that allow it to be filled at room temperature into voids in firewall penetration areas of electric wires and cables, joints in building interior materials, etc. This invention relates to a foamed fireproofing composition in the form of a putty.

Recently, there have been many reports of tragic cases of building fires caused by smoke and fire spread from various types of synthetic polymer interior materials, rubber, and plastic electric wires and cables.

For this reason, fire prevention measures have recently been emphasized, with laws and regulations related to fire prevention being strengthened, and people concerned are
Technological development related to fire resistance has become a pressing issue. Today, fire retardant materials and flame retardant materials are used in the interior materials of buildings, ships, vehicles, etc., and fire prevention measures are taken such as installing fire walls to protect emergency equipment. When the material itself is exposed to high heat, it may char, creating gaps at the joints that invite flames, speed up heat transfer to the back side, and spread the fire. Smoke and flames may leak through the area, causing damage to emergency equipment due to the spread of fire to electrical wires and cables. By the way, in order to provide fireproofing properties to such areas, a flame-retardant elastomer is kneaded with a non-combustible gas generating agent and made into a tape, which is attached to the joints of the above-mentioned interior materials via adhesive to prevent foaming in the event of a fire. Fire-retardant tapes have been proposed that act to block flames.
In addition, a putty-like composition that is used to fill cable penetration parts to prevent the spread of fire is a mixture of inorganic fibers such as asbestos fibers, inorganic pigments, and organic paint with a dispersion medium that is volatile at room temperature such as water or an organic solvent. There is. but,
The above-mentioned fire-retardant tape does not contain the carbonized foam layer-forming element described later, so it has insufficient heat insulation and fire-retardant properties, and furthermore, the tape itself has no adhesive properties, so other adhesives or pressure-sensitive adhesives must be used in combination. There are also difficulties in construction.

Further, since the putty-like composition contains a dispersion medium such as water and an organic solvent that is volatile at room temperature, after filling, the dispersion medium evaporates and the volume shrinks, resulting in incomplete filling. Furthermore, when it encounters flames, it does not have the ability to form a carbonized foam layer, so its insulation effect is extremely small. The present invention comprises (a) a hydrocarbon polyhydric alcohol, (b) a blowing agent, (c) a flame retardant dehydrating agent, and (d) a semi-drying oil, or a drying oil, which can be cured by air oxidation polymerization. It is made of a mixture of oil or room temperature curing resin and its curing agent, and the weight ratio of the components (a), (b), and (c) is at point α (6) on the triangular coordinates.
0, 10, 30), β point (60, 30, 10), γ point (
30,60,10), δ point (10,60,30), ε point (10,30,60) and ζ point (30,10,60)
The total amount of component (a), component (b), and component (c) is 100 to 100 parts by weight per 100 parts by weight of component (d). The present invention proposes a foamed fire-retardant putty that has a content of 500 parts by weight, has excellent filling workability, and has stable fire resistance.

The putty of the present invention has appropriate plasticity and adhesiveness at room temperature, so it can be filled into areas where electric wires and cables pass through, joints between interior materials of buildings, etc. during construction without using other adhesives or adhesives. In addition, the putty-like composition filled by the above-mentioned component (d) that is cured by air oxidation polymerization or chemically cured by reaction with a hardening agent exhibits a high degree of mechanical strength at room temperature. It never comes.

Furthermore, since the putty of the present invention does not require a dispersion medium such as water or an organic solvent that is volatile at room temperature during its production or application, the volume resulting from the volatilization and drying of the dispersion medium after filling is maintained. There is no shrinkage, which also ensures a good filling condition over a long period of time. Moreover, when encountering flames, the above (a) component, (b) component, (
It has the function of forming a carbonized foam layer with excellent fire resistance due to the synergistic effect of component (c) and the carbonized film of component (d), so the heat insulation and fire protection properties and fire spread prevention properties of the construction area are extremely excellent. The hydrocarbon polyhydric alcohol which is the component (a) used in the present invention is carbonized by reacting with the component (c), that is, the flame retardant dehydrating agent described below, and is carbonized by the decomposition of the component (b), that is, the blowing agent described later. The generated inert gas has the function of forming a spongy carbon foam layer with excellent mechanical strength through a synergistic effect with the carbonized film of component (d).Specific examples include monopentaerythritol, dipenta Examples include erythritol, tripentaerythritol, triethylene glycol, sorbitol, resorcinol, polypentaerythritol, glycerin, trimethylolmethane, trimethylolpropane, diethylene glycol, propylene glycol, hexamethylene glycol, inositol, and the like.

Among these components (a), preferred are monopentaerythritol, dipentaerythritol, and tripentaerythritol, and particularly preferred is monopentaerythritol in fine powder that passes through a 300-mesh sieve at least 9,570 ml of monopentaerythritol. It is. In the present invention, one or more types of component (a) are used. The blowing agent as component (b) used in the present invention has the function of thermally decomposing to release an inert gas such as nitrogen gas, carbon monoxide, carbon dioxide gas, or ammonia gas, and preferably Specific examples of melamine, urea-formaldehyde, aminoacetic acid, which are liquid at the mixing temperature with component (d) or powder that passes through a 100-mesh sieve at room temperature for 10,070 times, and have such functions and conditions.
trimethylolmelamine, hexamethylolmelamine,
Melamine resin, organic amines such as guanidine, dicyandiamide, butyl urea, polyamide resin, casein,
Organic amides such as azodicarbonamide and nitrososulfonamide, halogenated organic compounds such as chlorinated paraffin, parachloromethylenol, tetrachlorophthalic acid resin, pentachlorophenyl, glycenyl ether, and sulfone hydrazide such as benzenesulfone hydrazide. and guanyl compounds such as aminoguanylurea.

Among these, preferred are melamine, trimethylolmelamine, hexamethylolmelamine, dicyandiamide, etc., and particularly preferred is melamine in the form of a fine powder that passes through a 300-mesh sieve at least 9,570 times in total. In the present invention, one or more of them may be used. If the component (b) of the present invention is a solid having a particle size larger than the above, it is not preferable because the mechanical strength of the foamed layer tends to decrease. The flame retardant dehydrating agent which is the component (c) used in the present invention has the function of thermally decomposing and reacting with the hydroxyl group contained in the component (a) to form a foamed carbonized film, Ammonium salts such as monoammonium phosphate, diammonium phosphate, ammonium polyphosphate, ammonium sulfate, ammonium halide, melamine monophosphate,
melamine diphosphate, melamine triphosphate,
NH3 and P4O].

Phosphoric acid amines such as reaction products with phosphoric acid amines such as guanylurea phosphate, urea phosphate, polyphosphorylamide, phosphoryl trianilide, and
These include sulfuric acid amines such as hydrogen sulfate and paranitroaniline. Among these, preferred is the general formula H(n-m)+2(N
H4) MPnO3n+1 (W=0.7-1.1) with an average degree of polymerization of 20-400, or the general formula (NH4)n+2P003.

Ammonium polyphosphate is a linear condensate with an average degree of polymerization of 150 to 200 expressed by +1, and particularly preferred is a sieve of 300 mesh, which accounts for at least 95% of the total.
is a finely powdered ammonium polyphosphate that passes through. In the present invention, a mixture of two or more of them may be used. The above (a) component used in the present invention, (b)
The blending ratio of the components and component (c) is preferably determined by the α point (60, 10, 30) and the β point (60, 30) on the triangular coordinates shown in FIG.
30, 10), γ point (30, 60, 10), δ point (10
, 60, 30), ε point (10, 30, 60) and ζ point (
30, 10, and 60) within a region surrounded by straight lines sequentially connecting the points.

When used at a composition ratio outside this range, the degree of foaming is poor even when it comes into contact with flame. In the present invention, the total amount of components (a), (b), and (c) is 500 to 100 parts by weight, preferably 400 to 100 parts by weight, based on 100 parts by weight of component (d). Used at 150 parts by weight. (a) Ingredients, (
If the total amount of components b) and (c) is less than 100 parts by weight, the putty will not foam sufficiently even when it comes into contact with flames, and will not be able to exhibit its fireproof function. On the other hand, if the amount exceeds 500 parts, the adhesion of the mixture with component (d) decreases significantly, and it becomes brittle and cannot be putty-like and cannot be used for filling. Furthermore, (a) component and (b
) component and (c) component are also in the area indicated by the triangle in the triangular coordinates in Figure 1, that is, point A (50, 30, 20).
, point B (20,60,20) and point C (20,30,5
Particularly excellent fire resistance can be obtained if the area is within the area surrounded by straight lines connecting the points of 0) in sequence. Examples of the air-oxidizable hydrocarbon compound as component (d) used in the present invention include linseed oil, tung oil, linseed oil,
Drying oils such as eno oil, hempseed oil, soybean oil, and dehydrated castor oil; semi-drying oils such as cottonseed oil and rapeseed oil; preferred among these are linseed oil, tung oil, sinakiri oil, and hempseed oil; Particularly preferred is linseed oil.

Further, the room temperature curable resin refers to liquid rubbers such as epoxy resin, unsaturated polyester resin, urethane resin, and liquid polysulfide rubber in combination with a curing agent that can be cured at room temperature. The above (a) component, (b) component, (c
The putty of the present invention is prepared by adding fillers, carbon black, anti-aging agents, pigments, lubricants, curing accelerators, etc. that are usually added to rubber and plastics to the putty consisting of components () and (d). As long as it is 50 parts by weight or less per 100 parts by weight, it may be blended into the putty of the present invention.

The putty of the present invention is obtained by mixing and manufacturing in a conventional mixer, and the resulting mixture can be used in ordinary construction for the penetration of electric wires and cables into fire walls, the joints of building interior materials, etc. can be easily filled by the method. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, and comparative examples will also be given to demonstrate the remarkable effects of the present invention. Examples 1 to 9, Comparative Examples 1 to 5 Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 5 shown in Table 1 had a capacity of 11
The amount of each component is shown in parts by weight.

However, the compositions based on room temperature curable resins of Examples 1 to 7 and Comparative Examples 1 and 3 to 5 contain component (a) in the base resin,
Adding about 60% of the total amount of component (b) and component (c),
The remaining ingredients were added to the curing agent. Each composition was evaluated for kneading workability, foaming fireproofing ability, water resistance, and heat resistance according to the test method and evaluation criteria described below, and the results are shown in Tables 2 and 3. [Kneading workability] Using an experimental coater with a capacity of 11 and two stirring blades, in the case of compositions (Examples 1 to 7, Comparative Examples 1 and 3 to 5) based on a room temperature curable resin as the component (d) The base resin and curing agent are separately prepared as component (a), component (b), and component (c).
) Add about 60% of the mixture to the base resin and the remainder to the curing agent and knead.

On the other hand, compositions based on semi-drying oil or drying oil as component (d) (Examples 8 and 9, Comparative Example 2) have component (a),
Component (b) and component (c) are kneaded at the same time. The mixing conditions were as follows: stirring at room temperature to 80°C for 10 minutes, observing the cohesive state of the finished mixture by appearance and touch;
) For compositions based on room-temperature curing resins, the mixing workability of the base resin mixture and curing agent mixture at the specified blending ratio was observed by touch, and these were comprehensively evaluated as excellent or good. , judged in three stages: not possible. [Foaming fireproofing ability evaluation test method] 600C cable 3CX3.5m7j (outer diameter 13.51
Apply putty with a trowel to about 3U1 thickness on top of t0 about 30 degrees,
Leave it at room temperature for at least one week and use it as a sample.

In order to measure the temperature directly under the sheath during a combustion test on this sample, a thermocouple is inserted between the core 1 and the sheath at the point where the flame hits. The above sample is burned in a Conradson gas burner whose flame temperature is controlled to 1100 to 1200°C. Immediately after the sample contacts the flame, a voltage of AC6OO is applied between the lines and the time until short circuit occurs is measured.

Meanwhile, the temperature of the inner surface of the sheath at the center, which is in contact with the flame, is continuously recorded using a thermocouple inserted in advance.
The test results were ranked in five stages based on the criteria described below.

In other words, the short circuit time under AC6OO voltage application is 40 minutes or more, and the temperature of the inner surface of the sheath where the flame center is heated is 4.
Those with fire protection ability that can be heated to 00℃ for 30 minutes or more are excellent, short circuit time is 30 minutes or more, and heating time is 30 minutes or more.
Good if the short circuit time is 0 minutes or more, Good if the short circuit time is 10 minutes or more and the temperature rise time is 10 minutes or more, Acceptable if the short circuit time is 4 minutes or more and the temperature rise time is 4 minutes or more.Short circuit Those in which the time was 4 minutes or less and the heating time was 3 minutes or less were judged as unacceptable.
[Water resistance evaluation test method] Approximately 30 CT in length made in the same manner as above for fireproof foam
! A sample electric wire of L was left in a water tank whose temperature was controlled at 40°C with both ends sealed for 7 days, then taken out, and after drying, the foaming fireproofing ability was examined according to the above foaming fireproofing ability evaluation test method, and the results are shown in Table 4. Moisture resistance was expressed based on the criteria shown below.

[Heat resistance evaluation test method]

The length is about 30mm, made in the same way as the fireproof foam above. A wire sample was left in a gear open whose temperature was controlled at 70°C for 30 days, then taken out, and the foaming fireproofing ability was examined according to the above foaming fireproofing ability evaluation test method, and the heat resistance was evaluated based on the criteria shown in Table 4. was displayed.

[Brief explanation of drawings]

FIG. 1 shows triangular coordinates showing the composition ratio of the present invention.

Claims (1)

[Claims] 1 (a) a hydrocarbon polyhydric alcohol; (b) a blowing agent; (c) a flame-retardant dehydrating agent; and (d) a drying oil or semi-drying oil that can be cured by air oxidation polymerization. It consists of a mixture of a room temperature curable resin and a component consisting of its curing agent, and the above (a)
) component, (b) component, and (c) component on triangular coordinates, α point (60, 10, 30), β point (60, 3
3, 10), γ point (30, 60, 10), δ point (10,
60, 30), ε point (10, 30, 60) and ζ point (3
0, 10, 60), and the total amount of components (a), (b), and (c) is 100 parts by weight of component (d) above. 100~
A foamable fireproof putty characterized in that the content is in the range of 500 parts by weight.