JPS5945688B2 - Foaming fire protection composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition that has excellent fireproofing properties due to foaming action and also has excellent extrudability.

In recent years, due to the development of petrochemistry, many types of synthetic polymers have been used in large quantities over a wide range of areas, such as interior materials for buildings, vehicles, ships, etc., and electrical and thermal insulation materials.

However, some of these synthetic polymers, including some that are flame-retardant, are generally flammable, and for this reason, fires in buildings, vehicles, etc. tend to become large-scale and cause catastrophes. There is. In addition, electrical cables attached to fire prevention equipment often break down due to a fire, and as a result lose their electrical transport function, causing the fire prevention equipment to not be worked on at all costs, thereby exacerbating the fire. For this reason, fire prevention measures have recently become more important than ever, with laws and regulations regarding fire prevention being strengthened, and it has become a controversial issue among those involved in the development of technology related to fire prevention and fire resistance. Recently, foamable fire-retardant paints with various compositions having excellent fire-retardant properties have been developed.

The above-mentioned fire-retardant paint foams by itself when heated to a high temperature to form a heat insulating layer, which has the effect of protecting the object to be protected from fire.

However, the above-mentioned foamable fireproofing paints generally have poor moisture resistance, water resistance, weatherability, and heat resistance, and when used outdoors, they have the disadvantage that they lose their initial fireproofing performance in a short period of time due to rainwater, etc.

In addition, the paint usually has a dry film thickness of at least 17
It is used for coating to a thickness of nm or more, but in order to form such a thickness, it is necessary to repeat the coating several to more than ten times, which not only takes a considerable amount of time, but also allows the coating to be applied uniformly to a predetermined thickness. It requires a high degree of skill to apply the coating, and it is usually applied to an uneven thickness. by the way,
Due to its fire protection mechanism, non-uniformity in coating film thickness is often a fatal flaw in foaming fire protection paints. The reason for this is that in the event of a fire, the film of the paint gradually foams and is consumed from the surface layer to the internal layer, and until it is consumed, it does not protect the protected object from the fire. However, if there is a thin part in the coating, the foaming in that part will rapidly exceed the durability expected from the initial thickness, and this will reduce the fire protection performance of other parts where the foaming has not been consumed. As a result, this causes a significant decline in the fire protection function of the paint film.
Additionally, another notable drawback of intumescent fire protection paints is that the dry film has poor flexibility.

Therefore, when the object to be coated is deformed or bent, even temporarily, due to thermal history, mechanical vibration, wind force, or other external forces, the fireproof coating will crack and partially peel off. Particularly in the case of insulated wires, they are bent several times during manufacture and installation, and even after installation they are constantly deformed due to heat history, etc. It is very problematic from a practical point of view to protect it. However, the present inventors did not formulate a paint with a specific amount of a specific polymer in a specific amount ratio among the many known foaming fire retardants, but in other words, added a liquid dispersion medium or solvent to New findings have been obtained that when mixed without using foaming paints, it is possible to obtain a composition that does not have the above-mentioned drawbacks of conventionally known foamable fireproofing paints, has improved foaming fireproofing performance, and has excellent extrudability. The present invention was developed based on the above-mentioned new findings, and is based on whether (a) a hydrocarbon polyhydric alcohol or carbohydrates and (b) a mixture of the polymers described below are in liquid form at the kneading temperature; Or a blowing agent with a particle size that passes through a 100 mesh sieve at room temperature (c) a flame retardant dehydrating agent, and (d)
A polymer made by blending a halogen-free thermoplastic elastomer with a melt index of 0.1 or more and a viscosity of 150 or less with an inorganic filler in an amount of 10 to 50% by weight. The mixture and (e) a phosphate ester plasticizer are mixed in the absence of a liquid solvent or a liquid dispersion medium, and the above (a) component, (b)
The weight ratio of component and (c) component is at point α on triangular coordinates (
60, 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
), and the total amount of components (a), (b), and (c) is 65 to 30% by weight and the above component (d) is 30% by weight. The present invention proposes a foamable fireproofing composition characterized by comprising 55% by weight of component (e) and 5% to 15% by weight of component (e).

Component (a) used as a component of the composition of the present invention and (
The paint whose main components are component b) and component (c) is one of the conventionally known foaming fire retardant paints, and among the various known foaming fire retardants, those with the above ingredients are particularly suitable. and using the above-mentioned liquid or fine powder as the (b) component blowing agent, which is one element of the component, and kneading it with a specific polymer without changing the form of the paint. As shown in Figure 2, an extrudable composition can be obtained that has tremendous fire protection performance that is completely unimaginable based on the performance of known foamable fire protection paints.

According to the research conducted by the present inventors regarding the fire protection function of foaming fire retardant agents, it is not just that the degree of foaming of these fire retardants is high, the fire retardant ability is high; It is especially important that the material has high flame resistance.

Although the foamed film of conventionally known foamable fireproofing paints generally foams sufficiently, the resulting foamed film is mechanically fragile, so that it can easily resist flame pressure and wind pressure generated during a fire within a short time after foaming. or destroyed by fire in a relatively short period of time, and as a result, the insulation effect of the foam membrane is not sufficient, or the underlying fireproofing coating is foamed and consumed one after another, resulting in a current level of fireproofing performance. It feels like a step forward.

On the other hand, the composition of the present invention foams moderately when exposed to flame, and the foamed film formed has high mechanical strength and high burnout resistance, so it can withstand strong flames even under strong winds. Forms a strong foam membrane even when exposed to heat to insulate the protected object. Furthermore, due to the formation of a strong foamed film, the foaming consumption of the foamable fireproofing layer is slow, so that objects to be protected can be protected from flames for a long period of time. For example, certain compositions of the present invention may be applied in a 2 m thick extruded coating layer with a thickness of 60 m.
When applied to a 0V polyvinyl chloride insulated wire, the wire will have a voltage of 120
It maintains its insulation function for a long period of time, about 2 hours, directly above a flame at 0°C. This fact clearly shows the excellent fireproof performance of the composition of the present invention. The composition of the present invention has excellent extrusion processability and can be processed into a product with high plasticity, so a film of any thickness can be easily and uniformly formed on the object to be protected by extrusion, tape wrapping, etc. obtain.

Furthermore, the composition of the present invention has excellent water resistance, moisture resistance, weather resistance, heat resistance, etc., and therefore has the advantage that it can be used outdoors with a high degree of reliability. As mentioned above, the composition of the present invention has extremely excellent performance in various properties that cannot be matched by known foaming fire-retardant paints, but the composition satisfies all of the conditions described below. Only then can it be manufactured.

Now, the component (d) used in the present invention in order to realize such a remarkable foaming fireproofing effect has a melt index of 0.
．． A polymer mixture formed by blending 10 to 50% by weight of an inorganic filler with one or more halogen-free olefin-based copolymers or halogen-free thermoplastic elastomers with a viscosity of 1.50 or less, It is essential that the polymer mixture is used in an amount of 30 to 55% by weight based on the total amount of components (a), (b), (c), and (e) described below and component (d).

If the amount of the above polymer mixture is less than the above amount, the resulting foamed film will be similar to the foamed film of a foamable fire protection paint film and will easily collapse and scatter under the force of a flame, while if the amount is more than the above amount, foaming properties will deteriorate and fire protection will be prevented. Performance will be significantly reduced. Therefore, the blending amount of the above polymer mixture is preferably 35 to 45% by weight. Therefore, the polymer in component (d) used in the present invention is a non-halogen olefin copolymer having a melt index within the above range, that is, ethylene,
Olefins such as propylene and butene and vinyl acetate,
Copolymers with vinyl compounds such as acrylic esters,
Alternatively, copolymers of olefins such as copolymers of ethylene and α-olefins such as propylene, butene-1, or isobutylene, and mixtures of different grades and types of olefin copolymers are also included. Preferred examples include ethylene/vinyl acetate copolymer and ethylene/ethyl acrylate copolymer, and halogen-free thermoplastic elastomers with Mooney viscosity within the above range include natural rubber, EPDM, nitrile rubber, styrene rubber, etc.
Butadiene rubber, butyl rubber, other thermoplastic rubbers such as Uniroyal's TPRl and Ciel's KraitO
Examples include nGX.

Among the components (d), those with a melt index of less than 0.1 and those with a viscosity of more than 150 are listed in (a) above.
Mixing and moldability with components (b) and (c) are poor, and desired kneading properties, extrusion processability, and flexibility cannot be obtained. Then,
Component (d) used in the present invention is preferably one with a melt index of 1.0-10, or one with a melt index of 1.0-10, or one with a viscosity of
ML (1001C, 1+4)) 40-80. In the present invention, it is also possible to use two or more types of component (d) in combination. In addition, as the inorganic filler in component (d), any filler that can be added to rubber or plastic can be used, but preferred examples include silicate minerals (kaolin clay, calcined clay, talc, mica). , asbestos, calcium silicate, sericite, zeolite, slate powder, pumice powder, etc.), calcium carbonate,
Alumina monohydrate, natural silicic acid (diatomaceous earth, silica sand, silica powder), barium sulfate, calcium sulfate, magnesium carbonate, fine particle silicic acid (for example, trade names Aerosil, Niposil, Himil, Zeorex, Cavosil, etc.), etc. I can give an example. (d) If the amount of filler added in the component is less than 10% by weight, it will melt and drip during foaming and will have poor fire protection ability, and if it is 50% by weight or more, the required amount of the above components (a), (b), and (c) will be mixed. It is difficult to do so, and even if it is forcibly mixed in, the extrusion processability, flexibility, etc. are poor, and the foamability is poor, which adversely affects the fireproofing performance, making it impossible to put it to practical use. That is, the amount of filler added in component (d) is from 10 to 10 as specified in the present application.
50% by weight is suitable for practical use. Also,(
In component d), the above halogen-free polymer or elastomer and filler are kneaded in advance to provide a polymer mixture. may be added. The hydrocarbon polyhydric alcohols or hydrocarbon compounds used in the present invention, which are the component (a), react with the component (c), that is, the flame retardant dehydrating agent described below, and are carbonized.
It 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) by the inert gas generated by decomposition of the component, that is, the blowing agent. Examples of hydrogen-based polyhydric alcohols include monopentaerythritol, dipentaerythritol, tripentaerythritol, triethylene glycol, solpitol, resorcinol, polypentaerythritol,
Glycerin, trimethylolmethane, trimethylolpropane, diethylene glycol, propylene glycol, hexamethylene glycol, inositol, etc.
Examples of carbohydrate compounds include dextrin, starch, glucose, and sucrose.

Among these components (a), monopentaerythritol, dipentaerythritol, tripentaerythritol, and starch are preferred, and particularly preferred are fine powders that pass through a 300 mesh sieve at least 95% of the total. It is monopentaerythritol. 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 inert gas such as nitrogen gas, carbon monoxide, carbon dioxide gas, or ammonia gas, and ) 100% liquid at the kneading temperature with the polymer mixture of the components or 100% sieve at room temperature
Specific examples of powders that pass through and have such functions and conditions include melamine, urea formaldehyde,
Organic amines such as aminoacetic acid, trimethylolmelamine, hexamethylolmelamine, melamine resin, guanidine, dicyandiamide, butyl urea, polyamide resin, casein, azodicarbonamide, nitrososulfonamide and other organic amides, chlorinated paraffin, parachloromethane These include halogenated organic compounds such as xylenol, tetrachlorophthalic acid resin, pentachlorophenyl, and glycenyl ether, sulfone hydrazides such as benzenesulfone hydrazide, and guanyl compounds such as aminoguanylurea.

Among these, preferred are melamine, trimethylol melamine, hexamethylol melamine, dicyandiamide, etc. Particularly preferred are 300 mesh sieves with at least 950 mesh sieves. ) is a finely powdered melamine that passes through. 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 reason for this is not clear, but it is thought that it is difficult for coarse particles to form dense and uniform foams in the coexistence of a large amount of polymer. Used in the present invention (
The flame retardant dehydrating agent which is component c) has the function of thermally decomposing and reacting with the hydroxyl groups contained in component (a) to form a foamed carbonized film, and includes monoammonium phosphate, monoammonium phosphate, Ammonium salts such as diammonium phosphate, ammonium polyphosphate, ammonium sulfate, ammonium halide, melamine monophosphate, melamine diphosphate, melamine triphosphate, phosphoric acid amines such as reaction products of NH3 and P4OlO, guanyl These include phosphoric acid amides such as urea phosphate, urea phosphate, polyphosphorylamide, and phosphoryl trianilide, and sulfuric acid amines such as paranitroaniline hydrogen sulfate.

Among these, the preferred one is the general formula H (.

-Rll)+2(NH4)NlPnO3n+, (n/m
=0.7-1.1) Average degree of polymerization 20-40
0 or the general formula (NH4).

+2Pn03. Average degree of polymerization expressed as +1 150-2
Particularly preferred ammonium polyphosphates are linear condensates of 0.00 and particularly preferred are ammonium polyphosphates in the form of fine powders that pass through a 300 mesh sieve at least 95% of the total. In the present invention, a mixture of two or more of them may be used. The above (a) used in the present invention
) component, (b) component, and (c) component are the α point (60, 10, 30) and the β point (6
0, 30, 10), γ point (30, 60, 10), δ point (
10, 60, 30), ε point (10, 30, 60), and ζ point (30, 10, 60). When used at a different composition ratio, it will not foam even when it comes into contact with flames, and will have no fire protection ability.

In the present invention, the above (a) component, (b) component, and (c)
The components are used in an amount of 65 to 30% by weight of the total amount of the polymer mixture as component (d) and the phosphate ester plasticizer as component (e), and component (d) is 30 to 55% by weight, and further 5 to 15% by weight of component (e)
The total amount of components (a), (b), and (c) is preferably 60 to 40% by weight, 35 to 45% by weight of component (d), and 5 to 15% by weight of component (e). %.
By employing such a blending ratio, a fire protection composition with even higher performance can be obtained. Furthermore, (a) component, (b) component, and (c
) component is also in the area shown by the triangle in the triangular coordinates in Figure 1, that is, point A (55, 30, 15), point B (25,
60, 15), and the r point (25, 30, 45), particularly when the area is surrounded by a straight line connecting each of the points (25, 30, 45) in sequence, particularly excellent fire resistance performance can be obtained. Examples of the phosphoric acid ester plasticizer as component (e) include alkyl phosphates represented by the general formula (where R is hydrogen or an alkyl group), tricresyl phosphate, or tri(2,
Haloalkyl phosphates such as 3dipromopropyl) phosphate and tri(β-chloroethino(ha)phosphinate) are used.

In the present invention, the total amount of carbon black, anti-aging agents, pigments, lubricants, etc. that are usually blended into rubber and plastics is 10 parts by weight or less, preferably 7 parts by weight, per 100 parts by weight of the composition of the present invention. If it is below, it may be blended into the composition of the present invention.

In the present invention, it is particularly important to mix the above components without using a liquid solvent.

Even if a solvent or the like is used, foamed fireproof performance, water resistance, and weather resistance comparable to those of the composition of the present invention can be obtained, but compositions made using these liquids are The composition is inferior in flexibility to that of the present invention, and therefore has unreliable long-term reliability as a fireproof material.

The reasons why such liquids are not used in the present invention are as described above, but the decrease in flexibility when liquids are used is due to the chemical reaction when they are blended with large amounts of polymers of components (a) to (c) used in the present invention. I believe that the cause is physical/physical behavior. In addition, in the present invention, a high boiling point liquid that is blended as a component such as a plasticizer may be blended. Therefore, the composition of the present invention can be produced by mixing in a conventional method such as using a two-roll mixer or a Banbury mixer. Can be processed into desired shape. 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 extremely remarkable effects of the present invention.

[Examples 1 to 15, Comparative Examples 1 to 13] The compositions of Examples 1 to 15 shown in Table 1 and Comparative Examples 1 to 13 shown in Table 2 were mixed using two rolls.

In Tables 1 and 2, the amount of each component is % by weight.
It is shown in Each of the above compositions contains the ingredients shown in Tables 3 and 4 in the parts by weight shown in each table per 100 parts by weight of the formulation shown in Table 1 or 2. Each composition was prepared using a 600 VCV cable 3 x 35 m 1 L (
27F on top of outer diameter 13.5m1L)! In addition to extrusion coating with U thickness and evaluating the extrusion processability at that time, the resulting sample wire was used to evaluate the flexibility, foaming fire resistance, water resistance, yield resistance, heat resistance, etc. of the composition. The results are shown in Table 5. The test methods and evaluation criteria for each characteristic item are as described below. [Foaming fireproofing ability evaluation test method] Approximately 30 Cf of sample electric wire! In order to measure the temperature directly under the sheath during the combustion test by cutting into L, insert a thermocouple 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 temperature is controlled to a fire temperature of 1,100 to 1,200°C. Immediately after the sample comes into contact with the flame, a voltage of AC6OOV 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. That is, AC6O
The short-circuit time under OV voltage application is 40 minutes or more, and the fire protection ability is 30 minutes or more when the temperature of the inner surface of the sheath, where the flame center is heated, rises to 400°C.
Excellent if the short-circuit time is 30 minutes or more and heating time is 30 minutes or more; Good if the short-circuit time is 10 minutes or more and heating time is 10 minutes or more; short-circuit time is 4 minutes or more and same grade. Those with a heating time of 4 minutes or more were judged acceptable, and those with a short circuit time of 4 minutes or less and a heating time of 3 minutes or less were judged as unacceptable. In addition, the short circuit time of the ordinary 600 VCV cable 3 x 3.57 ft 71 t not coated with the foamable fireproof composition was 2 to 3 minutes, and the temperature rise time was within 2 minutes.

[Extrusion processability evaluation test method] 600VCV cable 3 x 3
5 m- (outer diameter 13.5 m!) The compositions of each example and comparative example were screwed onto a screw L/D: 15, screw diameter: 5
A piece of 2 mm thick was extruded using a Zero-Yu extruder, and the extrusion status was ranked in five stages according to the criteria described below.

In other words, the extruded coating should have substantially no fluctuation in the discharge amount and have extremely good smoothness and gloss, and the extruded coating should have substantially no fluctuation in the discharge amount and have extremely good smoothness. Good, if the discharge rate fluctuates slightly but the smoothness is good, if the discharge rate fluctuates, it is difficult to extrude, and the smoothness is rough and the texture is rough, then the extrusion is difficult. What was possible was determined to be impossible.

[Flexibility evaluation test method]

The length of the sample wire is approximately 50Cr! Cut it into L pieces and place it on a mandrel with an outer diameter of 12CffL, which is about 7 times the coating diameter, at room temperature.
8. Bending was repeated and the flexibility at that time and the number of bends until cracks appeared in the extruded coating layer were determined, and the flexibility was ranked on a five-point scale based on the following criteria.

In other words, those that have extremely good flexibility when bent and can be bent 70 times or more before cracks appear in the coating layer are excellent, and those that have good flexibility and can be bent 50 times or more are excellent. Excellent, those that have flexibility and have been bent 30 times or more are good, those that have poor flexibility and have been bent 10 or more times are acceptable, and those that have very poor flexibility and have been bent 9 times or less. It was determined that it was not possible.

[Water resistance evaluation test method]

The sample wire was cut to a length of about 70 cm, immersed in a water tank controlled at 30°C with both ends exposed above the water surface, left for 7 days, taken out, dried, and then subjected to the above foaming fireproofing performance evaluation test method. Therefore, the foaming fireproofing ability was investigated, and the water resistance was indicated based on the criteria shown in Table 6.

[Weather resistance evaluation test method]

The sample wire is about 30cm long! n, and measured it using a weather meter (Toyo Rika Kogyo Model WE-2, light source;
Carbon arc (2 lights), temperature: black panel thermometer 60 (C, rainfall cycle: 120 minute cycle, 18 minute rain)
After being exposed to water for 800 hours, the foaming fireproofing ability was examined according to the above-mentioned foaming fireproofing ability evaluation test method, and the weather resistance was expressed based on the criteria shown in Table 6.

[Heat resistance evaluation test method]

The sample wire was cut to a length of approximately 30 cm, left in a gear oven temperature-controlled at 70°C for 30 days, then taken out, and the foaming fire-retardant ability was examined according to the above-mentioned foaming fire-retardant ability evaluation test method, and the judgment was shown in Table 6. Heat resistance was indicated based on standards.

[Brief explanation of drawings]

FIG. 1 shows triangular coordinates showing the composition ratios of components (a) to (c) in the composition of the present invention.

Claims (1)

[Claims] 1(a) hydrocarbon polyhydric alcohol or carbohydrates;
(b) It is liquid at the kneading temperature of the polymer mentioned below, or it is 100% sifted through a 100 mesh sieve at room temperature.
(c) a flame retardant dehydrating agent; (d) a blowing agent of a particle size that passes through;
) a halogen-free olefin copolymer with a melt index of 0.1 or more or a halogen-free thermoplastic elastomer with a Mooney viscosity of 150 or less containing 10 to 50% by weight of an inorganic filler; and (e) a phosphate ester plastic. agent in the absence of a liquid solvent or a liquid dispersion medium, and the weight ratio of the components (a), (b), and (c) is at the α point (60, 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), and are within the area surrounded by straight lines sequentially connecting each point (30, 10, 60), and their (a) component, (b
) component, and the total amount of component (c) 65 to 30% by weight, (
A foamable fireproofing composition for molding, characterized by comprising 30 to 55% by weight of component d) and 5 to 15% by weight of component (e).