JPH108596A - Foamed fire-resistant molded article and foamed fire-retardant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the water-resistant, fire-resistant, and fireproof capacity of a molding, by molding a foaming fireproof composite including microcapsules in which a two-component polyurethane resin composite, thermo-expansive graphite, a vermiculite powder, and a polyphosphoric ammonium powder are coated with a resin, as an essential component. SOLUTION: A composite including microcapsules in which a polyurethane resin composite constituted of the first liquid including polyol and the second liquid including polyisocyanate, thermo-expansive graphite, a vermiculite powder, and a polyphosphoric acid ammonium powder are coated with a resin, as a essential component, is formed to have a required shape and a foaming fire proof molding. The thermo-expansive graphite is expanded by heating and the polyurethane resin composite is dehydrated and carbonized by polyphosphoric acid ammoniuml and a foamed body without scattering and dropping out is formed. Further, vermiculite powder expands to form a foamed composite and this foamed composite prevents smoke, flame, and gas at a fire from penetrating or flowing out.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a strong foamed carbonized film when inserted into joints, gaps, holes, etc. of the inner and outer walls of a general building and exposing the same to wood, etc. A foam-type fire-resistant molded article which has an effect of preventing flammable materials from being fired and preventing gas, etc. generated by smoke, flame, combustion, etc. from flowing out to the outside; The present invention relates to a foam type fire-retardant composition for obtaining

[0002]

2. Description of the Related Art In general buildings, openings opened for pipes and the like are closed with mortar or a sealing agent after the pipes are laid. In addition, inorganic materials such as mortar, gypsum, water glass, and the like are used for seals at joints of fire-resistant members used for interior panels and partitions for the purpose of fire resistance and sound insulation.

[0003] These inorganic materials and sealing agents are:
It is widely used because it is simple.

[0004] However, since inorganic materials are inevitable to shrink during the hardening process and are very hard after hardening, they are cracked in a short period of time due to micro-vibration and the like which cannot be avoided in general buildings. When an interface break occurs or the like occurs, a gap is easily formed, and does not necessarily show an original function. Interlayer displacement, in a high-rise building with an emphasis on followability, since the joints are made movable to absorb the displacement, a cured body of the inorganic material cannot be used, and a complex structure is taken. To ensure fire and sound insulation.

[0005] Further, most of the sealing agent is flammable, and the combustion residue has little effect on fire prevention at the opening.

Therefore, for example, a foamed asbestos body cut according to the joint width (for example, "Litflex" (trade name, manufactured by Nichias Corporation)) is provided on a movable joint of an exterior wall panel.
And the like are compression-inserted into a joint bottom, and a sealing finish is applied from above on the joint to impart waterproofness or the like, thereby imparting fire resistance to the movable joint.

However, since the foamed asbestos body is not deformed by heating at all, when it is cut into joint widths and inserted into the joints, the exterior wall panel is dehydrated and shrunk by heating, and the joints are deformed. When it is opened two to three times, a gap is formed, and it is difficult to completely stop the invasion of the flame.

In order to prevent the formation of such a gap, it is necessary to inject a wet foam type fire-resistant paint into movable joints of the exterior wall panel, and to inject a sealing agent from above on the movable joint of the exterior wall panel to impart waterproofness and airtightness. was suggested.

[0009] However, the above-mentioned wet foam type fire-resistant paint has high fire-protection performance, but has a problem in its own water resistance. Also,
There is a problem that it is difficult to inject the paint to a predetermined thickness. For example, when the wet foam type fire-retardant paint is injected from the nozzle into the joint while discharging from the nozzle, the nozzle does not move smoothly due to the hooking, so that the injection amount is not uniform. If the thickness of the fire protection paint is not constant,
The thickness of the sealing agent injected thereon becomes uneven, resulting in poor watertightness or waterproofness. In order to solve the drawbacks of the wet foam type fire retardant paint, a foam type fire retardant composition obtained by molding a foam type fire retardant composition containing the following components (i), (ii), (iii) and (iv) as essential components: A molded article is known (see JP-A-3-149283).

[0010] (i) a polyurethane resin composition comprising a first liquid containing a polyol and a second liquid containing a polyisocyanate, (ii) ammonium polyphosphate, (iii) a polyhydric alcohol, and (iv) an amino group-containing compound. Compound.

The above-mentioned foam-type fire-retardant composition can be formed into a predetermined shape depending on the construction site. Therefore, when a foamed fire-resistant molded article obtained by molding this composition is used, the application becomes easier and the uniform thickness can be easily achieved as compared with the case where the wet foamed fire-resistant paint is used. When a fire occurs, the foamed fire-resistant molded article expands (for example, 10 times or more) by heating, foams to form a carbonized layer,
This carbonized layer blocks the flammable underground material from flame and heat, thereby preventing the flammable underground material from burning. Also, even if a gap is generated due to cracking, shrinkage, vibration, etc. of the interior / exterior material due to heating, unlike the case of the foamed asbestos body, it expands and foams by heating to close the gap, so that smoke, flame, gas Etc. can be prevented from entering or flowing out.

However, the above-mentioned conventional foam-type fire-resistant molded article has the following disadvantages. Since the water resistance of ammonium polyphosphate, which is one of the essential components of the foamed fire-retardant composition as a raw material, is insufficient, the fire-prevention performance of the molded article may be reduced in a short period of time. In addition, when a fire occurs, the polyurethane resin in the molded product is softened and liquefied by heating and flows out from the joints, or the carbides fall off due to heating.

[0013] Therefore, compared to the above-mentioned conventional products, it has better water resistance and can maintain a high fire protection performance for a long period of time, and when a fire occurs, the polyurethane resin softened and liquefied by heating flows out and carbides are generated. The following components (i), (ii) and (iii) are essential in order to provide a foamed fire-resistant molded article that does not fall off and a foamed fire-retardant composition for obtaining this molded article. There has been proposed a foamed fire-retardant molded article obtained by molding a foamable fire-retardant composition as a component (Japanese Patent Application Laid-Open No. 7-70428).

A polyurethane resin composition comprising (i) a first liquid containing a polyol and a second liquid containing a polyisocyanate, (ii) heat-expandable graphite, and (iii) an ammonium polyphosphate powder coated with a resin. Microcapsules.

In this molded product, the heat-expandable graphite expands by heating, and the expanded graphite layer exhibits high fire resistance, and prevents the polyurethane resin liquefied and softened by heating from flowing out and preventing the carbide from falling off. Has been confirmed in experiments.

However, it is said that the composite expandable body of the expanded graphite layer and the carbonized layer formed by dehydrating and carbonizing the resin has good thermal conductivity and cannot sufficiently cope with a case where a higher level of fire protection performance is required. There was a problem.

[0017]

Therefore, the present invention has better water resistance than the above-mentioned conventional products, can maintain high fire protection performance for a long period of time, and, when a fire occurs, softens and liquefies by heating. Polyurethane resin does not flow out or carbides fall off,
A composite expandable body with low thermal conductivity and low thermal conductivity is made by a composite expandable body of a graphite layer formed by expansion of thermally expandable graphite due to heating in a fire and a carbonized layer formed by dehydration and carbonization of urethane resin. An object of the present invention is to provide a foamed fire-resistant molded article and a foamed fire-retardant composition for obtaining the molded article.

[0018]

Means for Solving the Problems In order to solve the above problems, the inventors have made various studies. As a result, by using vermiculite, it is possible to form a composite foam by heating, which has even lower thermal conductivity, and by using it together with heat-expandable graphite, the foam is scattered during heating, Experiments have confirmed that a relatively strong foamed composite can be obtained with less falling off, and the present invention has been completed.

Therefore, the foam type fire-retardant composition according to the present invention comprises the following components (A), (B), (C) and (D)
Is an essential component.

(A) A polyurethane resin composition comprising a first liquid containing a polyol and a second liquid containing a polyisocyanate, (B) thermally expandable graphite, (C) vermiculite powder, and (D) ammonium polyphosphate Microcapsules made by coating powder with resin.

The foamed fire-resistant molded article according to the present invention is obtained by molding the above-mentioned foamed fire-resistant composition according to the present invention.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The foamed fire-resistant molded article and the foamed fire-resistant composition of the present invention will be described in detail below.

The component (A) used in the present invention is a polyurethane resin composition comprising a first liquid containing a polyol and a second liquid containing a polyisocyanate. Since the polyurethane resin composition is a two-part composition, it is often a room temperature curing type. The use of a room temperature-curable polyurethane resin composition has the advantage that molding can be performed at a low temperature (for example, 110 ° C. or lower). However, the polyurethane resin composition used in the present invention is not limited to a room temperature curing type.

The polyol contained in the first liquid can be arbitrarily selected from one or more of those conventionally used as a polyol component of a two-component polyurethane resin composition of a room temperature-curable type. . Such polyols are not particularly limited, for example, polyester polyols derived from organic dicarboxylic acids and polyhydric alcohols, polyester polyols derived from lactones, castor oil, castor oil-modified polyols, polyether polyols, epoxy Modified polyol, silicone-based polyol, polyether polyester polyol having both the polyester unit and the polyether unit, (meth) acrylic acid-derived (meth)
Molecular weight of 300 to 3000 in acrylic polyol, etc.
Those having a hydroxyl value of 50 to 350 can be exemplified.
These polyols may be used alone or in combination of two or more. Although it does not specifically limit as said organic dicarboxylic acid, For example, phthalic acid, adipic acid, dimerized linoleic acid, maleic acid, etc. are used. The polyhydric alcohol is not particularly limited, but for example, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylolpropane, hexanetriol, glycerin, trimethylolethane, pentaerythritol and the like are used. The polyester polyol derived from lactone is not particularly limited, but examples include polybutyrolactone and polyvalerolactone. Although it does not specifically limit as a polyether polyol, For example, poly (oxypropylene) glycol, poly (oxypropylene) poly (oxyethylene)
Glycol, poly (oxybutylene) glycol, poly (oxytetramethylene) glycol, poly (oxypropylene) triol, poly (oxypropylene) poly (oxyethylene) triol, poly (oxypropylene) poly (oxyethylene) poly (oxypropylene) )
Triol and the like.

In the first liquid, it is possible to increase the reaction rate or increase the mechanical strength of a molded article by using the polyol and various crosslinking agents in combination. The crosslinking agent that can be used is not particularly limited. For example, aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, pentanediol, diethylene glycol, and dipropylene glycol; ethylenediamine, propylenediamine, butylenediamine, Aliphatic diamines such as pentamethylenediamine; aniline, phenylenediamine, 4,4'-
Aromatic amines such as methylene dianiline, 2-bis (p-aminophenyl) propane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, and 1,2-bis (2-aminophenylthio) ethane And the like.

As the polyisocyanate contained in the second liquid, there can be used a polyisocyanate used in a usual polyurethane resin composition, and it is not particularly limited. Examples thereof include hexamethylene diisocyanate and octamethylene diisocyanate. , Tolylene diisocyanate (TDI), 1,5-naphthalenediisocyanate, diphenylmethane-4,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 2-2'-diphenylpropylene-p, p'-diisocyanate, etc. Is mentioned.

The mixing ratio of the first liquid and the second liquid is not particularly limited, and usually, a polyol (eg, a polyester polyol or a polyether polyol) and a crosslinking agent (eg, an amine component) in the first liquid are used. And / or the diol component) are selected so that the total number of moles of active hydrogen of the second liquid and the number of moles of isocyanate groups of the polyisocyanate (eg, diisocyanate component) in the second liquid are substantially equal. One of them can be used in excess.

The component (B) used in the present invention is a heat-expandable graphite. This heat-expandable graphite is a graphite having a property that when heated, a compound existing between graphite layers thermally decomposes and the whole expands. Exists between the layers of this graphite and decomposes,
The compound is not particularly limited, for example, graphite acid sulfate, sodium graphite, potassium graphite,
Examples thereof include halogenated graphite, graphite oxide, graphitized aluminum chloride, and ferric chloride graphite. Thermal expansive graphite is
Known ones can be used.

The amount of the heat-expandable graphite is not particularly limited, but it is usually blended in a ratio of 10 to 100 parts by weight per 100 parts by weight of the polyurethane resin composition as the component (A). If the amount is smaller than this, the fire resistance becomes insufficient, and if the amount is larger than this, the material does not act as a fire protection by peeling off when heated, and the mechanical strength of the molded product is lowered, which is not preferable. Because.

The component (c) used in the present invention is a vermiculite powder. It is a hydrated silicate mineral also called hillite in Japan. It is a phyllosilicate very similar to the Pumice group mineral, a substance generated by changing peridotite by hydrothermal denaturation, or a secondary mineral generated by the collapse of the Pumice group mineral.

When the vermiculite powder is heated, c
It stretches significantly in the axial direction and extends 10 to 30 times its original thickness. Vermiculite itself has extremely low thermal conductivity, for example, about 1/4 that of silica sand (SiO ₂ ). Therefore, when the thermally expandable graphite as the component (B) is used alone, it is porous due to thermal expansion. However, by filling the voids with vermiculite, the heat conduction can be suppressed, and the fire protection performance can be reduced. Can be further improved. Thus, the combined use effect is exhibited by using the thermally expandable graphite and the vermiculite in combination.

The vermiculite powder used in the present invention is not heated and stretched, but is obtained by powdering ore as it is. The particle size is desirably 3 mm or less in terms of mixability and moldability, but is not limited thereto.

The amount of vermiculite used is not particularly limited, but is usually blended at a ratio of 10 to 300 parts by weight per 100 parts by weight of the polyurethane resin composition as the component (A). If the amount is smaller than this, the fire resistance becomes insufficient, and if the amount is larger than this, it is not preferable because it peels off upon heating and does not serve the role of fire protection, and the mechanical strength of the molded product is lowered. It is.

The component (D) used in the present invention is a microcapsule in which an ammonium polyphosphate powder is completely or almost completely covered with a resin.

The method for microencapsulating ammonium polyphosphate is not particularly limited, but examples thereof include an interfacial polymerization method and an in situ method.
Known methods such as a polymerization method, a curing method in liquid, a phase separation method, a drying method in liquid, a melt dispersion cooling method, a spray drying method, and a powder bed method can be employed. The resin that can be used for microencapsulation is not particularly limited, but is preferably one that forms a coating that is hardly permeable to water and has excellent water resistance.
For example, vinyl chloride resin, vinylidene chloride resin, epoxy resin, urethane resin, acrylic resin, phenol resin, vinyl acetate resin, cellulose resin, alkyd resin, shellac resin, diallyl phthalate resin, polyamide resin, melamine resin, urea resin, etc. No. These may be used alone or in combination of two or more. Among the above resins, a melamine formaldehyde resin is preferably used from the viewpoints of more complete coating with the resin, water resistance of the resin, strength of the capsule, and finer encapsulation.

The particle size of the ammonium polyphosphate microcapsules is not particularly limited,
It is preferably not more than μm. If the proportion of particles having a particle diameter of more than 100 μm increases, hard sedimentation occurs in the foamed fire-retardant composition, which makes it difficult to produce a foamed fire-retardant molded article, or makes uniform dehydration / carbonization difficult. To do
This is because it is not preferable.

The ammonium polyphosphate has a phosphorus content of 3
Those having 1.5 ± 0.5% by weight, a nitrogen content of 14.5 ± 0.5% by weight and a decomposition temperature of 275 ° C. or more are preferred. Such ammonium polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate (trade name “Sumisafe P”) manufactured by Sumitomo Chemical Co., Ltd.

The amount of the microcapsules of ammonium polyphosphate which is the component (D) is not particularly limited, but the polyurethane resin composition 1 which is the component (A)
It is preferably 20 to 150 parts by weight based on 00 parts by weight. When the compounding amount of the component (D) is below this range, it becomes difficult to effectively carbonize the entire organic substance, or it becomes impossible to expect sufficient foaming, and the compounding amount of the component (D) falls within the above range. If it exceeds, the viscosity of the foam-type fire-resistant composition becomes high and the production of the foam-type fire-resistant molded article becomes difficult due to the addition of the heat-expandable graphite and the like, and the foaming ratio decreases, which is not preferable. Because.

The components (B), (C) and (D) are often mixed and dispersed in the first liquid of the polyurethane resin composition of the component (A). The amount of addition is naturally restricted. However, component (A) ~
The mixing of (D) is not limited to this method.

In addition to the above-mentioned essential components (A) to (D), the foam type fire-retardant composition of the present invention is commonly used as necessary in ordinary two-part cold curing polyurethane resin compositions. One or more auxiliary components can be contained. Such auxiliary components (optional components) are not particularly limited, but include, for example, extenders such as silica, talc, barium sulfate; aluminum hydroxide, magnesium hydroxide, kaolin, calcium hydrogen phosphate, hectorite, and sulfurous acid. Sodium heptahydrate, ettringite,
Inorganic fillers that generate steam when heated, such as alunite, alunite, brucite (bluesite), diaspore, gibbsite (hydrargillite), kaolinite, montmorillonite, serpentine, slaked lime, gypsum, zinc phosphate, etc. Colorants such as iron oxide yellow, light yellow 50, iron oxide brown, iron oxide red, light blue 100, and chromium oxide green GN; catalysts such as organic tin compounds and organic lead compounds; dioctyl phthalate (also referred to as DOP) Various plasticizers such as triphenyl phosphate, tricresyl phosphate, tris (chloroethyl) phosphate and cresyl diphenyl phosphate; dehydrating agents; fibrous materials such as glass fiber, sepiolite, nylon fiber and vegetable fiber Substances; generally The foam, expands and dipentaerythritol used in the type of the refractory coating forming a carbide film, materials such as melamine; moth powder such as frit can be mentioned. These auxiliary components are used, for example, while being contained in the first liquid of the polyurethane resin composition of the component (A), but are not limited thereto.

The foam type fire-retardant composition of the present invention is not particularly limited. For example, it is formed into a desired shape after being mixed by a stirrer with a blade or the like. The molding method and conditions are not particularly limited, but, for example, may be poured into a container having a predetermined width, thickness, and length to form a sheet or film, or may be formed into a predetermined shape. Injection into the mold and molding, or
What is necessary is just to extrusion-mold and shape | mold using the dice designed to predetermined width | variety and thickness. By these molding methods, a foamed fire-resistant molded article having a uniform shape can be obtained.

When the foamed fire-resistant molded article of the present invention is obtained in the form of a sheet or a film, it may be cut at a predetermined width, or may be cut at a predetermined width to facilitate cutting. You may leave. When it is obtained in a tape shape or a bar shape, it may be cut at a predetermined length, or a cut may be made so as to be easily cut at a predetermined length.

The foamed fire-resistant molded article of the present invention can be used, for example, at joints or the like, or with a predetermined width and / or width.
Or cut into length and inserted. It can be easily inserted compared to the case of injecting wet fire protection paint,
Moreover, the thickness can be made more uniform. Here, the predetermined width and / or length refers to, for example, the width and / or length of a portion into which a foamed fire-resistant molded product is to be inserted, such as a width and / or length corresponding to the shape of a movable joint or an opening.
Or length.

The application site of the foamed fire-resistant molded article of the present invention is not particularly limited as long as it is a joint or the like where fire protection is required. It can be arbitrarily applied to joints such as exterior surfaces of various buildings such as floors and floors. Alternatively, openings other than joints may be used. In addition, it may be attached to a flat part such as an exterior material, a particle board, an iron plate in a sheet shape, or an exterior material,
The foamed fire-retardant composition may be applied to a particle board, an iron plate or the like and used.

The foamed fire-retardant composition of the present invention has a composition suitable for each part depending on the place where the molded article is to be constructed, and can be used in combination with various materials as necessary. For example, when joints to be applied are required to have other performances such as waterproofness and weather resistance in addition to fire resistance in the case where the foamed fire-resistant molded product is not sufficiently provided with the other performances, etc. It is effective to form a waterproof layer on this molded product. Although what forms this waterproof layer is not particularly limited, for example, commonly used sealing agents (for example, silicone-based sealing agents, modified silicone-based sealing agents, etc.),
Fixed watertight materials (for example, those made of ethylene propylene dimethyl rubber (also referred to as EPDM rubber)) and the like. It is more preferable to use one having flame retardancy.

[0046]

In the present invention, the above components (A), (B),
(C) and (D) are essential components to form a foamed fire-retardant composition, and a molded article of this composition is used as a foamed fire-retardant molded article.

The use of the two-component polyurethane resin composition as the component (A) accelerates the curing reaction of the foam-type fire-retardant composition, and reduces the volume shrinkage due to curing to keep the foam-type fire-retardant composition constant. It is easy to form into a shape. Therefore, as compared with the above-mentioned wet foam type fire-resistant paint, the construction is easy and the thickness is easily made uniform.

The heat-expandable graphite which is the component (B) expands about 100 times in volume when heated. The thermally expanded graphite layer blocks the flammable underground material and the like from burning and heat, thereby preventing the flammable underground material and the like from burning.
Even if a gap is formed due to cracking, shrinkage, vibration, etc. of the interior / exterior material due to heating, unlike the case of the foamed asbestos body, the heat-expandable graphite expands by heating to close the gap,
Prevent smoke, flame, gas, etc. from entering or leaving from gaps. In addition, the thermally expanded graphite layer absorbs the softened and liquefied polyurethane resin by heating and integrates with the resin between the layers, thereby preventing the polyurethane resin from flowing out and preventing the carbonized layer from falling off. I do. Therefore, the foamed fire-resistant molded article of the present invention has improved fire resistance as compared with the above-mentioned conventional foamed fire-resistant molded article, and can be used alone in general openings and joints or with a regular watertight material. Demonstrates high fire resistance even when used in combination.

The vermiculite powder, which is the component (c), expands 10 to 30 times in volume when heated to form a thermally expanded body having low thermal conductivity.

The process for forming the fire-resistant composite foam of the present invention is considered as follows. That is, the heat-expandable graphite expands first by heating, and at the same time, the polyurethane resin composition of the component (A) is dehydrated and carbonized by ammonium polyphosphate, and entangled and carbonized by the heat-expandable graphite expanded by heating. Due to the solidifying action of the resin component, a foam without scattering and falling off is formed. When the heating temperature is further increased, the vermiculite powder expands in the foam to form thermally expandable graphite, and the vermiculite fixed and expanded in the resin component carbonized and fixed, and the vermiculite expanded in this manner. Forms a foamed composite with expanded thermal expansive graphite and a carbonized and immobilized resin component.This foamed composite prevents fire, smoke, gas, etc. Can be prevented.

When the vermiculite powder is used without being used together with the heat-expandable graphite, the foaming temperature of the vermiculite is as high as 400 ° C. or more according to the fire prevention mechanism of this system in which the foam exhibits a fire-preventive performance. In addition, the carbide of the polyurethane resin composition of the component (A) which has been dehydrated and carbonized and fixed at a low temperature is destroyed by the foaming of vermiculite. The scattering and falling off of the foam cannot be prevented.

The compounding ratio with the heat-expandable graphite can be compounded at any ratio. If the ratio of vermiculite is increased, a composite foam with lower thermal conductivity can be made,
On the other hand, the composite foam easily scatters and falls off.

Accordingly, a preferable compounding ratio is in the range of 50 to 400 parts of vermiculite with respect to 100 parts of the heat-expandable graphite.

The component (D), ammonium polyphosphate, acts as a dehydration catalyst. That is, in a heating environment, the organic matter is dehydrated and carbonized to form a fire-resistant carbonized layer, and also itself forms a fire-resistant inorganic phosphoric acid film. In addition, it has a function as a foaming agent that decomposes upon heating to generate ammonia gas and expands organic substances. However, in the present invention, ammonium polyphosphate is used in a state where the powder is completely or almost completely covered with a resin and microencapsulated. Then
For example, the solubility of ammonium polyphosphate in water at 20 ° C. is at most 0.3% by weight or less, usually 0.1% by weight or less.
By weight or less, sufficient water resistance as a molded product is secured, and high fire protection performance is maintained for a long period of time.

[0055]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. However, the present invention is not limited to the following Examples. In the following Examples and Comparative Examples, "parts" represents "parts by weight".

Example 1 Polyether polyol [Average molecular weight: 3000, OH
V (hydroxyl value) @ 56] 32.9 parts of heat-expandable graphite (manufactured by Chuo Chemical Co., Ltd., trade name "heat-expandable graphite CA-6")
0 ") 19.8 parts, vermiculite powder 24.4 parts and microencapsulated ammonium polyphosphate 19.
4 parts were added and mixed with stirring. Here, the microencapsulated ammonium polyphosphate is obtained by coating ammonium polyphosphate having the same composition as ammonium polyphosphate (trade name "Sumisafe P") manufactured by Sumitomo Chemical Co., Ltd. with melamine formaldehyde resin by a liquid curing method. Having a particle diameter of 0.1 to 100 μm and a solubility in water at 20 ° C. of 0.1.
It was 3% by weight or less.

Further, an organic lead catalyst (lead octylate) 2.
0 parts were added and stirred for 5 minutes. Next, a TDI-based prepolymer [polyether polyol and TD
Urethane prepolymer with I (tolylene diisocyanate), average molecular weight 1500, NCO% ≒ 2.9%] 5
7.0 parts were added, and the mixture was stirred and mixed for 2 minutes to obtain a foam-type fire protection composition. Table 1 shows the amounts of the components used in the foam type fire protection composition.

This composition was poured into a polyethylene container of 5 mm × 100 mm × 150 mm, left for one day, taken out, and cut into 5 mm × 10 mm × 140 mm to obtain a foam-type fire-resistant molded article.

Examples 2 to 3 In the same manner as in Example 1, except that the composition of the foam type fire-retardant composition was as shown in Table 1,
The foamed fireproof composition having the same shape and size as in Example 1 was obtained by producing the foamed fireproof composition and molding the composition.

Comparative Example 1 Polyether polyol [Average molecular weight: 3000, OH
V (hydroxyl value) @ 56] 36.7 parts of heat-expandable graphite (manufactured by Chuo Chemical Co., Ltd., trade name "heat-expandable graphite CA-6")
0 ") 23.5 parts and microencapsulated ammonium polyphosphate 30.8 parts were added and mixed by stirring. Here, the microencapsulated ammonium polyphosphate is obtained by coating ammonium polyphosphate having the same composition as ammonium polyphosphate (trade name "Sumisafe P") manufactured by Sumitomo Chemical Co., Ltd. with melamine formaldehyde resin by a liquid curing method. Is obtained by
The particle size was 0.1 to 100 μm, and the solubility in water at 20 ° C. was 0.3% by weight or less.

Further, an organic lead catalyst (lead octylate) 2.
0 parts were added and stirred for 5 minutes. Next, a TDI-based prepolymer [polyether polyol and TD
Urethane prepolymer with I (tolylene diisocyanate), average molecular weight 1500, NCO% ≒ 2.9%] 6
By adding 3.3 parts and stirring and mixing for 2 minutes, a foam type fire protection composition was obtained. Table 1 shows the amounts of the components used in the foam type fire protection composition.

This composition was poured into a polyethylene container of 5 mm × 100 mm × 150 mm, left for 1 day, taken out, and cut into 5 mm × 10 mm × 140 mm to obtain a foamed fire-resistant molded article.

Comparative Example 2 The procedure of Comparative Example 1 was repeated, except that the composition of the foamed fire-resistant composition was as shown in Table 1,
The foamed fireproof composition having the same shape and size as Comparative Example 1 was obtained by producing the foamed fireproof composition and molding the composition.

[0064]

[Table 1] The foamed fire-resistant molded articles obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were subjected to the following fire resistance test and water resistance test. Table 2 shows the results.

Fire Resistance Test (1) Measurement of Backside Temperature As shown in FIG.
mm × 148mm × 12mm) 1 and fly ash slag cement (= NFC, non-asbestos) exterior material (65mm ×
140mm x 12mm) 2 are arranged side by side and stuck together, width 10
The joint part 3 of mm was produced. The foamed fire-resistant molded article 4 was inserted into the joint 3 to obtain a test body. After that, as shown in FIG.
And the back surface temperature after 30 minutes was measured with a thermocouple. In the figure, 5 is a gas burner, 6 is a thermocouple insertion hole,
7 is a thermocouple.

(2) Measurement of Foaming Ratio The foamed fire-resistant molded article was placed on a slate plate,
The state of foaming when foaming was performed by applying a flame of 0 ° C. was confirmed, and evaluated by the volume expansion factor.

(3) Strength of Carbide The test piece after the measurement of the expansion ratio was dropped freely from a height of 50 cm, and the appearance of the test piece was evaluated. The sample was evaluated as 〇 if there was no abnormality in appearance, △ if some abnormality was observed, and X if the test piece was broken.

(4) Dropping of carbonized layer Observed when measuring the back surface temperature. The case where the carbonized layer did not fall was evaluated as 〇, the case where there was no loss but some scattering was observed, and the case where a part of the carbonized layer was observed was evaluated as X.

(5) Outflow of Resin The foamed fire-resistant molded product was cut into 5 mm × 10 mm × 20 mm, placed on a slate plate, and heated with a gas burner. that time,
If there is no resin outflow, then 〇; if there is outflow, X
Was evaluated.

Water resistance test The foamed fire-resistant molded article was either immersed in tap water at 40 ° C. for one month or ii) naturally exposed for three months. The state when a 900 ° C. flame was applied after each of the tests i) and ii), and the condition of 90% without performing the tests of i) and ii).
Compared to the state when a flame of 0 ° C. was applied, the case where the foaming performance did not change was evaluated as ○, and the case where the foaming performance decreased was evaluated as X.

Comprehensive Evaluation From the results of the fire resistance test and the water resistance test of the foamed fire-resistant molded articles obtained in Examples 1 to 3 and Comparative Examples 1 and 2, the performance as a foamed fire-resistant molded article was comprehensively evaluated. Was evaluated. It is particularly excellent as a foam-type fire-resistant molded article, and can be used when a high level of fire protection is required. When it was not possible to respond to the case where X was required, X was evaluated.

[0072]

[Table 2]

[0073]

The foamed fire-resistant molded article according to the present invention comprises:
Inserted into joints, gaps, holes, etc. of the inner and outer walls of general buildings,
When exposed to flame, the effect of expanding and foaming to form a carbonized layer to prevent combustible materials such as wood can be greater than using thermally expandable graphite alone, and there is no However, since the carbonized layer formed by expansion and foaming by heating closes the gap, it is possible to prevent smoke, flame, gas generated by combustion or the like from entering or flowing out from the gap.

Since the foamed fire-resistant molded article can be formed into a molded article having a predetermined shape, it is easier to apply and has a uniform thickness as compared with the wet foamed fire-resistant paint described above.

The foamed fire-resistant molded article of the present invention has higher water resistance than the above-mentioned conventional foamed fire-resistant molded article.
Can be used alone for general openings and joints because it can maintain high fire protection over a long period of time and does not cause softened or liquefied polyurethane resin to flow out or the carbonized layer to fall off when heated. High fire resistance can be exhibited even when used in combination with a regular water honey material.

Further, due to its high fire-prevention performance, it may be adhered in a sheet form to a flat part such as an exterior material, particle board, iron plate, steel material, or the like, or may be applied to the exterior material, particle board, iron plate, steel material, etc. You can also paint and use things.

By molding the foam type fire-retardant composition according to the present invention, the above-mentioned excellent foam type fire-retardant molded article can be obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a test piece subjected to a fire protection test.

FIG. 2 is an explanatory diagram of a fire prevention test using the above test specimen.

Claims (2)

[Claims] 1. A foamed fire-resistant molded article obtained by molding a foamed fire-resistant composition comprising the following components (A), (B), (C) and (D) as essential components. (A) A polyurethane resin composition comprising a first liquid containing a polyol and a second liquid containing a polyisocyanate. (B) thermally expandable graphite. (C) Vermiculite powder. (D) Microcapsules obtained by coating ammonium polyphosphate powder with a resin. 2. A foam type fire-retardant composition comprising the following components (A), (B), (C) and (D) as essential components. (A) a polyurethane resin composition comprising a first liquid containing a polyol and a second liquid containing a polyisocyanate; (B) thermally expandable graphite; (C) a vermiculite powder; and (D) an ammonium polyphosphate powder. A microcapsule coated with a microcapsule.