JP2012007109A - Powder for fire resistances and foaming type fire prevention composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel material for making a urethane material nonflammable.SOLUTION: A powder for fire resistance includes (A) a thermal expansion nature graphite, (B) a microcapsule in which an ammonium polyphosphate powder is covered with a resin, and (C) an aluminum hydroxide powder, a melamine resin powder, and a pentaerythritol powder. The powder is blended with a composition for forming a polyurethane resin consisting of a first liquid containing polyol, and a second liquid containing polyisocyanate, and thereby the polyurethane resin can be made to be nonflammable.

Description

  The present invention relates to a novel fire-resistant powder and a foam-type fire-proof composition containing the same, and in particular, a novel fire-resistant powder having a light weight and sufficient fire resistance and used in combination with a urethane material, and the same The present invention relates to a foam-type fireproof composition containing

Urethane foam is widely used as a material for heat insulation and soundproofing. In addition, the material properties of urethane foam materials are wide, and various developments have been made from the viewpoints of foaming methods, expansion ratios, and the like.
For example, as a fire extinguishing method, a method of mixing a polyol material / isocyanate material and causing a curing reaction in a few seconds is a known technique.
The splendid heat insulation of polyurethane has been demonstrated in various fields, and it is used in buildings, factories, warehouses, etc., and is expected to expand in the future.
However, commercially available urethane materials cannot be stopped once a fire occurs because of their manufacturing characteristics. Therefore, a large amount of aluminum hydroxide or the like is mixed (30 to 50%), and nonflammability is measured. However, with these large amounts of flame retardant materials, the viscosity increased, and as expected, no foam expansion occurred, leaving a problem in manufacturing.
In addition, aluminum hydroxide can only produce the effect of lowering the temperature by generating water vapor for a certain period of time at high temperatures.
Furthermore, most of the expanded graphite was scattered and no effect was obtained.

In order to solve these problems, for example, the following technical proposals have been made.
Patent Document 1 relates to a hybrid fireproof coating structure that can significantly improve fireproof performance, and here, a composition of a foamable fireproof paint in which a resin binding material + ammonium phosphate + aluminum hydroxide + melamine resin + expanded graphite is mixed. Examples are described, and polyurethane resins are also described as examples of resin binders.
Patent Document 2 discloses (A) a polyurethane resin composition comprising a first liquid containing polyol and a second liquid containing polyisocyanate, (B) thermally expandable graphite, and (C) ammonium polyphosphate. There is described a foam-type fireproof composition comprising microcapsules in which powder is coated with a resin as an essential component.
However, even by these methods, the incombustibility of the urethane material is not yet sufficient, and improvement has been demanded.

Japanese Patent Laid-Open No. 11-222958 Japanese Patent Laid-Open No. 7-70428

  As described above, a material suitable for making a urethane material incombustible has not been found so far. Therefore, it is an object of the present invention to provide a novel material for making a urethane material incombustible.

  As a result of intensive studies for solving the above-mentioned problems, the present inventor further includes expansive graphite and ammonium polyphosphate powder coated with resin, and further contains aluminum hydroxide powder, melamine resin powder and pentaerythritol powder. It was found that the urethane material can be made non-combustible by using a mixture of the mixed powders, and the present invention has been completed.

That is, the present invention relates to the following fireproof powder and a foam-type fireproof composition containing the same.
(1) A refractory powder comprising the following components (A), (B) and (C).
(A) Thermally expandable graphite (B) Microcapsules formed by coating ammonium polyphosphate powder with resin (C) Aluminum hydroxide powder, melamine compound powder and pentaerythritol powder (2) The following components (A) and (B) (C) and (D) are contained, The foaming type fireproof composition characterized by the above-mentioned.
(A) Thermally expandable graphite (B) Microcapsules in which ammonium polyphosphate powder is coated with resin (C) Aluminum hydroxide powder, melamine compound powder and pentaerythritol powder (D) First liquid containing polyol and polyisocyanate A composition for forming a polyurethane resin comprising a second liquid containing

The fire-resistant powder of the present invention achieves incombustibility particularly by blending it with a polyurethane resin-forming composition, and the polyurethane resin blended with the fire-resistant powder of the present invention has sufficient fire resistance and light weight. In addition to having long-term durability performance and reliability, it is possible to apply a fireproof coating in a short time and to simplify the construction method.
Further, it is possible to provide a hybrid refractory material and a refractory coating method thereof.
Compared to products currently on the market, it is lightweight, durable and water-resistant, and can maintain high fire resistance and fireproof performance for a long period of time. It is possible to easily produce a foam-type fireproof molded product that does not fall off.

(1) Fire-resistant powder The fire-resistant powder of the present invention is preferable as a powder for making a polyurethane resin incombustible. However, in addition to a polyurethane resin, it can be blended with a resin used for a building material or the like. .
The refractory powder of the present invention contains the following components (A), (B) and (C).
(A) Thermally expandable graphite (B) Microcapsules formed by coating ammonium polyphosphate powder with resin (C) Aluminum hydroxide powder, melamine compound powder and pentaerythritol powder The fireproof powder of the present invention comprises the above components In addition, you may mix | blend the well-known material used for incombustibility.
The blending ratio of the components (A), (B) and (C) is not particularly limited as long as it can be used as a refractory powder. Usually, the component (B) is used with respect to 100 parts by weight of the component (A). Is 50 to 200 parts by weight, and component (C) is 50 to 200 parts by weight.
Below, the said component (A), (B) and (C) is demonstrated.

(Ingredient (A))
The heat-expandable graphite used as the component (A) in the present invention is graphite having the property that when heated, the compound existing between the graphite layers is thermally decomposed to expand as a whole. There is no particular limitation on the above-mentioned compound that exists between the graphite layers and thermally decomposes. For example, graphite acidic sulfate, sodium graphite, potassium graphite, halogenated graphite, graphite oxide, aluminum chloride graphitized, chloride Examples include ferric graphite. A well-known thing can be used for a thermally expansible graphite.
When the thermally expandable graphite is heated, the volume expands to about 100 times. The thermally expanded graphite layer prevents the combustible joint base material from burning by blocking the combustible joint base material from flame and heat. Moreover, since it expands by heating and closes the gap, smoke, flame, gas, etc. are prevented from entering or flowing out of the gap.

(Ingredient (B))
In the present invention, as the component (B), a microcapsule in which ammonium polyphosphate powder is coated with a resin is used.
Ammonium polyphosphate dehydrates and carbonizes organic matter in a heating environment to form a fireproof carbonized layer, and also forms a fireproof inorganic phosphate film. In addition, it also functions as a blowing agent that decomposes by heating to generate ammonia gas and expands organic matter.
The method for microencapsulating ammonium polyphosphate is not particularly limited. For example, interfacial polymerization method, in situ polymerization method, liquid curing method, phase separation method, liquid drying method, melt dispersion Known methods such as a 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 film that is less permeable to water and excellent in water resistance. For example, vinyl chloride resin, vinylidene chloride resin, epoxy resin, urethane resin, Examples thereof include acrylic resins, phenol resins, vinyl acetate resins, cellulose resins, alkyd resins, shellac resins, diallyl phthalate resins, polyamide resins, melamine resins, urea resins, and the like. These may use only 1 type and may use 2 or more types together.

The particle diameter of the ammonium polyphosphate microcapsules is not particularly limited, but is preferably 100 μm or less.
Ammonium polyphosphate is represented by (NH ₄ ) _{n + 2} P _n O _{3n + 1} (wherein n is an integer of 2 or more). Such an ammonium polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate (trade name “Sumisafe P”) manufactured by Sumitomo Chemical Co., Ltd.

(Ingredient (C))
In the present invention, as the component (C), aluminum hydroxide powder, melamine compound powder and pentaerythritol powder are used, but each may be separately blended with the other components (A) and (B) or in advance. You may mix | blend with a component (A) and (B) after preparing as a mixture. When mixing, it can mix by a well-known conventional method.
The aluminum hydroxide powder is not particularly limited, but preferably has an average secondary particle diameter of 0.4 to 4 μm measured by the microtrack method and has little or no secondary aggregation.
The aluminum hydroxide can be surface-treated with a surface treatment agent of a higher fatty acid and a coupling agent (silane-based, titanate-based or aluminum-based) as necessary. As this surface treatment method, a method of adding and mixing a surface treatment agent of 10% by weight or less, preferably 5% by weight or less with respect to aluminum hydroxide can be applied.
Moreover, in order to provide acid resistance to aluminum hydroxide, the surface can be treated with a silicon compound and / or a boron compound to form an acid-resistant film, or aluminum hydroxide treated with a surface treatment agent as necessary can be used.

The melamine compound powder includes melamine, derivatives thereof, and resins thereof. Examples of melamine derivatives include melam, melem, melon, benzoguanamine, melamine sulfate, melamine cyanurate, melamine polyphosphate, and the like.
The melamine resin is a condensation product that can be obtained by a known method by reacting aldehyde, particularly formaldehyde, with melamine or a derivative thereof. The melamine resin may be fully or partially etherified with an alkanol containing 1 to 6 carbon atoms.
The pentaerythritol powder is a polyhydric alcohol and includes a condensate. Examples thereof include monopentaerythritol, dipentaerythritol, tripentaerythritol, and polypentaerythritol.
In the component (C), the mixing ratio of the aluminum hydroxide powder, the melamine compound powder and the pentaerythritol powder is not particularly limited, but is usually used in a ratio of about 1: about 2: about 3.

(2) Foam-type fireproof composition The fire-resistant powder containing the above components (A), (B) and (C) is blended with the component (D) described below to obtain a foam-type fireproof composition. be able to.
(Component (D))
In the present invention, as the component (D), a polyurethane resin forming composition comprising a first liquid containing a polyol and a second liquid containing a polyisocyanate is used.

The polyol contained in the first liquid can be used by arbitrarily selecting one or more kinds from those conventionally used as a polyol component of a room temperature curing type two-component polyurethane resin composition. Such a polyol is not particularly limited, but for example, a polyester polyol derived from an organic dicarboxylic acid and a polyhydric alcohol, a polyester polyol derived from a lactone, a castor oil, a castor oil-modified polyol, a polyether polyol, an epoxy-modified Among polyols, silicon-based polyols, polyether polyester polyols having both the polyester units and the polyether units, (meth) acrylic polyols derived from (meth) acrylic acid, and the like, molecular weights of 300 to 3000, hydroxyl values of 50 to 350 or the like. These polyols may use only 1 type and may use 2 or more types together.
The organic dicarboxylic acid is not particularly limited, and for example, phthalic acid, adipic acid, dimerized linolenic acid, maleic acid and the like are used.
The polyhydric alcohol is not particularly limited, and 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, and examples thereof include polybutyrolactone and polyvalerolactone.
The polyether polyol is not particularly limited. For example, poly (oxypropylene) glycol, poly (oxypropylene) poly (oxyethylene) glycol, poly (oxybutylene) glycol, poly (oxytetramethylene) glycol, poly (oxygen) And oxypropylene) triol, poly (oxypropylene) poly (oxyethylene) triol, poly (oxypropylene) poly (oxyethylene) poly (oxypropylene) triol, and the like.

  In the first liquid, the polyol and various cross-linking agents can be used in combination to increase the reaction rate or increase the mechanical strength of the molded product. 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'-methylenedianiline, 2,2-bis (p-aminophenyl) propane, 3,3'-dichloro-4,4'-diamino And aromatic amines such as diphenylmethane and 1,2-bis (2-aminophenylthio) ethane.

  As the polyisocyanate contained in the second liquid, there can be used polyisocyanate used in ordinary polyurethane resin compositions, and there is no particular limitation. For example, hexamethylene diisocyanate, octamethylene diisocyanate, tolylene diene. Examples include isocyanate (also referred to as TDI), 1,5-naphthalene diisocyanate, diphenylmethane-4,4′-diisocyanate, biphenyl-4,4′-diisocyanate, 2,2′-diphenylpropylene-p, p′-diisocyanate, and the like. .

The blending ratio of the first liquid and the second liquid is not particularly limited, and is usually a polyol (for example, polyester polyol, polyether polyol) and a crosslinking agent (for example, an amine component and / or diol) in the first liquid. Component) is selected so that the total number of moles of active hydrogen and the number of moles of isocyanate groups of the polyisocyanate (for example, diisocyanate component) in the second liquid are approximately equal, but either one is excessive if desired It can also be used.
The blending ratio of the component (D) and the components (A), (B), and (C) is not particularly limited as long as it can be used as a foaming type fireproof composition, but is usually based on 100 parts by weight of the component (D). The total of components (A), (B) and (C) is 10 to 150 parts by weight.

  In addition to the components (A) to (D), the foam-type fireproof composition of the present invention contains 1 auxiliary component commonly used in ordinary two-component room temperature curable polyurethane resin compositions as necessary. Species or two or more species can be contained. Such auxiliary components (optional components) are not particularly limited, but include, for example, extender pigments such as silica, talc, and barium sulfate; aluminum hydroxide, magnesium hydroxide, kaolin, calcium hydrogen phosphate, hectorite, sulfurous acid Sodium heptahydrate, ettringite, alunite, water talc (blues), diaspore, gibbs (hydrhydrite), kaolinite, montmorillonite, serpentine, slaked lime, gypsum, zinc phosphate, etc. , Inorganic fillers that generate water vapor upon heating; colored pigments such as iron oxide yellow, light yellow 50, iron oxide brown, iron oxide red, light blue 100, chromium oxide green GN; catalysts such as organic tin compounds and organic lead compounds Dioctyl phthalate (with DOP Organic plasticizers such as referred to); triphenyl phosphate, tricresyl phosphate, tris (chloroethyl) phosphate, various phosphorus-based plasticizers such as cresyl diphenyl phosphate; dehydrating agents.

Although the foaming type fireproof composition of the present invention is not particularly limited, for example, it is mixed into a desired shape after being mixed with a bladed stirrer or the like. The forming method and conditions are not particularly limited. For example, the forming method and conditions may be cast into a sheet or film by casting into a container having a predetermined width, thickness, and length, or may be formed into a predetermined shape. What is necessary is just to inject | pour and shape | mold to a metal mold | die, or to carry out extrusion casting using the die | dye designed by the predetermined | prescribed width | variety and thickness.
Further, the foam-type fireproof molded article of the present invention may be inserted, for example, as it is in a joint portion or after being cut into a predetermined width and / or length.

  In addition, the application location of the foam-type fireproof molded product of the present invention is not particularly limited as long as it is a joint portion or the like that requires fireproofing properties. For example, the outer wall, ceiling, roof, floor, etc. of a general house It can be arbitrarily applied to joints such as exterior surfaces in various buildings. Alternatively, it may be an opening other than the joint. As the foam-type fireproof composition of the present invention, a composition suitable for each is selected depending on the place where the molded product is applied, and can be used in combination with various materials as necessary.

Specific examples and comparative examples of the present invention are shown below, but the present invention is not limited to the following examples.
1. Production of refractory powder [Example 1]
10-20 grams of thermally expandable graphite (commercial product) and 10-20 grams of microcapsules coated with ammonium polyphosphate powder with melamine resin, aluminum hydroxide powder (commercial product), melamine resin powder (commercial product) ) And pentaerythritol powder (commercially available product) in a ratio of 1: 2: 3 previously mixed and dispersed uniformly in an amount of 20 to 30 grams were added, and stirred and mixed to uniformly disperse to produce a refractory powder. .

2. Production of foam-type fireproofing composition [Example 2]
Polyol isocyanate (commercial product) is added as a first liquid for forming polyurethane resin and polyisocyanate (commercial product) as a second liquid for forming polyurethane resin to the fireproof powder prepared as described above, and shown in Table 1. A foaming fireproof composition was obtained by stirring and mixing at a ratio.

This composition was poured into a molding container, allowed to stand for a certain period of time, and then taken out to obtain a 900 mm × 1200 mm × 40 mm refractory urethane plate.
(Fire resistance test 1)
The urethane plates (Examples 2-1 to 2-6) thus obtained were replaced with the veneer plate for the urethane plates of Examples 2-1 and 2-2, and the aluminum plate for the urethane plates of Examples 2-3 and 2-4. And the urethane plates of Examples 2-5 and 2-6 were bonded to the steel plates, respectively, and a flame at 1100 ° C. was applied with a gas burner, and the plates after 20 minutes were observed. The results are shown in Table 2.

(Fire resistance test 2)
A fire-resistant urethane plate (900 mm x 1200 mm x 40 mm) selected in fire resistance test 1 was prepared by attaching it to a 40 mm thick plywood plate, aluminum plate, and steel plate. The fireproof performance test was conducted using the inside. In the test, the temperature of the furnace was raised from room temperature to nearly 1000 ° C. over 1 hour, and during that time, the surface temperature of the refractory plate used as the lid (temperature outside the furnace) was measured. The measurement results are shown in Tables 3-5.

(Fire resistance test 3)
Three kinds of refractory urethane materials selected in the above tests 1 and 2 are filled into a through portion having a diameter of about 20 to 50 mm provided in a concrete block having a length: about 200 mm × width: about 100 mm × thickness: about 70 mm, A flame at 1100 ° C. was applied with a gas burner, and changes in the concrete block were observed.
Similarly, as a comparative example, a general sealing material (commercial product) and another fireproof sealing material (commercial product) were also tested. The results are shown in Table 6.

Claims (4)

A fireproof powder comprising the following components (A), (B) and (C).
(A) Thermally expandable graphite (B) Microcapsules in which ammonium polyphosphate powder is coated with a resin (C) Aluminum hydroxide powder, melamine compound powder and pentaerythritol powder 2. The refractory powder according to claim 1, wherein the component (B) is 50 to 200 parts by weight and the component (C) is 50 to 200 parts by weight with respect to 100 parts by weight of the component (A). A foaming fireproofing composition comprising the following components (A), (B), (C) and (D).
(A) Thermally expandable graphite (B) Microcapsules formed by coating ammonium polyphosphate powder with resin (C) Aluminum hydroxide powder, melamine compound powder and pentaerythritol powder (D) First liquid containing polyol and polyisocyanate A composition for forming a polyurethane resin comprising a second liquid containing The foam-type fireproof composition according to claim 3, wherein the total amount of the components (A), (B) and (C) is 10 to 150 parts by weight with respect to 100 parts by weight of the component (D).