JPH03149283A - Fireproof molded foam and formable fireproofing composition - Google Patents

Abstract

PURPOSE:To realize the formation of a fireproof molded foam capable of preventing the penetration of smoke, flame, etc., even when a gap occurs due to a shrinkage in, e.g. an interior or exterior material, vibration, etc., by using as the essential constituents a two-pack polyurethane resin composition, ammonium polyphosphate, a polyhydric alcohol, and a compound containing amino groups. CONSTITUTION:A fireproof molded foam is formed by molding a foamable fireproofing composition comprising as the essential constituents a polyurethane resin composition (A) consisting of a first liquid containing a polyol and a second liquid containing a polyisocyanate; ammonium polyphosphate (B); a polyhydric alcohol (C); and a compound (D) containing amino groups. Although the proportions of A, B, C, and D are not particularly limited, it is desirable that the amounts of B, C and D be respectively 35-70 pts.wt., 5-30 pts.wt., and 5-30 pts.wt. based on 100 pts.wt. A.

Description

[Detailed Description of the Invention] [Industrial Application Field] This invention forms a strong foamed carbonized membrane when inserted into joints, gaps, holes, etc. of the inner and outer walls of general buildings and exposed to flame. This invention relates to a foamed fire-retardant molded product that is formed into a certain shape and has the function of preventing combustible materials such as wood from burning and preventing smoke, flames, gases generated by combustion, etc. from leaking out to the outside.

Furthermore, the present invention relates to a foamed fireproof composition for obtaining such a foamed fireproof molded article.

[Conventional technology]

Openings made for piping, etc. inside general buildings are sealed with mortar or sealant after the piping is installed. Furthermore, inorganic materials such as mortar, gypsum, and water glass are used to seal the joints of fire-resistant members used for interior panels, partitions, etc. for the purpose of fire resistance and sound insulation.

These inorganic materials and sealants are widely used because they are easy to use.

However, inorganic materials inevitably shrink during the curing process, and because they are extremely hard after curing, they can crack or break at the interface within a short period of time due to microtremors that cannot be avoided in general buildings. Due to breakage, etc., gaps are likely to occur (and do not necessarily show the original function.In addition, in high-rise buildings that emphasize interlayer displacement and followability, the joints are movable to absorb displacement. Since a cured product of the above-mentioned inorganic material cannot be used, a complicated structure is adopted to ensure fire resistance and sound insulation.

Moreover, most sealants are flammable, and at the same time, combustion residues have little effect on fire protection of openings.

For example, in the case of movable joints in exterior wall panels, a foamed asbestos material cut to fit the width of the joint (for example, "Lithoflex" manufactured by Nichias Corporation) is compressed and inserted into the bottom of the joint. From above, caulking is applied to make the movable joints waterproof and fireproof.

The foamed asbestos material does not deform at all when heated, so when it is cut to the joint width and inserted into the joint, the exterior wall panel dehydrates and shrinks due to heating, and the joint becomes 2 to 2.
In order to prevent the occurrence of gaps, which are difficult to completely prevent flames from entering when opened three times,
It was proposed to inject a wet-foam fire-retardant paint into the movable joints of exterior wall panels, and then inject a sealant over it to make it waterproof and airtight.

[Problem to be solved by the invention]

Although the above-mentioned wet foaming type fireproofing paint has high fireproofing performance, there are problems in that its own water resistance remains unsatisfactory and the technique for injecting it to a predetermined thickness is difficult. That is, when the wet-foaming fire protection paint is injected into the joint while being discharged from the nozzle, the nozzle gets stuck and does not move smoothly, making the injection amount uneven. If the wall thickness of the fire protection paint is not uniform, the thickness of the sealant injected over it will be uneven, resulting in poor watertightness or waterproofing.

Therefore, the present invention can prevent smoke, flames, etc. from entering even if gaps are created due to shrinkage or vibration of interior and exterior materials, etc., and is easier to apply than the above-mentioned wet foaming fire prevention paint. The first objective is to provide a foamed fire-retardant molded product that can be easily made to have a uniform thickness. Furthermore, a second object of the present invention is to provide a foamed fireproof composition for obtaining such a foamed fireproof molded article.

[Means to solve the problem]

The inventors have solved the drawbacks of conventional combinations of sealants and foamed asbestos, inorganic joint materials, and combinations of sealants and wet foam paints.
It expands and foams more than twice as much to form a carbonized layer that insulates combustible joint materials from flames, and also suppresses heat conduction to provide fireproofing properties to combustible joint materials. In order to provide the effect of preventing smoke and flame from flowing out,
I have done extensive research.

As a result, it was found that any material satisfying the following characteristics (a) to (d) is sufficient.

(8) In order to prevent smoke, flame, gases generated by combustion, etc. from entering through gaps created by cracks, contraction, etc., fill up the gaps by forming a carbonized layer that expands and/or foams through heating. -) The carbonized layer formed by expansion and/or foaming due to heating burns.
＜A structure that easily blocks heat.

(C)) Easy to apply with uniform thickness at joints, etc.

(d) If the gap is closed by expansion and foaming as described above, priority should be given to creating a uniform thickness over not creating a gap during construction.

In order to satisfy the above (a) and (false), it is sufficient to use a foamable organic resin composition that expands and foams when heated to form a carbonized layer. It was found that it is better to use the same resin composition as a molded product rather than as a wet paint.

As a result of studying organic resin compositions that satisfy the above (δ) to (d), the present invention was achieved.

Therefore, in order to solve the first problem, the present invention provides a foamed fireproofing composition formed by molding a foamed fireproofing composition containing the following components (A), (B), 0 and (A) as essential components. The first gist is plastic molded products.

(A) A polyurethane resin composition consisting of a first liquid containing a polyol and a second liquid containing a polyisocyanate.

(D) Ammonium polyphosphate.

(C) Polyhydric alcohol.

(D) Amine group-containing compound.

Moreover, in order to solve the above second problem, the present invention has the following features:
The second gist is a foamed fire protection composition containing the following components (A), (B), 0 and (2) as essential components.

(A) A polyurethane resin composition consisting of a first liquid containing a polyol and a second liquid containing a polyisocyanate.

(B) Ammonium polyphosphate.

0 Polyhydric alcohol.

(B) Amine group-containing compound.

The component (A) is a polyurethane resin composition consisting of a first liquid containing a polyol and a second liquid containing a polyisocyanate. The use of such a two-component polyurethane resin composition has the advantage that the curing reaction is quick, the volume shrinks little due to curing, and it is easy to mold into a fixed shape.

Since this polyurethane resin composition is two-component, it is often a room temperature curing type, but is not limited to a room temperature curing type. When using a room temperature curable polyurethane resin composition,
It has the advantage of not being molded at low temperatures (for example, 110° C. or lower).

The first liquid can be arbitrarily selected from those conventionally used as polyol components of two-component room-temperature curable polyurethane resin compositions to have a tSt or more.

Examples of such polyols include 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 polyols, and silicone polyols. , a polyester polyester polyol containing both a polyester unit and a polyether unit, a (meth)acrylic polyol derived from (meth)acrylic acid, etc., with a molecular weight of 300 to 3000 and a hydroxyl value of 50.
~350 can be mentioned. These polyols may be used alone or in combination of two or more. The organic dicarboxylic acids include phthalic acid,
Achinic acid, dimerized lyluic acid, maleic acid, etc. are used, and the polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylolpropane, hexanetriol, glycerin, trimethylolethane, pentaerythritol, etc. used. Polyester polyols derived from lactones include polybutyrolactone, polyvalerolactone, and the like. Examples of polyether polyols include poly(oxypropylene) glycol, poly(oxypropylene) poly(oxyethylene) glycol, poly(oxybutylene) glycol, poly(oxytetramethylene) glycol, poly(oxypropylene) triol, and poly(oxypropylene) glycol. propylene) poly (oxyethylene) triol, poly
Examples include (oxypropylene) poly(oxyethylene) poly(oxypropylene) triol.

In the first liquid, the polyol and various crosslinking agents can be used in combination to speed up the reaction rate and increase the mechanical strength of the molded product. Examples of crosslinking agents used in combination include aliphatic diols such as ethylene glycol, propylene glycol, butylene gelicol, pentanediol, diethylene glycol, and dipropylene glycol; aliphatic diols such as ethylene diamine, propylene diamine, butylene diamine, and pentamethylene diamine; Diamines, aniline, phenylene diamine, 4,4'-methylene dianiline, 2,2-bis(p-aminophenyl)propane, 3,3-dichloro-4,4-diaminophenylmethane, 1,2-bis( A-aminophenylthio)
Aromatic amines such as ethane are used.

Examples of the polyisocyanate in the second liquid include hexamethylene diisocyanate, octamethylene diisocyanate, tolylene diisocyanate, 1.5-
Naphthalene diisocyanate, diphenylmethane-4,
4'-diisocyanate, biphenyl-4,4'-diisocyanate, 2,2-diphenylpropylene-p, p
- Polyisocyanates used in common polyurethane resin coatings, such as diisocyanates, can be used.

The mixing ratio of the first liquid and the second liquid is usually determined based on the amount of active hydrogen in the polyol (e.g., polyester polyol, polyether polyol) and crosslinking agent (e.g., amine component and/or diol component) in the first liquid. The total number of moles is selected so that the number of moles of isocyanate groups in the polyisocyanate (for example, diisocyanate component) in the second liquid is approximately equal, but either one can be used in excess if desired.

The component (B) is ammonium polyphosphate. Ammonium polyphosphate is a dehydration catalyst that dehydrates and carbonizes organic substances in a heated environment to form a fireproof carbonized layer, and also forms a fireproof inorganic phosphoric acid film. Another function is that it decomposes when heated to generate ammonia gas, and also acts as a foaming agent that expands the organic matter that has been softened by heating.

The following two ammonium polyphosphates are used in this invention.
It is preferable that two conditions (1) and (2) are satisfied.

■ The dissolution rate in water at 20℃ is 5% by weight or less.Here, the dissolution rate in water at 20℃ is 1
This value was determined by measuring the dissolution rate after 10 g of ammonium polyphosphate was placed in 0.00 cc of water (A0° C.) and shaken for 30 volumes.

0 The decomposition temperature due to heating is 110°C or higher. Here, the decomposition temperature by heating is the temperature at which ammonium polyphosphate generates ammonia gas and decomposes by heating.

If the solubility of ammonium polyphosphate in water at 20° C. exceeds 5% by weight, the water resistance of the foamed fireproof molded article of the present invention may deteriorate. Further, when the decomposition temperature of ammonium polyphosphate by heating is less than 110°C,
Water adhering to ammonium polyphosphate, polyhydric alcohol, amine group-containing compounds, etc. cannot be completely removed, and foamed fire-retardant molded products can become bubbles due to hydrogen gas generated by the reaction between isocyphnate groups and water. If it contains a large amount, it may not exhibit sufficient fire protection performance and may have weak mechanical strength.

Various inorganic ammonium phosphate salts (for example, primary ammonium phosphate, secondary I77fit ammonium, There is also tertiary ammonium phosphate), but it may not satisfy the above conditions (1) and (2). Examples of ammonium polyphosphate satisfying the above conditions (1) and (2) include ammonium polyphosphate (trade name: SUMISAFE PMJ) manufactured by Sumitomo Chemical Industries, Ltd.

The amount of component (B) added is not particularly limited, but component (A)
100 parts by weight (hereinafter, "parts by weight" is simply referred to as "parts")
The ratio is preferably 35 to 70 parts. 3
If the amount is less than 5 parts, it may not be possible to effectively carbonize the entire organic substance, or sufficient foaming may not be expected. Further, if the amount exceeds 70 parts, the dehydration and carbonization effects may be too large to ensure sufficient expansion and foaming ratio.

The component (C) is a polyhydric alcohol. As the polyhydric alcohol, for example, one or more of mono-, di-, and tripentaerythritol is used. The foamed fireproof molded article of the present invention expands upon heating due to the addition of components, and is carbonized by a dehydration catalyst to form a desired foamed carbonized membrane. That is, component (C) is an indispensable component for foamed fire protection compositions.

The amount of the ingredient added is not particularly limited, but the amount of ingredient (A) 10
It is preferable to set it as the ratio of 5-30 parts with respect to 0 parts.

If the amount is less than 5 parts, expansion by heating may be insufficient. In addition, if it exceeds 30 parts, the above-mentioned components ( A) is a blowing agent. As blowing agents, nitrogen, carbon dioxide, ammonia,
Any device that generates gas such as water vapor or oxygen can be used as needed. Among these, amine group-containing compounds that generate large amounts of nitrogen gas and ammonia gas are most suitable as blowing agents for use in the present invention. Examples of the amine group-containing compound include melamine, dicyandiamide, azodicarbonamine, and urea, any of which can be used.

The amount of component (■) added is not particularly limited, but component (A) 10
It is preferable to set it as the ratio of 5-30 parts with respect to 0 parts.

If the amount is less than 5 parts, the effect as a foaming agent may become insufficient. Moreover, if it exceeds 30 parts, it may act as a combustion agent itself and may not exhibit sufficient fire prevention performance.

Note that components (B), (O, and (A) are all often mixed and dispersed in the first liquid, and due to this relationship, the amount of addition is naturally restricted. The mixing of colors) to (A) is not limited to this method.

The foamed fireproofing composition of this invention includes the above essential component (A).
- In addition to (A), if necessary, silica, talc, extender pigments such as barium sulfate, iron oxide yellow, light yellow 50, iron oxide brown,
Colorants such as Iron Oxide Red, Light Blue 100, and Chrome Oxide Green GN, pigments, catalysts such as organotin compounds and organolead compounds, dehydrating agents, and other auxiliaries commonly used in ordinary two-component cold-curing polyurethane resin paints. Components can be included. These components are contained in the first liquid, for example.

The foamed fire protection composition of the present invention is mixed using a bladed stirrer or the like, and is formed to a thickness equal to, for example, the depth of the groove in the joint section minus the thickness of the sealant injection. Its molding method/
Conditions include, for example, pouring into a container made to a predetermined width, thickness, and length to form a sheet or film, pouring into a mold to form a predetermined shape, or pouring into a container made to a predetermined width and thickness. It can be extruded and cast using a specially designed die. Thereby, a molded article with a uniform shape can be obtained.

When the foamed fireproof molded product is obtained in the form of a sheet or film, it may be cut to a predetermined width, or it may be cut to facilitate cutting to a predetermined width. Further, when obtained in the form of a tape or bar, it may be cut to a predetermined length, or may be cut to facilitate cutting to a predetermined length.

The foamed fire-retardant molded product is inserted into the joint as it is or after being cut to a predetermined width and/or length. It is easier to insert and has a more uniform thickness than injecting wet fire protection paint. The predetermined width and/or length here refers to, for example, - the width and/or length of the part into which the molded product is to be inserted, such as the width and/or length that matches the shape of the movable joint or opening; It is. Then, when a sealant is injected thereon, since the foamed fireproof molded product has a uniform thickness, the thickness of the sealant also becomes uniform.

The foamed fire-retardant molded product of the present invention can be applied to any joints that require fire-retardant properties, and is not particularly limited. Can be applied arbitrarily to joints on exterior surfaces of buildings. Alternatively, it may be an opening other than a joint.

Further, the foamed fireproofing composition of the present invention has a suitable composition depending on the place where the molded product is to be installed, and can be used in combination with various materials as necessary. For example, the joints to be applied are required to have waterproofness, weather resistance, etc. in addition to fire resistance, but if the foamed fire-retardant molded product does not have sufficient performance, It is useful to form a waterproof layer on top. Commonly used sealants (eg, silicone sealants, modified silicone sealants, etc.) can be used to form this waterproof layer. It is more preferable to use a flame retardant material.

[For production]

In this invention, by making the above-mentioned components (A) to (to) essential components, the foamed fire protection composition can be made into a molded product in a predetermined shape, and is easier to apply than conventional wet fire protection paints. Moreover, the thickness can be easily made uniform. In addition, compared to conventional foamed asbestos, it expands and foams when heated, so it can close gaps created during or after construction and prevent the entry of flames, smoke, gases generated by combustion, etc.

〔Example〕

Specific examples and comparative examples of the present invention are shown below, but the present invention is not limited to the following examples.

Example 1 - Polyester polyol heated to 110°C (average molecular weight -900, OHV (hydroxyl value) -160) 63.7
Ammonium polyphosphate [Product name [Sumisafe PM]]
J Sumitomo Chemical Co., Ltd.] 64.0 parts, dipentaerythritol 26.7 parts, and melamine 10.0 parts, and then heated at 110°C under reduced pressure of 0 to 5 ng for 3 to 5 hours. Stir to reduce moisture content to 500pp.
m or less. Then, 3,3'-dichloro-4,41
- Diaminodiphenylmethane (trade name manufactured by DuPont)
MOcAJ) 31 parts, MDA (4,4″-methylene dianiline) 0.6 parts, dehydrating agent (synthetic zeolite) 3.0 parts
and organotin catalyst [dibutyltin dilaurate (D
After adding 0.02 part of BTDL)) and continuing stirring under the same conditions for an additional 30 minutes, stirring was stopped and the mixture was cooled. This cooled material and the second liquid shown in Table 1 are mixed using a bladed stirrer (disper), poured into a stainless steel container made to a predetermined width, thickness, and length, and taken out the next day. It was molded into a plate shape, and cut into the following sizes: 10cm x 140cm, 10m+ x 50days, 10cm x 150cm to obtain molded products.

Examples 2 to 6 Molded products of the same size as Example 1 were obtained in the same manner as in Example 1, except that the formulations shown in Table 1 were used.

In addition, in Table 1, the epoxy modified polyol has an average molecular weight of 900 and OHV=250, and MOCA is
3. -Dichloro-4,4-diamino, diphenylmethane (trade name MOCAJ manufactured by DuPont), M
DA represents 4,41-methylene dianiline, MDI
represents 4,4'-diphenylmethane diisocyanate. The modified MDI is acid-modified MDI, and the MDI prepolymer has an average molecular weight of 1500.

Regarding each of the foamed fire protection compositions of the above Examples and Comparative Examples, the following fire protection test and water resistance test were conducted, and the results were summarized as
Shown in the table.

Juku Daifu Shun (1) Measuring the temperature on the back side As shown in Figure 1 (a), wood particles (1)
(14 B + nX 148 m
By arranging the sheets and pasting them together, a joint part 3 of @10 M was produced. At the same joint 3, a molded product (4 m x 1
0 crane x 140 garden) 4, and sealant ("Bana Home Sealant" manufactured by National Housing Industry Co., Ltd.) on top of it.
The sealant 5 was injected to a thickness of 8 m, and the same sealant 5 was dried indoors for 7 days. Thereafter, as shown in FIG. 1(b), a 900° C. flame was applied to five portions of the sealant in the joint portion 3 for 30 minutes, and the back surface temperature after 30 minutes was measured using a thermocouple. In the figure, 6 is a gas burner, 7 is a thermocouple insertion hole, and 8 is a thermocouple.

(A) Measurement of expansion ratio Molded product of foamed fire protection composition (4mm x 10cm x 50 irises)
was placed on a slate board and exposed to a flame at 900°C to cause foaming.The foaming state was confirmed and expressed as the volumetric expansion factor.

■Molded product of foamed fire protection composition (4mmX I QmX 1
50 cranes), i) due cycle test 500 hours, ii)
) 50 cycles of repeated heating and cooling tests were conducted.

After each test of i) and ii), the state when a flame of 900°C is applied, and the state when each test of i) and ii) is not performed.
A comparison was made with the state when a flame at 0° C. was applied, and an O indicates that there is no change in foaming performance, and an X indicates that the foaming performance has decreased.

Table 1 I 1 Thor 11111
11 Adult 1 Melamine 110.01 Fu0
111.711 Rho 4121.11 7.41 As shown in Table 1, each of the foamed fireproofing compositions of Examples has an extremely large foaming ratio of 10 times or more when heated, and the exterior material is dehydrated by heating. Even if the joint part expands 2 to 3 times larger due to shrinkage, the foamed carbonized film completely covers the gap and is highly effective in blocking the entry of flames, heat, etc. from the outside.

Furthermore, each of the foamed fireproofing compositions of Examples also has exceptionally high water resistance, ensuring long-term fireproofing performance.

Furthermore, the molded products of the foamed fireproofing compositions of the examples had a uniform thickness of 4 mm ± 0.1mm, and there was no unevenness in wall thickness like when wet foaming fireproofing paint was injected. There wasn't any.

The following fire resistance test was also conducted on the molded articles of the foamed fireproofing compositions of the examples. A test specimen IO having the structure and shape shown in FIGS. 2(a) and 2) was produced in the following manner. Wooden frame panel (A4mm x 64mm wood used) 14
A semi-non-combustible gypsum board 15 with a thickness of 12 m is attached to one side using a Stella pull fastener using vinyl acetate emulsion adhesive, and then a 65 m thick (8 kg/m)
glass wool 13 was inserted into the panel. A fiber-mixed fly ash slag cement board (thickness: 12 Wm) 12 was attached to the other side of the wooden frame panel 14 using screw force nails in combination with an elastic vinyl urethane adhesive. The molded product 4 of the foamed fireproofing composition of the example is inserted into the joint (width 10+■) 3 between the cement boards 12, and a sealant (sealant) 5 is placed on top of it.
was filled and dried in the same manner as when measuring the back surface temperature in the fire protection test. The type and amount of sealant used is modified silicone sealant ([Banahome Sealant]).
Nasiginal Housing Industry Co., Ltd.! ! ! ) to 120 g/m
, Molded product of the foamed fire protection composition of Example (thickness 3+ms+
) was set to 40 g/m (or 300 g/m). The dimensions of the test specimen were 1580 mm in height and 1000 mm in width. In Figure 2, 11 is a piece of wood measuring 38as x 64M,
The thick dashed line is a stellar pull. The joint area 3 is heated from the outdoor side using a thermocouple (JISC1602 (thermocouple)) 8 installed at a position approximately 1 CO+ away from the heating surface.
This was done so that the temperature indicated by the contact point was in line with the second grade fire protection (standard heating curve). The temperature on the back side of the joint into which the molded product of the foamed fire protection composition was inserted (temperature on the surface of the wooden frame) was measured at three points each using a dot recorder using a thermocouple.

The modified sealant ignites (heating side) 3 minutes after heating starts,
Some molded products started foaming in 6 minutes (heating side), and all molded products foamed in 9 minutes (heating side). In addition, after heating, the modified sealant inserted into the upper layer of the joint became white (discolored). All foamed and a black carbonized layer was formed (heated side).The joint opening after heating was 14n+ in all of the upper, middle and lower parts.The temperature on the back side of the joint at the above three points (wood The maximum temperatures (frame surface temperature) were 177°C (reaching time 23 minutes), 200°C (reaching time 22 minutes), and 216°C (reaching time 19 minutes).

〔Effect of the invention〕

The foamed fire-retardant molded product according to the present invention has the above-mentioned component (A
) ~ (A) are formed into a foamed fireproofing composition, which expands and foams when heated to form a carbonized layer, preventing the intrusion of smoke, flames, etc. even if gaps are created. Moreover, it is easier to apply than the above-mentioned wet foaming type fire prevention paint, and it is easier to form a uniform thickness.

The foamed fireproofing composition according to the present invention comprises the above component (A)
Since ~(B) is included as an essential component, it is possible to produce an excellent foamed fire-retardant molded product as described above.

[Brief explanation of the drawing]

FIG. 1(a) and...) are explanatory diagrams when conducting a fire protection test on the foamed fire protection composition of the example, and FIG.
FIG. 2 is an explanatory diagram when conducting a fire resistance test on the foamed fireproofing composition of the example, in which (a) is a cross-sectional view of a test specimen, and (the top of the figure) is an enlarged view of a portion thereof. Agent: Patent attorney Takehiko Matsumoto, ■L 1 N-~M Opening 1st day,

Claims (1)

[Scope of Claims] 1. A foamed fireproof molded article obtained by molding a foamed fireproofing composition containing the following components (A), (B), (C) and (D) as essential components. (A) A polyurethane resin composition consisting of a first liquid containing a polyol and a second liquid containing a polyisocyanate. (B) Ammonium polyphosphate. (C) Polyhydric alcohol. (D) Amine group-containing compound. 2. A foamed fire protection composition containing the following components (A), (B), (C) and (D) as essential components. (A) A polyurethane resin composition consisting of a first liquid containing a polyol and a second liquid containing a polyisocyanate. (B) Ammonium polyphosphate. (C) Polyhydric alcohol. (D) Amine group-containing compound.