JP6660180B2 - Thermal expansive refractory material and fire protection structure of resin sash using the same - Google Patents

Description

  The present invention relates to a heat-expandable refractory material and a fire prevention structure for a resin sash using the same.

Polyurethane foam that expands due to heat such as fire has been known for a long time, and is used not only for furniture such as sofas, but also for seat materials in aircraft, trains and buses.
Examples of the heat-expandable polyurethane foam used in these applications include a polyol component (A) containing at least one polyester polyol, at least one amino polyol and at least one halogen-containing polyol, and a polyisocyanate component (B). There has been proposed a heat-expandable polyurethane foam containing (Patent Document 1).

On the other hand, sashes are used as building members installed at openings of structures such as houses.
When a fire occurs inside or outside a structure such as a house, it is necessary to prevent the spread of fire due to the fire. It is important to improve the fire resistance of the sash so that the fire flames and the like do not spread through the sash.
In connection with this problem, a fire prevention structure for a resin sash has been proposed (Patent Document 2).
Specifically, for a sash provided with a frame material made of synthetic resin and a fire-resistant plate, a plurality of hollow portions are provided in the longitudinal direction of the frame material used for the sash, and the hollow portion flows. There has been proposed a fire prevention structure of a resin sash in which a heat-resistant expansible refractory material is injected and solidified.
If this resin sash has a fire protection structure, the resin sash can be obtained by extrusion molding using a synthetic resin, so that the productivity is excellent, and the resin sash is also lightweight and easy to handle.

  However, in order to improve the fire resistance of the heat-expandable refractory material, it was necessary to use a large amount of an inorganic filler. The more the inorganic filler is used, the higher the viscosity of the heat-expandable refractory material becomes. Therefore, there is a problem that the heat-expandable refractory material becomes difficult to handle.

Japanese Patent No. 5079944 JP 2012-20287 A

Even when a relatively large amount of inorganic filler is used, if a liquid dispersant is added to the heat-expandable refractory material, the viscosity of the heat-expandable refractory material is reduced, so that the material is easy to handle.
However, the present inventors have studied and, depending on the type of liquid dispersant used, can be obtained by injecting and solidifying a fluid heat-expandable refractory material into a hollow portion inside a frame material made of a synthetic resin. With regard to the fire protection structure of the resin sash, it has been discovered that the strength of the resin sash may decrease over time.
Upon further investigation, the present inventors have found that when the fire protection structure of the resin sash is exposed to heat such as fire, the fire-resistant plate material may warp due to heat such as fire.
When the strength of the resin sash decreases with the passage of time, when the resin sash is exposed to heat such as a fire, a gap is formed between the fire-resistant plate material and the resin frame material. There is a possibility that flame, smoke, etc. such as a fire may pass through the fire protection structure of the resin sash.
SUMMARY OF THE INVENTION An object of the present invention is to provide a thermally expandable fire-resistant material suitable for a fire-resistant structure of a resin sash exhibiting excellent fire resistance stably for a long period of time, and a fire-proof structure of a resin sash using the same.

  As a result of intensive studies by the present inventors to solve the above-mentioned problems, the present inventors have found that a thermally expandable refractory material used for applications injected into a hollow portion of a resin frame material having a hollow portion, wherein Thermal expansion that includes at least a resin component, (B) a thermal expansion component, (C) a liquid dispersant, and (D) an inorganic filler, wherein the liquid dispersant (C) has no plasticizing effect on the resin frame material. It has been found that a refractory material suitable for the purpose of the present invention has been completed.

That is, the present invention
[1] A heat-expandable refractory material used for applications injected into a hollow portion of a resin frame material having a hollow portion in a longitudinal direction,
(A) a reaction curable resin component,
(B) a thermal expansion component,
(C) a liquid dispersant,
And (D) an inorganic filler,
At least
When a molding material made of the same resin as the resin frame material is immersed in the liquid dispersant (C) at a temperature of 50 ° C. for 5 days, the molding before and after immersion in the liquid dispersant (C) is performed. A heat-expandable refractory material characterized in that the weight change of the material is less than 1%.

Also, one of the present invention,
[2] The heat-expandable refractory material according to [1], wherein the liquid dispersant (C) comprises a condensed phosphate ester.

Also, one of the present invention,
[3] The heat-expandable refractory material according to [1] or [2], wherein the liquid dispersant (C) has a viscosity at 25 ° C. of 0.1 to 50,000 mPa · s. is there.

Also, one of the present invention,
[4] The heat-expandable refractory material according to any one of [1] to [3], wherein the heat-expandable refractory material contains at least one of (E) a foaming agent and (F) a foam stabilizer. Is what you do.

Also, one of the present invention,
[5] The reaction-curable resin component (A) is a urethane resin foam, an epoxy resin foam, a phenol resin foam, a urea resin foam, an unsaturated polyester resin foam, an alkyd resin foam, a melamine resin foam, a diallyl phthalate resin foam, and silicone. The present invention provides the thermally expandable refractory material according to any one of the above [1] to [4], which is at least one selected from the group consisting of resin foams.

Also, one of the present invention,
[6] The above-mentioned [1] to [1], wherein the heat-expandable component (B) is at least one selected from the group consisting of a heat-expandable graphite, a nitrogen-based foaming agent, and a pulverized product of a heat-expandable resin composition. It is intended to provide the thermally expandable refractory material according to any one of [5].

Also, one of the present invention,
[7] The heat-expandable refractory material according to any one of the above [1] to [6], wherein the heat-expandable refractory material contains a catalyst (G).

Also, the present invention
[8] a resin frame material having a hollow portion in the longitudinal direction;
A plate material having fire resistance installed in an opening formed by the resin frame material,
A support member for supporting the plate material having fire resistance,
A first thermally expandable refractory material injected into the hollow portion of the resin frame material,
A second thermally expandable refractory material provided between the plate material having the fire resistance and the resin frame material,
A fixing member for fixing the support member and the resin frame member, a fire prevention structure of a resin sash,
The fixing member penetrates the support member, and is inserted into a hollow portion of the resin frame member to fix the support member and the resin frame member,
The second heat-expandable refractory material contacts the resin frame material, the support member, and a boundary portion of the fire-resistant plate material from at least one surface side of the fire-resistant plate material,
The first heat-expandable refractory material is the heat-expandable refractory material according to any one of the above [1] to [7], and provides a fireproof structure for a resin sash.

Also, one of the present invention,
[9] The fire protection structure for a resin sash according to the above [8], wherein the second heat-expandable refractory material is provided without any gap around the entire circumference along the side surface of the fire-resistant plate material. Things.

Also, one of the present invention,
[10] The above-mentioned [8] or [9], wherein a thermal expansion ratio of the first thermally expandable refractory material is in a range of more than 1 to 5 times under a heating condition of 600 ° C. for 30 minutes. The present invention provides a fire prevention structure for the resin sash described above.

Also, one of the present invention,
[11] The support member has a substantially U-shaped cross-section (here, “substantially U-shaped” means that all corners are right-angled or U-shaped with rounded corners; the same applies hereinafter). The present invention provides a fire prevention structure for a resin sash according to any one of the above [8] to [10], comprising at least one of a metal member and an inorganic member.

Also, one of the present invention,
[12] The viscosity at 25 ° C. of the first thermally expandable refractory material before the first thermally expandable refractory material is injected into the hollow portion of the resin frame material is 1000 to 100000 mPa · s. Range,
Any of the above [8] to [11], wherein the first thermally expandable refractory material loses fluidity in the hollow portion of the resin frame material at 25 ° C. after being injected into the hollow portion of the resin frame material. A fire prevention structure for a resin sash according to any one of the above.

Also, one of the present invention,
[13] The fire protection structure of the resin sash according to any of [8] to [12], wherein the second heat-expandable refractory material includes at least a reaction-curable resin component, a heat-expansion component, and an inorganic filler. Is provided.

Also, one of the present invention,
[14] The second heat-expandable refractory material, in addition to at least one selected from the group consisting of a reaction-curable resin component, a thermosetting resin component, and a thermoplastic resin component, a heat-expandable component and an inorganic filler. The present invention provides a fire prevention structure for a resin sash according to any one of the above [8] to [13], obtained by molding a resin composition containing at least:

Also, one of the present invention,
[15] A supporting material is inserted into a hollow portion of the resin frame material in contact with a lower end of the fire-resistant plate material,
The support material includes a metal,
The cross-section of the support member is at least one of a substantially U-shape and a tubular shape, and provides the fire-resistant structure of the resin sash according to any one of [8] to [14].

Also, one of the present invention,
[16] The resin frame member has a plate member supporting portion for supporting a surface of the fire-resistant plate member,
A heat-expandable fire-resistant tape is installed between the plate having fire resistance and the plate support, between the plate having fire resistance and the support member, and at least one of the hollow portions of the plate support. And
The present invention provides the fire-resistant structure for a resin sash according to any one of the above [8] to [15], wherein the thermal expansion start temperature of the heat-expandable refractory tape is in the range of 150 to 200 ° C.

Also, one of the present invention,
[17] The resin according to any of [8] to [16], wherein the fixing member penetrates the support member and the resin frame member to fix the support member and the resin frame member. A sash fire protection structure is provided.

Also, one of the present invention,
[18] a fixing auxiliary member connected to the fixing member,
The fixing auxiliary member is inserted into a hollow portion of the resin frame material,
The above [8] to [8], wherein the fixing member penetrates the support member and is connected to a fixing auxiliary member inserted into a hollow portion of the resin frame member to fix the support member and the resin frame member. 17] The present invention provides a fire prevention structure for a resin sash according to any one of the above items.

  The heat-expandable refractory material according to the present invention is used for an application to be injected into a hollow portion of a resin frame material having a hollow portion in a longitudinal direction. As the reaction-curable resin component cures over time, the viscosity increases. When the viscosity becomes a certain value or more, it becomes difficult to inject the heat-expandable refractory material into the hollow portion of the resin frame material. Therefore, by using the liquid dispersant (C), the heat-expandable refractory material is used. The viscosity can be adjusted so that the material can be easily handled, and the heat-expandable refractory material according to the present invention can be easily handled.

The present inventors have studied and found that some of the additives plasticize the resin frame material and reduce its strength with the passage of time.
On the other hand, in the case of the present invention, when the molding material made of the same resin as the resin frame material is immersed in the liquid dispersant at a temperature of 50 ° C. for 5 days, before immersion in the liquid dispersant (C) By using the liquid dispersant (C) in which the weight change of the molding material after immersion is less than 1%, it is possible to prevent a decrease in strength that occurs with the passage of time.

Since the heat-expandable refractory material according to the present invention does not have a plasticizing effect on the resin frame material, it can be applied to a resin sash.
Since the fire prevention structure of the resin sash according to the present invention uses the resin frame material into which the first heat-expandable refractory material described in any of the above [1] to [7] is used, Light weight and easy to handle.
Further, the fire prevention structure of the resin sash according to the present invention is exposed to a flame such as a fire, and the fire-resistant plate used for the fire prevention structure of the resin sash is warped to have the fire resistance with the resin frame material. There may be a gap between the plate material. Even in this case, the second thermally expandable refractory material contacts the resin frame material, the support member, and the boundary between the fire-resistant plate materials from at least one surface side of the fire-resistant plate material. Therefore, the heat of a fire or the like expands the second thermally expandable refractory material to form an expanded residue. Since the expansion residue blocks the gap generated between the resin frame material and the fire-resistant plate material, the fire protection structure of the resin sash according to the present invention is excellent in fire protection.

  When the thermal expansion ratio of the heat-expandable refractory material is in a range of more than 1 time and 5 times or less under a heating condition of 600 ° C. for 30 minutes, the fire prevention structure of the resin sash according to the present invention may cause a fire or the like. Even when exposed to the flame, an expansion residue of the thermally expandable refractory material having relatively excellent strength is formed at the place where the resin frame material was located. Since the formed expansion residue has relatively high strength, it is possible to prevent the expansion residue from peeling and falling off from the fire protection structure of the resin sash. Further, since the fire-resistant plate material can be supported by the expanded residue, it is possible to prevent a gap from being formed between the resin frame material and the fire-resistant plate material. Therefore, the fire protection structure of the resin sash according to the present invention is excellent in fire protection.

  Further, by using at least one of a metal member and an inorganic member having a substantially U-shaped cross section as the support member, even when the fire prevention structure of the resin sash is exposed to a flame such as a fire, the support member has the fire resistance. Can be held. Therefore, the fire protection structure of the resin sash according to the present invention is excellent in fire protection.

  Further, the viscosity at 25 ° C. of the first thermally expandable refractory material before being injected into the resin frame material is in the range of 1000 to 100000 mPa · s, and is injected into the resin frame material. Later, by using the first heat-expandable refractory material that loses fluidity in the hollow portion of the resin frame material at 25 ° C., the fire-resistant structure of the resin sash according to the present invention can be obtained. The fire prevention structure of such a resin sash is easy to handle.

  In addition, by inserting a supporting material containing a metal into the hollow portion of the resin frame material in contact with the lower end of the fire-resistant plate material, it is possible to prevent the resin frame material from being easily warped due to the weight of the fire-resistant plate material. it can. As a result, a gap is less likely to be formed between the resin frame material and the fire-resistant plate material, so that the fire prevention structure of the resin sash according to the present invention is excellent in fire protection.

  Further, when the resin frame material has a plate material support portion for supporting the surface of the fire-resistant plate material, a heat-expandable fire-resistant tape is provided between the fire-resistant plate material and the plate material support portion. The heat-expandable refractory tape expands due to heat from a fire or the like to form an expansion residue by being disposed between the plate having the property and the support member, and at least one of the hollow portions of the plate support. . Since the expansion residue blocks the gap generated between the resin frame material and the fire-resistant plate material, the fire protection structure of the resin sash according to the present invention is excellent in fire protection.

  In the case where the fixing member penetrates the support member and the resin frame material, and fixes the surface of the support member facing the side surface of the fire-resistant plate material and the outer peripheral surface of the resin frame material. Even when the fire prevention structure of the resin sash according to the present invention is exposed to a flame such as a fire, a gap can be prevented from being formed between the resin frame material and the fire-resistant plate material. The fire protection structure of the resin sash according to the above is excellent in fire protection.

  Further, a fixing auxiliary member may be inserted into a hollow portion of the resin frame material, and a fixing member may be connected to the fixing auxiliary member through the support member to fix the support member and the resin frame material. For this reason, even if the fire prevention structure of the resin sash according to the present invention is exposed to a flame such as a fire, a gap can be prevented from being formed between the resin frame material and the fire-resistant plate material. The fire prevention structure of the resin sash according to the invention is excellent in fire protection.

FIG. 1 is a schematic front view for illustrating a first embodiment of a fire prevention structure for a resin sash according to the present invention. FIG. 2 is a cross-sectional view of the fire prevention structure of the resin sash according to the first embodiment along the line AA in FIG. FIG. 3 is a schematic cross-sectional view of a principal part of the fire prevention structure of the resin sash according to the first embodiment along the line AA in FIG. 1. FIG. 4 is a schematic front view for explaining the structure of the fire protection structure of the resin sash according to the first embodiment of the present invention. FIG. 5 is a schematic cross-sectional view of a principal part of the fire prevention structure of the resin sash according to the first embodiment, taken along line AA. FIG. 6 is a schematic cross-sectional view of a principal part of a fire prevention structure of a resin sash according to Comparative Reference Example 1. FIG. 7 is a schematic cross-sectional view of a principal part of a fire prevention structure for a resin sash according to Comparative Reference Example 2. FIG. 8 is a schematic cross-sectional view of a principal part of a fire prevention structure for a resin sash according to Comparative Reference Example 3. FIG. 9 is a schematic front view of the fire prevention structure of the resin sash according to the first application example. FIG. 10 is a schematic cross-sectional view of a principal part of a fire prevention structure for a resin sash according to the first application example. FIG. 11 is a schematic cross-sectional view of a principal part of a fire prevention structure for a resin sash according to Application Example 2. FIG. 12 is a schematic cross-sectional view of a principal part of a fire prevention structure for a resin sash according to the third application example. FIG. 13 is a schematic cross-sectional view of a principal part of a fire prevention structure for a resin sash according to Application Example 4. FIG. 14 is a schematic cross-sectional view of a principal part for describing a relationship between a fixing auxiliary member and a thermally expandable refractory material.

First, the heat-expandable refractory material according to the present invention will be described.
The heat-expandable refractory material includes at least (A) a reaction-curable resin component, (B) a heat-expandable component, (C) a liquid dispersant, and (D) an inorganic filler.

Among the components of the heat-expandable refractory material, the reaction-curable resin component (A) will be described first.
As the reaction-curable resin component (A), for example, the viscosity increases due to the progress of the reaction of the components contained in the reaction-curable resin component with the passage of time. There is no particular limitation as long as the fluidity is lost.
Examples of the reaction-curable resin component include, for example, urethane resin, isocyanurate resin, epoxy resin, phenol resin, urea resin, unsaturated polyester resin, alkyd resin, melamine resin, diallyl phthalate resin, Silicone resin and the like can be mentioned.

Examples of the urethane resin include those containing a polyisocyanate compound as a main agent and a polyol compound as a curing agent. Further, a catalyst, a foaming agent, a foam stabilizer and the like can be used in combination with the urethane resin.
Examples of the polyisocyanate compound which is a main component of the urethane resin include aromatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate.

  Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

  Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldisicyclohexylmethane diisocyanate.

Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and the like.
One or more kinds of the polyisocyanate compounds can be used.
The main ingredient of the urethane resin is preferably diphenylmethane diisocyanate or the like because of its ease of use and availability.

  Examples of the polyol compound as a curing agent for the urethane resin include aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolak, cresol novolak, and the like.
Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldisicyclohexylmethanediol, and the like.
Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and the like.
As the polyester polyol, for example, a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, ε-caprolactone, a polymer obtained by ring-opening polymerization of a lactone such as α-methyl-ε-caprolactone And condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols.

Here, specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, succinic acid, and the like.
Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol, and the like. Can be
Specific examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

  Examples of the polymer polyol include, for example, a polymer obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, or methacrylate to the aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, or the like. , Polybutadiene polyol, or a hydrogenated product thereof.

As the polyether polyol, for example, in the presence of at least one kind of low-molecular-weight active hydrogen compound having two or more active hydrogens, ethylene oxide, propylene oxide, at least one kind of alkylene oxide such as tetrahydrofuran is subjected to ring-opening polymerization. And the polymer obtained by the above method.
Examples of the low-molecular-weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol;
Triols such as glycerin and trimethylolpropane,
Examples thereof include amines such as ethylenediamine and butylenediamine.

The isocyanate index [(moles of isocyanate groups) / (moles of all active hydrogen groups including water) × 100] in the present invention is usually in the range of 50 to 500. It is preferably in the range of 60 to 450, and more preferably in the range of 70 to 400.
When the isocyanate index is less than 50, the obtained rigid polyurethane foam may not have sufficient flame retardancy and mechanical strength, and when it is more than 500, the obtained rigid polyurethane foam has high brittleness and adhesive strength. Tends to decrease.

  A catalyst (G) can be used for the urethane resin. Examples of the catalyst (G) include triethylamine, triethylenediamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl-N'-dimethylaminoethylpiperazine, an imidazole compound in which a secondary amine functional group in an imidazole ring is substituted with a cyanoethyl group And the like.

Next, an isocyanurate resin, which is a kind of urethane resin, can be used as the reaction-curable resin component (A).
As the isocyanurate resin, for example, the polyurethane resin described above is used, and the isocyanate group contained in the polyisocyanate compound, which is the main component of the polyurethane resin, is reacted and trimerized to promote isocyanurate ring formation. And the like.

In order to promote the formation of the isocyanurate ring, for example, as the catalyst (G), tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylamino) Alkyl) Aromatic compounds such as hexahydro-S-triazine, alkali metal salts of carboxylic acids such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate, and quaternary ammonium salts of carboxylic acids may be used.
The main component and the curing agent of the isocyanurate resin are the same as in the case of the polyurethane resin.

  Next, examples of the epoxy resin include a resin obtained by reacting a monomer having an epoxy group as a main agent with a curing agent.

  Examples of the monomer having an epoxy group include bifunctional glycidyl ethers such as polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, and propylene oxide-bisphenol A. Type, hydrogenated bisphenol A type, bisphenol A type, bisphenol F type and the like.

  Examples of the glycidyl ester type include monomers such as hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type, and p-oxybenzoic acid type.

  Further, as the polyfunctional glycidyl ether type, monomers such as phenol novolak type, orthocresol type, DPP novolak type, dicyclopentadiene type, and phenol type are exemplified.

  One or more of these can be used.

Examples of the curing agent include a polyaddition type curing agent and a catalyst type curing agent.
Examples of the polyaddition type curing agent include polyamine, acid anhydride, polyphenol, and polymercaptan.
Examples of the catalyst-type curing agent include tertiary amines, imidazoles, Lewis acid complexes and the like.
The method for curing these epoxy resins is not particularly limited, and can be performed by a known method.

  In order to adjust the melt viscosity, flexibility, adhesiveness and the like of the resin component, a mixture of two or more resin components can be used.

Next, examples of the phenol resin include a resol-type phenol resin composition.
The resol-type phenol resin composition contains, for example, a resol-type phenol resin as a main agent, a curing agent, and the like.

Examples of the main agent of the phenol resin include, for example, phenols such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, and resorcinol, and modified products thereof, and aldehydes such as formaldehyde, paraformaldehyde, furfural, and acetaldehyde. Examples thereof include, but are not limited to, those obtained by reacting in the presence of an amount of an alkali such as sodium hydroxide, potassium hydroxide, or calcium hydroxide.
The mixing ratio of the phenols and the like to the aldehydes is not particularly limited, but is usually in the range of 1.0: 1.5 to 1.0: 3.0 in molar ratio. The mixing ratio is preferably in the range of 1.0: 1.8 to 1.0: 2.5.

  Examples of the curing agent for the phenol resin include inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphtholsulfonic acid, and phenolsulfonic acid. Can be

Next, examples of the urea resin include a composition containing urea as a main agent, formaldehyde as a curing agent, a basic compound as a catalyst, and an acidic compound.
The urea and formaldehyde form a urea resin by a polymerization reaction.

Next, examples of the unsaturated polyester resin include a composition containing an unsaturated polybasic acid as a main agent, a polyol compound as a curing agent, a catalyst, and the like.
Specific examples of the main component of the unsaturated polyester resin include maleic anhydride and fumaric acid.

Specific examples of the curing agent for the unsaturated polyester resin include the polyol compounds used for the urethane resin described above.
The unsaturated polyester resin may be used in combination with a saturated polybasic acid such as phthalic anhydride or isophthalic acid, if necessary.

Further, a vinyl monomer for crosslinking such as styrene, vinyl toluene, methyl methacrylate and the like, which polymerizes with the main component of the unsaturated polyester resin, can be added.
Specific examples of the catalyst for the unsaturated polyester resin include t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyoctoate, and t-butylperoxy. Organic peroxides such as isopropyl carbonate and 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexanone.

Next, examples of the alkyd resin include a composition containing a polybasic acid as a main agent, a polyol compound as a curing agent, oil and fat, and the like.
Specific examples of the main agent of the alkyd resin include maleic anhydride, phthalic anhydride, and adipic acid.

Specific examples of the curing agent for the alkyd resin include the polyol compounds used for the urethane resin described above.
Examples of the fats and oils include soybean oil, coconut oil, linseed oil and the like.

Next, examples of the melamine resin include a composition containing melamine as a main agent, formaldehyde as a curing agent, and the like.
If necessary, benzoguanamine or the like can be added to the composition.

Next, examples of the diallyl phthalate resin include a composition containing a polybasic acid such as phthalic anhydride as a main agent, allyl alcohol as a curing agent, and a crosslinking agent.
Examples of the crosslinking agent include styrene and vinyl acetate.

  Next, as the silicone resin, for example, a composition containing a platinum compound such as dialkylsilyl dichloride or dialkylsilyl diol as a main agent, a trialkylsilyl chloride or trialkylsilyl diol as a reaction inhibitor, a platinum compound such as chloroplatinic acid as a curing agent, or the like Can be mentioned.

Specific examples of the dialkylsilyl dichloride include dimethylsilyl dichloride, diethylsilyl dichloride, dipropylsilyl dichloride, and the like.
Specific examples of the dialkylsilyldiol include dimethylsilyldiol, diethylsilyldiol, dipropylsilyldiol, and the like.
Specific examples of the trialkylsilyl chloride include, for example, trimethylsilyl chloride, triethylsilyl chloride, tripropylsilyl chloride, and the like.
Specific examples of the trialkylsilyldiol include, for example, trimethylsilylol, triethylsilylol, and tripropylsilylol.
The reaction inhibitor binds to the end of the polysiloxane main chain and controls the reaction to control the degree of polymerization of the polysiloxane main chain.

The reaction-curable resin component (A) used in the present invention is preferably a thermosetting resin in order to prevent melting easily even when exposed to heat such as fire.
The reaction curable resin component used in the present invention is more preferably an epoxy resin, a urethane resin, a phenol resin or the like from the viewpoint of handleability.

  The reaction-curable resin component (A) used in the present invention can be used by preliminarily reacting a main agent with a curing agent or the like in advance.

  One or more of the main component and the curing agent of the reaction-curable resin component (A) and the catalyst (G) contained in the thermally expandable refractory material used in the present invention can be used.

  The heat-expandable refractory material was foamed by using a foaming agent (E) and a foam stabilizer (F) in combination with the reaction-curable resin component (A) contained in the heat-expandable refractory material according to the present invention. It can be cured in a state.

Examples of the foaming agent (E) include water,
Low-boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane and cycloheptane;
Chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride,
Fluorine compounds such as trichloromonofluoromethane and trichlorotrifluoroethane; hydrofluorocarbons such as CHF ₃ , CH ₂ F ₂ and CH ₃ F;
Fluorine compounds such as trichloromonofluoromethane and trichlorotrifluoroethane,
Hydrochlorofluorocarbon compounds such as dichloromonofluoroethane, (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane));
Examples thereof include organic physical foaming agents such as ether compounds such as diisopropyl ether or a mixture of these compounds, and inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas.

  The amount of the foaming agent (E) used with respect to the reaction-curable resin component (A) is appropriately set according to the reaction-curable resin component (A) to be used. It is usually in the range of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the conductive resin component.

Examples of the foam stabilizer (F) include an organic silicon-containing surfactant.
The amount of the foam stabilizer used for the reaction-curable resin component is appropriately set depending on the reaction-curable resin component to be used. For example, for example, 0 parts by weight relative to 100 parts by weight of the resin component is used. It is preferably in the range of 0.01 to 5 parts by weight.

  One or more foaming agents (E) and foam stabilizers (F) can be used, respectively.

  The reaction-curable resin component (A) used in the present invention preferably has a foaming function in order to cure the heat-expandable refractory material in a foamed state, and specifically includes a urethane resin foam and an isocyanurate. It is preferable to use one or more of resin foam, epoxy resin foam, phenol resin foam, urea resin foam, unsaturated polyester resin foam, alkyd resin foam, melamine resin foam, diallyl phthalate resin foam, silicone resin foam and the like. .

  By curing the thermally expanded refractory material in a foamed state, the cured thermally expanded refractory material can be given a heat insulating effect of air bubbles, and a door, sash, or the like installed at an opening or the like of a structure. The heat insulating property of the building member into which the thermally expandable refractory material has been injected can be improved.

Next, the thermal expansion component (B) among the components of the thermal expansion refractory material will be described.
The thermal expansion component (B) expands upon heating. Specific examples of the thermal expansion component (B) include inorganic expansion components such as vermiculite, kaolin, mica, and thermal expandable graphite. , A nitrogen-based foaming agent such as melamine, and a pulverized molded product of a heat-expandable resin composition.

  The heat-expandable graphite is a conventionally known substance, and powders such as natural scale graphite, pyrolytic graphite, and quiche graphite are mixed with inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, concentrated nitric acid, perchloric acid, and perchloric acid. It was treated with a strong oxidizing agent such as chlorate, permanganate, dichromate, dichromate, hydrogen peroxide, etc. to produce a graphite intercalation compound, and maintained a layered structure of carbon. It is a kind of crystalline compound as it is.

  It is preferable to use the heat-expandable graphite obtained by the acid treatment as described above, which is further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like.

  Examples of the aliphatic lower amine include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like.

  Examples of the alkali metal compound and the alkaline earth metal compound include hydroxides, oxides, carbonates, sulfates, and organic acid salts of potassium, sodium, calcium, barium, magnesium and the like.

  The particle size of the heat-expandable graphite is preferably in the range of 20 to 200 mesh.

  When the particle size is 20 mesh or more, the dispersibility is improved, so that kneading with a resin component or the like becomes easy. When the particle size is 200 mesh or less, a sufficient refractory heat-insulating layer is easily obtained because the degree of expansion of graphite is large.

  Commercial products of the neutralized thermally expandable graphite include, for example, “GRAFGUARD # 160” and “GRAFGUARD # 220” manufactured by UCAR CARBON, and “GREP-EG” manufactured by Tosoh.

  Examples of the nitrogen-based blowing agent include melamine and isocyanurates.

Examples of the pulverized molded product of the heat-expandable resin composition include, for example, those obtained by pulverizing a commercially available heat-expandable refractory sheet or the like.
Specific examples of the heat-expandable refractory sheet and the like used in the pulverized molded product include, for example, Fibroc (registered trademark) manufactured by Sekisui Chemical Co., Ltd .; resin components such as epoxy resin and rubber resin; A molded product of a heat-expandable resin composition containing a thermal expansion component, a phosphorus compound, an inorganic filler and the like), a fire barrier manufactured by Sumitomo 3M Limited (a sheet material composed of a resin composition containing chloroprene rubber and vermiculite, expansion coefficient: 3) Times, thermal conductivity: 0.20 kcal / m · h · ° C.), a sheet material composed of a resin composition containing a polyurethane resin and heat-expandable graphite, manufactured by Mitsui Kinzoku Kagaku Kagaku KK, expansion rate: 4 times, heat Conductivity: 0.21 kcal / m · h · ° C.) and the like.

A method of cutting a commercially available heat-expandable refractory sheet or the like into small pieces by a cutting machine or the like, or a method of pulverizing a commercially available heat-expandable refractory sheet or the like through a crushing roll, etc. A crushed product can be obtained.
The pulverized molded product of the heat-expandable resin composition preferably has a size of 5 to 20 mesh.

  When the particle size of the pulverized product of the heat-expandable resin composition is 5 mesh or more, the dispersibility is improved, so that kneading with a resin component or the like becomes easy. Further, when the particle size is 20 mesh or less, a sufficient refractory heat insulating layer is easily obtained because the degree of expansion of graphite is large.

Next, the liquid dispersant (C) among the components of the heat-expandable refractory material will be described.
The liquid dispersant (C) is liquid at a temperature of 25 ° C. When the liquid dispersant (C) is used, the viscosity of the heat-expandable refractory material according to the present invention can be prevented from becoming too large, and the heat-expandable refractory material can be easily handled.
From the viewpoint of easy handling, the viscosity of the liquid dispersant (C) is preferably in the range of 0.1 to 50,000 mPa · s, and more preferably in the range of 1.0 to 30,000 mPa · s.

The heat-expandable refractory material according to the present invention is used for an application to be injected into a hollow portion of a resin frame material having a hollow portion in a longitudinal direction, but a molding material made of the same resin as the resin frame material is used. When immersed in the liquid dispersant at a temperature of 50 ° C. for 5 days, the change in weight of the molding material before and after immersion in the liquid dispersant (C) is less than 1%.
By using the liquid dispersant (C) that satisfies this condition, it is possible to prevent the strength of the resin frame material from decreasing over time.

Examples of the liquid dispersant (C) satisfying such conditions include a condensed phosphoric ester.
Examples of the condensed phosphoric acid ester include a halogen-free non-halogenated ester and a halogen-containing halogenated ester.

Examples of the non-halogenated ester include tetraphenyl-m-phenylene bis (phosphate), bisphenol A bis (diphenyl phosphate), and a mixture of polyoxyalkylene phosphate and aromatic condensed phosphate.
The following can also be used as commercial products.
IUPAC name: Phosphpric trichloride, reaction products with 4,4'-isopropylidenediphenol and phenol (Cas-No. 5945-33-5,181028-79-51, ADEKA, Adekastab FP series, trade name FP-600),
IUPAC name: Phosphpric trichloride, polymer with 1,3-benzenedio 1, phenyl ester (ADEKA Corporation, Adekastab FP series, trade name PFR),
Daihachi Chemical Co., Ltd., product name CR733S, CR741, PX200, DAIGARD 580, DAIGARD 610

As the halogenated ester, for example, the following can be used as commercial products.
Daihachi Chemical Industry Co., Ltd., product name CR504L, CR570, DAIGUARD540

  One or more liquid dispersants (C) can be used.

  By using an ester as the liquid dispersant (C), it is possible to prevent a decrease in strength over time due to plasticization of the resin frame material.

  Next, the inorganic filler (D) among the components of the above-mentioned heat-expandable refractory material will be described.

  Examples of the inorganic filler (D) include, but are not particularly limited to, silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, and calcium hydroxide. , Magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, potassium sulfate, barium sulfate, gypsum fiber, potassium salts such as calcium silicate, vermiculite , Kaolin, mica, talc, clay, mica, montmorillonite, bentonite, activated clay, sebiolite, imogolite, sericite, glass fiber, glass beads, silica balun, aluminum nitride, boron nitride, silicon nitride, carbon Rack, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, Examples include slag fibers, fly ash, inorganic phosphorus compounds, silica-alumina fibers, alumina fibers, silica fibers, zirconia fibers, and the like.

  One or more of these can be used.

  The inorganic filler plays a role of an aggregate, and contributes to an increase in strength of an expanded heat insulating layer generated after heating and an increase in heat capacity.

  For this reason, calcium carbonate, metal carbonates represented by zinc carbonate, aluminum hydroxide which imparts an endothermic effect upon heating in addition to the role of aggregates, and hydrous inorganic substances represented by magnesium hydroxide are preferred, and alkali metals, alkalis An earth metal and a metal carbonate of the periodic table IIb or a mixture of these and the above-mentioned hydrous inorganic substance is preferred.

Further, a phosphorus compound can be added as an inorganic filler (D) to the heat-expandable refractory material according to the present invention.
The phosphorus compound is used for improving the flame retardancy, or for exhibiting a thermal expansion function in combination with a nitrogen compound, an alcohol or the like.

The phosphorus compound is not particularly limited, for example, red phosphorus,
Various phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate,
Metal phosphates such as sodium phosphate, potassium phosphate, and magnesium phosphate;
Ammonium polyphosphates,
Examples include a compound represented by the following chemical formula 1.

  One or more of these phosphorus compounds can be used.

  Among these, from the viewpoint of fire resistance, red phosphorus, a compound represented by the following chemical formula, and ammonium polyphosphates are preferable, and ammonium polyphosphates are more preferable in terms of performance, safety, cost, and the like.

上記化学式中、Ｒ^１及びＲ^３は、水素、炭素数１〜１６の直鎖状若しくは分岐状のアルキル基、又は、炭素数６〜１６のアリール基を表す。

In the above chemical formula, R ¹ and R ³ represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms.

R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, Represents an aryloxy group represented by Formulas 6 to 16.

  Examples of the compound represented by the chemical formula include, for example, methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonic acid, 2, 3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid , Diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid, and the like.

  Among them, t-butylphosphonic acid is expensive, but is preferable in terms of high flame retardancy.

  The ammonium polyphosphates are not particularly limited, and include, for example, ammonium polyphosphate, melamine-modified ammonium polyphosphate, and the like.Ammonium polyphosphate is preferably used in terms of flame retardancy, safety, cost, handleability, and the like. Used.

  Commercial products include, for example, “Trade name: EXOLIT AP422” and “Trade name: EXOLIT AP462” manufactured by Clariant.

  The phosphorus compound is considered to react with a metal carbonate such as calcium carbonate and zinc carbonate to promote the expansion of the metal carbonate.In particular, when ammonium polyphosphate is used as the phosphorus compound, a high expansion effect is obtained. can get.

  In addition, it acts as an effective aggregate and forms a residue having high shape retention after burning.

  The nitrogen compound is not particularly limited, but is preferably a melamine compound or the like. The alcohol is not particularly limited, but is preferably a polyhydric alcohol such as pentaerythritol.

  When the inorganic filler used in the present invention is granular, the particle size is preferably in the range of 0.5 to 200 μm, more preferably in the range of 1 to 50 μm.

  When the addition amount of the inorganic filler is small, the dispersibility greatly affects the performance, and therefore, those having a small particle size are preferable. However, when the particle size is 0.5 μm or more, secondary aggregation can be prevented, and the dispersibility is good. Becomes

  Also, when the amount of the inorganic filler is large, as the high filling proceeds, the viscosity of the resin composition increases and the moldability decreases, but the viscosity of the resin composition is decreased by increasing the particle size. In view of the above, those having a large particle size are preferable in the above range.

  In addition, when the particle size is 200 μm or less, it is possible to suppress a decrease in surface properties of the molded article and mechanical properties of the resin composition.

  Among the above-mentioned inorganic fillers, metal carbonates such as calcium carbonate and zinc carbonate which play an aggregate role; hydrated inorganic materials such as aluminum hydroxide and magnesium hydroxide which impart an endothermic effect upon heating in addition to the role of the aggregate Is preferred.

  It is considered that the combined use of the hydrated inorganic substance and the metal carbonate greatly contributes to improvement of the strength of the combustion residue and increase of the heat capacity.

  Among the inorganic fillers, in particular, water-containing inorganic substances such as aluminum hydroxide and magnesium hydroxide, endothermic occurs due to water generated by a dehydration reaction at the time of heating, and a high temperature resistance is obtained with a reduced temperature rise. This is preferable in that the oxide remains as a residue and the combustion residue functions as an aggregate, thereby improving the strength of the combustion residue.

  In addition, magnesium hydroxide and aluminum hydroxide have different temperature ranges in which the dehydrating effect is exerted, so when used together, the temperature range in which the dehydrating effect is exerted becomes wider, and a more effective temperature rise suppression effect is obtained. Is preferred.

  When the particle size of the hydrous inorganic substance is small, the bulk becomes large and it becomes difficult to achieve high packing. Therefore, in order to increase the dehydration effect, the particle size is preferably large for high filling.

  Specifically, it is known that when the particle size is 18 μm, the filling limit is improved about 1.5 times as compared with the particle size of 1.5 μm.

  Further, by combining a material having a large particle size and a material having a small particle size, higher filling can be achieved.

  Commercial products of the above-mentioned hydrous inorganic substances include, for example, as aluminum hydroxide, “trade name: Heidilite H-42M” (trade name: 1 μm; manufactured by Showa Denko KK); (Manufactured by Showa Denko KK).

  Commercial products of the calcium carbonate include, for example, “Product name: Whiten SB Red” having a particle size of 1.8 μm (manufactured by Shiraishi Calcium Co., Ltd.) and “Product name: BF300” having a particle size of 8 μm (manufactured by Bihoku Powder Chemical Co., Ltd.) And the like.

  As described at the beginning, the heat-expandable refractory material according to the present invention includes the above-described reaction-curable resin component, the heat-expandable component, the resin composition including the inorganic filler, and the above-described phosphorus compound. These compounds can be mentioned, and then their composition will be described.

  The heat-expandable refractory material preferably contains the reaction-curable thermal expansion component in an amount of 5 to 100 parts by weight and the inorganic filler in an amount of 10 to 200 parts by weight based on 100 parts by weight of the reaction-curable resin component. .

  Further, the total of the reaction-curable thermal expansion component and the inorganic filler is preferably in the range of 20 to 300 parts by weight.

  Such a heat-expandable refractory material expands by heat of a fire or the like to form a heat expansion residue. According to this composition, the heat-expandable material expands due to heat such as fire, and can obtain a required volume expansion coefficient. After expansion, the heat-expandable residue having predetermined heat insulating performance and predetermined strength. Can be formed, and stable fire resistance performance can be achieved.

When the amount of the reaction-curable thermal expansion component is 10 parts by weight or more, a necessary expansion ratio is obtained, and thus sufficient fire resistance and fire prevention performance are obtained.
On the other hand, when the amount of the thermal expansion component is 150 parts by weight or less, the fluidity of the thermally expandable refractory material at 25 ° C. can be ensured.

When the amount of the inorganic filler is 50 parts by weight or more, a decrease in volume of the thermal expansion residue after combustion is small, and a thermal expansion residue for fireproof insulation is obtained.
Further, since the ratio of combustibles increases, the flame retardancy may decrease.

  On the other hand, when the amount of the inorganic filler is 300 parts by weight or less, the fluidity of the thermally expandable refractory material at 25 ° C. can be ensured.

  When the total amount of the thermal expansion component and the inorganic filler in the heat-expandable refractory material is 60 parts by weight or more, the amount of the thermal expansion residue after combustion is not insufficient and sufficient fire resistance is easily obtained. It is suitable for actual use with little decrease in physical properties.

  Further, the heat-expandable refractory material according to the present invention, as long as the object of the present invention is not impaired, if necessary, a plasticizer such as phthalic acid ester, adipic acid ester, phosphate ester, phenolic, amine-based, In addition to sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, cross-linking agents, lubricants, softeners, additives for pigments, tackifier resins, adhesives for polybutene, petroleum resins, etc. It may contain an antisettling agent such as a imparting agent, glass powder, amorphous silica, microgel, castor oil wax, and amide wax.

The viscosity at 25 ° C. of the heat-expandable refractory material according to the present invention is preferably in the range of 1,000 to 100,000 mPa · s, based on the value before being injected into the hollow portion of the resin frame material.
When the viscosity is 1000 mPa · s or more, the heat-expandable refractory material can be easily filled even in a narrow gap in the hollow portion of the resin frame material. Further, the pressure for injecting the heat-expandable refractory material into the hollow portion of the resin frame material and the pressure of the injection device do not become unnecessarily high, so that the injection can be easily performed.
In addition, when the viscosity is 100000 mPa · s or less, it is difficult to entrain air when injecting the thermally expandable refractory material into the hollow portion of the resin frame material, and it becomes easy to inject a desired filling amount. In addition, since the components of the heat-expandable refractory material are less likely to separate and become non-uniform at the time of injection, the composition of the heat-expandable refractory material is kept uniform in the hollow portion of the resin frame material. Thus, desired fire resistance performance can be exhibited.
The viscosity is more preferably in the range of 2,000 to 100,000 mPa · s, and even more preferably in the range of 3,000 to 100,000 mPa · s.

  The viscosity of the heat-expandable refractory material can be adjusted by selecting the type of the reaction-curable resin component of the heat-expandable refractory material according to the present invention. By selecting a liquid reaction-curable resin component having a low viscosity at 25 ° C., the viscosity of the heat-expandable refractory material at 25 ° C. can be reduced. Conversely, by selecting a liquid reaction curable resin component having a high viscosity at 25 ° C., the viscosity of the thermally expandable refractory material at 25 ° C. can be increased.

The viscosity of the heat-expandable refractory material can also be adjusted by changing the weight ratio of the thermal expansion component and the inorganic filler contained in the heat-expandable refractory material.
For example, when the weight ratio of the thermal expansion component, the inorganic filler and the like contained in the thermal expansion refractory material is reduced, the viscosity of the thermal expansion refractory material at 25 ° C. can be reduced. In addition, the viscosity can be reduced by appropriately selecting a liquid inorganic filler at a temperature of 25 ° C.
Conversely, when the weight ratio of the thermal expansion component, the inorganic filler, and the like contained in the thermal expansion refractory material is increased, the viscosity of the thermal expansion refractory material at 25 ° C. can be increased.

The thermal expansion start temperature and the thermal expansion ratio of the thermally expandable refractory material can be changed by adjusting the thermal expansion start temperature and the thermal expansion ratio of the thermally expandable graphite included in the thermally expandable refractory material, respectively. .
Since the thermal expansion graphite having a different thermal expansion start temperature and a thermal expansion ratio is commercially available, a desired thermal expansion start temperature can be obtained by selecting a desired thermal expansion start temperature and a thermal expansion graphite having a thermal expansion ratio. And a thermally expandable refractory material having a thermal expansion ratio.

Next, a method for producing the heat-expandable refractory material will be described.
Although there is no particular limitation on the method for producing the heat-expandable refractory material, for example, a method of suspending the heat-expandable refractory material in an organic solvent, or heating and melting to form a paint, a solvent, A method such as preparing a slurry by dispersing, or when the reaction-curable resin component contained in the heat-expandable refractory material contains a component that is solid at a temperature of 25 ° C., the heat-expandable refractory material is used. The resin composition can be obtained by a method such as melting under heating.

  The heat-expandable refractory material uses a known device such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a raikai machine, and a planetary stirrer. And can be obtained by kneading.

Alternatively, a main agent having a reactive functional group such as an isocyanate group or an epoxy group and a curing agent may be separately kneaded with a filler or the like, and kneaded with a static mixer, a dynamic mixer, or the like immediately before injection. .
Further, it can also be obtained by kneading the components of the heat-expandable refractory material excluding the catalyst and the catalyst just before injection.

  By the method described above, the thermally expandable refractory material according to the present invention can be obtained.

The thermally expandable refractory material obtained as described above has fluidity at a temperature of 25 ° C., and can be injected into the hollow portion of the resin frame material.
Here, having fluidity refers to a case where the heat-expandable refractory material does not have a certain shape when allowed to stand, and having no fluidity means that the heat-expandable refractory material is allowed to stand. It refers to a case having a certain shape.

The heat-expandable refractory material is not particularly limited as long as it is insulated by the expansion layer when exposed to a high temperature such as at the time of fire, and has a strength of the expansion layer. It is preferable that the volume expansion coefficient after heating under the condition is in the range of more than 1 time and 5 times or less.
If the volume expansion coefficient is less than 1, the expanded volume may not sufficiently fill the burned-out portion of the resin component, and the fire protection performance may be reduced. On the other hand, if it exceeds 5 times, the strength of the expansion layer is reduced, and the effect of preventing penetration of the flame may be reduced. More preferably, the volume expansion coefficient is in the range of 1.2 to 5 times, and still more preferably in the range of 1.3 to 4 times.

In order for the inflatable layer to be self-supporting, the inflatable layer must have a high strength. The strength of the inflatable layer is set to 0 using a 0.25 cm ² indenter in a compression tester. It is preferable that the stress at break when measured at a compression speed of 0.1 m / s is 0.05 kgf / cm ² or more. If the stress at break is less than 0.05 kgf / cm ² , the adiabatic expansion layer may not be able to stand on its own, and the fire protection performance may be reduced. More preferably, it is 0.1 kgf / cm ² or more.

The above-described thermally expandable refractory material can be used for a resin sash.
Next, specific examples of uses of the present invention will be described.
The present invention relates to a fire prevention structure for a resin sash. Next, a resin sash used in the present invention will be described.
Examples of the resin sash used in the present invention include, for example, detached houses, apartment houses, high-rise houses, high-rise buildings, commercial facilities, buildings such as public facilities, passenger ships, transport ships, and ships such as ferry ships ( Hereinafter, it is referred to as a “structure such as a house”.).
As an example, for example, those used for an opening / closing window, a fixed window, and the like can be given, but the present invention is not limited to these.

  The resin sash used in the present invention is obtained by injecting a heat-expandable refractory material into a resin frame material. A first embodiment according to the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic front view for illustrating a first embodiment of a fire prevention structure for a resin sash according to the present invention. FIG. 2 is a cross-sectional view of the fire protection structure of the resin sash according to the first embodiment along the line AA in FIG. 1, and FIG. 3 is a first embodiment along the line AA in FIG. It is a principal part sectional view of the fire prevention structure of the resin sash concerning this.

In FIGS. 1 to 3, a resin sash is fixed to a rectangular opening formed in a structure 1 such as a house, and has a resin frame material 10 as an outer frame material and a fire resistance inside the resin frame material. And a plate member 20 having the same.
By injecting the first heat-expandable refractory material into the hollow portion inside the resin frame member 10 or the like, the fire-resistant structure 100 of the resin sash according to the first embodiment is obtained.

The resin frame member 10 is composed of left and right vertical frame members 11 and 12 and upper and lower horizontal frame members 13 and 14, and the inside surrounded by each of the frame members 11 to 14 is an opening.
On the other hand, the plate material 20 having fire resistance closes the opening.
Frames 11 to 14 as vertical and horizontal frame members constituting the resin frame member 10 are formed of synthetic resin. The fire-resistant plate 20 is not particularly limited as long as it has fire resistance. For example, a plate formed of an inorganic material, a metal material, or the like can be used.

Examples of the synthetic resin used for the frames 11 to 14 include chlorine-containing resins such as polyvinyl chloride, polyolefin resins such as polyethylene and polypropylene, and polyester resins such as polyethylene terephthalate and polybutylene terephthalate.
As the synthetic resin, it is preferable to use hard vinyl chloride from the viewpoint of durability and flame retardancy.
Each frame can be molded by extrusion molding or injection molding using a synthetic resin such as hard vinyl chloride.
One or more kinds of the synthetic resins can be used.

Examples of the inorganic material used for the fire-resistant plate 20 include glass, gypsum, ceramic, cement, calcium silicate, and pearlite.
Examples of the metal material used for the fire-resistant plate 20 include an aluminum material, a stainless steel material, a steel material, an alloy material, and the like.
The inorganic material and the metal material may be used alone or in combination of two or more.

First, the vertical frame members 11 and 12 constituting the resin frame member 10 will be described in detail.
The vertical frame bodies 11 and 12 are formed by cutting a long material obtained by extruding hard vinyl chloride, and have a hollow portion penetrating along the longitudinal direction.
The vertical frame bodies 11 and 12 are provided with rectangular hollow portions 11a and 12a having large cross-sectional shapes and hollow portions 11b, 11b, 12b and 12b having small widths.

Further, the vertical frame members 11 and 12 have plate material support portions 30 and 31 for supporting the surface 21 of the fire-resistant plate material 20 among the surface 21 and the side surface 22 of the fire-resistant plate material 20. Each is installed.
The plate support portions 30 and 31 are formed integrally with the vertical frame members 11 and 12, respectively.
The plate support portions 30 and 31 have hollow portions 11c and 12c, respectively.
The plate support portions 30 and 31 are installed in parallel with the surface 21 of the fire-resistant plate 20 and are installed on the packing installation portions 11d, 11e, 12d and 12e of the plate support portions 30 and 31 and the like. Synthetic resin packings 32 to 35 support the surface 21 of the plate material 20 having the fire resistance.
Since the synthetic resin packings 32 to 35 are commercially available, these commercially available products can be appropriately selected and used.
The horizontal frame members 13 and 14 constituting the resin frame member 10 also have a similar structure, not shown.

As illustrated in FIG. 3, after the first heat-expandable refractory material 15 is injected into all the insides of the hollow portions 11a and 11c, the first heat-expandable refractory material is inserted inside the hollow portions 11a and 11c. Material 15 has lost fluidity. The same applies to the hollow portions 12a and 12c.
Although not shown, after the first thermally expandable refractory material 15 is similarly injected into the hollow portions penetrating the horizontal frame members 13 and 14 in the longitudinal direction, the horizontal frame members 13 and 14 are also The first thermally expandable refractory material 15 loses fluidity inside the hollow portion.
The structure of the vertical frame members 11 and 12 is the same as that of the horizontal frame members 13 and 14, and the same applies to the following description.

As described above, the first heat-expandable refractory material 15 is injected into the hollow portion of the resin frame material 10 in a direction along the surface of the plate member 20 and loses fluidity by contacting the inner wall surface of the hollow portion. I have.
These first heat-expandable refractory materials 15 are arranged in parallel with the plane of the fire-resistant plate 20 and form a fire-resistant surface together with the fire-resistant plate 20. The fire-resistant surface thus formed fills almost the entire surface along the fire-resistant plate 20 inside the resin frame 10 in a direction perpendicular to the fire-resistant plate 20.

  When the fire prevention structure 100 of the resin sash according to the first embodiment is viewed from the outside or the front of the room, that is, a direction perpendicular to the direction along the fire-resistant plate member 20, the fire resistance in the center has the fire resistance. A first heat-expandable refractory material 15 is located on the outer periphery of the plate member 20 in front of the hollow portions of the vertical frame members 11 and 12 and the horizontal frame members 13 and 14, and all first heat-expandable refractory materials 15 are provided. Refractory material 15 is injected along the surface of plate 20 to form a refractory surface.

When injecting the first heat-expandable refractory material 15 into the hollow portion of the resin frame member 10, for example, the first heat-expandable refractory material 15 is inserted into the hollow portion of the resin frame member 10 while depressurizing the hollow portion of the resin frame member 10. One thermally expandable refractory material 15 can be injected.
Further, the first thermally expandable refractory material 15 can be injected into the hollow portion of the resin frame member 10 by applying pressure by a pressure injection means having a piston, a cylinder and the like.
The composition of the first thermally expandable refractory material 15 is the same as that described above.

Further, a fixing member 50 penetrating a support member 40 for supporting the side surface 22 of the plate member 20 having fire resistance reaches the hollow portion of the vertical frame bodies 11 and 12. The support member 40 has a substantially U-shaped cross section.
The support member 40 exemplified in FIGS. 2 and 3 is made of a metal material in the case of the first embodiment 100, but the support member 40 uses at least one of a metal material and an inorganic material. Can be. About the specific example of the said metal material and an inorganic material, the thing similar to the thing used for the above-mentioned board material 20 which has fire resistance can be used.
Since the supporting member 40 has a substantially U-shaped cross section, the side surface 22 of the fire-resistant plate 20 is provided inside the supporting member 40 with the surface 41 of the supporting member 40 facing the side surface 22. Side can be inserted.
Thus, the plate member 20 having the fire resistance can be supported by the support member 40.

  A fixing member 50 is provided inside the vertical frame members 11 and 12 so as to penetrate the support member 40. With this fixing member 50, the support member 40 and the resin frame member 10 can be fixed.

In the fire prevention structure 100 of the resin sash according to the first embodiment, the second heat-expandable fire-resistant material 150 is provided at the boundary between the resin frame material 10, the support member 40, and the fire-resistant plate material 20. On the other hand, the plate 10 having fire resistance is in contact with at least one surface side.
It is preferable that the second heat-expandable refractory material 150 is in continuous contact with each of the resin frame material 10, the support member 40, and the fire-resistant plate material 20.
In the fire prevention structure 100 for a resin sash according to the first embodiment, it is more preferable that the second heat-expandable fire-resistant material is installed without gaps all around the side surface of the fire-resistant plate material. .
When the fire prevention structure 100 of the resin sash according to the first embodiment is exposed to a flame such as a fire, the fire-resistant plate material 20 is warped, and the resin frame material 10 and the fire-resistant plate material 20 There may be gaps between them. Even in this case, the second heat-expandable refractory material is in contact with the resin frame material, the support member, and a boundary portion of the fire-resistant plate material from at least one surface of the fire-resistant plate material. Therefore, the heat of a fire or the like expands the second thermally expandable refractory material 150 to form an expanded residue. Since the expansion residue closes a gap generated between the resin frame member 10 and the fire-resistant plate member 20, the fire protection structure 100 of the resin sash according to the present invention is excellent in fire protection.

  Although the structure of the vertical frame members 11 and 12 has been described, the same applies to the case of the horizontal frame members 13 and 14.

  The heat-expandable refractory material 15 according to the present invention is used for an application to be injected into a hollow portion of a resin frame material having a hollow portion in a longitudinal direction, and this heat-expandable refractory material is used for a resin sash. As the first heat-expandable refractory material, a second heat-expandable refractory material 150 can be used in addition to the first heat-expandable refractory material.

  The first thermally expandable refractory material 15 and the second thermally expandable refractory material 150 used for the resin sash application may be the same or different.

The thermal expansion start temperature of the first thermally expandable refractory material 15 is preferably in the range of 180 to 250 ° C.
If the thermal expansion start temperature of the first heat-expandable refractory material 15 is in the range of 180 to 250 ° C., the expansion residue generated by the heat of the fire or the like from the first heat-expandable refractory material 15 first It is possible to prevent the described expansion of the second thermally expandable refractory material 150 from being hindered.

As the second heat-expandable refractory material 150 used in the present invention, the same material as in the case of the first heat-expandable refractory material can be used.
Further, as the second heat-expandable refractory material, for example, in addition to at least one selected from the group consisting of a reaction-curable resin component, a thermosetting resin component and a thermoplastic resin component, a heat-expandable component and an inorganic filler A thermally expandable refractory member formed by molding a resin composition containing at least
Specifically, for example, an epoxy resin, thermally expandable graphite, a phosphorus compound, a molded product of a thermally expandable resin composition containing an inorganic filler, butyl rubber, thermally expandable graphite, a phosphorus compound, an inorganic filler. And the like obtained by molding a heat-expandable resin composition containing the same.

Further, as the second heat-expandable refractory material 150 used in the present invention, a tape-shaped material can be used.
A commercially available tape-shaped second heat-expandable refractory material 150 can be used, for example, Fibroc (registered trademark) manufactured by Sekisui Chemical Co., Ltd. A resin compound containing epoxy resin or rubber, a phosphorus compound, and heat-expandable graphite. And a sheet material of a heat-expandable resin composition containing an inorganic filler and the like), a fire barrier (a sheet material made of a resin composition containing chloroprene rubber and vermiculite, a coefficient of expansion: 3 times) of Sumitomo 3M Limited. Thermal conductivity: 0.20 kcal / m · h · ° C., Mejihikat (a sheet material composed of a resin composition containing a polyurethane resin and thermally expandable graphite, manufactured by Mitsui Kinzoku Kagaku Kabushiki Kaisha, expansion coefficient: 4 times, thermal conductivity) : 0.21 kcal / m · h · ° C.).

  Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

According to the composition shown in Table 1, the heat-expandable refractory material was divided into the isocyanate component (X) and the component (Y) other than the isocyanate, and each component was stirred using a planetary stirrer.
Specifically, a polyurethane resin was used as the heat-expandable refractory material. As the reaction-curable resin component (A), a polyether polyol (trade name: T400, manufactured by Mitsui Chemicals) is used as a curing agent for the polyurethane resin, and a polyisocyanate compound (trade name: M200, Mitsui Chemicals) is used as the main component of the polyurethane resin. Was used.
As the liquid dispersant (C), PFR (trade name, manufactured by ADEKA Corporation, IUPAC name: Phosphpric trichloride, polymer with 1,3-benzenedio 1, phenyl ester, CAS number: 57583-54-7) was used.
In Table 1, APP means ammonium polyphosphate, and MPP means melamine polyphosphate.
A polyisocyanate compound as a main component of the urethane resin and a polyether polyol as a curing agent were adjusted so that the isocyanate index became 105.
When the component (X) and the component (Y) were mixed, the heat-expandable refractory material hardened while foaming over time. A test piece (60 mm × 60 mm × 20 mm) was cut out from the cured product and used for the following test.

[Measurement of viscosity]

Next, the viscosities of the X component and the Y component were measured. The viscosity was measured at 25 ° C. using a B-type rotary viscometer (manufactured by Viscotec) for viscosity measurement. The rotational speed of the B-type rotary viscometer at the time of measurement is 20 rpm when the viscosity of the Y component is less than 20,000 mPa · s, and 10 rpm when the viscosity is 20,000 mPa · s or more and less than 100,000 mPa · s. , 100,000 mPa · s or more, 5 rpm, the spindle of R6 was used, the X component was 30 rpm, and the spindle of R2 was used.
The respective viscosities of the obtained X component and Y component were added at a ratio of a weight ratio of the X component and the Y component to obtain an overall viscosity. This value is shown in Table 1.
When the measured value of the viscosity is less than 30,000 (mPa · s), ◎ when the viscosity is in the range of 30,000 to 100,000 (mPa · s), and x when the viscosity exceeds 100,000 mPa · s. The results are described in Table 2.

[Fire resistance: measurement of expansion ratio]
Heating was performed at a temperature of 600 ° C. for 30 minutes using an electric furnace.
A test piece having a width of 60 mm, a length of 60 mm, and a thickness of 20 mm is put into an electric furnace heated to 600 ° C., and the volume is measured from the width, length, and thickness before and after heating. The value obtained by the division was defined as the expansion ratio.
The results are shown in Table 1 as ○ when the expansion ratio is in the range of 1 to 5, and x when the expansion ratio is less than 1 and contracted.

[Fire resistance: Residual hardness measurement]
By compressing the expansion residue after heating at a temperature of 600 ° C. for 30 minutes using an electric furnace at 0.1 cm / s, the breaking strength of the expansion residue is measured using a compression tester (manufactured by Kato Tech Co., Ltd.). It was measured.
The results are shown in Table 1, where ○ indicates a value of 0.1 kgf / cm ² or more and × indicates a value of less than 0.1 kgf / cm ² .
When the residue hardness is 0.1 kgf / cm ² or more, the expanded residue can be lifted by hand.

[Plastic Effect of Liquid Dispersant on Resin Frame Material: Measurement of Weight Change]
The end material of polyvinyl chloride used for the resin frame material was immersed in the liquid dispersant (C) shown in Table 1, and allowed to stand at a temperature of 50 ° C. for 5 days.
Next, the polyvinyl chloride remnants were taken out of the liquid dispersant (C), the liquid dispersant (C) adhering to the surface of the polyvinyl chloride remnants was wiped off with a rag, and the weight was measured. .
The percentage of the increase in weight after the end of the test with respect to the weight before the start of the test is shown in percentage. The results are shown in Table 1 with the case where this value is less than 1% by weight as ○ and the case where this value is not less than 1% by x.

[Plastic effect of liquid dispersant on resin frame material: Measurement of hardness change]
The end material of polyvinyl chloride used for the resin frame material was immersed in the liquid dispersant (C) shown in Table 1, and allowed to stand at a temperature of 50 ° C. for 5 days.
Next, the polyvinyl chloride scrap was removed from the liquid dispersant (C), and the liquid dispersant (C) adhering to the polyvinyl chloride scrap was wiped off with a rag.
After the end of the test, a hardness test using a pencil was performed on the polyvinyl chloride scrap according to the test method of JIS K 5600-5-4.
The pencil height of the scraps not immersed in the liquid dispersant (C) was F.
The results are shown in Table 1, with the case where the surface hardness of the end material of the polyvinyl chloride after the test was a pencil having a hardness of F was represented by ○, and the case where the surface hardness was lower than the hardness F was represented by ×.

In the case of Example 1 shown in Table 1, as a isocyanate, 59.5 parts by weight of M400 manufactured by Mitsui Chemicals, Inc. was used instead of M200 manufactured by Mitsui Chemicals, Inc.
The amount of the heat-expandable graphite was 17.7 parts by weight, the amount of APP (ammonium polyphosphate) was 24.2 parts by weight, and the amount of calcium carbonate was 24.2 parts by weight.
Further, as the liquid dispersant (C), DAIGARD 540 (a mixture of a halogen-containing condensed phosphoric acid ester and a halogen-containing phosphoric acid ester; a product of Daihachi Chemical Industry Co., Ltd .; Used 10 parts by weight of a polyoxyalkylenebisdichloroalkyl phosphate (CAS number: 184530-92-5) and a mixture of tris (β-chloropropyl) phosphate (CAS number: 13674-84-5). Otherwise, the test was performed in the same manner as in Example 1. Table 1 shows the results.

In the case of Example 1 shown in Table 1, 52.3 parts by weight of T80 manufactured by Mitsui Chemicals, Inc. was used as the isocyanate instead of M200 manufactured by Mitsui Chemicals, Inc.
The amount of the polyether polyol was 47.7 parts by weight, the amount of pure water was 1.43 parts by weight, the amount of the foam stabilizer was 0.77 parts by weight, and the amount of the urethanization catalyst was 0. 0.77 parts by weight, 17.7 parts by weight of the heat-expandable graphite, 24.2 parts by weight of APP (ammonium polyphosphate), and 24.2 parts by weight of calcium carbonate. did.
In addition, as the liquid dispersant (C), DAIGARD 580 (a mixture of polyoxyalkylene phosphate and aromatic condensed phosphate, manufactured by Daihachi Chemical Co., Ltd. instead of PFR manufactured by ADEKA of Example 1; component 1) CAS No. 227089-98-7, and component 2 used in the same manner as in Example 1 except that 10 parts by weight of CAS No .: 125597-219, 172589-68-3 and 115-86-6 were used. The test was performed. Table 1 shows the results.

In the case of Example 1 shown in Table 1, as a polyether polyol, 47.6 parts by weight of T700 manufactured by Mitsui Chemicals, Inc. was used instead of T400 manufactured by Mitsui Chemicals, Inc.
In addition, 27.3 parts by weight of GREP-HE manufactured by Tosoh Corporation was used in place of ADT351 manufactured by ADT of Example 1 as the heat-expandable graphite.
The amount of isocyanate used was 52.4 parts by weight, the amount of pure water was 1.4 parts by weight, the amount of the foam stabilizer was 0.7 parts by weight, and the amount of the urethane-forming catalyst was 0.7 parts by weight. Parts by weight were used.
As the liquid dispersant (C), 10 parts by weight of ADE600 FP600 (bisphenol A bis (diphenyl phosphate); CAS No .: 5945-33-5) was used instead of ADEKA PFR in Example 1. The test was performed in the same manner as in Example 1 except for the above. Table 1 shows the results.

In the case of Example 1 shown in Table 1, 40.5 parts by weight of Mitsui Chemicals SOR400 was used as a polyether polyol instead of Mitsui Chemicals T400.
The amount of the heat-expandable graphite was 17.7 parts by weight, the amount of APP (ammonium polyphosphate) was 24.2 parts by weight, and the amount of calcium carbonate was 24.2 parts by weight.
The test was performed in the same manner as in Example 1 except that 10 parts by weight of DAIGARD 540 manufactured by Daihachi Chemical Industry Co., Ltd. was used as the liquid dispersant (C) instead of PFR manufactured by ADEKA. Table 1 shows the results.

In the case of Example 1 shown in Table 1, the amount of the thermally expandable graphite was 22.7 parts by weight, the amount of the APP (ammonium polyphosphate) was 21.7 parts by weight, and the amount of the calcium carbonate was 21.7 parts by weight. It was 21.7 parts by weight.
The test was performed in the same manner as in Example 1, except that 10 parts by weight of DAIGARD 540 manufactured by Daihachi Chemical Industry Co., Ltd. was used as the liquid dispersant (C) in place of PFR manufactured by ADEKA of Example 1. did. Table 1 shows the results.

In the case of Example 1 shown in Table 1, the amount of the heat-expandable graphite was 37.7 parts by weight, the amount of APP (ammonium polyphosphate) was 6.7 parts by weight, and the amount of calcium carbonate was It was 6.7 parts by weight.
The test was performed in the same manner as in Example 1, except that 10 parts by weight of DAIGARD 540 manufactured by Daihachi Chemical Industry Co., Ltd. was used as the liquid dispersant (C) in place of PFR manufactured by ADEKA of Example 1. did. Table 1 shows the results.

In the case of Example 1 shown in Table 1, 48.8 parts by weight of a polyester polyol (trade name: ES253, manufactured by Mitsui Chemicals, Inc.) was used instead of the polyether polyol.
The amount of isocyanate used was 51.2 parts by weight, the amount of pure water was 1.46 parts by weight, the amount of foam stabilizer was 0.73 parts by weight, and the amount of urethanizing catalyst was 0.73 parts by weight. The amount of APP (ammonium polyphosphate) was 11.7 parts by weight, and the amount of calcium carbonate was 11.7 parts by weight.
In addition, 27.7 parts by weight of GREP-EG manufactured by Tosoh Corporation was used instead of ADT351 manufactured by ADT of Example 1 as the heat-expandable graphite.
As the liquid dispersant (C), instead of PFR manufactured by ADEKA of Example 1, CR504L manufactured by Daihachi Chemical Industry Co., Ltd. (mixture of a halogen-containing condensed phosphate ester and a halogen-containing phosphate ester. Is a mixture of polyoxyalkylene bisdichloroalkyl phosphate (CAS number: 184530-92-5) and tris (β-chloropropyl) phosphate (CAS number: 13674-84-5). The test was carried out in the same manner as in Example 1 except that 10 parts by weight of the condensed phosphoric acid ester and the halogen-containing phosphoric acid ester were different. Table 1 shows the results.

In the case of Example 1 shown in Table 1, 47.7 parts by weight of a polyester polyol (trade name: RFK505, manufactured by Kawasaki Kasei Co., Ltd.) was used instead of the polyether polyol.
The amount of isocyanate used was 52.3 parts by weight, the amount of pure water was 1.43 parts by weight, the amount of foam stabilizer was 0.72 parts by weight, and the amount of the urethane-forming catalyst was 0.72 parts by weight. Parts by weight, the amount of thermally expandable graphite used was 37.7 parts by weight, the amount of APP (ammonium polyphosphate) used was 6.7 parts by weight, and the amount of calcium carbonate used was 6.7 parts by weight.
The test was performed in the same manner as in Example 2 except that 10 parts by weight of DAIGARD 540 manufactured by Daihachi Chemical Industry Co., Ltd. was used as the liquid dispersant (C) instead of PFR manufactured by ADEKA of Example 1. did. Table 1 shows the results.

In the case of Example 1 shown in Table 1, 21.7 parts by weight of MPP (melamine polyphosphate) was used instead of APP (ammonium polyphosphate).
The amount of the heat-expandable graphite was 22.7 parts by weight, and the amount of the calcium carbonate was 21.7 parts by weight.
The test was performed in the same manner as in Example 1, except that 10 parts by weight of DAIGARD 540 manufactured by Daihachi Chemical Industry Co., Ltd. was used as the liquid dispersant (C) in place of PFR manufactured by ADEKA of Example 1. did. Table 2 shows the results.

  In the case of Example 10 shown in Table 2, the test was performed in the same manner as in Example 10 except that 21.7 parts by weight of APP (manufactured by Clariant, trade name: AP462) was used instead of MPP. . Table 2 shows the results.

  In the case of Example 10 shown in Table 2, 21.7 parts by weight of APP (manufactured by Clariant, trade name: AP422) was used instead of MPP, and silica was replaced with 21.7 parts by weight of calcium carbonate of Example 10. The test was carried out in the same manner as in Example 10 except that parts by weight were used. Table 2 shows the results.

  In the case of Example 12 shown in Table 2, in the same manner as in Example 12 except that 21.7 parts by weight of titanium oxide (trade name: SA-1 manufactured by Sakai Chemical Co., Ltd.) was used instead of silica. The test was performed. Table 2 shows the results.

  The test was performed in the same manner as in Example 12 except that 21.7 parts by weight of zinc oxide was used instead of silica in Example 12 shown in Table 2. Table 2 shows the results.

In the case of Example 4 shown in Table 1, 45 parts by weight of Tosoh GREP-EG was used as the thermally expandable graphite instead of Tosoh GREP-HE.
The amount of APP (ammonium polyphosphate) used was 6.7 parts by weight, and the amount of calcium carbonate used was 6.7 parts by weight.
The test was performed in the same manner as in Example 1 except that 10 parts by weight of PDE manufactured by ADEKA was used instead of FP600 manufactured by ADEKA in Example 4 as the liquid dispersant (C). Table 2 shows the results.

In the case of Example 15 shown in Table 2, the amount of the heat-expandable graphite was set to 60 parts by weight.
In addition, 6.7 parts by weight of Clariant's AP462 was used instead of Clariant's AP422 used in Example 15, and 6.7 parts by weight of silica was used instead of calcium carbonate. The test was performed as in the case. Table 2 shows the results.

In the case of Example 15 shown in Table 2, 80 parts by weight of GREP-HE manufactured by Tosoh Corporation was used instead of GREP-EG manufactured by Tosoh Corporation as the thermally expandable graphite.
The test was performed in the same manner as in Example 15 except that 6.7 parts by weight of MPP was used instead of the APP used in Example 15, and 6.7 parts by weight of titanium oxide was used instead of calcium carbonate. Was carried out. Table 2 shows the results.

[Comparative Example 1]
In the case of Example 1 shown in Table 1, CDP (monophosphate ester, cresyl diphenyl phosphate, CAS No., CAS No.) manufactured by Daihachi Chemical Industry Co., Ltd. was used as the liquid dispersant (C) instead of PFR manufactured by ADEKA. A test was conducted in the same manner as in Example 1 except that 26444-49-5) was used in an amount of 10 parts by weight. Table 3 shows the results.

[Comparative Example 2]
In the case of Example 1 shown in Table 1, as a liquid dispersant (C), instead of PFR manufactured by ADEKA, TCP (monophosphate ester, tricresyl phosphate manufactured by Daihachi Chemical Industry Co., Ltd., CAS number: The test was carried out in the same manner as in Example 1 except that 10 parts by weight of 1330-78-5) was used. Table 3 shows the results.

[Comparative Example 3]
In the case of Example 1 shown in Table 1, as a liquid dispersant (C), instead of PFR manufactured by ADEKA, TMCPP (monophosphate ester; tris (chloropropyl) phosphate) manufactured by Daihachi Chemical Industry Co., Ltd. A test was carried out in the same manner as in Example 1 except that 10 parts by weight of CAS No .: 13674-84-5) were used. Table 3 shows the results.

［実施例１８］
The viscosities of the liquid dispersants (C) used in Examples 1 to 17 and the liquid dispersants used in Comparative Examples 1 to 3 are as follows.

[Example 18]

  In Example 18, a fire protection structure 200 made of a resin sash was manufactured and a fire resistance test was performed. This test and its results will be described. The structure of the fire prevention structure 200 for the resin sash according to Example 18 is the same as that of the fire prevention structure 100 for the resin sash according to the above-described first embodiment. 3 is the same as the fire prevention structure 100 of the resin sash according to the first embodiment, and thus the description is omitted.

  FIG. 4 is a schematic front view for explaining the structure of the fire protection structure 200 for the resin sash according to Embodiment 18 of the present invention. FIG. 5 is a schematic cross-sectional view of a principal part of the fire prevention structure 200 for the resin sash according to the eighteenth embodiment, taken along line AA of FIG.

  As shown in FIG. 4, a fire-resistant plate 201 made of glass is supported by a resin frame 202 made of hard vinyl chloride having a hollow portion formed therein along the longitudinal direction.

In order to reproduce an opening of a structure such as a house for a fire test, a calcium silicate plate 204 is surrounded around the fire-resistant plate 201 and the frame 202 without gaps.
As shown in FIG. 5, a plurality of hollow portions 210 to 212 are provided along the longitudinal direction inside a resin frame member 202 used for the fire protection structure 200 of the resin sash.

Next, according to the composition of Example 3 shown in Table 1, the first thermally expandable refractory material 15 was divided into an X component and a Y component, and each component was stirred using a planetary stirrer.
Specifically, a polyurethane resin was used as the heat-expandable refractory material. As the X component, an isocyanate compound was used as a main component of the polyurethane resin.
Using a component other than the isocyanate compound polyurethane resin as the Y component,
An isocyanate index [(moles of isocyanate groups) / (moles of all active hydrogen groups including water) × 100] of an isocyanate compound which is a main component of the urethane resin and a polyether polyol which is a curing agent is 105. It was adjusted to become.

Next, as shown in FIGS. 4 and 5, among the hollow portions of the resin frame member 202 made of hard vinyl chloride having a hollow portion formed therein along the longitudinal direction, The A component and the B component were injected over the entire circumference of the resin frame member 202 while maintaining the above mixing ratio.
The injected first heat-expandable refractory material 15 hardened while foaming inside the hollow portion 210, lost its fluidity, and formed a urethane resin foam.

The thermal expansion start temperature of the first thermally expandable refractory material 15 was 210 ° C. The second heat-expandable refractory material 150 used in the present invention had the composition shown in Example 7 of Table 1, and its thermal expansion start temperature was 170 ° C.
The thermal expansion start temperature in the present invention is a temperature at which expansion starts due to heat, and it can be confirmed that the test piece starts expanding when the test piece is carefully heated. The temperature at which this expansion can be visually confirmed is the thermal expansion start temperature.

  The thermal expansion ratio of the first heat-expandable refractory material 15 and the thermal expansion ratio of the second heat-expandable refractory material 150 are 1.2 times and 2.times. It was twice.

As shown in FIG. 5, in the fire prevention structure 200 for a resin sash according to the fifteenth embodiment, a second heat-expandable fire-resistant material 150 is provided between the fire-resistant plate 201 and the resin frame 202. ing. The second thermally expandable refractory material 150 covers the support member 40.
Further, the second thermally expandable refractory material 150 was provided between the plate material 201 having the fire resistance and the plate material supporting portion 40 over the entire circumference of the plate material 201 having the fire resistance.

  The fire prevention structure 200 of the resin sash according to Example 18 is exposed to a flame such as a fire, and the fire-resistant plate 201 is warped, so that the space between the resin frame 202 and the fire-resistant plate 201 is formed. There may be gaps. Also in this case, a second heat-expandable fire-resistant material 150 is provided between the fire-resistant plate 201 and the resin frame member 202, and the second heat-expandable fire-resistant material 150 covers the support member 40. Therefore, the heat of a fire or the like expands the second thermally expandable refractory material 150 to form an expanded residue. Since the expansion residue blocks a gap generated between the resin frame member 202 and the fire-resistant plate member 201, the fire protection structure 200 for the resin sash according to Example 18 is excellent in fire protection.

[Fire test]
A fire resistance test was performed on the fire-resistant reinforced building member 200 according to the conditions of ISO834. The fire resistance test was performed until the flame penetrated the fire-resistant reinforced building member 200.
As a result of the fire resistance test, the case where no leakage of the flame was observed for 20 minutes or more from the surface opposite to the heated surface was evaluated as 、, and the case where leakage of the flame was observed for less than 20 minutes was evaluated as ×. The results are shown in Table 5.

  At the start of the fire resistance test, the first heat-expandable refractory material 15 on the heating surface side expanded to form a thermal expansion residue. Even after a lapse of 20 minutes from the start of the fire resistance test, no fire leakage was observed in the fire-resistant reinforced building member 200 of Example 15.

[Smoke barrier test]
In the above fire resistance test, 場合 indicates that smoke did not leak from the surface opposite to the heated surface for 20 minutes or more, and X indicates that smoke leaked for less than 20 minutes. The results are shown in Table 5.

[Expansion residue autonomy test]
After performing the fire resistance test, the expansion residues obtained from the first heat-expandable refractory material 15 and the second heat-expandable refractory material 150 were collected, and the autonomy of each expansion residue was observed.
The case where the expanded residue collapsed under its own weight and maintained a certain shape without being collapsed by its own weight was evaluated as O, and the case where the expanded residue collapsed under its own weight was evaluated as x. The results are shown in Table 5.

In the case of Example 19, the thermal expansion ratio of the first thermally expandable refractory material 15 and the thermal expansion ratio of the second thermally expandable refractory material 150 are 2.2 times and 1.3 times, respectively. The test was performed in exactly the same manner as in Example 18 except that was used.
The compositions used for the first heat-expandable refractory material 15 and the second heat-expandable refractory material 150 are the same as those described in Example 7 of Table 1 and Example 6 of Table 1, respectively. .
Table 5 shows the results.

In the case of Example 20, the thermal expansion ratio of the first thermally expandable refractory material 15 and the thermal expansion ratio of the second thermally expandable refractory material 150 are 2.4 times and 2.4 times, respectively. The test was performed in exactly the same manner as in Example 18 except that was used.
Each of the compositions used for the first heat-expandable refractory material 15 and the second heat-expandable refractory material 150 is the same as that described in Example 15 of Table 2.
Table 5 shows the results.

In the case of Example 21, the thermal expansion ratio of the first thermally expandable refractory material 15 and the thermal expansion ratio of the second thermally expandable refractory material 150 are 4.5 times and 1.1 times, respectively. The test was performed in exactly the same manner as in Example 18 except that was used.
The compositions used for the first heat-expandable refractory material 15 and the second heat-expandable refractory material 150 are the same as those described in Example 17 of Table 2 and Example 2 of Table 1, respectively. .
Table 5 shows the results.

[Comparative Example 6]
In the case of Comparative Example 6, the thermal expansion ratio of the first thermally expandable refractory material 15 and the thermal expansion ratio of the second thermally expandable refractory material 150 are 0.4 times and 0.4 times, respectively. The test was performed in exactly the same manner as in Example 18 except that was used.
Each of the compositions used for the first heat-expandable refractory material 15 and the second heat-expandable refractory material 150 is the same as that described in Comparative Example 5 of Table 3.
Table 5 shows the results.

[Comparative Example 7]
In the case of Comparative Example 7, the thermal expansion ratio of the first thermally expandable refractory material 15 and the thermal expansion ratio of the second thermally expandable refractory material 150 are 5.5 times and 5.5 times, respectively. The test was performed in exactly the same manner as in Example 18 except that was used.
Each of the compositions used for the first heat-expandable refractory material 15 and the second heat-expandable refractory material 150 is the same as that described in Comparative Example 4 of Table 3.
Table 5 shows the results.

[Comparative Reference Example 1]
Comparative Reference Example 1 is a modification of Example 18.
FIG. 6 is a schematic cross-sectional view of a principal part of a fire prevention structure 320 of a resin sash according to Comparative Reference Example 1.
In the case of Example 18, the second heat-expandable refractory material 150 was disposed in contact with the resin frame member 202, the support member 40, and the plate member 201 having fire resistance.
On the other hand, in the case of Comparative Reference Example 1, the difference is that the second thermally expandable refractory material 150 is provided with a space provided between the support member 40 and the plate material support portion 30.
Other than that, it is the same as the case of the eighteenth embodiment.
In the case of Comparative Reference Example 1, the fixing member 50 can move, and a gap is created between the fire-resistant plate 201 and the resin frame 202.

[Comparative Reference Example 2]
FIG. 7 is a schematic cross-sectional view of a principal part of a fire prevention structure 370 for a resin sash according to Comparative Reference Example 2.
Comparative Reference Example 2 is a modification of Example 18.
In the case of Example 18, the first heat-expandable refractory material 15 is injected into the hollow portions 211 and 212 without injecting the first heat-expandable refractory material 15 into the hollow portion 210. The same applies to a hollow portion not shown in FIG.
In the case of Comparative Reference Example 2, when heated, the fixing member 50 can move, and a gap is generated between the fire-resistant plate 201 and the resin frame 202.

[Comparative Reference Example 3]
Comparative Reference Example 3 is a modification of Example 18.
FIG. 8 is a schematic cross-sectional view of a principal part of a fire prevention structure 380 of a resin sash according to Comparative Reference Example 3.
In Comparative Reference Example 3, the second heat-expandable refractory material 150 was not used.
In the case of Comparative Reference Example 3, the fixing member 50 can move, and a gap is generated between the fire-resistant plate 201 and the resin frame 202.

[Application Example 1]
The resin sash fire protection structure 390 according to the application example 1 is a modified example of the resin sash fire protection structure 200 according to the eighteenth embodiment.
FIG. 9 is a schematic front view of the fire prevention structure 390 of the resin sash according to the first application example. FIG. 10 is a schematic cross-sectional view of the fire prevention structure 390 of the resin sash according to the application example 1. The cross-sectional view in FIG. 9 is a schematic main-portion cross-sectional view along the line BB in FIG.
As shown in FIG. 10, in the fire prevention structure 390 of the resin sash according to the application example 1, the second heat-expandable fire-resistant material 150 is in contact with the fire-resistant plate 201, the resin frame 202, and the support member 40. is set up.

As shown in FIG. 10, a support member 70 having a substantially U-shaped cross section is inserted into a hollow portion inside the horizontal frame body 14 below the resin frame member 202. Examples of the support member 70 used in Application Example 1 include a member made of metal.
As the metal, for example, an aluminum material, a stainless steel material, a steel material, an alloy material, or the like can be used.
Although the cross section of the support member 70 used in the application example 1 is substantially U-shaped, a cylindrical support member may be used.
If the support member 70 is not used, a gap is easily generated between the fire-resistant plate 201 and the horizontal frame 14 due to the weight of the fire-resistant plate 201.
On the other hand, by inserting the support member 70 into a resin frame material that is in contact with the lower end of the fire-resistant plate material 201, that is, into the hollow portion inside the horizontal frame body 14, the fire-resistant plate material 201 and the A gap can be prevented from being formed between the horizontal frame 14 and the horizontal frame 14.
For this reason, the fire prevention structure 390 of the resin sash according to the application example 1 is excellent in fire protection.

[Application Example 2]
The resin sash fire prevention structure 400 according to the application example 2 is a modification of the resin sash fire prevention structure 200 according to the eighteenth embodiment.
FIG. 11 is a schematic cross-sectional view of a fire prevention structure 400 for a resin sash according to the second application example.
A heat-expandable refractory tape 60 is provided inside the hollow portion 212 of the plate support portion 220 of the resin frame member 202.
Note that the heat-expandable fire-resistant tape 60 may be provided between the plate 201 having fire resistance and the plate support portion 220 and between the plate 201 having fire resistance and the support member 40.

  As the heat-expandable fire-resistant tape 60 used in the present invention, for example, a heat-expandable resin composition containing a resin component such as an epoxy resin or rubber, a phosphorus compound, a heat-expandable graphite, an inorganic filler and the like can be used. And the like.

The thermal expansion start temperature of the thermally expandable refractory tape 60 can be changed by adjusting the thermal expansion start temperature of the thermally expandable graphite contained in the thermally expandable resin composition.
Since heat-expandable graphites having different thermal expansion start temperatures are commercially available, by selecting a heat-expandable graphite having a target thermal expansion start temperature, the heat-expandable refractory tape 60 having a desired thermal expansion start temperature can be obtained. Is obtained.

The thermal expansion start temperature of the heat-expandable refractory tape 60 used in the present invention is preferably in the range of 150 to 200 ° C, and more preferably in the range of 160 to 180 ° C.
If the thermal expansion start temperature of the heat-expandable fire-resistant tape 60 is in the range of 150 to 200 ° C., the gap generated between the resin frame material 10 and the fire-resistant plate material 20 due to heat of a fire or the like is quickly closed. can do.

The thermal expansion ratio of the heat-expandable refractory tape 60 is preferably in a range of more than 10 times and 60 times or less, more preferably more than 15 times and 50 times or less under heating conditions of 600 ° C. × 30 minutes. .
If the coefficient of thermal expansion of the heat-expandable fire-resistant tape 60 is in a range of more than 10 times and not more than 60 times, a gap generated between the resin frame material 10 and the fire-resistant plate 20 due to heat of a fire or the like. The closure can be reliably performed.

  As the heat-expandable fire-resistant tape 60 used in the present invention, a commercially available product can be used. For example, Fibroc (registered trademark) manufactured by Sekisui Chemical Co., Ltd. A resin containing epoxy resin or rubber as a resin component, a phosphorus compound, heat-expandable graphite And a sheet material of a heat-expandable resin composition containing an inorganic filler and the like), a fire barrier (a sheet material made of a resin composition containing chloroprene rubber and vermiculite, a coefficient of expansion: 3 times) of Sumitomo 3M Limited. Thermal conductivity: 0.20 kcal / m · h · ° C., Mejihikat (a sheet material composed of a resin composition containing a polyurethane resin and thermally expandable graphite, manufactured by Mitsui Kinzoku Kagaku Kabushiki Kaisha, expansion coefficient: 4 times, thermal conductivity) : 0.21 kcal / m · h · ° C.).

The heat-expandable fire-resistant tape 60 used in the present invention is preferably made of a heat-expandable resin composition.
It is more preferable that the heat-expandable fire-resistant tape 60 be a tape formed by laminating at least a heat-expandable resin composition layer and a base material layer.
Examples of the substrate layer include a cloth such as a nonwoven fabric, a metal layer, and an inorganic material layer.
More specifically, it is more preferable that the heat-expandable fire-resistant tape 60 be a tape obtained by laminating one or more of a heat-expandable resin composition layer, an inorganic fiber layer, a metal foil layer, and the like.

Examples of the heat-expandable resin composition layer include those obtained by molding the heat-expandable resin composition.
Examples of the inorganic fibers used in the inorganic fiber layer include rock wool, ceramic wool, silica-alumina fiber, alumina fiber, silica fiber, zirconia fiber, and ceramic blanket.

  Examples of the metal foil used for the metal foil layer include metal foils such as aluminum foil, copper foil, stainless steel foil, tin foil, lead foil, tin-lead alloy foil, clad foil, and anti-lead foil.

  The heat-expandable fire-resistant tape 60 used in the present invention is formed by laminating a heat-expandable resin composition layer and a nonwoven fabric layer, or a heat-expandable resin composition layer from the side of the fire-resistant plate material 20, It is more preferable to use a fiber layer and a metal foil layer laminated in this order.

  When the heat-expandable fire-resistant tape 60 includes a metal foil, it is preferable that the metal foil is disposed on the outermost layer from the viewpoint of handleability.

  Further, the heat-expandable fire-resistant tape 60 used in the present invention is obtained by applying an adhesive to the adhesive surface, and adding an adhesive component to the heat-expandable resin composition constituting the heat-expandable fire-resistant tape 60. The heat-expandable fire-resistant tape 60 itself may be made to have an adhesive property.

The thermal expansion start temperature of the thermally expandable refractory material 15 is preferably in the range of 180 to 250 ° C.
If the thermal expansion start temperature of the thermally expandable refractory material is in the range of 180 to 250 ° C., an expansion residue generated from the thermally expandable refractory material by heat such as a fire may cause the expansion of the thermally expandable refractory tape described above. It is possible to prevent the expansion from being hindered.

The heat-expandable fire-resistant tape 60 used in Application Example 2 was Sekisui Chemical Co., Ltd. (registered trademark: Fiblock), in which a non-woven fabric layer was laminated on both sides of a heat-expandable resin composition layer. The outermost surface is coated with an adhesive.
Further, the heat-expandable fire-resistant tape 60 was placed between the fire-resistant plate material 201 and the plate-material support portion 220 over the entire circumference of the fire-resistant plate material 201.
The thermal expansion start temperature of the thermally expandable refractory tape 60 used in the present invention was 170 ° C.

The heat-expandable refractory tape 60 may be installed in the hollow part 212 of the plate supporting part 220.
The heat of a fire or the like causes the heat-expandable refractory tape 60 to expand to form an expansion residue. Since the expansion residue blocks the space between the resin frame member 202 and the fire-resistant plate member 201, the fire protection structure 400 of the resin sash according to the application example 2 is excellent in fire protection.

[Application Example 3]
The resin sash fire protection structure 410 according to the application example 3 is a modified example of the resin sash fire protection structure 200 according to the eighteenth embodiment.
FIG. 12 is a schematic cross-sectional view of a principal part of a fire prevention structure for a resin sash according to the third application example.
In the case of Example 18, the fixing member 50 was inserted into the hollow portion of the resin frame member 202.
On the other hand, in the case of the application example 3, the difference is that the fixing member 50 is fixed to the fixing plate 80 provided on the outer peripheral surface 16 of the resin frame member 202 through the resin frame member 202.
Examples of the material of the fixing plate 80 used in the present invention include a metal material and an inorganic material.
Specific examples of the metal material and the inorganic material used for the fixing plate 80 are the same as those of the above-described plate material 20 having fire resistance.

In the case of the present invention, by using the fixing plate 80, the fixing member 50 more stably allows the support member 40 to face the side surface 22 of the fire-resistant plate member 201 and the resin frame member. 202 can be fixed to the outer peripheral surface 16.
Accordingly, it is possible to prevent a gap from being formed between the resin frame member 202 and the fire-resistant plate member 201, so that the fire prevention structure 410 of the resin sash according to the application example 3 has excellent fire resistance.

[Application Example 4]
The fire prevention structure 420 of the resin sash according to the application example 4 is a modified example of the fire prevention structure 200 of the resin sash according to the eighteenth embodiment.
FIG. 13 is a schematic cross-sectional view of a principal part of a fire prevention structure 420 for a resin sash according to Application Example 4.
FIG. 14 is a schematic cross-sectional view of a principal part for explaining the relationship between the fixing auxiliary member 80 inserted into the hollow part 210 of the resin frame member 202 and the thermally expandable refractory material injected into the hollow part 11a. .
A dashed line BB in FIG. 14 illustrates the reference surface when the surface 21 forming the fire-resistant surface of the plate material 201 having fire resistance is set as the reference surface. Here, the fire-resistant surface of the plate material 20 having the fire resistance is the A side in FIG.
In the present invention, the volume of the heat-expandable refractory material 15 contained in the hollow portion 210 of the resin frame material 202 on the fire-resistant surface A side from the reference surface of the resin frame material 202 is smaller than the reference surface. It is necessary that the volume is larger than the volume of the fixing auxiliary member 80 included in the hollow portion 210 of the resin frame member 202 on the fireproof surface A side.
This relationship is the same for all hollow portions included in the resin frame member 202.

  The volume of the heat-expandable refractory material 15 contained in the hollow portion 210 of the resin frame member 202 on the fire-resistant surface A side from the reference surface is smaller than the resin frame member 202 on the fire-resistant surface A side from the reference surface. Is larger than the volume of the fixing auxiliary member 80 included in the hollow portion 210, even when the fire prevention structure of the resin sash according to the present invention is exposed to a flame such as a fire, the flame moves to the opposite side of the fireproof surface A. Can be reached.

It is preferable that the fixing auxiliary member 80 be made of at least one of wood and fiber-reinforced plastic because of excellent handleability.
Examples of the wood include natural wood, molded wood obtained by hardening a piece of wood, a wood sheet, and the like with a resin.
Examples of the fiber reinforced plastic include fiber reinforced urethane foam. As the fiber-reinforced urethane foam, a commercially available product such as Eslon (registered trademark; Sekisui Chemical Co., Ltd.) can be selected and used.

In the hollow portion 210, the fixing auxiliary member may be installed over the entire circumference in the hollow portion or may be partially installed, and can be appropriately selected.
The fixing auxiliary member may be appropriately selected as having a triangular prism having a triangular cross section or a quadrangular prism having a rectangular cross section.
The same applies to the case where the resin frame is a fixed frame and the case where the resin frame is a movable frame.

  Although the structure of the vertical frames 11 and 12 has been described, the same applies to the case of the horizontal frames 13 and 14.

Further, the fixing member 50 penetrates the supporting member 40 and is connected to the fixing auxiliary member 80 in the hollow portion of the resin frame member 202. Therefore, even when the fire prevention structure 400 of the resin sash according to the sixth embodiment is exposed to heat such as a fire, it is possible to prevent a gap from being generated between the resin frame member 202 and the fire-resistant plate 201. it can.
For this reason, the fire prevention structure 420 of the resin sash according to the application example 4 has excellent fire resistance.

  Note that the resin sash according to the present invention is not limited to a fixed resin sash, and for example, a pull-out that can move an opening / closing door, an opening / closing window, a vertical sliding window, a horizontal sliding window, and a plurality of windows in a direction parallel to each other. It can be applied to difference opening windows.

DESCRIPTION OF SYMBOLS 1 Structure 10,202 Resin frame material 11,12 Vertical frame 11a, 11b, 11c, 12a, 12b, 12c, 210, 211, 212 Hollow part 11d, 11e, 12d, 12e Packing installation part 13, 14 Horizontal frame 15, 150 Thermally expandable refractory material 16 Peripheral surface of resin frame material 20, 201 Plate material 21 Surface of plate material 22 Side surface of plate material 30, 31 Plate material support 32, 33, 34, 35 Packing 40 Support member 50 Fixing member 60, 61 , 62 Thermal expansive fire-resistant tape 70 Support material 100, 200, 300, 370, 380, 390, 400 Fire prevention structure of resin sash 201 Plate material 202 Resin frame material 204 Calcium silicate

Claims (17)

A thermally expandable refractory material used for applications injected into a hollow portion of a resin frame material having a hollow portion in a longitudinal direction,
(A) a reaction curable resin component,
(B) a thermal expansion component,
(C) a liquid dispersant comprising a condensed phosphate ester,
And (D) an inorganic filler,
At least
On the basis of the value before being injected into the hollow portion of the frame material, the viscosity at 25 ° C. is in the range of 1000 to 100000 mPa · s,
When a molding material made of the same resin as the resin frame material is immersed in the liquid dispersant (C) at a temperature of 50 ° C. for 5 days, the molding before and after immersion in the liquid dispersant (C) is performed. A thermally expandable refractory material characterized in that the weight change of the material is less than 1%.   The heat-expandable refractory material according to claim 1, wherein the viscosity of the liquid dispersant (C) at 25 ° C is in the range of 0.1 to 50,000 mPa · s.   The heat-expandable refractory material according to claim 1 or 2, wherein the heat-expandable refractory material contains at least one of (E) a foaming agent and (F) a foam stabilizer.   The reaction-curable resin component (A) is selected from urethane resin foam, epoxy resin foam, phenol resin foam, urea resin foam, unsaturated polyester resin foam, alkyd resin foam, melamine resin foam, diallyl phthalate resin foam and silicone resin foam. The heat-expandable refractory material according to any one of claims 1 to 3, which is at least one selected from the group consisting of:   The thermal expansion component (B) is at least one selected from the group consisting of a heat-expandable graphite, a nitrogen-based blowing agent, and a pulverized product of a heat-expandable resin composition. The heat-expandable refractory material according to 1.   The heat-expandable refractory material according to any one of claims 1 to 5, wherein the heat-expandable refractory material includes a catalyst (G). A resin frame material having a hollow portion in the longitudinal direction,
A plate material having fire resistance installed in an opening formed by the resin frame material,
A support member for supporting the plate material having fire resistance,
A first thermally expandable refractory material injected into the hollow portion of the resin frame material,
A second thermally expandable refractory material provided between the plate material having the fire resistance and the resin frame material,
A fixing member for fixing the support member and the resin frame member, a fire prevention structure of a resin sash,
The fixing member penetrates the support member, and is inserted into a hollow portion of the resin frame member to fix the support member and the resin frame member,
The second heat-expandable refractory material contacts the resin frame material, the support member, and a boundary portion of the fire-resistant plate material from at least one surface side of the fire-resistant plate material,
The fire-resistant structure of a resin sash, wherein the first heat-expandable refractory material is the heat-expandable refractory material according to claim 1.   The resin sash according to claim 7, wherein the second heat-expandable refractory material is provided continuously along the entire circumference along the side surface of the plate material having fire resistance. Fire protection structure.   9. The fire protection of the resin sash according to claim 7, wherein a thermal expansion ratio of the first thermally expandable refractory material is in a range of more than 1 to 5 times under a heating condition of 600 ° C. × 30 minutes. Construction.   The fire prevention structure for a resin sash according to any one of claims 7 to 9, wherein the support member comprises at least one of a metal member and an inorganic member having a substantially U-shaped cross section. The first heat-expandable refractory material has a viscosity at 25 ° C. of the first heat-expandable refractory material before being injected into a hollow portion of the resin frame material, in a range of 1000 to 100000 mPa · s,
The said 1st thermally expandable refractory material loses fluidity in the hollow part of the said resin frame material at 25 degreeC after inject | poured into the hollow part of the said resin frame material. Fire protection structure of resin sash.   The fire prevention structure of a resin sash according to any one of claims 7 to 11, wherein the second heat-expandable refractory material includes at least a reaction-curable resin component, a heat expansion component, and an inorganic filler.   The second heat-expandable refractory material, in addition to at least one selected from the group consisting of a reaction-curable resin component, a thermosetting resin component, and a thermoplastic resin component, includes at least a heat-expandable component and an inorganic filler. The fire prevention structure for a resin sash according to any one of claims 7 to 12, wherein the resin sash is formed by molding a resin composition. Supporting material is inserted into the hollow portion of the resin frame material in contact with the lower end of the fire-resistant plate material,
The support material includes a metal,
The fire prevention structure for a resin sash according to any one of claims 7 to 13, wherein a cross section of the support member is at least one of a substantially U-shape and a cylindrical shape. The resin frame member has a plate supporting portion for supporting the surface of the fire-resistant plate,
A heat-expandable fire-resistant tape is installed between the plate having fire resistance and the plate support, between the plate having fire resistance and the support member, and at least one of the hollow portions of the plate support. And
The fire protection structure for a resin sash according to any one of claims 7 to 14, wherein the thermal expansion start temperature of the thermally expandable fire-resistant tape is in the range of 150 to 200C.   The fire prevention structure for a resin sash according to any one of claims 7 to 15, wherein the fixing member penetrates the support member and the resin frame member to fix the support member and the resin frame member. Having a fixing auxiliary member connected to the fixing member,
The fixing auxiliary member is inserted into a hollow portion of the resin frame material,
17. The fixing member according to claim 7, wherein the fixing member penetrates the supporting member and is connected to a fixing auxiliary member inserted into a hollow portion of the resin frame member to fix the supporting member and the resin frame member. The fire prevention structure of the resin sash according to any one of the above.

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