JP2002138596A - Fireproof board and fireproof adhesive compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fireproof board without danger, even in case of fire, of being softened by heat and causing carbide to drop off as a result, and also capable of checking the spread of the fire by means of a good fireproof foam layer to be formed therein. SOLUTION: A fireproof board with a sheet material applied to at least one face of a base material is provided wherein, the sheet material is adhered to the base material by an adhesive including (a) a binder, (b) a foaming agent including at least one selected from azo-compound, hydrazo-compound, nitroso- compound and sulfonyl-hydrazide-compound, (c) expansive graphite expanding at between 200 and 400 degrees centigrade, (d) thermally decomposable nitrogen- containing-compound, (e) at least one from branched polyalcohol and saccharide, and (f) a fire retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fire-resistant board and a fire-resistant adhesive composition which are foamed in a fire to prevent the spread of fire.

[0002]

2. Description of the Related Art Gypsum board products are mainly used as building material boards such as base materials and finishing materials used for walls and ceilings in building structures. Generally, gypsum board is based on gypsum as the main raw material,
On both sides and side surfaces in the length direction (flow direction during molding),
Gypsum board base paper is coated as a sheet material. The flame resistance of such a gypsum board is 9.
The case of 5 mm, 2nd class of flame retardance, 12.5 mm and 15.0 mm is defined as 1st class of flame retardant. As is apparent from this, the fire prevention performance of the gypsum board depends on the thickness of the gypsum itself. When such a gypsum board is used for interior construction of a building structure, in order to further improve the fire resistance and fire resistance of the structure, a means of stacking and bonding a building material board such as a gypsum board is adopted. Have been. For example, 15m
m plasterboard on both sides, two on each side
It has a fire resistant wall for hours. However, increasing the thickness of the wall or ceiling in this way has the disadvantage of affecting the indoor space, partitions, and the structure of the fittings.

[0003] In this respect, for example, a decorative board using an adhesive mixed with a foaming agent as an adhesive for bonding a substrate and decorative paper is known. Such a decorative board is such that when exposed to fire, the adhesive layer foams to provide a fire-resistant and heat-resistant effect, and has the advantage that the boards need not be overlapped as described above. But,
Boards using conventional foaming adhesive, when exposed to fire, the fire-resistant foam layer that gradually foams, or,
In a short period of time, the flame heat is transmitted to the base material through a part of the fire-resistant foam layer, and the fire spread cannot be stopped sufficiently. .

Accordingly, the present invention is to provide a fire-resistant board capable of forming a good fire-resistant foam layer and preventing the spread of fire, without fear of softening due to heating and dropping of carbide when a fire occurs. Make it an issue. Further, the present invention provides
A second object is to provide a fire-resistant adhesive composition which is not inferior in adhesiveness and which foams well when a fire occurs and functions as a fire-resistant foamed layer.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies under the above-mentioned problems, and as a result, the surface of the foamed refractory foamed layer has an irregular shape. The inventors have found that heat is concentrated and the heat resistance is inferior, resulting in heat propagation, and the present invention has been completed based on such findings.

That is, the present invention is a fire-resistant board having a sheet material adhered to at least one surface of a substrate, wherein the sheet material comprises a binder, an azo compound, a hydrazo compound,
A blowing agent comprising at least one selected from a nitroso compound and a sulfonyl hydrazide compound;
Affixed to the base material via an adhesive containing expandable graphite having a temperature of 00 to 400 ° C., a thermally decomposable nitrogen-containing compound, at least one selected from a branched polyhydric alcohol and a saccharide, and a flame retardant. Pertains to the fireproof board being worn. Further, the present invention relates to the fire-resistant board, wherein the foaming agent is a compound which is decomposed at substantially the same temperature as the foaming start temperature of the expandable graphite. Further, the binder is used in an amount of 3 to 100 parts by weight of the adhesive.
70 parts by weight, the foaming agent is 1 to 20 parts by weight, the expandable graphite is 3 to 50 parts by weight, the thermally decomposable nitrogen-containing compound is 5 to 80 parts by weight, the branched polyhydric alcohol and saccharides At least one selected from the group consists of 5 to 80 parts by weight and the flame retardant is 1 to 30 parts by weight.

In such a fire-resistant board, when flame heat is applied to the sheet material due to the occurrence of a fire, a foaming agent composed of at least one selected from an azo compound, a hydrazo compound, a nitroso compound and a sulfonyl hydrazide compound is decomposed together with the expandable graphite to form a bond. A porous structure in which the material and the flame retardant structure are strong is formed, and a refractory foam layer having excellent surface smoothness is formed. Further, by blending at least one selected from the group consisting of a thermally decomposable nitrogen-containing compound and a branched polyhydric alcohol and a saccharide, the strength of the fire-resistant foam layer is further improved. Therefore, there is no portion inferior in heat resistance, and there is no unevenness in heat resistance over the entire area of the fire resistant foam layer.

The present invention also provides a binder, an azo compound,
A hydrazo compound, a nitroso compound, and a blowing agent comprising at least one selected from a sulfonyl hydrazide compound; and an expandable graphite having an expansion temperature of 200 to 400 ° C;
A thermally decomposable nitrogen-containing compound, at least one selected from a branched polyhydric alcohol and a saccharide, a thermally decomposable nitrogen-containing compound, at least one selected from a branched polyhydric alcohol and a saccharide, and a flame retardant. And a refractory adhesive composition containing the same.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a fire-resistant board and a fire-resistant adhesive composition of the present invention will be described. The refractory adhesive composition of the present invention can use a conventionally used synthetic resin for an adhesive as a binder. For example, polyester resin, silicone resin, epoxy resin, vinyl acetate resin, urethane resin, alkyd resin, acrylic resin,
Examples thereof include a vinyl chloride resin and a vinyl acetate / vinyl versatate copolymer resin. These resins may be used alone, copolymerized, or a mixture thereof. These resins can be used as room-temperature-curable or heat-curable one-pack or two-pack resins, or as resin emulsions dispersed in water or an organic dispersion medium. The resin emulsion may be a reaction-curable or self-crosslinking type modified emulsion.
As the resin emulsion, a vinyl acetate resin emulsion or a vinyl acetate / vinyl versatate copolymer resin emulsion is preferably used.

The amount of the binder is preferably 3 to 70 parts by weight, more preferably 5 to 50 parts by weight in terms of solid content in 100 parts by weight of the refractory adhesive composition of the present invention. Is preferred.

The expandable graphite used in the present invention is a graphite containing a thermally decomposable compound between layers, and has a temperature of about 200 ° C.
Graphite which expands when heated to 400 ° C., particularly preferably 250 ° C. to 350 ° C. to form voids. In such graphite, an interlayer compound is thermally decomposed by heating to generate gas, and expands in a worm shape by the gas pressure to form a honeycomb structure. Specific examples of the expandable graphite include graphite acid sulfate, sodium graphite, potassium graphite, halogen graphite, graphite oxide, aluminum chloride graphite, and ferric chloride graphite.

The compounding amount of the expandable graphite is preferably 3 to 50 parts by weight, more preferably 6 to 35 parts by weight, in terms of solid content in 100 parts by weight of the refractory adhesive composition of the present invention. Is preferred.

The blowing agent comprising one selected from the group consisting of an azo compound, a hydrazo compound, a nitroso compound and a sulfonyl hydrazide compound used in the present invention is an azo compound which decomposes at a temperature substantially equal to the expansion start temperature of the expandable graphite. , A hydrazo compound, a nitroso compound, or a sulfonyl hydrazide compound. Specifically, for example, azodicarbonamide (decomposition temperature 1
95-202 ° C.), hydrazodicarbonamide, 2,2′-hydrazoisobronitrile,
2′-hydrazobis-2,4-dimethylvaleronitrile, 4,4′-hydrazobis-4-cyanovaleric acid, 1,
1′-hydrazobiscyclohexanecarbonitrile, dimethyl-2,2′-hydrazobisisobutyl ester,
2,2′-hydrazobis- (2-amidinopropane) 2
Examples thereof include hydrazo compounds such as hydrochloride, nitroso compounds such as dinitrosopentamethylenetetramine (decomposition temperature: 200 to 205 ° C.), and sulfonyl hydrazide compounds. These may be used alone or in combination of two or more. Further, auxiliary agents such as zinc oxide, zinc stearate, and urea may be mixed as a foaming auxiliary. Among them, those using a hydrazo compound alone or using a hydrazo compound and urea in combination are preferable, and those using hydrazodicarbonamide alone or using both hydrazodicarbonamide and urea are particularly preferable. When hydrazodicarbonamide alone or when hydrazodicarbonamide and urea are used in combination, a strong cross-linking layer or a thermosetting resin foam layer is formed at the time of combustion, so that the heat insulating effect is high and a heat transfer barrier is provided. is there.

One compounding amount selected from azo compounds, hydrazo compounds, nitroso compounds and sulfonyl hydrazide compounds used in the present invention is 1 to 100 parts by weight in terms of solid content in 100 parts by weight of the fire-resistant adhesive composition of the present invention. The amount is preferably 20 parts by weight, more preferably 1.5 to 15 parts by weight.

The flame retardant used in the present invention is not particularly limited, and examples thereof include ammonium polyphosphate,
Trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresidyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, aromatic condensed phosphate, tris (2
-Chloroethyl) phosphate, phosphorus compounds such as red phosphorus,
Examples thereof include borates such as magnesium hydroxide, aluminum hydroxide, boric acid, and ammonium borate, boron, bromine-based flame retardants, phosphazene-based flame retardants, and silicone-based flame retardants. Among these, ammonium polyphosphate, tris (2-chloroethyl) phosphate, ammonium borate, and phosphazene-based flame retardants are preferred.
These may be used alone or in combination of two or more. Further, when a silicone-based flame retardant (for example, silicone powder or the like) is used in combination, the solid SiO ₂ , Si
In order to form combustion residue like C, the insulation effect is high,
It is preferable because it becomes a heat transfer barrier.

The compounding amount of the flame retardant is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, in terms of solid content in 100 parts by weight of the refractory adhesive composition of the present invention. Is preferred.

Furthermore, examples of the thermally decomposable nitrogen-containing compound used in the present invention include dicyandiamide, melamine, methylolmelamine, benzoguanamine and the like. The compounding amount is preferably from 5 to 80 parts by weight, more preferably from 8 to 60 parts by weight in terms of solid matter, in 100 parts by weight of the refractory adhesive composition of the present invention.

Further, among at least one selected from the branched polyhydric alcohols and saccharides used in the present invention,
Examples of the branched polyhydric alcohol include pentaerythritol, dipentaerythritol, tetrapentaerythritol and the like. Various monosaccharides and polysaccharides can be used as the saccharide, and specific examples include saccharose, glucose, sucrose, cellulose, amylose, amylopectin, hemicellulose and the like. Industrially, natural saccharides containing plural or some other components of such saccharides are preferably used. For example, starch such as flour, potato starch, corn starch and the like can be preferably used. These may be used alone or in combination of two or more. These act as carbonized layer forming aids,
It is preferably used because it has a high heat insulating effect and serves as a heat transfer barrier. The compounding amount is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight in terms of solid content in 100 parts by weight of the refractory adhesive composition of the present invention.

The fire-resistant adhesive composition of the present invention may further comprise glass fiber, potassium titanate fiber, and boric acid as an inorganic lightweight aggregate in addition to the above-mentioned components. Magnesium fiber, aluminum borate fiber, titania fiber, pulp fiber, wollastonite, zonotolite, silica alumina fiber, shirasu balloon, glass balloon, perlite fiber, natural pumice, expanded perlite, silicate, carbonate, aluminum oxide, talc ,
Clay, mica, etc. can be added. Further, a thixotropy-imparting agent or a pigment such as titanium dioxide can be blended. In addition, various components can be blended with the fire-resistant adhesive composition of the present invention as long as the effects of the present invention are not impaired.

The refractory adhesive composition of the present invention can be produced by mixing the components using a blender, kneader, disper or the like. There are no particular restrictions on the order in which the components are blended, and the order in which the components are uniformly mixed can be appropriately set. When a two-component curable resin is used as a binder component or when components having mutual reactivity are used together, a two-component or multi-component refractory adhesive composition combining stable components is used. Mix immediately before use. The method for applying the refractory adhesive of the present invention is not particularly limited, and a general method such as brush coating, spatula coating, trowel coating, spray coating, roller coating, and trowel coating can be used.

The refractory adhesive composition of the present invention can be applied to various base materials such as gypsum, resin, metal, ceramic, wood material (such as plywood). Specifically, on at least one surface of the substrate, the fire-resistant adhesive composition of the present invention is applied by various methods, and a sheet material such as decorative paper or wallpaper is adhered thereon, whereby the present invention is applied. Such a fireproof board can be obtained. For example, when gypsum is used as a base material (in the case of a gypsum board), a fire-resistant gypsum board can be obtained by using the fire-resistant adhesive of the present invention as an adhesive layer between a surface base paper and gypsum. Further, the fire-resistant adhesive composition of the present invention can also be used as an adhesive for attaching a cloth or the like as a finish sheet to a gypsum board or a plywood.

Further, the fire-resistant adhesive composition of the present invention can be used for various building materials (for example, flooring materials, roofing materials, plywood, furniture, etc.).
Boards such as gypsum board, cloths such as wallpaper, square materials)
It can be used in a wide variety of applications, from bonding during processing and molding to bonding during construction and compounding. For example, it can be used as an adhesive when joining building material boards (for example, conventional gypsum boards). Further, it can be used as an adhesive when manufacturing a combustible wood board such as a plywood or a particle board. For example, the plywood is composed of three or four layers, but by using the refractory adhesive of the present invention between layers, it is possible to form a refractory foam layer at the time of fire and to block the flame heat. Furthermore, it can be used for bonding between flammable wood boards and for bonding to flammable wood boards when building flammable wood boards as interior of building structures, or as a base adjustment material. . Furthermore, it can be used in fields other than building materials.

When the fire-resistant adhesive of the present invention is used, when the temperature of the expandable graphite as an active ingredient in the fire-resistant adhesive composition is raised to the expansion temperature (about 200 ° C.) by flame heat at the time of a fire, Almost simultaneously with the expansion of the expandable graphite, the binder and the flame retardant are foamed by the decomposition of the foaming agent, thereby forming a uniform and strong fire-resistant foam layer. Further, by blending at least one selected from the group consisting of a thermally decomposable nitrogen-containing compound and a branched polyhydric alcohol and a saccharide, the strength of the fire-resistant foam layer is further improved. Therefore, a fire-resistant board (for example, a gypsum board) using such an adhesive significantly improves the fire-resistant maintenance time when a fire occurs. Therefore, the fire-resistant board of the present invention can be prevented from spreading to the entire building structure in the event of a fire only by being applied to the building structure according to the conventional usage.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. Examples 1 to 3 and Comparative Examples 1 to 2 Each component was mixed at the compounding ratio (parts by weight in terms of solid content) shown in Table 1, and after adding 30 parts by weight of water, a disperser and a three-roll mill were used. Mix well to prepare a foamable refractory adhesive.

[0025]

[Table 1]

The components used in the examples and comparative examples are as follows.・ Vinyl acetate / vinyl versatate copolymer emulsion (trade name “Pegal 620”, manufactured by Toatsu Gas Co., Ltd.)
(Solid content: 47% by weight) Hydrazodicarbonamide (trade name "HDCA" manufactured by Otsuka Chemical Co., Ltd.)-Thermal expansion graphite 200 to 400 [deg.] C. (trade name "80LTE-U" manufactured by Sumitomo Chemical Co., Ltd.)-Thermal expansion Graphite 1000 ° C (Sumitomo Chemical Co., Ltd.
-Dicyandiamide (trade name: Dicyandiamide SKW)-Pentaerythritol (Mitsubishi Gas Chemical Co., Ltd., trade name "Pentaerythritol")-Ammonium borate (Yoneyama Chemical Co., Ltd., trade name) "Ammonium borate")-Ammonium polyphosphate (manufactured by Hoechst Japan KK, trade name "Hostafram AP462")-Titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., trade name "Taipek R980")

Test Example 1 150 × 150 with backside coated with gypsum board base paper
The dry thickness of the foamable refractory adhesive prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was applied to the surface of a gypsum substrate of × 8.0 mm.
Coat so as to be 0 mm. Before the foamable refractory adhesive dried, a gypsum board base paper (for the front side) was adhered to produce a foamable refractory board coated on both sides.
A gas burner (crater 60) using propane gas as a heat source, with the surface of each foamable refractory board thus prepared facing downward.
mm) is fixed so that the distance between the tips becomes 150 mm, the flame is radiated from the gas burner so as to contact the substantially central surface of the test specimen, and the heating temperature of the surface is 800.
It adjusted so that it might be -900 ° C. Then, the temperature of the back surface in contact with the flame and the scorching state of the gypsum board base paper on the back surface were observed at predetermined time intervals. Table 2 shows the results.

[0028]

[Table 2]

As shown in Table 2, the fire-resistant boards prepared from the fire-resistant adhesives of Examples 1 to 3 were foamed by heating to form a uniform foamed layer. The layer thickness is 40 mm for the fire-resistant board of Example 1, 40 mm for the fire-resistant board of Example 2,
The fireproof board of Example 3 was 50 mm. Regarding the fire and heat resistance, the base paper for the gypsum board on the back side slightly started to scorch after about 30 minutes in each example, but the scorched color appeared even after heating for 60 minutes (FIG. 1 to FIG. 1). 3). From this, it was confirmed that the fireproof boards of Examples 1 to 3 were extremely excellent in fireproof performance.

On the other hand, in the foamable fireproof board made of the foamable fireproof adhesive of the comparative example, the fireproof adhesive foamed due to overheating to form a foamed layer, but the foamed layer was thinner than the example. . Specifically, in the fire-resistant board of Comparative Example 1, the thickness of the foam layer was 20 mm, and the foam layer at the end of the board warped, and a uniform foam layer could not be formed. The gypsum board base paper of the board of Comparative Example 1 also started to scorch at about 20 minutes on the back side and was scorched black after 60 minutes (see FIG. 4). The thickness of the foam layer of the fire-resistant board of Comparative Example 2 was 15 mm, and a uniform foam layer was formed. However, because the thickness of the foamed layer was thin, the base paper for the gypsum board on the back side started to scorch at about 10 minutes after heating, and was scorched black at about 40 minutes after heating and cracked due to heat at 50 minutes after heating (see FIG. 5).

[0031]

As described above, according to the fire-resistant board according to the present invention, the adhesive interposed between the sheet material and the base material forms a foamed layer having excellent fire resistance and heat resistance. Spread of fire can be effectively prevented. Furthermore, according to the fire-resistant board according to the present invention, good adhesion can be exhibited by being interposed between members, and when a fire occurs, it can be foamed uniformly and sufficiently to function as a fire-resistant heat-resistant foamed layer. .

[Brief description of the drawings]

FIG. 1 is a photograph as a substitute of a drawing, showing a state after heating of a refractory board of Example 1.

FIG. 2 is a drawing substitute photograph showing a state after heating of the refractory board of Example 2.

FIG. 3 is a drawing substitute photograph showing a state after heating of the refractory board of Example 3.

FIG. 4 is a photograph as a drawing showing a state after heating of the fireproof board of Comparative Example 1.

FIG. 5 is a photograph as a substitute of a drawing, showing a state after heating of the fireproof board of Comparative Example 2.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 21/04 C09K 21/04 21/10 21/10 (72) Inventor Koji Koizumi Nakatanicho, Akashi City, Hyogo Prefecture 888 Meiko Kagaku Kogyo Co., Ltd. (72) Inventor Tetsushi Fujimoto 888 Meiji Kagaku Kogyo Co., Ltd. (72) Inventor Kohei Tosa 3-chome Ote-dori, Chuo-ku, Osaka-shi, Osaka No. 27 No. 27 Otsuka Chemical Co., Ltd. F-term (reference) 2E001 DE01 FA11 FA16 GA06 GA25 GA26 HA03 HA14 HB01 HC02 HC04 HC07 HD00 4F100 AA01A AA01C AA37B AE06A AE06C AH02H AH03B AH04B AJ03H AT00A AT00C BA02 CA03 BA03 BA07 BA03 BA01 BA03 BA01 4H028 AA03 AA06 AA07 AB03 AB04 BA03 BA04 4J040 BA112 BA132 DC021 DE021 DF021 EC001 ED001 ED091 EF031 EK031 HA026 HA056 HA116 HA286 HA326 HB04 HB11 HC14 HC15 HC1 6 HC17 HC25 HD17 HD24 HD28 HD30 JA05 JB09 KA36 KA37 KA42 LA08 MA06 MA08 MA09 MB03 NA12

Claims (4)

[Claims] 1. A fire-resistant board having a sheet material attached to at least one surface of a substrate, wherein the sheet material is at least one selected from a binder and an azo compound, a hydrazo compound, a nitroso compound, and a sulfonyl hydrazide compound. 1
Bonding comprising a foaming agent comprising a seed, an expandable graphite having an expansion temperature of 200 to 400 ° C., a thermally decomposable nitrogen-containing compound, at least one selected from a branched polyhydric alcohol and a saccharide, and a flame retardant A fire-resistant board, which is attached to the base material via an agent. 2. The fire-resistant board according to claim 1, wherein the foaming agent is a compound which starts to decompose at substantially the same temperature as the foaming start temperature of the expandable graphite. 3. The binder according to claim 1, wherein the binder is 3 to 70 parts by weight, the foaming agent is 1 to 20 parts by weight, the expandable graphite is 3 to 50 parts by weight, and The nitrogen compound is 5 to 80 parts by weight, at least one selected from the group consisting of branched polyhydric alcohols and saccharides is 5 to 80 parts by weight, and the flame retardant is 1 to 30 parts by weight. 2. The fire-resistant board according to 2. 4. A binder, a foaming agent comprising at least one selected from an azo compound, a hydrazo compound, a nitroso compound and a sulfonyl hydrazide compound; an expandable graphite having an expansion temperature of 200 to 400 ° C .; A fire-resistant adhesive composition comprising a nitrogen-containing compound, at least one selected from branched polyhydric alcohols and saccharides, and a flame retardant.