JP2000169853A - Refractory covering material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a refractory covering material composition capable of maintaining its refractory performance for a long period of time, excellent in waterproofness and weather resistance and useful for a refractory coating, or the like, by blending a binder, or the like, and graphite, or the like. SOLUTION: This refractory covering material composition is obtained by blending (A) preferably 6-40 wt.% binder such as a polyvinyl acetate resin emulsion and/or a vinyl acetate/vinyl versatate copolymer emulsion (B) preferably 1-20 wt.% at least one or more kinds selected from an azo compound, a hydrazo compound, a nitroso compound and a sulfonylhydrazide compound, (C) preferably 4-70 wt.% expandable graphite or graphite of a mixture of the expandable graphite with a graphite other than the expandable graphite, (D) preferably 6-84 wt.% thermally decomposable nitrogen-containing compound such as dicyandiamide and (E) preferably 4-80 wt.% one or more kinds selected from a branched chain type polyhydric alcohol such as pentaerythritol and a saccharide such as glucose. (Provided that phosphorus or phosphorus compounds are not blended).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a refractory coating composition. More specifically, fire resistance useful as a fire-resistant paint,
The present invention relates to a refractory coating material composition having heat resistance and fire protection performance.

[0002]

2. Description of the Related Art Steel frames and concrete base materials, which are structural driving bodies of buildings, have a sudden decrease in mechanical strength due to high heat at the time of fire. It is known to use inorganic lightweight aggregates such as perlite, asbestos and vermiculite to impart fire resistance. However, since these refractory coating materials require a thickness of about 1 to 5 cm for complete coating of the base material, a thinner coating thickness is required from the viewpoint of space saving. In addition, this method has a disadvantage that the working environment is deteriorated due to dust scattering at the time of on-site construction.

[0003] In recent years, therefore, there has been proposed a foamable refractory paint which has improved these disadvantages, that is, a refractory coating material composition which expands upon heating to form a refractory foam layer. For example, Japanese Unexamined Patent Publication No. 5-86310 discloses a paint made of a one-pack modified epoxy resin using ammonium polyphosphate as a foaming agent. JP-A-5-70540 discloses a foamed refractory paint using ammonium polyphosphate as a foaming agent, expandable graphite as a carbonized layer forming agent, and a phosphorus compound as a flame retardant. JP-A-9-183978 discloses a fire-resistant coating material composition using low-temperature expandable graphite and a phosphoric acid compound. JP-A-55-118987 discloses a fire-retardant composition using expandable graphite and a phosphorus compound in combination.

The foamable refractory coating material of the prior art uses a phosphoric acid compound as a foaming agent, specifically, orthophosphoric acid, polyphosphoric acid, ammonium phosphate, melamine phosphate, ammonium polyphosphate and the like. However, it has the following disadvantages.

That is, conventional foamable refractory coating materials have not been able to sufficiently satisfy the strength of the carbonized foam layer formed during a fire. In addition, since the phosphoric acid compound has water solubility, the water resistance of the coating itself becomes insufficient, or the phosphoric acid compound flows out of the coating due to exposure to natural wind and rain. There was a drawback that it could not be expressed.

On the other hand, in recent years, the problem of protecting the global environment has been regarded as important, and the whole paint is shifting to a water-based or water-dispersible system which is friendly to the global environment. Are required. However, when a phosphoric acid compound is added to the water-dispersed synthetic resin emulsion-type foamable refractory paint, the decrease in water resistance and the decrease in fire resistance of the coating film due to the water solubility of the phosphoric acid compound are particularly remarkable. Heretofore, it has been considered difficult to develop a water-dispersed resin emulsion type refractory paint.

[0007] The foaming temperature of a phosphoric acid compound represented by ammonium polyphosphate is 25 in actual use.
Since the temperature is around 0 to 300 ° C., which is close to the temperature (about 350 ° C.) at which the mechanical properties of the steel frame ordinary steel material decreases at the time of the fire, the time for maintaining the fire resistance performance of the ordinary steel is short.

In view of the above prior art, an object of the present invention is to provide a refractory coating material composition which can be formed into a thin film and has excellent fire resistance performance. Another object of the present invention is to provide a fire-resistant coating material composition having excellent weather resistance and water resistance.
Another object of the present invention is to provide an emulsion-type fire-resistant coating composition having excellent fire resistance. Another object of the present invention is to provide a fire-resistant coating material composition capable of securing a long time for maintaining fire resistance performance of a steel material.

[0009]

Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and have found an excellent refractory coating material composition and completed the present invention. That is, the present invention
(A) a binder, (B) at least one selected from azo compounds, hydrazo compounds, nitroso compounds, and sulfonyl hydrazide compounds, (C) graphite, (D) a thermally decomposable nitrogen-containing compound, and (E) a branched polyvalent compound. The present invention relates to a refractory coating material composition containing at least one selected from alcohols and saccharides.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Each component of the fire-resistant coating composition of the present invention will be described below. (A) Examples of the binder include various coating resins and inorganic binders. Specific examples of coating resins include polyester resins, silicone resins, epoxy resins, vinyl acetate resins, ethylene / vinyl acetate copolymer resins, vinyl acetate / vinyl versatate copolymer resins, urethane resins, alkyd resins, amino alkyd resins, An acrylic resin, a modified acrylic resin, a styrene / butadiene copolymer resin, an acrylonitrile / butadiene copolymer resin, a vinyl chloride resin and the like can be mentioned. These may be used alone or in combination of two or more.

These resins can be used as a one-part or two-part resin which is curable at room temperature or heat, or a resin emulsion 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, and a polyvinyl acetate resin emulsion and a vinyl acetate / vinyl versatate copolymer resin emulsion are particularly preferably used.

Examples of the inorganic binder include silicates, borates, gypsum, and other various cements.
(A) The compounding amount of the binder is preferably 6 to 40% by weight, more preferably 7 to 30% by weight in terms of solid content in the refractory coating material composition of the present invention.

As the component (B), azo compounds such as azodicarbonamide and azobisisobutyronitrile, hydrazodicarbonamide, 2,2'-hydrazoisobutyronitrile, 2,2'-hydrazobis-2, 4-dimethylvaleronitrile, 4,4'-hydrazobis-4-cyanovaleric acid, 1,1'-hydrazobiscyclohexanecarbonitrile, dimethyl-2,2'hydrazobisisobutyl ester, 2,2'-hydrazobis (2- Examples thereof include hydrazo compounds such as amidinopropane) dihydrochloride, nitroso compounds such as dinitrosopentamethylenetetramine, and sulfonyl hydrazide compounds such as p-toluenesulfonyl hydrazide and p, p'-oxybis (benzenesulfonyl hydrazide). 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 foaming auxiliary agents. Above all, it is preferable to use a hydrazo compound alone or a combination of a hydrazo compound and urea, and it is particularly preferable to use a hydrazodicarbonamide alone or a combination of hydrazodicarbonamide and urea.

The compounding amount of the component (B) is preferably 1 to 20% by weight, more preferably 1.5 to 15% by weight in terms of solid content in the refractory coating material composition of the present invention. Is good.

[0015] Examples of the graphite (C) include at least one selected from flaky graphite, flaky graphite, artificial graphite, earthy graphite, and expandable graphite. Above all, it is preferable to use expandable graphite alone or to use expandable graphite and another graphite at the same time, since a strong and dense carbonized foam layer can be formed at the time of fire and stable fire resistance is exhibited.

Expandable graphite is a graphite containing a thermally decomposable compound between layers. When heated to about 200 to 1000 degrees, the intercalated compound is thermally decomposed to generate gas, and the gas pressure causes a worm-like state. Is a graphite having a property of expanding into a honeycomb structure having a space. As a specific example,
Graphite acid sulfate, sodium graphite, potassium graphite, halogenated graphite, graphite oxide, aluminum chloride graphite,
Ferric chloride graphite and the like can be mentioned.

The compounding amount of (C) graphite is preferably 4 to 70% by weight, more preferably 9 to 50% by weight in terms of solid content in the refractory coating material composition of the present invention. preferable. The amount of the expandable graphite is 3 to 50% by weight.
And more preferably 6 to 30% by weight. The compounding amount of the graphite other than the expandable graphite is preferably about 1 to 20% by weight, preferably 2 to 15% by weight in terms of solid content in the refractory coating material composition of the present invention.

(D) Examples of the thermally decomposable nitrogen-containing compound include dicyandiamide, melamine, methylolmelamine, benzoguanamine and the like. (D) The compounding amount of the thermally decomposable nitrogen-containing compound is preferably 6 to 84% by weight, more preferably 8 to 70% by weight in terms of solid content in the refractory coating material composition of the present invention. Is good.

(E) Among the at least one selected from branched polyhydric alcohols and sugars, 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, flour, potato starch,
Starch such as corn starch can be preferably used. These may be used alone or in combination of two or more.

The component (E) acts as a carbonized layer forming agent,
The compounding amount is preferably from 4 to 80% by weight, more preferably from 10 to 70% by weight in terms of solid content in the refractory coating material composition of the present invention.

It is preferred that the fire-resistant coating composition of the present invention contains various flame retardants. Such flame retardants include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresidyl phosphate,
Phosphate-based flame retardants such as trixylenyl phosphate, cresyl diphenyl phosphate, aromatic condensed phosphate, and tris (2-chloroethyl) phosphate;
Antimony flame retardants such as antimony trioxide; phosphazene flame retardants such as phenoxyphosphazene; phosphorus flame retardants such as red phosphorus; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; boric acid; Examples thereof include a flame retardant and a bromine-based flame retardant. When a flame retardant is used, the amount of the flame retardant is preferably 1 to 30% by weight, more preferably 3 to 20% by weight in terms of solid content, in the refractory coating material composition of the present invention. Is good.

In the fire-resistant coating composition of the present invention, glass fiber, potassium titanate fiber, magnesium borate and the like are used in addition to the above-mentioned components in addition to a crack preventing agent for the coating for strengthening the foamed layer and an inorganic lightweight aggregate. 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. Also, a thixotropic agent and an ultraviolet absorber, an ultraviolet stabilizer, titanium dioxide,
Pigments such as red iron oxide and yellow iron oxide can be blended.

Further, various components can be added to the fire-resistant coating material composition of the present invention as long as the effects of the present invention are not impaired. The refractory coating material composition of the present invention can be produced by mixing each component of the composition 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. (A) When a two-component curable resin is used as a binder component, or when mutually reactive components are used in combination, a two-component or multi-component refractory coating material composition combining stable components. It can be used by mixing immediately before use.

The method of applying the refractory coating material composition of the present invention is not particularly limited, and it can be applied by any method such as brush coating, spray coating, roller coating, and trowel coating.
After coating, heating may be performed if necessary. Alternatively, a method of pasting into a substrate a material previously formed into a plate shape, a film shape, or the like may be used. The fire-resistant coating material composition of the present invention,
It can be suitably used as a fire-resistant coating material for main structural parts of bridges and buildings, such as steel columns such as H-section steel and concrete.

Further, the fire-resistant coating material composition of the present invention comprises a resin,
It can be applied to various base materials such as metals, ceramics, wood materials, etc., and can be used for seating areas such as stadiums and theaters, various building materials for construction, building wood, interior and exterior wall materials, roof base materials, ceiling materials,
It can be suitably used as a fire protection material for flooring materials, wood pallets for transportation, furniture and the like.

[0026]

The present invention will be described in more detail with reference to the following examples.

Examples 1 to 3 and Comparative Example 1 Each component was mixed at the mixing ratio (parts by solids) shown in Table 1, and 30 parts by weight of water was further added. The refractory coating composition was prepared by adding and mixing well.

Comparative Example 2 The components were mixed well using a disper and a three-roll mill at the mixing ratios (parts by solids) shown in Table 1 to prepare a fire-resistant coating material composition.

[0029]

[Table 1]

The components used in the examples and comparative examples are as follows. Acrylic ester copolymer resin emulsion (trade name;
Movinyl 727, Hoechst Gosei Co., Ltd., solid content 49-51% by weight). Vinyl acetate / vinyl versatate copolymer resin emulsion (trade name: Pegal 620, manufactured by High Pressure Gas Co., Ltd.)
Solids content 47% by weight). Acrylic resin A (trade name; Briolite AC80, manufactured by Goodyear Chemical Co., Ltd.). Acrylic resin B (trade name; Briolite AC4, manufactured by Goodyear Chemical Co., Ltd.). Ammonium polyphosphate (trade name; Hostafram AP4)
62, manufactured by Hoechst Japan KK). Thermal expandable graphite (trade name: TEG80LTE-U, 80 mesh, manufactured by Sumikin Chemical Co., Ltd.). Graphite (trade name; OS carbon powder AT-40, average particle size 4 μm, manufactured by Oriental Sangyo Co., Ltd.). Hydrazocarbonamide (trade name: HDCA, manufactured by Otsuka Chemical Co., Ltd.). Dicyandiamide (reagent). Pentaerythritol (reagent). Dipentaerythritol (reagent). Melamine (reagent). Titanium dioxide (trade name; Taitake R-950, manufactured by Ishihara Sangyo Co., Ltd.).

Test Example 1 The fire-resistant coating materials of Examples and Comparative Examples were applied to a substrate (hot-rolled steel plate) of 300 × 300 × 3.2 mm so that the dry coating film became 2 mm. Was formed. This refractory coating was heated in a gas incinerator for one hour based on the standard heating curve specified in JIS A1304, and the temperature of the back surface of the hot-rolled steel sheet was measured. In addition, the shape of the foam layer, the state of adhesion to the steel sheet, the cell diameter, and the presence or absence of peeling of the foam layer were visually determined. Table 1 shows the results.

In Examples 1 to 3, a good foamed layer was formed without peeling, cracking, cracking, etc. of the foamed layer, and fire resistance was exhibited.
The refractory coating film of Comparative Example 1 had poor foaming properties and burned and peeled off 3 minutes after heating. In Comparative Example 2, since the foaming start temperature was high and the cell diameter was rough, the back surface temperature was increased, and the fire resistance of the steel sheet was 4%.
It could only be maintained for about 0 minutes.

Test Example 2 A refractory coating film prepared in the same manner as in Test Example 1 was subjected to an accelerated weathering test for 1000 hours using a carbon arc lamp type weathering tester, and then based on a standard heating curve specified in JISA1304. After heating for 1 hour in a gas incinerator, the temperature of the back surface of the hot-rolled steel sheet was measured. Table 2 shows the results.

[0034]

[Table 2]

In Examples 1 to 3, a good foam layer was formed without peeling, cracking, cracking, etc. of the foam layer, and the fire resistance was exhibited.
The fire-resistant coating film of Comparative Example 1 had poor foaming properties and burned and peeled off in 1 minute after heating. In Comparative Example 2, since the foaming start temperature was high and the cell diameter was rough, the back surface temperature increased, and the fire resistance of the steel sheet could be maintained for only about 20 minutes.

Example 4 A fire-resistant coating material was produced on a trial basis using polyvinyl acetate dissolved in a toluene / xylene mixed organic solvent in place of the binder of the synthetic resin emulsion of Example 2, and the same as in Test Examples 1 and 2. The test was performed. As a result, all exhibited the same good fire resistance performance as in Example 2.

Example 5 Instead of the binder of the synthetic resin emulsion of Example 3, vinyl acetate / vinyl acetate dissolved in a toluene / xylene mixed organic solvent was used.
A refractory coating material was trial manufactured using a vinyl versatate copolymer resin, and the same tests as in Test Examples 1 and 2 were performed. As a result, all exhibited the same good fire resistance performance as in Example 3.

[0038]

According to the fire-resistant coating composition of the present invention, the foaming start temperature is reduced to about 200 ° C. by blending at least one selected from azo compounds, hydrazo compounds and sulfonyl hydrazide compounds. By foaming to form a carbonized foam layer, it is possible to secure a long time for maintaining the fire resistance performance of the steel material.

Further, in the refractory coating material composition of the present invention containing the expandable graphite, the expandable graphite expands as the surface temperature increases, forming a dense carbonized foamed layer. It can be significantly improved.

Further, the refractory coating composition of the present invention comprises:
Since the phosphoric acid compound used as an essential component in the conventional foam type refractory coating material composition is not added, the water resistance and weather resistance are remarkably improved, and the fire resistance performance can be maintained over a long period of time. And water-based emulsion paints.

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[Procedure amendment]

[Submission date] July 27, 1999 (July 7, 1999
7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

[0009]

Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and have found an excellent refractory coating material composition and completed the present invention. That is, the present invention
(A) a binder, (B) at least one selected from azo compounds, hydrazo compounds, nitroso compounds, and sulfonyl hydrazide compounds, (C) graphite, (D) a thermally decomposable nitrogen-containing compound, and (E) a branched polyvalent compound. At least one selected from alcohols and sugars (but phosphorus
Or a phosphorus compound is not blended) . Furthermore, if the component (B) is a hydrazo compound,
The refractory coating material composition is at least one selected from the group consisting of:
According to. Further, the present invention provides (A) a binder, (B) a hydra
At least one selected from azo compounds, (C) graphite,
(D) a thermally decomposable nitrogen-containing compound and (E) a branched polyvalent alcohol.
At least one compound selected from coal and sugar
The present invention relates to a refractory coating material composition comprising: Further, the (A) binding
The agent is a resin emulsion;
Related. In addition, the (C) graphite may be expanded graphite or expanded graphite.
Is a mixture of expandable graphite and graphite other than expandable graphite.
The present invention relates to a fire covering material composition. In addition, the total refractory coating material composition
(A) 6 to 40% by weight of a binder in terms of solid content therein,
(B) 1 to 20% by weight of component, (C) 4 to 70% by weight of graphite
%, (D) 6 to 84% by weight of a thermally decomposable nitrogen-containing compound,
(E) a small amount selected from branched polyhydric alcohols and sugars;
At least one kind of the refractory coating material blended at 4 to 80% by weight.
According to the adult.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Koizumi 888 Nakatani-cho, Akashi-shi, Hyogo Meiken Chemical Industry Co., Ltd. Within Otsuka Chemical Co., Ltd. CD021 CF021 CF031 CF051 CG141 CG161 DB001 DD001 DD121 DD231 DG001 DL031 HA036 JA21 JB14 JB16 JB18 JB19 JB21 JB36 JC26 KA02 KA07 MA10 NA15 NA27 PB05 PC04

Claims (6)

[Claims] 1. A binder, (B) at least one selected from an azo compound, a hydrazo compound, a nitroso compound and a sulfonyl hydrazide compound, (C) graphite,
A fire-resistant coating composition comprising (D) a thermally decomposable nitrogen-containing compound and (E) at least one selected from a branched polyhydric alcohol and a saccharide. 2. The composition according to claim 1, wherein the component (B) is at least one selected from hydrazo compounds. 3. The refractory coating composition according to claim 1, wherein (A) the binder is a resin emulsion. 4. The fire-resistant coating composition according to claim 3, wherein (A) the binder is a polyvinyl acetate resin emulsion and / or a vinyl acetate / vinyl versatate copolymer resin emulsion. 5. The graphite according to claim 1, wherein (C) the graphite is expandable graphite or a mixture of expandable graphite and graphite other than expandable graphite.
4. The refractory coating material composition of 4. 6. A total amount of (A) 6 to 40% by weight of a binder, (B) 1 to 20% by weight of a component, (C) 4-70% by weight of graphite, 6. The fire-resistant coating material composition according to claim 1, further comprising: D) 6 to 84% by weight of a thermally decomposable nitrogen-containing compound and (E) 4 to 80% by weight of at least one selected from the group consisting of branched polyhydric alcohols and saccharides.