JP2006036969A - Method for fireproof-covering of steel material surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for fireproof-coating of a steel material surface, excellent in rust prevention and close adhesion with the steel material surface (a metal surface), securing an excellent anti-rust property even against existing generated rust or an already presenting coated film, excellent in close adhesion with the generated rust or the already presenting coated film and exhibiting excellent fireproof property. <P>SOLUTION: This method for fireproof-coating of the steel material surface is characterized by applying an anti-rust undercoating material containing (A) a chelate-modified epoxy resin, (B) a ketimine compound, (C) an anion-exchanging type compound and (D) an organic solvent, and then laminating an expandable fireproof material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a fireproof coating method that exhibits excellent adhesion and rust prevention properties on the surface of a steel material.

  Conventionally, when providing steel structures such as buildings with fire resistance, the rust prevention properties of the steel materials are taken into consideration, and a rust preventive primer having a rust prevention property is applied to the steel material surface. A method of laminating refractory materials is widely adopted.

For example, Patent Document 1 discloses a method in which a water-based anticorrosive primer composed of hydraulic cement, a synthetic resin emulsion, a fiber agent, and / or a hollow filler is used as an undercoat, and a foamed fireproof paint is coated.
Further, Patent Document 2 discloses a method in which a rust-preventing paint using borate and / or phosphate as a rust-preventing pigment is primed and a fire-resistant coating layer is formed thereon using a foam-type fire-resistant paint. Yes.

JP 2000-212472 A JP 2001-64548 A

By the way, as a case where a steel structure such as a building is provided with fire resistance, there is a case where fire resistance is imparted by repainting not only newly built properties but also repaired properties.
In particular, when fire resistance is imparted by repainting, there are many cases where generated rust or existing coating film remains on the steel surface of the steel structure. Although it is preferable to apply a rust-proofing primer and laminate a refractory material, in reality, it is difficult to remove all generated rust and existing coating films.
When applying a rust-preventive primer to the steel surface where such generated rust or existing coating film remains, the performance of the rust-preventive primer is rust-proof and the steel surface (metal surface) In addition to the adhesiveness, performance such as generated rust and adhesion with existing coating films is also required.

  However, in the rust preventive primer described in Patent Document 1 and Patent Document 2, when the generated rust is present, the permeability to the generated rust is insufficient and the rust cannot be sufficiently fixed, Since it is difficult to suppress the occurrence of rust, there are cases where a sufficient rust prevention effect cannot be obtained. Moreover, when the existing coating film exists, the adhesiveness with the existing coating film may be insufficient, and the coating film may be easily peeled off. As a result, sufficient fire resistance may not be obtained.

  The present invention has been made in view of such problems, and is excellent in rust prevention, adhesiveness to the steel surface (metal surface), and excellent in the presence of generated rust and existing coatings. The present invention provides a fireproof coating method for the surface of a steel material that ensures rustproofness, is excellent in generated rust and adhesion to existing coating films, and exhibits excellent fireproof performance.

That is, the present invention has the following characteristics.
1. On the steel surface, A. A chelate-modified epoxy resin; Ketimine compounds, C.I. Anion exchange compound, D.I. A method for fire-resistant coating of a steel material surface, comprising applying a rust-proof primer containing an organic solvent and then laminating a fire-resistant material.
2. The rust-proof primer is A. B. 100 parts by weight of the chelate-modified epoxy resin 5 to 40 parts by weight of a ketimine compound, C.I. 0.01 to 100 parts by weight of anion exchange compound, D.I. 10 to 300 parts by weight of an organic solvent is contained. The fireproof coating method of the steel material surface as described in 2.
3. D. 40% by weight or more of the organic solvent is an aliphatic hydrocarbon organic solvent. Or 2. The fireproof coating method of the steel material surface as described in 2.

  The fireproof coating method on the steel surface of the present invention has excellent rust prevention and adhesion to the steel surface (metal surface), and ensures excellent rust prevention even if generated rust or existing coatings exist. It has excellent adhesion to rust and existing coating films, and can exhibit excellent fire resistance.

  Hereinafter, the present invention will be described in detail together with the best mode for carrying out the invention.

  The present invention provides an A.I. Chelate-modified epoxy resin (hereinafter also referred to as “component (A)”), B. Ketimine compound (hereinafter also referred to as “component (B)”), C.I. Anion exchange type compound (hereinafter also referred to as “component (C)”), D.I. It is characterized by laminating a refractory material after applying an anticorrosive primer containing an organic solvent (hereinafter also referred to as “component (D)”).

  Examples of the steel structure and the like that are the subject of the present invention include pillars, beams, walls, floors, ceilings, stairs, roofs, and the like, which are main structural members of general buildings and civil engineering structures. Examples of steel surfaces such as steel structures include, for example, cold rolled steel, aluminum steel, stainless steel, copper steel, hot dip galvanized steel, hot dip galvanized steel, electrogalvanized steel, and electroalloy plated steel. , Steel surfaces such as alloy-plated steel, copper-plated steel, tin-plated steel, etc., or steel materials with surface treatments such as phosphate-based or chromate-based on these steel surfaces, Cu, Ni, Cr, P, Examples thereof include a steel material surface containing a small amount of an element such as Mo and having an antirust effect. Furthermore, the steel material surface etc. which were coat | covered with the well-known coating film are mentioned.

  A rust-preventive primer containing the component (A), the component (B), the component (C), and the component (D) is applied to the surface of such a steel material.

Component (A) has excellent permeability to the generated rust, exhibits excellent rust prevention by physical fixation to the generated rust, and against rust scattered on the steel material surface and existing coating film It is a component that causes chelate reaction and exhibits excellent rust prevention by chemical immobilization. Moreover, since it has excellent adhesion to generated rust, steel material surface, existing coating film, and refractory material, it is a component that can enhance rust prevention performance and fire resistance performance. Moreover, it has the effect | action which selectively interrupts the influence from an external environment, and can prevent permeation | transmission of corrosive ions, such as a chlorine ion which causes rust formation.
The component (B) acts as a crosslinking agent for the component (A) to form a strong coating film, and has a property of reacting with moisture serving as a corrosion factor. Therefore, the water | moisture content which exists on the steel material surface can be reduced, and a rust prevention effect can be improved.
The component (C) has an effect of enhancing the rust prevention effect by collecting and immobilizing corrosive ions such as chlorine ions which are corrosive factors.
(D) component is a component which shows the permeability | transmittance excellent with respect to generated rust, without being influenced by the temperature at the time of coating, and the surface temperature of a base material.
The rust preventive primer of the present invention has the above components (A), (B), (C), and (D) as essential components, thereby providing extremely excellent rust preventive properties due to their synergistic effects. Can show.

  The component (A) is an epoxy resin containing a functional group having a chelate-forming ability at the basic skeleton, side chain or terminal of the epoxy resin.

  Examples of the epoxy resin include glycidyl ether type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and novolak type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, cyclic aliphatic epoxy resins, Examples thereof include brominated epoxy resins and the like, or those modified with polyester resins, phenol resins, melamine resins, and the like.

  Examples of the functional group having chelate forming ability include functional groups having coordination ability such as carboxyl group, sulfonic acid group, phosphoric acid group, hydroxyl group, amino group, and carbonyl group. Particularly preferred are a hydroxyl group, a phosphate group, a carboxyl group, a carbonyl group, and the like.

The component (A) contains a functional group having such chelate-forming ability in the basic skeleton, side chain, and terminal of the epoxy resin described above. For example, a ketone-modified epoxy resin, a phosphoric acid-modified epoxy resin, etc. Preferably used.
(A) The molecular weight of a component is 1000-10000 normally, Preferably it is 1500-6000.

The component (B) mainly acts as a crosslinking agent for the component (A) and forms a strong coating film.
The component (B) is a compound represented by the chemical formula 1 and is generally a compound having a carbonyl compound (O = CR ₁ R ₂ ) (hereinafter also referred to as “component (B-1)”) and a primary amino group. It is a compound obtained by the reaction of (—NH ₂ ) (hereinafter also referred to as “component (B-2)”).

(Chemical formula 1)
-N = CR ₁ R ₂
(B)
(R ₁ and R ₂ in the formula may be the same or different and are represented by a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenylalkyl group.)

  Specifically, it is obtained by a reaction represented by Chemical Reaction Formula 1.

(Chemical reaction formula 1)
_{O = CR 1 R 2 + -NH} 2 → -N = CR 1 R 2 + H 2 O
(B-1) (B-2) (B)

As the component (B-1), the general formula: O = CR ₁ R ₂ (wherein R ₁ and R ₂ may be the same or different, and are a hydrogen atom, an alkyl group, a cycloalkyl group, a phenylalkyl group. In particular, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; aldehydes such as acetaldehyde and benzaldehyde And so on.

  The component (B-2) is not particularly limited as long as it is a compound having one or more primary amino groups in one molecule. For example, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, poly Aliphatic amines such as (oxypropylene) diamine; Aromatic amines such as xylylenediamine, diaminodiphenylmethane, and phenylenediamine; Alicyclic amines such as isophoronediamine and 1,3-bisaminomethylcyclohexane, Polyoxyethylenediamine And polyether amines such as polyoxypropylene diamine and polyoxyethylene propylene diamine.

  The component (B) thus obtained reacts with the generated rust, moisture present in the existing coating film, moisture in the atmosphere, etc., as shown in chemical reaction formula 2, and (B-1) component ( B-2) A component is obtained.

(Chemical reaction formula 2)
_{-N = CR 1 R 2 + H} 2 O → O = CR 1 R 2 + -NH 2
(B) (B-1) (B-2)

Thus, moisture, which is one of the corrosion factors, is consumed and reduced by reaction with the component (B). Further, the curing reaction is started by the component (B-2) and the component (A) generated by this reaction.
Thus, in order to initiate the curing reaction of the component (B-2) and the component (A), the reaction between the component (B) and moisture (chemical reaction formula 2) is essential. Therefore, until the reaction between the component (B) and moisture (chemical reaction formula 2) proceeds to some extent, the curing reaction of the component (B-2) and the component (A) hardly proceeds. Therefore, the fluidity of the coating material is maintained, and it is possible to penetrate deeply into the generated rust.
Next, when the reaction between the component (B) and moisture (chemical reaction formula 2) proceeds to some extent, the curing reaction of the component (B-2) and the component (A) proceeds, strengthening and reinforcing the rust that was fragile, It is possible to form a strong coating film having a barrier property from the external environment and excellent in rust prevention and adhesion.
Moreover, (B-1) component also has an effect | action as a solvent and has the effect of improving the permeability | transmittance to generated rust.

  The mixing ratio of the component (B) is 5 to 40 parts by weight, preferably 8 to 20 parts by weight, based on the solid content of the component (B) with respect to 100 parts by weight of the solid content of the component (A). When the amount is less than 5 parts by weight, the reaction with the component (A) does not sufficiently occur, and a strong coating film cannot be formed. When there are more (B) components than 40 weight part, reaction with (A) component will occur easily and a pot life will become short.

  In the present invention, a curing accelerator can be used in the reaction of the aforementioned component (A) and component (B). Examples of the curing accelerator include triethylamine, dibutylmethylamine, N, N-dimethylpropylamine, benzyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, 1,5-diazabicyclo [4,3, 0] nonene-5,1,8-diazabicyclo [5,4,0] undecene-7,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7,1,4-diazabicyclo [2] 2.2] tertiary amines such as octane, N-methylpyrrolidine, N, N′-dimethylpiperazine, 2,4,6-tris (dimethylaminomethyl) phenol, phenols such as diisopropylphenol and pt-butylphenol Acrylates such as trimethylolpropane acrylate and pentaerythritol tetraacrylate Compound, isocyanate compound and the like can be mentioned. By using such a curing accelerator, the curing reaction can be promoted and a strong coating film can be formed.

  The mixing ratio of the curing accelerator is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the solid content of the component (A). When the amount is less than 0.01 part by weight, the curing reaction at a low temperature is not sufficiently accelerated, and it may be difficult to form a strong coating film. When there are more hardening accelerators than 20 weight part, reaction of (A) component and (B) component occurs easily and there exists a tendency for a pot life to become short.

The component (C) is a component that collects corrosive ions such as chlorine ions that cause rust and immobilizes the corrosive ions.
As such (C) component, what is represented by the following general formula is mentioned, for example.
General formula: [X _1-a Y _a (OH) ₂ ] ^{a +} [A ⁿ⁻ _{a / n} · mH ₂ O] ^a−
(X: Mg, Mn, Cu , Ni, Fe, Zn, Ca, 2 bivalent metal element such as Co, Y: Al, Co, Cr, In, 3 trivalent metal element such as ^Fe, A n-: CO N ^{2 such} as ₃ ²⁻ , OH ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , F ⁻ , Br ⁻ , MnO ₄ ⁻ , CH ₃ COO ⁻ , Fe (CN) ₆ ³⁻ , oxalate ion, and salicinate ion Anion, 0 <a <1.0, m> 0, n is an integer of 1 to 4)

As the metal element constituting the component (C), in the general formula, X: divalent metal element such as Mg, Mn, Cu, Ni, Fe, Zn, Ca, Co, Y: Al, Co, Cr, In And trivalent metal elements such as Fe. Each of X and Y may be composed of one component metal element, or a part thereof may be substituted with another metal element.
These X and Y can be used in any combination, but particularly suitable combinations include, for example, Mg—Al, Ca—Al, Zn—Al, Zn—Cr, Mn—Al and the like. it can.
The anion constituting the component (C), in the general ^{_{formula, A n-: CO 3 2-,}} OH -, HNO 2 -, NO 3 -, SO 4 2-, F -, Br -, MnO 4 - , CH ₃ COO ⁻ , Fe (CN) ₆ ³⁻ , oxalic acid ions, salicic acid ions, and other n-valent anions (n is an integer of 1 to 4).

Each An ^n- may be composed of one component anion, or a part thereof may be substituted with another anion. In the present invention, A ^n-is replaced with corrosive ions chlorine ions or the like which causes rust, it is to exhibit corrosion protection. The ^n- Such ^A, in _particular, ^CO 3 _2-, HNO ₂ ^- is preferably used and the like. If A ^n- is as this increases the more corrosion protection.

As a particularly preferred form of the component (C),
General formula: [Mg _1-a Al _a (OH) ₂ ] ^{a +} [CO ₃ ²⁻ _{a / 2} · mH ₂ O] ^a− (0 <a <1.0, m> 0)
Hydrotalcite represented by
General formula: [Ca _1-a Al _a (OH) ₂ ] ^{a +} [CO ₃ ²⁻ _{a / 2} · mH ₂ O] ^a− (0 <a <1.0, m> 0)
And hydrocalumite represented by

  Moreover, (C) component will not be specifically limited if the above anion exchange type compounds are contained, For example, the modified material of inorganic oxides, such as a titanium oxide and a zinc oxide, etc. are mentioned.

  The mixing ratio of the component (C) is 0.01 to 100 parts by weight, preferably 0.01 to 20 parts by weight, and more preferably 0.05 to 100 parts by weight of the solid content of the component (A). -10 parts by weight. When the amount is less than 0.01 parts by weight, an excellent rust prevention effect cannot be obtained. When the amount of the component (C) is more than 100 parts by weight, the cost is increased, and an effect sufficient to match it cannot be obtained.

(D) component is a component which shows the permeability | transmittance which was excellent mainly with respect to generated rust. The component (D) may be appropriately set depending on the components (A) to (C), and in particular, those capable of dissolving the components (A) and (B) are used.
Examples of the component (D) include alcohol-based organics such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, diacetone alcohol, ethylene glycol, and propylene glycol. Solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol t-butyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol Ether organic solvents such as monomethyl ether, acetone, methyl ethyl , Organic solvents such as ketones such as methyl isobutyl ketone and diisobutyl ketone, n-butane, n-hexane, cyclohexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, etc. Aliphatic hydrocarbon organic solvents, aromatic hydrocarbon solvents such as toluene, xylene and solvent naphtha, and ester organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate and isobutyl acetate, etc. In addition to these, terpin oil, mineral spirit, HAWS, Solvesso 100, Solvesso 150, Swazol 310, Swazole 1000, Swazol 1500, and the like can be used, and one or more can be used in combination.
By using such a component (D), the fluidity of the coating material is maintained without being affected by the temperature of the coating or the surface temperature of the steel material, and the rust-preventing primer material has excellent permeability to generated rust. Can be obtained.

  In the present invention, it is particularly preferable that 40% by weight or more (preferably 45% by weight or more, more preferably 50% by weight or more) of the organic solvent is an aliphatic hydrocarbon organic solvent. When the amount of the aliphatic hydrocarbon organic solvent is 40% by weight or more, the lifting phenomenon of the existing coating film can be further alleviated when it is applied to the existing coating film, and the rust-preventing primer material having better adhesion Can be obtained.

  The mixing ratio of the component (D) is 10 to 300 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the solid content of the component (A). When the component (D) is less than 10 parts by weight, the permeability to the generated rust may be inferior. When there are more (D) component than 300 weight part, drying of a coating film may become slow.

In the present invention, it is preferable to further add a fatty acid-modified epoxy resin. Examples of fatty acid-modified epoxy resins include dimer acid-modified epoxy resins. By blending such a fatty acid-modified epoxy resin, a coating film excellent in flexibility can be obtained.
The mixing ratio of the fatty acid-modified epoxy resin is not particularly limited. However, the solid content of the fatty acid-modified epoxy resin is 10 to 100 parts by weight, preferably about 30 to 70 parts by weight with respect to 100 parts by weight of the solid content of the component (A). is there.

  As the resin component, in addition to the resin as described above, a known resin can be blended to the extent that the effects of the present invention are not impaired. Such resins include acrylic resin, urethane resin, epoxy resin, vinyl acetate resin, silicon resin, fluorine resin, acrylic / vinyl acetate resin, acrylic / urethane resin, acrylic / silicone resin, silicon-modified acrylic resin, ethylene / acetic acid Examples include vinyl / veova resin, ethylene / vinyl acetate resin, vinyl chloride resin, chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, and butadiene rubber.

  In addition to the above components, the rust preventive primer of the present invention is a color pigment, extender pigment, rust preventive pigment, coupling agent, thickener, leveling agent, plasticizer, and algae preventive effect. Agents, antifungal agents, antibacterial agents, dispersants, antifoaming agents, ultraviolet absorbers, antioxidants and the like can also be contained.

  Examples of color pigments include titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, red potato, molybdate orange, permanent red, and permanent. Carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, bitumen, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine One or more of violet, zinc pigment, aluminum pigment, pearl pigment and the like can be used.

  Examples of extender pigments include heavy calcium carbonate, cold water stone, light calcium carbonate, white carbon, talc, kaolin, clay, porcelain clay, china clay, diatomaceous earth, barite powder, barium sulfate, precipitated barium sulfate, quartz sand, and quartzite. Examples thereof include powder, quartz powder, resin beads, glass beads, and hollow balloons, and one or more of these can be used.

  Examples of the rust preventive pigment include phosphoric acid rust preventive pigments such as zinc phosphate, iron phosphate, and aluminum phosphate, and phosphite rust preventive pigments such as zinc phosphite, iron phosphite, and aluminum phosphite. Pigment, calcium molybdate, aluminum molybdate, barium molybdate anticorrosive pigments such as vanadium oxide, vanadium antirust pigments such as vanadium oxide, strontium chromate, zinc chromate, calcium chromate, potassium chromate, barium chromate chromate Examples include rust preventive pigments, finely divided silica such as water-dispersed silica and fumed silica, and one or more of these can be used.

As the coating method of the rust preventive primer of the present invention, brush coating, glazing coating, roller coating, spray coating, electrostatic coating, roll coater, curtain flow coater, dipping coating, electrodeposition coating, etc. can be used. A roller or a brush is preferable in terms of workability, coating property, and the like.
Moreover, when the generated rust and the existing coating film exist on the steel material surface, it can be cleaned using a wire brush or the like in advance, or can be polished using a polishing tool.
The coat-weight is not particularly limited, it is usually ^{0.05kg / m 2 ~0.15kg / m 2} .

In the present invention, a refractory material, which will be described later, is laminated after the rust-proof primer is applied.
This invention can show the outstanding adhesiveness by also laminating | stacking the refractory material mentioned later after apply | coating the rust preventive primer mentioned above, Furthermore, it can show the outstanding fire resistance performance.
Moreover, you may apply a well-known primer, especially a rust prevention primer, etc. before laminating | stacking a refractory material. By applying such a primer, adhesion can be further enhanced. Further, by applying a rust preventive primer, the rust preventive property and adhesion can be further improved.

  It does not specifically limit as a refractory material, A well-known thing can be used. Examples thereof include foaming refractory materials such as foamable refractory paints and foamable refractory sheets, and non-foaming refractory materials such as cement-based fireproof coating materials. In the present invention, it is particularly preferable to use a foamable refractory material.

The foamable refractory material is not particularly limited as long as it foams when the ambient temperature reaches a predetermined foaming temperature due to a fire or the like and forms a carbonized heat insulating layer, and a known or commercially available product can be used.
An example of the foamable refractory material is a foamable fireproof paint, and examples of the constituents include those containing a binder, a flame retardant, a foaming agent, a carbonizing agent, and the like.

  Examples of binders include organic bonds such as acrylic resin, vinyl acetate resin, polyester resin, phenol resin, petroleum resin, vinyl chloride resin, epoxy resin, urethane resin, alkyd resin, propylene rubber, chloroprene rubber, butyl rubber, and isobutylene rubber. Agents. These can be used alone or in combination of two or more. Further, if necessary, an inorganic binder such as cement, gypsum, water glass, silicone resin or the like can be used in combination.

The flame retardant generally exhibits at least one effect such as a dehydration cooling effect, an incombustible gas generation effect, and a binder carbonization promoting effect in a fire, and has an action of suppressing the burning of the binder. The flame retardant used in the present invention is not particularly limited as long as it has such an action, and the same flame retardant as in known refractory materials can be used. For example, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, tri (β-chloroethyl) phosphate, tributyl phosphate, tri (dichloropropyl) phosphate, triphenyl phosphate, tri (dibromopropyl) phosphate Organophosphorus compounds such as phosphate, chlorophosphonate, bromophosphonate, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphate, di (polyoxyethylene) hydroxymethyl phosphonate; chlorination Chlorine compounds such as polyphenyl, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, pentachloride fatty acid ester, perchloropentacyclodecane, chlorinated naphthalene, tetrachlorophthalic anhydride; trioxide Nchimon, antimony compounds such as antimony pentachloride; phosphorus trichloride, phosphorus pentachloride, ammonium phosphate, phosphorus compounds such as ammonium polyphosphate; other zinc borate, boron compounds such as boric acid sodium and the like. A flame retardant can be used individually or in combination of 2 or more types.
In the present invention, it is particularly preferable to use ammonium polyphosphate as the flame retardant. In the case of using ammonium polyphosphate, the dehydration cooling effect and the incombustible gas generation effect can be more effectively exhibited.

  The content of the flame retardant is not limited, but is usually 200 to 600 parts by weight, preferably 250 to 450 parts by weight with respect to 100 parts by weight of the solid content of the binder.

  The foaming agent generally plays a role of generating a non-combustible gas in the event of a fire, foaming the carbonizing binder and the carbonizing agent, and forming a foamed layer having pores. As a foaming agent, what is employ | adopted by the well-known foaming refractory material can also be used. Examples of such foaming agents include melamine and derivatives thereof, dicyandiamide and derivatives thereof, azodicarbonamide, urea, thiourea, bistetrazole diguanidine, azobistetrazole diguanidine, azobistetrazole diaminoguanidine, and the like.

  Although content of a foaming agent is not limited, It is 40-200 weight part normally with respect to 100 weight part of solid content of a binder, Preferably it is 40-100 weight part.

  The carbonizing agent generally has a function of forming a foamed layer having a greater thickness due to heat insulation properties by dehydrating and carbonizing itself together with carbonization of the binder due to fire. The carbonizing agent is not particularly limited as long as it has such an action, and the same carbonizing agent as that in a known foamable refractory material can be used. For example, starch, casein, etc. other than polyhydric alcohols such as pentaerythritol, dipentaerythritol, trimethylolpropane and the like can be mentioned. These can be used alone or in combination of two or more. In the present invention, dipentaerythritol is particularly preferable because it is excellent in dehydration cooling effect and foam layer forming action.

  The content of the carbonizing agent is not particularly limited, but is usually 40 to 150 parts by weight, preferably 50 to 100 parts by weight with respect to 100 parts by weight of the solid content of the binder.

The present invention can further contain a filler. In the event of a fire, the filler has sufficient strength, has an effect of keeping the foamed foam layer stable, and can effectively suppress the temperature rise of the base material.
Examples of fillers include silicates such as talc; carbonates such as calcium carbonate and sodium carbonate; metal oxides such as aluminum oxide, titanium dioxide, and zinc oxide; natural minerals such as clay, clay, shirasu, mica, and silica. And the like.
The content of the filler is usually 40 to 200 parts by weight, preferably 50 to 150 parts by weight with respect to 100 parts by weight of the solid content of the binder. When the filler is less than 40 parts by weight, the strength of the foam layer is insufficient, and the foam layer may disappear or collapse. There exists a possibility that a foaming ratio may fall with a filler.

  In addition, the foamable fire-resistant paint of the present invention can be blended with a color pigment, a fiber, a plasticizer, a dispersant, a catalyst, a solvent, and the like, as necessary, within a range that does not impair the effects of the present invention. Furthermore, expansive graphite, unexpanded vermiculite, etc. can also be blended.

  The foamable fireproof paint of the present invention can be obtained by uniformly mixing the above components. The order of mixing the components is not particularly limited. In the mixing, a known device such as a mixer or a kneader may be used.

  When laminating a foamable fire-resistant paint, it may be applied by applying it once or several times using a coating device such as a spray, a roller or a brush. Although the thickness of the foamable fireproof layer finally formed may be appropriately set depending on the desired fireproof performance, application site, and the like, it is usually about 0.2 to 5 mm.

In the present invention, the foamable fire-resistant paint is formed into a sheet form by a known method in advance, impregnated in a cloth-like material such as a nonwoven fabric or a woven fabric, a non-combustible cloth-like material (metal It is also possible to laminate foamable fireproof sheets such as those laminated on foil, etc., laminated on incombustible steel, laminated on heat insulating plate, or laminated on these. it can. As a method of laminating, for example, lamination may be performed by a method of pasting using a known adhesive, a method of pasting by heat sealing, or the like.
The thickness of such a foamable fireproof sheet may be set as appropriate depending on the desired fireproof performance, application site, and the like, but is usually about 0.2 to 5 mm.

  In this invention, in order to protect the fireproof layer formed with the fireproof material, an overcoat layer can also be laminated | stacked as needed. Such a top coat layer can be formed by applying a known top coat. As the top coating, for example, an acrylic resin, urethane resin, acrylic silicon resin, fluororesin, or the like can be used. The clear coating may be applied by a known coating method, and a coating instrument such as a spray, a roller, or a brush can be used.

  Hereinafter, an Example is shown and the characteristic of this invention is clarified more.

(Preparation of rust-proof primer)
Using the raw materials shown in Table 1, the raw materials were mixed in the raw material composition shown in Table 2 to prepare a rust-proof primer.

(Evaluation of rust preventive primer)
The surface of an iron plate (JIS G3141 SPCC) (7 cm x 15 cm) was coated with a rust-proof primer with a brush at 0.08 kg / m ² and cured for 7 days in standard conditions (23 ° C, 50% RH). The following test was conducted using the test piece as a test specimen.

1. Rust prevention test The test specimen was subjected to a salt spray resistance test for 120 hours by the method described in JIS K 5400: 1990 9.1. Evaluation is as follows. The results are shown in Table 3.
A: No swelling or peeling of the coating film was found, and no rust was found.
○: Almost no rust was found.
Δ: Part of rust was observed.
X: Swelling / peeling of the coating film was observed, and generation of rust was observed.

2. Adhesion test JIS K 5400: 1990 8.5.3. For the test specimen after the salt spray test. The adhesion test was performed by the method described in (X-cut tape method). Evaluation is as follows. The results are shown in Table 3.
A: No peeling of the coating film was found.
○: There was almost no peeling of the coating film.
Δ: Some peeling of the coating film was observed.
X: The coating film was peeled off.

Further, the surface of a rusted iron plate (JIS G3141 SPCC) (7 cm × 15 cm) was simply cleaned with a wire brush, and the prepared rust-preventing primer was applied with a brush with a coating amount of 0. A test specimen was prepared by coating at 08 kg / m ² . After coating, each test was carried out under standard conditions (23 ° C., 50% RH) for 7 days.

3. Anti-corrosion test A salt spray test similar to the rust prevention test (iron plate) was performed. The evaluation is as follows. The results are shown in Table 3.
A: No swelling or peeling of the coating film was found, the progress of rust was not progressing, and no rust was found.
○: The progress of rust and the occurrence of rust were hardly observed.
Δ: Some progress of rust and generation of rust were observed.
X: Swelling / peeling of the coating film was observed, rust progress and rust generation were observed.

4). Adhesion test 2. For test specimen after salt spray test, The adhesion test similar to the adhesion test (iron plate) was performed. Evaluation is as follows. The results are shown in Table 3.
A: No peeling of the coating film was found.
○: There was almost no peeling of the coating film.
Δ: Some peeling of the coating film was observed.
X: The coating film was peeled off.

5. Rust penetration test The cross section of the test specimen after coating was observed with a stereomicroscope (SZ6045TRPT: Olympus Corporation) to evaluate the penetration into rust. The evaluation was carried out by a four-step evaluation from ◎ (excellent in penetration into rust) to ○, Δ, and X (no penetration into rust was observed). The results are shown in Table 3.

(Production of foaming fireproof paint)
Using the raw materials shown in Table 4, the raw materials were mixed in the raw material composition shown in Table 4 to produce a foamable fireproof coating material.

Example 1
(Example 1-1)
The surface of an iron plate (JIS G3141 SPCC) (7 cm × 15 cm) (hereinafter also referred to as “iron plate”) was coated with a rust-proof primer 1 with a brush at 0.08 kg / m ² , and the standard state (20 After curing for 7 days at ± 1 ° C and 65 ± 5% RH), apply foaming fireproof paint with a brush at 0.5 kg / m ² and cure for 7 days under standard conditions to obtain a test specimen The following tests were conducted.

(Rust prevention test)
JIS K 5400: 1990 8.5.3. In accordance with the method described in (X-cut tape method), an X-shaped cut was made on the test body, and salt water spray was performed for 120 hours by the method described in JIS K 5400: 1990 9.1. Evaluation is as follows. The results are shown in Table 5.
A: No occurrence of rust was found.
○: Almost no rust was found.
(Triangle | delta): Generation | occurrence | production of rust was seen by the X-shaped cut part.
X: The outflow of rust was seen from the X-shaped cut part.

(Adhesion test)
In the rust prevention test, after spraying with salt water, JIS K 5400: 1990 8.5.3. The adhesion test was performed according to the method described in (X-cut tape method). Evaluation is as follows. The results are shown in Table 5.
A: No peeling of the coating film was found.
○: There was almost no peeling of the coating film.
Δ: Some peeling of the coating film was observed.
X: The coating film was peeled off.

(Example 1-2)
Instead of an iron plate (JIS G3141 SPCC) (7 cm x 15 cm), a rusted iron plate (JIS G3141 SPCC) (7 cm x 15 cm) is simply rusted with a wire brush (hereinafter "rust iron plate") In addition, a test body was obtained in the same manner as in Example 1-1, and the same rust prevention test and adhesion test as in Example 1-1 were performed. The results are shown in Table 5.

(Fire resistance test)
Moreover, in Example 1, the fire resistance test was implemented using the test body obtained in Example 1-1 and Example 1-2, respectively. In the test method, heating was performed for a certain time (1 hour) according to a standard heating curve of ISO834, and after cooling to room temperature, the foaming ratio of the foamed layer was measured.
As a result, both exhibited an excellent expansion ratio and had excellent fire resistance.

(Example 2)
(Example 2-1)
The surface of an iron plate (JIS G3141 SPCC) (7 cm × 15 cm) is coated with rust-proof primer 1 with a brush at 0.08 kg / m ² and cured for 7 days in a standard state (23 ° C., 50% RH). After that, Mirak Bowsey M (manufactured by SK Kaken Co., Ltd., anti-corrosion primer) was applied with a brush at 0.1 kg / m ² , cured for 7 days in a standard state, and further a foamed fireproof paint was applied with a brush. Coating was performed at 0.5 kg / m ² , curing was performed in a standard state for 7 days, a test body was obtained, and the same rust prevention test and adhesion test as in Example 1 were performed. The results are shown in Table 5.

(Example 2-2)
Instead of an iron plate (JIS G3141 SPCC) (7 cm x 15 cm), a rusted iron plate (JIS G3141 SPCC) (7 cm x 15 cm) is simply rusted with a wire brush (hereinafter "rust iron plate") In addition, a test body was obtained in the same manner as in Example 2-1, and the same rust prevention test and adhesion test as in Example 1-1 were performed. The results are shown in Table 5.

(Example 3)
A test body was obtained in the same manner as in Example 2 except that the rust-proof primer 1 was replaced with the rust-proof primer 2, and the same rust-proof test and adhesion test as in Example 1 were performed. The results are shown in Table 5.

(Example 4)
A test body was obtained in the same manner as in Example 2 except that the rust-proof primer 1 was changed to the rust-proof primer 3, and the same rust-proof test and adhesion test as in Example 1 were performed. The results are shown in Table 5.

(Example 5)
A test body was obtained in the same manner as in Example 2 except that the rust-proof primer 1 was replaced with the rust-proof primer 4, and the same rust-proof test and adhesion test as in Example 1 were performed. The results are shown in Table 5.

(Example 6)
A test body was obtained in the same manner as in Example 2 except that the rust-proof primer 1 was changed to the rust-proof primer 5, and the same rust-proof test and adhesion test as in Example 1 were performed. The results are shown in Table 5.

(Example 7)
A test body was obtained in the same manner as in Example 2 except that the rust-proof primer 1 was replaced with the rust-proof primer 6, and the same rust-proof test and adhesion test as in Example 1 were performed. The results are shown in Table 5.

(Example 8)
A test body was obtained in the same manner as in Example 2 except that the rust-proof primer 1 was replaced with the rust-proof primer 7, and the same rust-proof test and adhesion test as in Example 1 were performed. The results are shown in Table 5.

(Comparative Example 1)
A test body was obtained in the same manner as in Example 2 except that the rust-proof primer 1 was replaced with the rust-proof primer 8, and the same rust-proof test and adhesion test as in Example 1 were performed. The results are shown in Table 5.

(Comparative Example 2)
(Comparative Example 2-1)
Example A foamed fire-resistant paint was applied to the surface of an iron plate (JIS G3141 SPCC) (7 cm × 15 cm) with a brush at 0.5 kg / m ² and cured for 7 days in a standard state to obtain a test sample. The same rust prevention test and adhesion test as in 1-1 were performed. The results are shown in Table 5.

(Comparative Example 2-2)
Comparative Example 2 using a rusted iron plate with a wire brush instead of a rusted iron plate (JIS G3141 SPCC) (7 cm × 15 cm) instead of an iron plate (JIS G3141 SPCC) (7 cm × 15 cm) The test body was obtained by the same method as -1, and the same rust prevention test and adhesion test as in Example 1-1 were performed. The results are shown in Table 5.

Claims (3)

  On the steel surface, A. A chelate-modified epoxy resin; Ketimine compounds, C.I. Anion exchange compound, D.I. A method for fire-resistant coating of a steel material surface, comprising applying a rust-proof primer containing an organic solvent and then laminating a fire-resistant material.   The rust-proof primer is A. B. 100 parts by weight of the chelate-modified epoxy resin 5 to 40 parts by weight of a ketimine compound, C.I. 0.01 to 100 parts by weight of anion exchange compound, D.I. The fireproof coating method for a steel material surface according to claim 1, comprising 10 to 300 parts by weight of an organic solvent. D. The fireproof coating method for a steel material surface according to claim 1 or 2, wherein 40% by weight or more of the organic solvent is an aliphatic hydrocarbon organic solvent.